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    • 专利摘要:
    The present invention provides a novel olefin polymerization catalyst having excellent olefin polymerization activity, and a polymerization method for producing a low molecular weight polymer with high polymerization activity when polymerized using the transition metal compound. The present invention provides at least one compound selected from a transition metal compound represented by the following general formula and an organometallic compound (B-1), an organoaluminum oxy compound (B-2) and an ionizing ionic compound (B-3) ( The olefin is polymerized in the presence of a catalyst consisting of B). [Wherein M is a transition metal atom of Groups 4 to 5 of the periodic table, m is 1 to 4, R 1 is H, C 1 to C 5 are a straight chain hydrocarbon group and a bicyclic hydrocarbon group sharing at least one or more carbons; Or 3 to 5 membered alicyclic hydrocarbon group, R 2 to R 6 are hydrogen, halogen, hydrocarbon group, X is hydrogen, halogen atom, etc., n is the number satisfying the valence of M.]
    公开号:KR20020097026A
    申请号:KR1020020034586
    申请日:2002-06-20
    公开日:2002-12-31
    发明作者:이시이세이이치；미타니마코토；사이토준지；마츠우라사다히코；마츠카와나오토；츠루가즈타카；후지타데루노리
    申请人:미쓰이 가가쿠 가부시키가이샤；
    IPC主号:
    专利说明:

    Catalyst for olefin polymerization, polymerization method of olefin, ethylene polymer obtained by the method, and uses thereof
    [1] The present invention relates to a catalyst for olefin polymerization, a polymerization method of olefins using the catalyst, a low molecular weight ethylene polymer obtained by the polymerization method, and a use of these low molecular weight ethylene polymers, and more particularly, a high polymerization activity. A novel olefin polymerization catalyst having a olefin, a polymerization method of an olefin using the catalyst, a low molecular weight ethylene polymer having a narrow molecular weight distribution and a high content of vinyl or vinylidene group at a main chain terminal position, and modified substances thereof, and their It is about a use.
    [2] Conventionally, as a catalyst for manufacturing olefin polymers, such as an ethylene polymer and an ethylene-alpha-olefin copolymer, the titanium type catalyst which consists of a titanium compound and an organoaluminum compound, and the vanadium type catalyst which becomes a vanadium compound and an organoaluminum compound are known. .
    [3] Moreover, as a catalyst which can manufacture an olefin polymer with high polymerization activity, the Ziegler-type catalyst which consists of metallocene compounds, such as a zirconocene, and an organoaluminum oxy compound (aluminooxane) is known.
    [4] Also, as a new olefin polymerization catalyst, Japanese Patent Laid-Open No. 11-315109 discloses a transition metal compound having a salicylicinimine ligand, which describes that the complex exhibits high olefin polymerization activity. Further, Japanese Patent Application Laid-Open No. 2001-2731 discloses a novel low molecular weight ethylene polymer containing a double bond at one end, a modified product of a single end double bond, and their use (toner) which can be produced by using the transition metal compound. Release agent, pigment dispersant, lubricant for vinyl chloride resin).
    [5] However, in order to exhibit higher performance in these applications and to use it in another application, a double bond at the one end position of the polymer main chain (hereinafter referred to as a "double end double bond" in the following description). It was required to make the content rate of higher.
    [6] An object of the present invention is to provide a novel olefin polymerization catalyst having excellent olefin polymerization activity, and a polymerization method for producing a low molecular weight polymer with high polymerization activity when polymerizing using the transition metal compound.
    [7] The present invention also provides a low molecular weight ethylene polymer having a single terminal double bond at a high ratio, and a modified product obtained by treating the single terminal double bond with a specific modifier, and the use of these low molecular weight ethylene polymers and modified bodies. For the purpose.
    [8] The first olefin polymerization catalyst according to the present invention is characterized by being a (A) transition metal compound represented by the following general formula (I).
    [9]
    [10] Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    [11] m represents an integer of 1 to 4,
    [12] R 1 represents a straight chain hydrocarbon group having 1 to 5 carbon atoms (C n ′ H 2n ′ + 1 , n ′ = 1 to 5) or a hydrogen atom,
    [13] R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    [14] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [15] n is a number satisfying the valence of M,
    [16] X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a heterocyclic compound residue, a silicon group, a germanium group , Or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be combined with each other to form a ring.)
    [17] In the first olefin polymerization catalyst, (A) in the transition metal compound represented by the general formula (I), M is a transition metal atom of Group 4 of the periodic table, m is 2, n is 2, and R 1 is the group a straight-chain hydrocarbon group of a carbon number of 1~5 (C n 'H 2n' + 1, n '= 1~5) or a hydrogen atom is preferred.
    [18] In the first catalyst for olefin polymerization, (A) In the transition metal compound represented by the general formula (I), it is preferable that M is a zirconium atom and R 1 is a methyl group, an ethyl group or a hydrogen atom.
    [19] The second olefin polymerization catalyst according to the present invention is characterized by being a (A) transition metal compound represented by the following general formula (II).
    [20]
    [21] Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    [22] m represents an integer of 1 to 4,
    [23] R 1 is a 3 to 5 membered alicyclic hydrocarbon group which may have one or a plurality of substituents,
    [24] R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    [25] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [26] n is a number satisfying the valence of M,
    [27] X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a heterocyclic compound residue, a silicon group, a germanium group , Or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be combined with each other to form a ring.)
    [28] In the second olefin polymerization catalyst, (A) in the transition metal compound represented by the general formula (II), M is a Group 4 transition metal atom of the periodic table, m is 2, n is 2, and R 1 Is preferably a 3 to 5 membered alicyclic hydrocarbon group which may have one or a plurality of substituents.
    [29] In the second catalyst for olefin polymerization, (A) in the transition metal compound represented by the general formula (II), M is a zirconium atom, and R 1 is a 3 to 5 membered ring which may have one or a plurality of autocyclic groups. It is preferable that it is an alicyclic hydrocarbon group.
    [30] The third olefin polymerization catalyst according to the present invention is characterized by (A) a transition metal compound represented by the following general formula (III).
    [31]
    [32] Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    [33] m represents an integer of 1 to 4,
    [34] R 1 represents a dicyclic hydrocarbon group which shares at least one or more carbon atoms having 4 to 20 carbon atoms, which may have one or a plurality of substituents;
    [35] R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    [36] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [37] n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a hetero A cyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be formed.)
    [38] In the third olefin polymerization catalyst (A) in the transition metal compound represented by the general formula (III), M is a transition metal atom of Group 4 of the periodic table, m is 2, n is 2, and R 1 is It is preferable that it is a bicyclic hydrocarbon group which shares one or two carbon atoms of 4 to 20 carbon atoms which may have one or a plurality of substituents.
    [39] Further, the third catalyst for olefin polymerization (A) in the transition metal compound represented by the general formula (III), R 1 may have one or a plurality of substituents, and share two carbon atoms having 4 to 20 carbon atoms. It is preferable that it is a bicyclic hydrocarbon group.
    [40] In the third olefin polymerization catalyst, (A) in the transition metal compound represented by the general formula (III), M may be a zirconium atom, R 1 may have one or a plurality of substituents, and may have 5 to 20 carbon atoms. It is more preferable that it is a bridge | bicyclic bicyclic aliphatic hydrocarbon group which shares two carbons of.
    [41] Moreover, the catalyst for olefin polymerization of this invention is (A) the transition metal compound represented with the said general formula (I), (II), or (III), (B) (B-1) organic metal compound, (B -2) It is preferable that it is at least 1 sort (s) of compound chosen from the organic aluminum oxy compound and the compound which reacts with (B-3) transition metal compound (A) and forms an ion pair.
    [42] The olefin polymerization method of the present invention is characterized in that at least one olefin is polymerized in the presence of the catalyst for olefin polymerization as described above.
    [43] The low molecular weight ethylene-based polymer produced in the present invention contains a vinyl or vinylidene-type double bond at one end, and a low molecular weight ethylene-based (co) composed of ethylene alone or ethylene and an α-olefin having 3 to 10 carbon atoms. Polymer. Examples of the α-olefin having 3 to 10 carbon atoms used in the present invention include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, etc. are mentioned, 1 type, or 2 or more types of these are used. Among these, propylene and 1-butene are especially preferable.
    [44] The structural unit derived from ethylene in the low molecular weight ethylene polymer of the present invention is 81 to 100 mol%, preferably 90 to 100 mol%, particularly preferably 94 to 100 mol%. On the other hand, the structural unit derived from a C3-C10 alpha olefin is 0-19 mol%, Preferably it is 0-10 mol%, More preferably, it is 0-6 mol%.
    [45] The intrinsic viscosity ([η]) measured in 135 degreeC and decalin of the low molecular weight (co) polymer of this invention is 0.39 dl / g or less, Preferably it is 0.25 dl / g or less. The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the low molecular weight ethylene polymer of this invention is 7,000 or less, Preferably it is 5,000 or less.
    [46] The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the low molecular weight ethylene polymer of the present invention, that is, the molecular weight distribution (Mw / Mn) is 1.1 to 2.5, Preferably it is the range of 1.2-2.2.
    [47] The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows using GPC-150 by Millipore. The separation column is TSK GNH HT, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is orthodichlorobenzene (wakwang pure) and BHT (anionless) as an antioxidant. (Drug) It was made to move to 1.Oml / min using 0.025 weight%, the sample concentration was 0.1 weight%, the sample injection quantity was 500 microliters, and the differential refractometer was used as a detector. Standard polystyrene was used by Tosoh Corporation.
    [48] The ratio of the vinyl or vinylidene type double bond measured by <1> H-NMR or IR in the low molecular weight ethylene polymer of this invention (in the following description, this ratio is referred to as "double bond content rate" or "one end vinylation rate"). Is more than 90% of the front end, more preferably 94% or more.
    [49] For 1 H-NMR, the polymer was completely dissolved in orthodichlorobenzene containing a small amount of deuterated benzene as a lock solvent in the measurement sample tube, and then measured at 120 ° C. In chemical shift, the peak of tetramethylsilane was made into Oppm, and the chemical shift of the other peak was determined.
    [50] The double bond content in the low molecular weight polymer consisting only of ethylene is determined by 1 H-NMR. The peak of each hydrogen of the polymer is observed at a peak (A) of 0.65 to 0.85 ppm and a peak (B) and (C) of vinyl group at 4.85 to 5.0 ppm and 5.5 to 5.8 ppm, respectively. . When the peak areas of each peak (A), (B) and (C) are S A , S B and S C , respectively, the double bond content (U%) can be calculated by the following formula.
    [51]
    [52] In the above formula, the molecule represents the area amount of the peak by the terminal vinyl group, and the denominator represents the area amount of the peak by the terminal methyl group. In addition, the terminal vinyl group and terminal vinylidene group of the copolymer which consists of ethylene and an alpha olefin are quantified by the method disclosed by Unexamined-Japanese-Patent No. 2001-2731.
    [53] The low molecular weight ethylene-based copolymer according to the present invention is a single-ended terminal vinyl or terminal vinylidene group of the polymer main chain, epoxidizing agent, sulfonating agent, maleic anhydride and its derivatives, hydroborating agent, organoaluminum hydride, silylating agent, halogenating agent By treatment with at least one compound selected from the group consisting of oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, halogen-containing groups or tin-containing groups, Can be. Examples of the epoxidation agent used as the modifier in the present invention include formic acid-hydrogen peroxide (H 2 O 2 ), m-chloroperbenzoic acid, and the like. Sulfonating agents include sulfuric acid-acetic anhydride. Examples of the hydroborating agent include diborane, trimethylborane, 9-boranebicyclo [3.3.1] nonane, and the like. Examples of the organoaluminum hydride include diisobutylaluminum hydride. Silylating agents include triethoxysilyl hydride / H 2 PtCl 2 and trimethoxysilyl hydride / H 2 PtCl 2 . Examples of the halogenating agent include hydrogen bromide, hydrogen chloride and hydrogen iodide.
    [54] Specific modification conditions (details such as temperature, time, type of catalyst, amount of catalyst, etc.) by these modifiers can be carried out according to the conditions described in Die Makromolecular Chemie Makromolecular Symposia 48/49, 317-332, 1991.
    [55] For example, an oligomer having an oxygen-containing group whose terminal is modified with maleic anhydride, an oligomer containing an amide group and an amine group, and the like are suitable as paint additives and pigment dispersants due to thixotropy provision.
    [56] Moreover, the oligomer which has a silicon containing group, a tin containing group, etc. is suitable for the use of a polyvinyl chloride lubricant, lubricants, such as engineering plastics, paper processing agents, etc.
    [57] The paint modifier according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This paint modifier is excellent in a gloss removal effect and improves abrasion resistance of a coating film. Specifically, the woodwork paint is given a sense of quality, and durability is improved.
    [58] The gloss agent according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This varnish has excellent gloss and improves coating film properties. Specifically, the performance of automobile waxes and stairs polishes is improved.
    [59] The mold release agent for resin molding which concerns on this invention contains the low molecular weight ethylene polymer which the terminal may be modified as mentioned above. This mold release agent provides mold release property to a thermoplastic resin and a thermosetting resin. Therefore, the molding cycle of resin can be improved.
    [60] The rubber processing aid according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This preparation is excellent in mold release property, fluidity | liquidity, and improves the dispersibility of a filler and a pigment. Specifically, the molding cycle and the extrusion characteristics are improved.
    [61] The paper quality improving agent which concerns on this invention contains the low molecular weight ethylene polymer which the terminal may be modified as mentioned above. This paper quality improver improves moisture resistance, gloss, surface hardness, blocking resistance, and wear resistance. Specifically, it gives a sense of quality and improves durability.
    [62] The wear resistance improving agent for inks according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This wear resistance improving agent imparts wear resistance and heat resistance to the surface of the ink. Specifically, the sharpness of the ink is improved.
    [63] The fiber processing aid according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This preparation imparts flexibility and lubricity at the time of fiber processing of the resin. Specifically, high speed sewing property and tear strength are improved.
    [64] The hot melt additive according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This additive imparts heat resistance and fluidity to the hot melt adhesive. Specifically, it improves the quality in heat-resistance demand fields (automobiles, building materials).
    [65] The electrical insulation agent which concerns on this invention contains the low molecular weight ethylene polymer which the terminal may be modified as mentioned above. This electrical insulation is excellent in electrical property, and improves a softening point. Specifically, the electrical insulation characteristics of the film capacitors are improved.
    [66] The compounding agent of the natural wax which concerns on this invention contains the low molecular weight ethylene polymer which the terminal may be modified as mentioned above. This compounding agent improves surface hardness and a softening point. Specifically, the performance of crayons and candles is improved.
    [67] The antifogging agent of the polyolefin film by this invention contains the low molecular weight ethylene polymer which the terminal may be modified as mentioned above. This antifogging agent is excellent in compatibility with resin, and suppresses the bleed out of the resin surface. Specifically, the durability of the film is improved.
    [68] The release agent for toners according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This toner release agent imparts offset resistance to the fixing roll. Specifically, image sharpness is improved.
    [69] The pigment dispersant according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This pigment dispersant is excellent in wettability with various pigments and improves durability. Specifically, it can be set as a high concentration masterbatch.
    [70] The lubricant for vinyl chloride resins according to the present invention contains a low molecular weight ethylene polymer which may have a terminal modified as described above. This lubricant is excellent in the balance of the lubricant and has a long life. Specifically, productivity is improved, leading to reduction of power consumption.
    [71] In addition, the low molecular weight ethylene-based copolymer or modified product thereof synthesized as described above can be copolymerized with homopolymerization or at least one olefin selected from ethylene and an alpha -olefin having 3 to 10 carbon atoms as a macromonomer. It can also be used for a coupling reaction. As a C3-C10 alpha olefin used at this time, the alpha olefin used at the time of manufacture of said low molecular weight ethylene polymer can be illustrated. The polymer obtained by using a low molecular weight ethylene polymer or its modified body as a macromonomer is a novel polymer having a new skeleton, and is used in various applications as such or as a resin composition containing the same. For example, by copolymerizing with ethylene, a long chain branched polyethylene can be produced in which the number of branched chains and the molecular weight of the branched part are arbitrarily controlled. Moreover, when manufacturing an amorphous polymer by copolymerization of ethylene / alpha-olefin, by copolymerizing the macromonomer of polyethylene, non-crystalline and crystalline part can coexist in a polymer molecule, and high performance copolymer can be manufactured. In addition, this copolymer can be used as a modifier for polypropylene resins, and can be mix | blended in the ratio of 1-30 weight part with respect to polypropylene resin, for example.
    [72] <Embodiment of the Invention>
    [73] Hereinafter, the polymerization method of the olefin in this invention is demonstrated concretely.
    [74] In addition, in this specification, the term "polymerization" is used by the meaning containing not only a homopolymerization but copolymerization, and the word "polymer" is used by the meaning containing not only a homopolymer but a copolymer.
    [75] The olefin polymerization catalyst according to the present invention is (A) the transition metal compound represented by the general formulas (I), (II) and (III), or (A) the general formulas (I), (II) and (III). To form an ion pair by reacting with the transition metal compound represented by the formula (I), (B) (B-1) organic metal compound, (B-2) organic aluminum oxy compound, and (B-3) transition metal compound (A). It is formed with at least 1 sort (s) of compound chosen from a compound.
    [76] (A) transition metal compound
    [77] The (A) transition metal compound which comprises the 1st olefin polymerization catalyst which concerns on this invention is a compound represented with the following general formula (I).
    [78]
    [79] (In addition, although N ...... M shows generally coordinating, in this invention, even if it coordinates, it is not necessary to coordinate.)
    [80] In general formula (I), M represents the transition metal of group 4-5 of a periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, Preferably it is a metal atom of group 4, Specifically Is titanium, zirconium, hafnium, and more preferably zirconium. m represents the integer of 1-4, Preferably it is 1-2, Especially preferably, it is 2.
    [81] R 1 represents a straight-chain hydrocarbon groups (C n 'H 2' + 1, n '= 1 to 5) or a hydrogen atom of 1 to 5 carbon atoms. Specifically as a C1-C5 linear hydrocarbon group of R <1> , a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group is mentioned. In these, a methyl group, an ethyl group, and n-propyl group are preferable.
    [82] As R 1 , a methyl group, an ethyl group, and a hydrogen atom are more preferable.
    [83] R 2 to R 6 may be the same as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, a sulfur containing group, a phosphorus containing group, and a silicon containing group , A germanium-containing group or a tin-containing group, two or more of these may be linked to each other to form a ring,
    [84] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [85] Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group. -30, Preferably 1-20 linear or branched alkyl group;
    [86] Linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as vinyl group, allyl group, and isopropenyl group;
    [87] Linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as an ethynyl group and a propargyl group:
    [88] Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and adamantyl group;
    [89] Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group, and fluorenyl group;
    [90] Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group;
    [91] Alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group, etc. are mentioned.
    [92] Hydrogen atom may be substituted by the said halogen group by halogen, For example, a C1-C30 halogenated hydrocarbon group, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group, is mentioned.
    [93] Moreover, the said hydrocarbon group may be substituted by other hydrocarbon group, For example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned.
    [94] In addition, the hydrocarbon group heterocyclic compound residues; Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonato groups, hydroxy groups, peroxy groups, and carboxylic acid anhydride groups; 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, amino groups comprising ammonium salts Nitrogen-containing groups such as; Boron-containing groups such as borandiyl group, boranetriyl group, and diboranyl group; Mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothianic acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl Sulfur-containing groups such as groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfphenyl groups: phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, and phosphite groups, silicon-containing groups, You may have a germanium containing group or a tin containing group. Among these, in particular, C1-C1, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group 30, preferably 1-20 linear or branched alkyl groups; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group; 1 to 5 substituents such as a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms or an alkoxy group, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms or an aryloxy group Substituted substituted aryl group etc. are preferable.
    [95] Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group and the phosphorus-containing group include those similar to those exemplified above.
    [96] Examples of the heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygenated compounds such as furan and pyran and sulfur-containing compounds such as thiophene, and heterocyclic compound residues thereof. And groups in which substituents such as alkyl and alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms are further substituted.
    [97] Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon substituted silyl group and hydrocarbon substituted siloxy group, and specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group and triethylsilyl group , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-tbutylsilyl group, dimethyl (pentafluorophenyl) silyl group, and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenyl silyl group, triphenylsilyl group and the like are preferable. In particular, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.
    [98] Examples of the germanium-containing group and tin-containing group include those in which silicon of the silicon-containing group is substituted with germanium and tin.
    [99] For example, the R 2 ~R 6 described in the following, will be described in detail. As an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc. are mentioned specifically ,.
    [100] Specific examples of the alkylthio group include methylthio group and ethylthio group.
    [101] As an aryloxy group, a phenoxy group, 2, 6- dimethylphenoxy group, 2, 4, 6-trimethyl phenoxy group etc. are mentioned specifically ,.
    [102] As an aryl thi group, a phenylthio group, a methylphenylthio group, a naphthylthio group, etc. are mentioned specifically ,.
    [103] Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, and the like. Specific examples of the ester group include acetyloxy group, benzoyloxy, methoxycarbonyl group, phenoxycarbonyl group, p-chlorophenoxycarbonyl group and the like.
    [104] Specific examples of the thioester group include acetylthio group, benzoylthio group, methylthiocarbonyl group, and phenylthiocarbonyl group.
    [105] Specific examples of the amide group include acetamide group, N-methylacetamide group, and N-methylbenzamide group.
    [106] As an imide group, an acetimide group, a benzimide group, etc. are mentioned specifically ,. Specific examples of the amino group include dimethylamino group, ethylmethylamino group, diphenylamino group, and the like.
    [107] Specific examples of the imino group include methylimino group, ethylimino group, propylimino group, butylimino group, and phenylimino group.
    [108] As a sulfone ester group, a methyl sulfonate group, an ethyl sulfonate group, a sulfonate phenyl group, etc. are mentioned specifically ,.
    [109] As a sulfonamide group, a phenyl sulfonamide group, N-methyl sulfonamide group, N-methyl- p-toluene sulfonamide group, etc. are mentioned specifically ,.
    [110] In the present invention, R 6 is particularly preferably a branched alkyl group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and more preferably Phenylethyl group, diphenylmethyl group, cumyl group, diphenylethyl group, triphenylmethyl group, and a carbon atom such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. It is preferably a group selected from 3 to 30, preferably 3 to 20, cyclic saturated hydrocarbon groups, and also 6 to 30 carbon atoms, preferably 6 to 6, such as phenyl, naphthyl, fluorenyl, anthracenyl and phenanthryl. It is also preferable that it is a 20 aryl group or a hydrocarbon substituted silyl group.
    [111] R 2 to R 6 may be a hydrocarbon ring containing two or more of these groups, preferably adjacent groups, connected to each other to form an alicyclic ring, an aromatic ring, or a hetero atom such as a nitrogen atom, and these rings may have a substituent. You may have more.
    [112] In addition, when m is two or more, two groups of groups represented by R <2> -R <6> may be connected. In addition, when m is two or more, R <1> , R <2> , R <3> , R <4> , R <5> , and R <6> may mutually be same or different.
    [113] n is a number satisfying the valence of M, specifically, it is 0-5, Preferably it is 1-4, More preferably, it is an integer of 1-3.
    [114] X is hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium containing Group or a tin-containing group. In addition, when n is two or more, they may mutually be same or different.
    [115] Halogen atoms include fluorine, chlorine, bromine and iodine.
    [116] As a hydrocarbon group, the same thing as what was illustrated by said R <2> -R <6> is mentioned. Specifically, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, an icosyl group; C3-C30 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group; Alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group: arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; Aryl groups such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl, anthryl group, phenanthryl group, etc. may be mentioned, but are not limited thereto. . These hydrocarbon groups also include halogenated hydrocarbons, specifically, hydrogen in which at least one of the hydrocarbon groups of 1 to 20 carbon atoms is substituted with halogen.
    [117] Among these, those having 1 to 20 carbon atoms are preferable.
    [118] As a heterocyclic compound residue, the same thing as what was illustrated by said R <2> -R <6> is mentioned.
    [119] As an oxygen containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, A hydroxyl group; Alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, butoxy; Aryloxy groups such as phenoxy group, methylphenoxy group, dimethylphenoxy and naphthoxy group; Arylalkoxy groups such as phenylmethoxy group and phenylethoxy group: acetoxy group; Although carbonyl group etc. are mentioned, It is not limited to these.
    [120] As a sulfur containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, a methyl sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, p-toluene Sulfonate groups such as sulfonate groups, trimethylbenzenesulfonate groups, triisobutylbenzenesulfonate groups, p-chlorobenzenesulfonate groups and pentafluorobenzenesulfonate groups; Sulfinate groups such as methyl sulfinate group, phenyl sulfinate group, benzyl sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group and pentafluorobenzene sulfinate group; Alkylthio group; Although an arylthio group etc. are mentioned, It is not limited to these.
    [121] Specific examples of the nitrogen-containing group include those exemplified by the above R 2 to R 6 , specifically, an amino group; Alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, diethylamino group, dibutylamino group and dicyclohexylamino group; Although an arylamino group or alkylarylamino group, such as a phenylamino group, a diphenylamino group, a totolylamino group, a dinaphthylamino group, and a methylphenylamino group, etc. are mentioned, It is not limited to these.
    [122] A boron-containing group Specifically, BR 4 may be mentioned (R is hydrogen, an alkyl group, a substituent FIG aryl group, a halogen atom or the like).
    [123] Specifically as a phosphorus containing group, Trialkyl phosphine groups, such as a trimethyl phosphine group, a tributyl phosphine group, and a tricyclohexyl phosphine group; Triaryl phosphine groups, such as a triphenyl phosphine group and a tritolyl phosphine group; Phosphite groups (phosphides) such as methyl phosphide group, ethyl phosphite group and phenyl phosphite group; Phosphonic acid group: Although a phosphinic acid group etc. are mentioned, It is not limited to these.
    [124] Specific examples of the silicon-containing group include those exemplified by the above R 2 to R 6 , and specifically, a phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, and tripropylsilyl group Hydrocarbon substituted silyl groups such as tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, and trinaphthylsilyl group; Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; Silicon substituted alkyl groups such as trimethylsilylmethyl group; Silicon substituted aryl groups, such as a trimethylsilylphenyl group, etc. are mentioned.
    [125] Specific examples of the germanium-containing group include those exemplified by the above R 2 to R 6 , and specific examples include a group in which silicon of the silicon-containing group is substituted with germanium.
    [126] Specific examples of the tin-containing group include those similar to those exemplified in the above R 2 to R 6 , and more specifically, groups in which silicon of the silicon-containing group is substituted with tin are mentioned.
    [127] Specific examples of the halogen-containing group include, but are not limited to, fluorine-containing groups such as PF 6 and BF 4 , chlorine-containing groups such as ClO 4 and SbCl 6, and iodine-containing groups such as IO 4 .
    [128] Specific examples of the aluminum-containing group include AlR 4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but is not limited thereto.
    [129] In addition, when n is two or more, the some group represented by X may mutually be same or different, and the some group represented by X may combine with each other, and may form the ring.
    [130] The (A) metal compound which comprises the 2nd olefin polymerization catalyst used by this invention is a compound represented with the following general formula (II).
    [131]
    [132] (Although N ····· M is generally indicated to be harmful, the present invention does not need to be coordinated.)
    [133] In Formula (II), M represents a transition metal of Groups 4 to 5 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, and tantalum, preferably a metal atom of Group 4, specifically Is titanium, zirconium, hafnium, and more preferably zirconium.
    [134] m represents the integer of 1-4, Preferably it is 1-2, Especially preferably, it is 2.
    [135] R 1 represents a 3 to 5 membered alicyclic hydrocarbon group which may have one or a plurality of substituents. As an alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group are mentioned specifically ,.
    [136] The substituent of R 1 is not particularly limited, but a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, Although it is group chosen from heterocyclic compound residue, the hydrocarbon group or hydrocarbon substituted silyl group containing these groups is mentioned.
    [137] As may have the R 1 substituents, specifically, hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, butoxy group, phenoxy group, ethoxy group, dimethylamino group, dimethylamino Ethyl group, nitromethyl group, nitroethyl group, cyanomethyl group, cyanoethyl group, trimethylsilyl group, triethylsilyl group, etc. are mentioned.
    [138] In the 3 to 5 membered alicyclic hydrocarbon group having two or more substituents of R 1 , there are no particular restrictions on the positions of the two or more substituents.
    [139] R 2 to R 6 may be the same as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, a sulfur containing group, a phosphorus containing group, and a silicon containing group , A germanium-containing group or a tin-containing group, two or more of these may be linked to each other to form a ring,
    [140] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [141] Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
    [142] Specifically as a hydrocarbon group, carbon number, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. Linear or branched alkyl groups of 1 to 30, preferably 1 to 20;
    [143] Linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as vinyl group, allyl group, and isopropenyl group;
    [144] Linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as an ethynyl group and a propargyl group;
    [145] Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and adamantyl group;
    [146] Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group, and fluorenyl group;
    [147] Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as a phenyl group, benzyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group and anthracenyl group;
    [148] Alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group, etc. are mentioned.
    [149] The said hydrocarbon group may be substituted by the hydrogen atom by halogen, For example, a C1-C30 halogenated hydrocarbon group, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group, is mentioned.
    [150] Moreover, the said hydrocarbon group may be substituted by other hydrocarbon group, For example, aryl group substituted alkyl groups, such as a benzyl group and a cumyl group, etc. are mentioned.
    [151] In addition, the hydrocarbon group heterocyclic compound residues; Oxygen-containing groups such as alkoxy, aryloxy, ester, ether, acyl, carboxyl, carbonate, hydroxy, peroxy and carboxylic anhydride groups; 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, amino groups comprising ammonium salts Nitrogen-containing groups such as; Boron-containing groups such as borandiyl group, boranetriyl group, and diboranyl group; Mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothianic acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl Sulfur-containing groups such as groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfphenyl groups; You may have phosphorus containing groups, such as a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphite group, a silicon containing group, a germanium containing group, or a tin containing group.
    [152] Among these, in particular, carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group 30, preferably 1-20 linear or branched alkyl groups; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group; 1 to 5 substituents such as a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms or an alkoxy group, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms or an aryloxy group Substituted aryl groups and the like are preferable.
    [153] Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group and the phosphorus-containing group include those similar to those exemplified above.
    [154] Examples of the heterocyclic compound residue include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygenated compounds such as furan and pyran and sulfur-containing compounds such as thiophene, and residues of these heterocyclic compounds. 1-30, Preferably the group which further substituted by substituents, such as an alkyl group of 1-20, an alkoxy group, etc. are mentioned.
    [155] As a silicon-containing group, a silyl group, a siloxy group, a hydrocarbon substituted silyl group, a hydrocarbon substituted siloxy group, etc. Specifically, methyl silyl group, dimethyl silyl group, trimethyl silyl group, ethyl silyl group, diethyl silyl group, triethyl silyl group , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group, and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group and the like are preferable. In particular, trimethylsilyl group, triethylsilyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxane group include trimethylsiloxy.
    [156] Examples of the germanium-containing group and tin-containing group include those in which silicon of the silicon-containing group is substituted with germanium and tin.
    [157] For example, the R 2 ~R 6 described in the following, will be described in detail.
    [158] As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc. are mentioned specifically ,.
    [159] As an alkyl thi group, methylthio group, ethylthio group, etc. are mentioned specifically ,.
    [160] As an aryloxy group, a phenoxy group, 2, 6- dimethylphenoxy group, 2, 4, 6-trimethyl phenoxy group etc. are mentioned specifically ,.
    [161] As an aryl thi group, a phenylthio group, a methylphenylthio group, a naphthylthio group, etc. are mentioned specifically ,.
    [162] Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group and the like.
    [163] Specific examples of the ester group include an acetyloxy group, benzoyloxy group, methoxycarbonyl group, phenoxycarbonyl group, p-chlorophenoxycarbonyl group and the like.
    [164] Specific examples of the thioester group include acetylthio group, benzoylthio group, methylthiocarbonyl group, and phenylthiocarbonyl group.
    [165] Specific examples of the amide group include acetamide group, N-methylacetamide group, and N-methylbenzamide group.
    [166] Specific examples of the imide group include an acetimide group and a benzimide group.
    [167] Specifically as an amino group, a dimethylamino group, an ethylmethylamino group, a diphenylamino group, etc. are mentioned.
    [168] As an imino group, a methyl imino group, an ethyl imino group, a propyl imino group, a butyl imino group, a phenyl imino group, etc. are mentioned specifically ,.
    [169] Specifically as a sulfone ester group, a methyl sulfonate group, an ethyl sulfonate group, a sulfonate phenyl group, etc. are mentioned.
    [170] As a sulfone amide group, a phenyl sulfonamide group, N-methyl sulfonamide group, N-methyl- p-toluene sulfonamide group, etc. are mentioned specifically ,.
    [171] In the present invention, R 6 is particularly preferably a branched alkyl group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and more preferably Phenylethyl group, diphenylmethyl group, cumyl group, diphenylethyl group, triphenylmethyl group, and a carbon atom such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. It is preferably a group selected from 3 to 30, preferably 3 to 20 cyclic saturated hydrocarbon groups, or 6 to 30 carbon atoms such as phenyl, naphthyl, fluorenyl, anthranyl, phenanthryl, and preferably 6 to 30 carbon atoms. It is also preferable that it is a 20 aryl group or a hydrocarbon substituted silyl group.
    [172] R 2 to R 6 may be a hydrocarbon ring containing two or more of these groups, preferably adjacent groups, connected to each other to form an alicyclic ring, an aromatic ring, or a hetero atom such as a nitrogen atom, and these rings may have a substituent. You may have more.
    [173] In addition, when m is two or more, two groups of groups represented by R <2> -R <6> may be connected. In addition, when m is two or more, R <1> , R <2> , R <3> , R <4> , R <5> , and R <6> may mutually be same or different.
    [174] n is the number which satisfy | fills the valence of M, Specifically, it is 0-5, Preferably it is 1-4, More preferably, it is an integer of 1-3.
    [175] X is hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium containing Group or a tin-containing group. In addition, when n is two or more, they may mutually be same or different.
    [176] Halogen atoms include fluorine, chlorine, bromine and iodine. As a hydrocarbon group, the same thing as what was illustrated by said R <2> -R <6> is mentioned. Specifically, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, an icosyl group; C3-C30 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group; Alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group; Arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; Aryl groups, such as a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, etc. are mentioned, but it is not limited to these. . In addition, these hydrocarbon groups also include a halogenated hydrocarbon, specifically, a group in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
    [177] Among these, those having 1 to 20 carbon atoms are preferable.
    [178] Examples of the heterocyclic compound residues include the same as those exemplified for the above R 2 to R 6 .
    [179] As an oxygen containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, A hydroxyl group; Alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group; Aryloxy groups such as phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthoxy group; Arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; Acetoxy group; Although carbonyl group etc. are mentioned, It is not limited to these.
    [180] As a sulfur containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, a methyl sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, p- Sulfonate groups such as toluenesulfonate group, trimethylbenzenesulfonate group, triisobutylbenzenesulfonate group, p-chlorobenzenesulfonate group and pentafluorobenzenesulfonate group; Sulfinate groups such as methyl sulfinate group, phenyl sulfinate group, benzyl sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group and pentafluorobenzene sulfinate group; Alkylthio group; Although an arylthio group etc. are mentioned, It is not limited to these.
    [181] Specific examples of the nitrogen-containing group include those exemplified by the above R 2 to R 6 , specifically, an amino group; Alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and dicyclohexylamino group; Although an arylamino group or alkylarylamino group, such as a phenylamino group, a diphenylamino group, a totolylamino group, a dinaphthylamino group, and a methylphenylamino group, etc. are mentioned, It is not limited to these.
    [182] A boron-containing group Specifically, BR 4 may be mentioned (R is hydrogen, an alkyl group, a substituent FIG aryl group, a halogen atom or the like).
    [183] Specifically as a phosphorus containing group, Trialkyl phosphine groups, such as a trimethyl phosphine group, a tributyl phosphine group, and a tricyclohexyl phosphine group; Triaryl phosphine groups, such as a triphenyl phosphine group and a tritolyl phosphine group: phosphite groups (phosphide groups), such as a methyl phosphite group, an ethyl phosphite group, and a phenyl phosphite group; Phosphonic acid groups; Although a phosphinic acid group etc. are mentioned, It is not limited to these.
    [184] Specific examples of the silicon-containing group include those exemplified by the above R 2 to R 6 , and specifically, a phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, and tripropylsilyl group Hydrocarbon substituted silyl groups such as tricyclohexylsilyl group, triphenylsilyl, methyldiphenylsilyl group, tritolylsilyl group and trinaphthylsilyl group; Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; Silicon substituted alkyl groups, such as trimethylsilylmethyl: Silicon substituted aryl groups, such as a trimethylsilylphenyl group, etc. are mentioned.
    [185] Specifically as a germanium containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, the group which substituted the silicon of the said silicon containing group by germanium is mentioned.
    [186] Specific examples of the tin-containing group include those similar to those exemplified in the above R 2 to R 6 , and more specifically, groups in which the silicon of the silicon-containing group is substituted with tin.
    [187] Specific examples of the halogen-containing group include, but are not limited to, fluorine-containing groups such as PF 6 and BF 4 , chlorine-containing groups such as ClO 4 and SbCl 6, and iodine-containing groups such as IO 4 .
    [188] Specific examples of the aluminum-containing group include AlR 4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but is not limited thereto.
    [189] In addition, when n is two or more, the some group represented by X may mutually be same or different, and the some group represented by X may combine with each other, and may form the ring.
    [190] The (A) transition metal compound constituting the third catalyst for olefin polymerization according to the present invention is a compound represented by the following general formula (III).
    [191]
    [192] (Although N ····· M is generally indicated to be doubled, it is not necessary to be doubled in the present invention.)
    [193] In Formula (III), M represents a transition metal of Groups 4 to 5 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, and tatalum, preferably a metal atom of Group 4, specifically As titanium, zirconium, hafnium, More preferably, it is zirconium.
    [194] m represents the integer of 1-4, Preferably it is 1-2, Especially preferably, it is 2.
    [195] R 1 is a bicyclic aliphatic hydrocarbon group which shares one or more carbon atoms having 4 to 20 carbon atoms which may have one or a plurality of substituents, and specifically, as a bicyclic aliphatic hydrocarbon group, spiro [2.2] pentane, spiro [ 2.3] hexane, spiro [2.4] heptane, spiro [2.5] octane, spiro [3.3] heptane, spiro [3.4] octane, spiro [3.5] nonane, spiro [4.4] nonane, spiro [4.5] decane, spiro [5.5] Undecane, bicyclo [1.1.0] butane, bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [3.1.0] hexane, bicyclo [3.2.0] heptane, bicyclo [3.3.0] octane, bicyclo [4.1.0] heptane, bicyclo [4.2.0] octane, bicyclo [4.3.0] nonane, bicyclo [4.4.0] decane, bicyclo [1.1.1] Pentane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane, bicyclo [ 3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2] decane, bicyclo [3.3.3] undecane, and the like. have.
    [196] Preferably, R 1 is a bicyclic aliphatic hydrocarbon group which shares two carbon atoms having 4 to 20 carbon atoms which may have one or a plurality of substituents, and specific examples of the bicyclic aliphatic hydrocarbon group include bicyclo [1.1. 0] butane, bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [3.1.0] hexane, bicyclo [3.2.0] heptane, bicyclo [3.3.0] octane, bi Cyclo [4.1.0] heptane, bicyclo [4.2.0] octane, bicyclo [4.3.0] nonane, bicyclo [4.4.0] decane, bicyclo [1.1.1] pentane, bicyclo [2.1.1 ] Hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane, bicyclo [3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2] decane, bicyclo [3.3.3] undecane, and the like.
    [197] More preferably, R 1 is an alternating bicyclic aliphatic hydrocarbon group which shares two carbon atoms having 5 to 20 carbon atoms which may have one or a plurality of substituents, and specifically, as a bicyclic aliphatic hydrocarbon group, bicyclo [ 1.1.1] pentane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [3.1.1] heptane, bicyclo [3.2.1] octane , Bicyclo [3.2.2] nonane, bicyclo [3.3.1] nonane, bicyclo [3.3.2] decane, bicyclo [3.3. 3] Undecan etc. are mentioned.
    [198] Especially preferably, R 1 is bicyclo [2.2.1] heptane, which may have one or a plurality of substituents.
    [199] The substituent of R 1 is not particularly limited, but a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon substituted silyl group, a hydrocarbon substituted siloxy group, an oxygen containing group, a sulfur containing group, a nitrogen containing group, a phosphorus containing group, a halogen containing group, Or a hydrocarbon or a hydrocarbon-substituted silyl group containing a group selected from heterocyclic compound residues.
    [200] As may have the R 1 substituents, specifically, hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, butoxy group, phenoxy group, ethoxy group, dimethylamino group, dimethylamino Ethyl group, nitromethyl group, nitroethyl group, cyanomethyl group, cyanoethyl group, trimethylsilyl group, triethylsilyl group, etc. are mentioned.
    [201] In the bicyclic hydrocarbon group which has two or more substituents of said R <1> , there is no restriction | limiting in particular in the position of two or more substituents.
    [202] R 2 to R 6 may be the same as or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, a sulfur containing group, a phosphorus containing group, a silicon containing group, A germanium-containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    [203] Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    [204] Halogen atoms include fluorine, chlorine, bromine and iodine.
    [205] Specifically as a hydrocarbon group, carbon number, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. Linear or branched alkyl groups of 1 to 30, preferably 1 to 20;
    [206] Linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as vinyl group, allyl group, and isopropenyl group;
    [207] Linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as an ethynyl group and a propargyl group;
    [208] Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and adamantyl group;
    [209] Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group, and fluorenyl group;
    [210] Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group;
    [211] Alkyl-substituted aryl groups, such as a tolyl group, an isopropylphenyl group, t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group, etc. are mentioned.
    [212] The said hydrocarbon group may be substituted by the hydrogen atom by halogen, For example, a C1-C30 halogenated hydrocarbon group, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group, is mentioned.
    [213] Moreover, the said hydrocarbon group may be substituted by other hydrocarbon group, For example, aryl group substituted alkyl groups, such as a benzyl group and cumyl, etc. are mentioned.
    [214] In addition, the hydrocarbon group heterocyclic compound residues; Oxygen-containing groups such as alkoxy, aryloxy, ester, ether, acyl, carboxyl, carbonate, hydroxy, peroxy and carboxylic anhydride groups; 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, amino groups comprising ammonium salts Nitrogen-containing groups such as: boron-containing groups such as borandiyl, boranetriyl, and diboranyl; Mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothianic acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl Sulfur-containing groups such as groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfphenyl groups; You may have phosphorus containing groups, such as a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphite group, a silicon containing group, a germanium containing group, or a tin containing group.
    [215] Among these, in particular, C1-C1, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group 30, preferably 1-20 linear or branched alkyl groups; Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, and anthracenyl group; 1 to 5 substituents such as a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms or an alkoxy group, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms or an aryloxy group Substituted aryl groups and the like are preferred.
    [216] Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group include those mentioned above.
    [217] Examples of the heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygenated compounds such as furan and pyran and sulfur-containing compounds such as thiophene, and these heterocyclic compound residues. The group which further substituted by substituents, such as a C1-C30, Preferably it is an alkyl group of 1-20, an alkoxy group, etc. are mentioned.
    [218] As a silicon-containing group, a silyl group, a siloxy group, a hydrocarbon substituted silyl group, a hydrocarbon substituted siloxy group, etc. Specifically, methyl silyl group, dimethyl silyl group, trimethyl silyl group, ethyl silyl group, diethyl silyl group, triethyl silyl And diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl phenylsilyl group, triphenylsilyl group and the like are preferable. In particular, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxane group.
    [219] Examples of the germanium-containing group and tin-containing group include those in which silicon of the silicon-containing group is substituted with germanium and tin.
    [220] For example, the R 2 ~R 6 described in the following, will be described in detail.
    [221] As an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc. are mentioned specifically ,.
    [222] As an alkylthio group, a methylthio group, an ethylthio group, etc. are mentioned specifically ,.
    [223] As an aryloxy group, a phenoxy group, 2, 6- dimethylphenoxy group, 2, 4, 6-trimethyl phenoxy group etc. are mentioned specifically ,.
    [224] Specific examples of the aryl thio group include phenylthio group, methylphenylthio group, naphthyl thio group, and the like.
    [225] Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, and the like. Specific examples of the ester group include an acetyloxy group, benzoyloxy group, methoxycarbonyl group, phenoxycarbonyl group, p-chlorophenoxycarbonyl group and the like.
    [226] Specific examples of the thioester group include acetylthio group, benzoylthio group, methylthiocarbonyl group, and phenylthiocarbonyl group.
    [227] Specific examples of the amide group include acetamide group, N-methylacetamide group, and N-methylbenzamide group.
    [228] Specific examples of the imide group include an acetimide group and a benzimide group.
    [229] Specifically as an amino group, a dimethylamino group, an ethylmethylamino group, a diphenylamino group, etc. are mentioned.
    [230] As an imino group, a methyl imino group, an ethyl imino group, a propyl imino group, a butyl imino group, a phenyl imino group, etc. are mentioned specifically ,.
    [231] As a sulfone ester group, a methyl sulfonate group, an ethyl sulfonate group, a sulfonate phenyl group, etc. are mentioned specifically ,.
    [232] Specifically as a sulfonamide group, a phenyl sulfonamide group, N-methyl sulfonamide group, N-methyl- p-toluene sulfonamide group, etc. are mentioned.
    [233] R 2 to R 6 may be a hydrocarbon ring containing two or more of these groups, preferably adjacent groups connected to each other to form an alicyclic ring, an aromatic ring or a hetero atom such as a nitrogen atom, and these rings may be substituted with a substituent. You may have more.
    [234] In addition, when m is two or more, two groups of groups represented by R <2> -R <6> may be connected. In addition, when m is two or more, R <1> , R <2> , R <3> , R <4> , R <5> , and R <6> may mutually be same or different.
    [235] n is a number satisfying the valence of M, specifically 0-5, Preferably it is 1-4, More preferably, it is an integer of 1-3.
    [236] X is hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium containing Group or a tin-containing group. In addition, when n is two or more, they may mutually be same or different.
    [237] Halogen atoms include fluorine, chlorine, bromine and iodine.
    [238] As a hydrocarbon group, the same thing as what was illustrated by said R <2> -R <6> is mentioned. Specifically, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, an icosyl group; C3-C30 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group; Alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group; Arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; Aryl groups, such as a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, etc. are mentioned, but it is not limited to these. . In addition, these hydrocarbon groups also include halogenated hydrocarbons, specifically, those in which at least one hydrogen of a hydrocarbon group of 1 to 20 carbon atoms is substituted with halogen.
    [239] Among these, those having 1 to 20 carbon atoms are preferable.
    [240] As a heterocyclic compound residue, the same thing as what was illustrated by said R <2> -R <6> is mentioned.
    [241] As an oxygen containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, A hydroxyl group; Alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group; Aryloxy groups such as phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthoxy group; Arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; Acetoxy group; Although carbonyl group etc. are mentioned, It is not limited to these.
    [242] As a sulfur containing group, the thing similar to what was illustrated by said R <2> -R <6> is mentioned, Specifically, a methyl sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, p- Sulfonate groups such as toluenesulfonate group, trimethylbenzenesulfonate group, triisobutylbenzenesulfonate group, p-chlorobenzenesulfonate group and pentafluorobenzenesulfonate group; Sulfinate groups such as methyl sulfinate group, phenyl sulfinate group, benzyl sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group and pentafluorobenzene sulfinate group; Alkylthio group; Although an arylthio group etc. are mentioned, It is not limited to these.
    [243] Specific examples of the nitrogen-containing group include those exemplified by the above R 2 to R 6 , specifically, an amino group; Alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and dicyclohexylamino group; Although an arylamino group or alkylarylamino group, such as a phenylamino group, a diphenylamino group, a totolylamino group, a dinaphthylamino group, and a methylphenylamino group, etc. are mentioned, It is not limited to these.
    [244] A boron-containing group Specifically, BR 4 may be mentioned (R is hydrogen, an alkyl group, a substituent FIG aryl group, a halogen atom or the like).
    [245] Specifically as a phosphorus containing group, Trialkyl phosphine groups, such as a trimethyl phosphine group, a tributyl phosphine group, and a tricyclohexyl phosphine group; Triaryl phosphine groups, such as a triphenyl phosphine group and a tritolyl phosphine group; Phosphite groups (phosphide groups) such as methyl phosphite group, ethyl phosphite group and phenyl phosphite group; Phosphonic acid groups; Although a phosphinic acid group etc. are mentioned, It is not limited to these.
    [246] Specific examples of the silicon-containing group include those exemplified by the above R 2 to R 6 , and specifically, a phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, and tripropylsilyl group Hydrocarbon substituted silyl groups such as tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, and trinaphthylsilyl group; Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; Silicon substituted alkyl groups such as trimethylsilylmethyl group; Silicon substituted aryl groups, such as a trimethylsilylphenyl group, etc. are mentioned.
    [247] Specific examples of the germanium-containing group include those exemplified by the above R 2 to R 6 , and specific examples include a group in which silicon of the silicon-containing group is substituted with germanium.
    [248] Specific examples of the tin-containing group include those similar to those exemplified in the above R 2 to R 6 , and more specifically, groups in which the silicon of the silicon-containing group is substituted with tin.
    [249] Specific examples of the halogen-containing group include, but are not limited to, fluorine-containing groups such as PF 6 and BF 4 , chlorine-containing groups such as ClO 4 and SbCl 6, and iodine-containing groups such as IO 4 .
    [250] Specific examples of the aluminum-containing group include AlR 4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but is not limited thereto.
    [251] In addition, when n is two or more, the some group represented by X may mutually be same or different, and the some group represented by X may combine with each other, and may form the ring.
    [252] Although the specific example of the transition metal compound represented by (A) said general formula (I), (II), (III) is shown below, it is not limited to these.
    [253]
    [254]
    [255]
    [256]
    [257]
    [258]
    [259]
    [260]
    [261]
    [262]
    [263]
    [264]
    [265]
    [266]
    [267]
    [268]
    [269]
    [270]
    [271]
    [272]
    [273]
    [274] In the above examples, Me is methyl group, Et is ethyl group, n-Pr is normal propyl group, i-Pr is isopropyl group, n-Bu is normal butyl group, i-Bu is isobutyl group, t- Bu represents a tertiary butyl group, Ad represents an adamantyl group, and Ph represents a phenyl group.
    [275] In the present invention, a transition metal compound in which zirconium metal is substituted with titanium and hafnium may be used in the above compounds. The manufacturing method of such a transition metal compound (A) is not specifically limited, For example, it can manufacture as follows. First, the ligand constituting the transition metal (A) reacts a salicylic compound with a primary amine compound (R 1 -NH 2 , R 1 means the same as above), for example, an alkylamine compound. Obtainable by sequencing. Specifically, both starting compounds are dissolved in a solvent. As a solvent, although a general thing can be used for this reaction, Among these, alcohol solvents, such as methanol and ethanol, or hydrocarbon solvents, such as toluene, are preferable. Then, when the mixture is stirred at room temperature under reflux conditions for about 1 to 48 hours, the corresponding ligand is obtained in good yield. When synthesizing a ligand compound, an acid catalyst such as formic acid, acetic acid or paratoluenesulfonic acid may be used as the catalyst. In addition, when a molecular sieve, anhydrous magnesium sulfate or anhydrous sodium sulfate is used as a dehydrating agent or dehydrating by Dean Stark, it is effective in advancing reaction.
    [276] Next, the corresponding transition metal compound can be synthesized by reacting the ligand thus obtained with the transition metal M-containing compound. Specifically, the synthesized ligand is dissolved in a solvent and, if necessary, brought into contact with a base to produce a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylate at low temperature, and then cooled at -78 ° C to room temperature. Or under reflux conditions for about 1 to 48 hours. As a solvent, although a general thing can be used for this reaction, Among these, polar solvents, such as ether and tetrahydrofuran (THF), hydrocarbon solvents, such as toluene, etc. are used preferably. Moreover, as a base used when manufacturing a phenoxide salt, metal salts, such as lithium salts, such as n-butyllithium, and sodium salts, such as sodium hydride, triethylamine, pyridine, etc. can be illustrated, but it is limited to this. It is not.
    [277] In addition, depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without producing the phenoxide salt. In addition, the metal M in the synthesized transition metal compound may be exchanged with another transition metal according to a conventional method. For example, when at least one of R 1 to R 6 is hydrogen, substituents other than hydrogen can be introduced at any stage of the synthesis.
    [278] Moreover, the reaction solution of a ligand and a metal compound can also be used for superposition | polymerization as it is, without isolating a transition metal compound.
    [279] (B-1) Organic Metal Compound
    [280] As an organic metal compound (B-1) used for this invention, the organometallic compound of group 1, 2, 12, and 13 of the periodic table as follows is used specifically ,.
    [281] (B-1a) Formula R a m Al (OR b ) n H p X q
    [282] (In formula, R <a> and R <b> may mutually be same or different, and represent a C1-C15, Preferably 1-4 hydrocarbon group, X represents a halogen atom, m is 0 <m <= 3, n is An organic aluminum compound represented by 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3 and m + n + p + q = 3.
    [283] (B-1b) general formula M 2 AlR a 4
    [284] In the formula, M 2 represents Li, Na or K, and R a represents a hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
    [285] (B-1c) General Formula R a R b M 3
    [286] Group 2 of the periodic table represented by formula (R a and R b may be the same as or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn, or Cd.) Or dialkyl compounds of Group 12 metals.
    [287] As an organoaluminum compound which belongs to said (B-1a), the following compounds etc. can be illustrated.
    [288] Formula R a m Al (OR b ) 3-m
    [289] (In formula, R <a> and R <b> may mutually be same or different, and represent a C1-C15, Preferably 1-4 hydrocarbon group, and m is a number of preferably 1.5 <= m <= 3.) Organoaluminum compounds,
    [290] Formula R a m AlX 3-m
    [291] In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3.
    [292] Formula R a m AlH 3-m
    [293] In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4, and m is preferably 2 ≦ m <3.
    [294] Formula R a m Al (OR b ) n X q
    [295] (In formula, R <a> and R <b> may mutually be same or different, and represent a C1-C15, Preferably 1-4 hydrocarbon group, X represents a halogen atom, m is 0 <m <= 3, n is 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3).
    [296] More specifically, examples of the organoaluminum compound belonging to (B-1a) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum. n-alkylaluminum;
    [297] Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, trit-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, Tribranched alkyl aluminum such as tri4-methylpentyl aluminum, tri2-methylhexyl aluminum, tri3-methylhexyl aluminum, and tri2-ethylhexyl aluminum;
    [298] Tricycloalkyl aluminum, such as tricyclohexyl aluminum and tricyclooctyl aluminum;
    [299] Triaryl aluminum, such as triphenyl aluminum and tritolyl aluminum;
    [300] Dialkyl aluminum hydrides such as diisobutyl aluminum hydride;
    [301] (iC 4 H 9 ) x Al y (C 5 H 10 ) z
    [302] Trialkenyl aluminum, such as triisoprenyl aluminum represented by (wherein x, y, z is a positive number and z≥2x) etc .;
    [303] Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide;
    [304] Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide;
    [305] Alkyl aluminum sesqui alkoxides, such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
    [306] Partially alkoxylated alkylaluminum having an average composition represented by R a 2.5 Al (OR b ) 0.5 and the like;
    [307] Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diiso Dialkyl aluminum aryl oxides such as butyl aluminum (2,6-di-t-butyl-4-methylphenoxide) and isobutyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide);
    [308] Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
    [309] Alkyl aluminum seski halides, such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;
    [310] Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide;
    [311] Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
    [312] Other partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride;
    [313] Partially alkoxylated and halogenated alkyl aluminum, such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide, etc. are mentioned.
    [314] Moreover, the compound similar to (B-1a) can also be used, For example, the organoaluminum compound which two or more aluminum compounds couple | bonded via the nitrogen atom is mentioned. As such a compound specifically there may be mentioned 2, and (C 2 H 5) 2 AlN (C 2 H 5) Al (C 2 H 5).
    [315] Examples of the compound belonging to the above (B-1b) include LiAl (C 2 H 5 ) 4 , LiAl (C 7 H 15 ) 4 , and the like. In addition, as the (B-1) organic metal compound, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, and propylmagnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.
    [316] In addition, a compound in which the organoaluminum compound may be formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium may be used.
    [317] Among the organic metal compounds (B-1), organoaluminum compounds are preferable.
    [318] The above-mentioned (B-1) organic metal compounds are used individually by 1 type or in combination of 2 or more types.
    [319] (B-2) Organic Aluminum Oxy Compound
    [320] The (B-2) organic aluminum oxy compound used by this invention may be a conventionally well-known aluminoxane and may be a benzene-insoluble organoaluminum oxy compound as illustrated by Unexamined-Japanese-Patent No. 2-78687.
    [321] A conventionally known aluminoxane can be manufactured, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
    [322] (1) Compounds containing adsorption water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and cerium chloride hydrate, such as trialkylaluminum A method of adding an organoaluminum compound to react adsorbed or crystalline water with an organoaluminum compound.
    [323] (2) A method of directly reacting water, ice or water vapor to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
    [324] (3) A method in which an organic tin compound such as dimethyl tin oxide or dibutyl tin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.
    [325] The aluminoxane may also contain a small amount of organometallic components. The solvent or unreacted organoaluminum compound may be distilled off from the recovered solution of aluminoxane and then re-dissolved in a solvent or suspended in a poor solvent of aluminoxane.
    [326] As an organoaluminum compound used when manufacturing an aluminoxane, the organoaluminum compound similar to what was illustrated as an organoaluminum compound which belongs to said (B-1a) is mentioned.
    [327] Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are especially preferable.
    [328] Such organoaluminum compounds can be used individually by 1 type or in combination of 2 or more types.
    [329] Examples of the solvent used in the production of the aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cimen, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and cyclopentane. Alicyclic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and diesel or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, in particular chlorinated bromide Can be mentioned. Moreover, ethers, such as ethyl ether and tetrahydrofuran, can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.
    [330] In addition, the benzene-insoluble organoaluminum oxy compound used in the present invention is an Al component dissolved in benzene at 60 ° C. in general in terms of Al atom, usually 10% or less, preferably 5% or less, particularly preferably 2% or less, that is, And insoluble or poorly soluble in benzene.
    [331] As an organoaluminum oxy compound used by this invention, the organoaluminum oxy compound containing boron represented by the following general formula (IV) is mentioned.
    [332]
    [333] In formula, R <7> represents a C1-C10 hydrocarbon group.
    [334] R <8> may mutually be same or different and represents a hydrogen atom, a halogen atom, and a C1-C0 hydrocarbon group.
    [335] The organoaluminum oxy compound containing boron represented by the said general formula (IV) is the temperature of -80 degreeC-room temperature in the inert solvent, the alkylboronic acid and organoaluminum compound represented by the following general formula (V) in inert gas atmosphere. It can be prepared by reacting for 1 minute to 24 hours.
    [336]
    [337] (Wherein R 7 represents the same group as above).
    [338] Specific examples of the alkyl boronic acid represented by the general formula (V) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boronic acid Acids, cyclohexyl boronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid, and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid are preferable. These are used individually by 1 type or in combination of 2 or more types.
    [339] As an organoaluminum compound made to react with such alkyl boronic acid, the organoaluminum compound similar to what was illustrated as an organoaluminum compound which belongs to said (B-1a) is mentioned specifically.
    [340] Among them, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.
    [341] The above-mentioned (B-2) organic aluminum oxy compounds are used individually by 1 type or in combination of 2 or more types.
    [342] (B-3) A compound that forms an ion pair by reacting with a transition metal compound
    [343] As a compound (B-3) (hereinafter referred to as an "ionized ionic compound") which reacts with the transition metal compound (A) used in the present invention to form an ion pair, Japanese Unexamined Patent Application Publication No. Hei 1-501950, Lewis acids and ionic compounds disclosed in Japanese Patent Application Laid-Open No. 1-502036, JP-A 3-179005, JP-A 3-179006, JP-A 3-207703, JP-A 3-207704, and USP-532l106. A compound, a borane compound, a carborane compound, etc. are mentioned. Moreover, a heteropoly compound and an isopoly compound are also mentioned. Specifically, Lewis acids include, BR 3 (R is brought Figure a phenyl group or fluorine being a substituent such as a methyl group with fluorine, methyl, trifluoromethyl) can be exemplified by a compound represented by, for example, trifluoroacetate Boron, triphenyl boron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, etc. are mentioned.
    [344] As an ionic compound, the compound represented by the following general formula (VI) is mentioned, for example.
    [345]
    [346] In formula, R <9> can mention H <+> , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyl trienyl cation, a ferrocenium cation which has a transition metal.
    [347] R 10 to R 13 may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
    [348] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.
    [349] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri (n-butyl) ammonium cation;
    [350] N, N-dialkyl anninium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; And dialkyl ammonium cations such as di (isopropyl) ammonium cation and dicyclohexyl ammonium cation.
    [351] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation.
    [352] As R 9, a carbonium cation, an ammonium cation, or the like is preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation is particularly preferable. Moreover, a trialkyl substituted ammonium salt, a N, N- dialkylanilinium salt, a dialkyl ammonium salt, a triaryl phosphonium salt etc. are mentioned as an ionic compound.
    [353] Specific examples of the trialkyl substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium Tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, Tri (n-butyl) ammonium tetra (o-tolyl) boron; etc. may be mentioned.
    [354] Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethyl anilinium tetra (pentafluorophenyl) boron etc. are mentioned.
    [355] Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexyl ammonium tetra (phenyl) boron and the like.
    [356] Moreover, as an ionic compound, triphenyl carbenium tetrakis (pentafluoro phenyl) borate, N, N- dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenyl Carbenium pentafluorophenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (VII) or (VIII), etc. are also mentioned.
    [357]
    [358] (Wherein Et represents an ethyl group)
    [359]
    [360] As a borane compound, specifically, for example
    [361] Decaborane;
    [362] Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decarborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] Dodecaborate, bis [tri (n-butyl) ammonium] decarborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate Salts of anions;
    [363] Such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobalate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) And salts of metal borane anions.
    [364] Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbate caborane and dodecahydride-1-phenyl-1,3-dicarbono. Naborane, dodecahydride-1-methyl-1,3-dicarbananaborane, undecahydride-1,3-dimethyl-1,3-dicarbananaborane, 7,8-dicarboundacaran , 2,7-dicarbound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane , Tri (n-butyl) ammonium-1-carbadocarborate, tri (n-butyl) ammonium-1-carbodecarborate, tri (n-butyl) ammonium-1-carbadodecarborate, tri (n-butyl ) Ammonium-1-trimethylsilyl-1-carbadecarborate, tri (n-butyl) ammonium bromo-1-carbadodecarborate, tri (n-butyl) ammonium-6-carbadecarborate, tri (n-butyl Ammonium-7-carbodecaborate, tri (n-butyl) ammonium-7,8-dicarboound Borate, tri (n-butyl) ammonium-2,9-dicarbodecaborate, tri (n-butyl) ammoniumdodecahydride-8-ethyl-7,9-dicarbodecarborate, tri (n- Butyl) Ammonium Untecahydride-8-ethyl-7,9-dicarbound carborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbound carborate, tri ( n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbound carborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbound carborate Salts of anions such as tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbodecaborate;
    [365] Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbound cabo Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundcarborate) cobalt salt (III), tri (n-butyl) ammonium bis (undecahydrate Ryde-7,8-dicarbound carborate) nickel (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbound carborate) copper acid (III), tri ( n-butyl) ammonium bis (undecahydride-7,8-dicarounddeborate) gluconate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8 -Dicarbound carborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbound carborate) chromate (III), tri ( n-butyl) ammonium bis (tribromooctahydride-7,8- Carbodecarborate) cobalt (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbodecaborate) chromate (III), bis [tri (n-butyl) ammonium ] Bis (Undecahydride-7-carbodecarborate) manganate (IV), Bis [tri (N-butyl) ammonium] bis (Undecahydride-7-carborate carborate) cobaltate (III) And metal carborane anion salts such as bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbodecaborate) nickel acid salt (IV).
    [366] The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or two or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, invanadic acid, germano vanadinic acid, bisovanadic acid, inniobic acid, germano niobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdate acid, germano molybdate acid, arsenomolybdate acid, Tin molybdate, phosphotungstic acid, germano tungstic acid, tin tungstic acid, phospholipid vanadic acid, phosphot vanadic acid, germano tungst vanadic acid, phospholipid tungsten vanadic acid, germano molybdenum Strvanadinic acid, inmolybdenum tungstic acid, inmolybdate niobic acid, and salts of these acids, for example metals of Groups 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium Salts with beryllium, magnesium, calcium, strontium, barium and the like, organic salts with triphenylethyl salt and the like can be used, but are not limited thereto.
    [367] Said (B-3) ionizing ionic compound is used individually by 1 type or in combination of 2 or more types.
    [368] When using the transition metal compound according to the present invention as a catalyst, when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a cocatalyst component is used in combination, very high polymerization activity is exhibited with respect to the olefin compound.
    [369] In addition, the catalyst for olefin polymerization according to the present invention is selected from the transition metal compound (A), (B-1) organic metal compound, (B-2) organic aluminum oxy compound, and (B-3) ionized ionic compound. A carrier (C) as described later may be used as necessary with at least one compound (B).
    [370] (C) carrier
    [371] The (C) carrier used in the present invention is an inorganic or organic compound, and is a granular or fine particulate solid.
    [372] Among the inorganic compounds, porous oxides, inorganic chlorides, clays, clay minerals or ion exchange layered compounds are preferable.
    [373] As the porous oxide, specifically, SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , or the like, or a composite or mixture containing them is used, for example Natural or synthetic zeolites, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , Si0 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO and the like can be used. Can be. Among these, it is preferable to have SiO 2 and / or Al 2 O 3 as the main component.
    [374] In addition, the inorganic oxide is a small amount of Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg (NO 3 ) 2 , Al (nO 3) 3, Na 2 O, also there is no hindrance to contain a carbonate, sulfate, nitrate and oxide components, such as K 2 O, Li 2 O.
    [375] Although the nature and state of such a porous oxide differ depending on a kind and a manufacturing method, the support | carrier used preferably for this invention has a particle diameter of 10-300 micrometers, Preferably it is 20-200 micrometers, and specific surface area is 50-1000 m <2>. / g, preferably in the range of 100 to 700 m 2 / g, and the pore volume is preferably in the range of 0.3 to 3.0 cm 3 / g. Such a carrier can be calcined and used at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.
    [376] As the inorganic chloride, MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2, and the like are used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Moreover, what melt | dissolved the inorganic chloride in solvents, such as alcohol, and then precipitated in particulate form with a precipitation agent can also be used.
    [377] The clay used in the present invention is usually composed mainly of clay minerals. In addition, the ion-exchange layered compound used by this invention is a compound which has the crystal structure in which the surface comprised by ionic bond etc. was laminated | stacked in parallel by weak bonding force with each other, and the ions contained are interchangeable. Most clay minerals are ion exchange layered compounds. In addition, these clays, clay minerals and ion-exchange layered compounds are not limited to those of natural acids, but artificial composites may be used.
    [378] In addition, a clay, a clay mineral or ion-exchangeable layered compounds, clays, clay minerals, and, hexagonal fine packing type, antimony type, CdCl 2 type and CdI and ion crystalline compounds having a crystal structure of the layer, such as type 2 It can be illustrated.
    [379] Such clays, clay minerals, kaolin, bentonite, wood clay, kairome clay, allophene, hiscingelite, pyrophyllite, mica group, montmorillonite group, vermiculite group, chlorite group, pariezolite , Kaolinite, nacrite, dickite, halosite, and the like. Examples of the ion-exchange layered compound include α-Zr (HAsO 4 ) 2 H 2 O, α-Zr (HPO 4 ) 2 , α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) 2, α-Ti (HAsO 4) 2 · H 2 O, α-Sn (HPO 4) 2 · H 2 O, γ-Zr (HPO 4) 2, and the like can be mentioned γ-Ti (HPO 4) 2 , γ-Ti (NH 4 PO 4) 2 · H 2 O , such as a polyhydric crystalline sanseongyeom of metal.
    [380] The clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, with a radius of 20 kPa or more measured by the mercury porosimetry. Here, pore volume is measured about the range of pore radius of 20-30,000 kPa by the mercury intrusion method using a mercury borometer.
    [381] When a pore volume of less than 0.1 cc / g having a pore diameter of 20 mm 3 or more is used as a carrier, it tends to be difficult to obtain high polymerization activity.
    [382] It is also preferable to chemically process the clay and clay mineral used in the present invention. As the chemical treatment, any one of surface treatment for removing impurities adhering to the surface, treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like. In addition to removing impurities from the surface, the acid treatment increases surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. In alkaline treatment, the crystal structure of clay is destroyed, resulting in a change in the structure of clay. In addition, in the salt treatment and the organic substance treatment, ionic complexes, molecular complexes, organic derivatives, and the like can be formed, and the surface area and the interlayer distance can be changed.
    [383] The ion-exchange layered compound used in the present invention may be a layered compound in a state where the interlayer is enlarged by exchanging the interlayer exchangeable ions with other bulky ions using ion exchangeability. These bulky ions play a supporting role in supporting the layered structure and are commonly called pillars. In addition, the introduction of another substance between the layers of the layered compound is called intercalation. Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , and metal alkoxides such as Ti (OR) 4 , Zr (OR) 4 , PO (OR) 3 and B (OR) 3 . Hydrocarbon groups); metal hydroxide ions such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2 2+ , Fe 3 O (OCOCH 3 ) 6 ] +, and the like. . These compounds can be used individually or in combination of 2 or more types. When these compounds are intercalated, polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si (OR) 4 , Al (OR) 3 , and Ge (OR) 4 , SiO 2, etc. Colloidal inorganic compounds and the like may coexist. Moreover, as a filler, the oxide etc. which are produced by heat dehydration after intercalating the said metal hydroxide ion between layers are mentioned.
    [384] The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as it is, or may be used after treatment such as ball milling or sieving. Moreover, you may use after adding and adsorb | sucking water newly or heat-dehydrating. Moreover, you may use individually or you may use in combination of 2 or more type.
    [385] Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
    [386] Examples of the organic compound include granular to particulate solids having a particle diameter in the range of 10 to 300 µm. Specifically, a (co) polymer produced from a C2-C14 α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component ) Polymers and their modified forms can be exemplified.
    [387] The catalyst for olefin polymerization according to the present invention is selected from the transition metal compound (A), (B-1) organic metal compound, (B-2) organic aluminum oxy compound, and (B-3) ionized ionic compound. In addition to at least one compound (B) and, if necessary, the carrier (C), a specific organic compound component (D) as described later may be contained as necessary.
    [388] (D) organic compound component
    [389] In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer, as necessary. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.
    [390] As alcohols and phenolic compounds, what is represented by R <14> -OH is used normally, and R <14> represents a C1-C50 hydrocarbon group or a C1-C50 halogenated hydrocarbon group.
    [391] As alcohols, R 14 is preferably a halogenated hydrocarbon. Moreover, as a phenolic compound, the thing in which the (alpha), (alpha) '-position of a hydroxyl group was substituted by C1-C20 hydrocarbon is preferable.
    [392] As carboxylic acid, the thing represented by R <15> -COOH is used normally. R 15 represents a hydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbon group of 1 to 50 carbon atoms, and particularly preferably a halogenated hydrocarbon group of 1 to 50 carbon atoms.
    [393] As a phosphorus compound, the phosphoric acid which has a P-O-H bond, the phosphate which has a P-OR, a P = O bond, and a phosphine oxide compound are used preferably. As a sulfonate, what is represented by the following general formula (IX) is used.
    [394]
    [395] In the formula, M is an element of Groups 1 to 14 of the periodic table.
    [396] R <16> is hydrogen, a C1-C20 hydrocarbon group, or a C1-C20 halogenated hydrocarbon group.
    [397] X is a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, and a C1-C20 halogenated hydrocarbon group. m is an integer of 1-7, n is 1 <= n <7.
    [398] Next, the manufacturing process of the catalyst for olefin polymerization by this invention is shown.
    [399] In the case of superposition | polymerization, the usage and addition order of each component are arbitrarily selected, but the following methods are illustrated.
    [400] (1) A method of adding component (A) alone to a polymerizer.
    [401] (2) A method of adding component (A) and component (B) to the polymerization reactor in any order.
    [402] (3) The method of adding a catalyst component and component (B) which supported component (A) to the support (C) in an arbitrary order to a polymerizer.
    [403] (4) A method of adding the catalyst component and component (A) in which component (B) is supported on carrier (C) to the polymerization reactor in any order.
    [404] (5) A method of adding a catalyst component carrying component (A) and component (B) on a carrier (C) to a polymerizer.
    [405] In each method of said (2)-(5), at least 2 or more of each catalyst component may be made to contact previously.
    [406] In each method of said (4) and (5) in which the component (B) is supported, you may add the component (B) which is not supported as needed in arbitrary order. In this case, the component (B) may be the same or different.
    [407] In addition, the solid catalyst component on which component (A) is carried on component (C) and the solid catalyst component on which component (A) and component (B) are supported may be prepolymerized. The catalyst component may be further supported on the polymerized solid catalyst component.
    [408] In the polymerization method of olefin according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing olefin in the presence of the catalyst for olefin polymerization as described above.
    [409] In this invention, superposition | polymerization can be performed by any of liquid phase polymerization methods, such as dissolution polymerization and suspension polymerization, or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, heptane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcycloheptane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons, such as ethylene chloride, chlorobenzene, and dichloromethane, or a mixture thereof, etc. are mentioned, The olefin itself can also be used as a solvent.
    [410] When the olefin is polymerized using the catalyst for olefin polymerization as described above, the component (A) is usually 10 -12 to 10 -2 moles, preferably 1 -10 to 10 -3 moles per 1 liter of the reaction volume. Used in amounts
    [411] Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) and all transition metal atoms (M) in component (A), usually from 0.01 to 100,000, preferably from 0.05 to 50,000 It is used in quantities that become. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the total transition metal (M) in component (A), usually 10 to 500,000, preferably It is used in the quantity which becomes 20-100,000. Component (B-3) has a molar ratio [(B-3) / M] of the transition metal atom (M) in component (B-3) and component (A), usually 1 to 10, preferably 1 to 5 It is used in the amount that it becomes.
    [412] Component (D) is a component whose molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5 when component (B) is component (B-1). When (B) is component (B-2), the component (B) is a component (B) in an amount such that the molar ratio [(D) / (B-2)] is usually 0.01 to 2, preferably 0.005 to 1. In the case of B-3), the molar ratio [(D) / (B-3)] is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.
    [413] In addition, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually normal pressure to 100 kg / cm 2, preferably normal pressure to 50 kg / cm 2, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Moreover, superposition | polymerization can also be performed dividing into two or more stages with different reaction conditions.
    [414] The low molecular weight ethylene polymer according to the present invention described above is obtained according to the above process. In addition, the terminal double bond in this polymer may be modified.
    [415] The release agent for toners according to the present invention is a low molecular weight ethylene polymer which may have a terminal modified according to the present invention. This mold release agent is used as a component of the toner for electrostatic image development together with a binder resin (a), a coloring agent (b), and a charge control agent etc. as needed. The number average molecular weight of this mold release agent is 300-2,000, Preferably it is 400-1,000.
    [416] As long as it is a thermoplastic resin generally mix | blended with the developing material of an electrostatic charge image, said binder resin (a) may be any, and it does not restrict | limit in particular. For example, styrene resin, styrene acrylic ester acid copolymer, acrylic resin, styrene-butadiene resin, ketone resin, maleic acid resin, polyester resin, polyvinyl acetate resin, coumaronic acid resin, phenol resin, silicone resin, polyurethane, Epoxy resin, terpene resin, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, ethylene vinyl acetate copolymer, rosin resin, etc. are mentioned. Among these, styrene-acrylic acid ester copolymer, polyester aromatic resin, and epoxy resin having good fixability at a suitable softening point (90 ° C to 120 ° C) are particularly preferable.
    [417] The coloring agent of the above (b) may be any compound as long as it is generally blended with the developing material of the electrostatic charge image, and there is no particular limitation. For example, carbon black, phthalocyanine blue, aniline blue, arco oil blue, chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine B lake, carmine 6B, quinacridone derivatives, etc. And pigments or dyes, and these may be used alone or in combination of two or more.
    [418] The mixing ratio of the release agent for toner of the present invention is usually about 100/1 to 10/0 to 5 / 0.5 to 40 by weight ratio, preferably the ratio of the binder resin / colorant / charge control agent / release agent of the present invention. 100/1 to 6 / 0.5 to 2/10 to 20.
    [419] The pigment dispersing agent which concerns on this invention turns into the low molecular weight ethylene polymer which the terminal by this invention may be modified. This dispersant is mixed with a pigment, then mixed with a colored resin, kneaded and granulated by an extruder, and used as a dry color, color compound or master batch. The compounding ratio of the said pigment dispersant is 25-200 weight part normally with respect to 100 weight part of pigments, Preferably it is the range of 50-150 weight part. The number average molecular weight is in the range of 1,000 to 5,000, and preferably in the range of 1,500 to 3,000. Examples of the colorant resin that can be used include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polystyrene, ABS, and the like. Styrene resins, polycarbonate resins obtained from bisphenol-A and phosgene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, thermoplastic resins such as polyamide resin, polyphenylene oxide resin and polyvinyl chloride and phenolic resins And thermosetting resins such as epoxy resins.
    [420] In particular, the pigment dispersant of the present invention can be suitably used for a thermoplastic resin.
    [421] The pigment which can be used can be used with all the pigments conventionally known for coloring of synthetic resin. Specific examples of the pigment include metals such as aluminum, silver, and gold; Carbonates such as calcium carbonate and barium carbonate; Oxides such as ZnO and TiO 2 ; Hydroxides such as Al 2 O 3 nH 2 O and Fe 2 O 3 nH 2 O; Sulfates such as CaSO 4 and BaSO 4 ; Nitrates such as Bi (OH) 2 NO 3 ; Chlorides such as PbCl 2 ; Chromate salts such as CaCrO 4 and BaCrO 4 ; Chromates, manganates and permanganates such as CoCrO 4 ; Borate salts such as Cu (BO) 2 ; Uranates such as Na 2 U 2 O 7 and 6H 2 O; Nitrites such as K 3 Co (NO 2 ) 6 .3H 2 O; Silicates such as SiO 2 ; Arsenates and arsenites such as CuAsO 3 Cu (OH) 2 ; Acetates such as Cu (C 2 H 3 O 2 ) 2 .Cu (OH) 2 ; phosphates such as (NH 4 ) 2 MnO 2 (P 2 O 7 ) 2 ; Natural organic pigments, such as inorganic pigments such as aluminates, molybdates, zincates, antimonates, tungstates, selenides, titanates, iron cyanide salts, phthalates, CaS, ZnS and CdS, and cotinyl lakes and mother lakes Nitroso pigments such as naphthol green Y and naphthol green B; Nitro pigments such as naphthol yellow S and pigment croline 2G; Permanent red 4R; Azo pigments such as kanji yellow, Variant carmine 68 and Scarlet 2R; Basic dye lakes such as maracaine green, rhodamine B, acid dye lakes such as acid green lake, eosin lakes, and mordant dye lakes such as alizarin lake, flupurin lake, thio indigo red B, And organic pigments such as phthalocyanine pigments such as vat salt dye pigments such as intansrene and orange, phthalocyanine blue and phthalocyanine green.
    [422] Although the pigment dispersant of this invention can be used also for coloring by the method of any one of the coloring by the dry color method, the coloring by the color compound method, or the coloring by the master batch method, Especially, it can use especially preferably for the master batch method. .
    [423] The lubricant for polyvinyl chloride resins according to the present invention is a low molecular weight ethylene-based polymer which may have a terminal modified according to the present invention. In the polyvinyl chloride composition using the lubricant of the present invention, the blending ratio of the lubricant is in the range of 0.05 to 5 parts by weight, and preferably 0.1 to 3 parts by weight based on 100 parts by weight of polyvinyl chloride. The polymer used as a lubricant has a number average molecular weight in the range of 40 to 4,00 parts by weight, preferably in the range of 500 to 1000 parts by weight, and in the case of using a modified product modified at the terminal, The acid value of is in the range of 2 to 70, preferably in the range of 10 to 50. When the acid value of the modified body is 70 or more, the initial activity of the lubricant decreases, and the anti-sticking effect decreases below 10. In addition, when the number average molecular weight of the lubricant is 400 or less, the anti-sticking effect to the metal is inferior, and when the number average molecular weight is 4,000 or more, the activity is lowered in the early and late first half. Moreover, in the compounding quantity ratio of a lubricating agent, an activity effect is lacking at 0.05 weight part or less, and activity becomes excess at 5 weight part or more, and plasticization of a composition becomes difficult.
    [424] In order to use said modified body as a lubricating agent, unsaturated carboxylic acid or its anhydride is hold | maintained as a monomer which modifies the one side terminal vinyl group or vinylidene group containing oligomer of the polymer chain of the low molecular weight ethylene polymer of this invention, As acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, itaconic acid, itaconic anhydride, 3-cyclohexene carboxylic acid, 4-cyclohexene carboxylic acid, 5-norbornene -2, 3-dicarboxylic acid, etc. are mentioned.
    [425] The polyvinyl chloride resin containing the polyvinyl chloride resin additive of the present invention is polyvinyl chloride or polyvinyl chloride in polyethylene, polypropylene, ABS resin, MBS resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate, and the like. Even if mixed, it can be used without a trouble. In addition, you may mix | blend a heat resistant stabilizer with these compositions.
    [426] As the heat resistant stabilizer to be used, any one may be used as long as it exhibits a stabilizing effect on the polyvinyl chloride resin. For example, a lead compound, a cadmium compound, a barium compound, a calcium compound, a zinc compound, an organic tin compound, an epoxy compound, and a chelate And mixtures thereof are used.
    [427] The polyvinyl chloride composition containing the lubricant according to the present invention may contain other lubricants, fillers, pigments, dyes, plasticizers, antistatic agents and weathering stabilizers.
    [428] Since the composition containing the lubricant according to the present invention has excellent initial activity, the adhesiveness to the metal is reduced, the molding can be performed stably, and the continuous operation can be performed for a long time.
    [429] The low molecular weight ethylene polymer according to the present invention can be widely used for applications in which well-known low molecular weight polyethylene such as wax is used. In this case, various additives can be added and used as needed.
    [430] For example, when the low molecular weight ethylene polymer according to the present invention is used as a paint modifier, the surface of the coating film can be modified, for example, the gloss removal effect is excellent, the wear resistance of the coating film can be improved, and the quality of the woodwork coating is high. A feeling can be provided and durability can be improved.
    [431] When the low molecular weight ethylene polymer according to the present invention is used as a polishing agent such as car wax, step polish, or the like, the gloss is excellent and the coating film properties can be improved.
    [432] The low molecular weight ethylene polymer according to the present invention is suitable as a mold releasing agent for resin molding, and can provide a mold release property to a thermoplastic resin or a thermosetting resin to improve a molding cycle.
    [433] The low molecular weight ethylene polymer according to the present invention has excellent compatibility with rubber, is suitable as a rubber processing aid for imparting releasability to rubber and adjusting viscosity, and when used as a rubber processing aid, dispersibility of filler and pigment By improving and giving mold release property and fluidity | liquidity to rubber, the molding cycle at the time of rubber molding and extrusion characteristics can be improved.
    [434] The low molecular weight ethylene polymer according to the present invention is suitable as a paper quality improving agent for improving the activity and surface modification of paper, and when used as a paper quality improving agent, it can improve moisture resistance, gloss, surface hardness, blocking resistance and wear resistance. Thereby, it gives a sense of quality to paper and can improve durability.
    [435] The low molecular weight ethylene polymer according to the present invention is suitable as a wear resistance improving agent for ink, and when used as a wear resistance improving agent, wear resistance and heat resistance on the surface of the ink can be improved.
    [436] The low molecular weight ethylene polymer according to the present invention is suitable as a fiber processing aid. When the fiber is used as a fiber processing aid in the resin processing, it can impart flexibility and activity to the fiber.
    [437] The low molecular weight ethylene polymer according to the present invention is suitable as a hot melt additive and can impart heat resistance and fluidity to the hot melt adhesive. It is possible to improve the quality of hot melt adhesives in fields requiring heat resistance of automobiles and building materials.
    [438] The low molecular weight ethylene polymer according to the present invention is suitable as an electrical insulation, and for example, the electrical insulation and heat resistance of a film capacitor can be improved.
    [439] The low molecular weight ethylene polymer according to the present invention is suitable as a compounding agent of natural wax such as crayons and candles, and can improve surface hardness and softening point.
    [440] By the polymerization method of the olefin by this invention, the polymer which shows favorable polymerization activity and is narrow in molecular weight distribution can be obtained. Moreover, when copolymerizing 2 or more types of olefins, an olefin copolymer with a narrow composition distribution can be obtained.
    [441] <Example>
    [442] Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these.
    [443] The structure of the compounds obtained in Synthesis Examples were determined using, for example, 1 H NMR 270MHz (Japan Electronics and GSH-270), FD- Mass spectrometry (Japan Electronics and SX-102A).
    [444] In addition, in this Example, intrinsic viscosity ([η]) was measured in 135 degreeC and decalin.
    [445] (1) synthesis of ligands
    [446] [Synthesis of Ligand L-1]
    [447] Synthesis Example
    [448] Into a 30 ml reactor sufficiently dried and argon-substituted, 2.02 g (10.9 mmol) of 3-t-butylsalicylaldehyde, 10 ml of toluene and 0.86 g (40% aqueous solution, 11.1 mmol) of methylamine were injected, and at room temperature 24 Stirred for time. The reaction solution was concentrated under reduced pressure to obtain 2.05 g (yield 99%) of a yellow oil represented by the following formula L-1.
    [449] 1 H NMR (CDCl 3 ):
    [450] 1.43 (s, 9H), 3.46 (s, 3H), 6.79 (t, 1H), 7.07-7.32 (m, 2H), 8.32 (s, 1H), 14.1 (s, 1H)
    [451]
    [452] Hereinafter, ligands L-2 to L-5 were synthesized from the corresponding phenol compounds and alkylamine compounds by the same method.
    [453] [Synthesis result of ligand L-2]
    [454] 1 H NMR (CDCl 3 ):
    [455] 0.95 (s, 2H), 0.97 (s, 2H), 1.42 (s, 9H), 2.93 (m, 1H), 6.79 (t, 1H), 7.05-7.29 (m, 2H), 8.47 (s, 1H) , 13.3 (s, 1H)
    [456] [Synthesis result of ligand L-3]
    [457] 1 H NMR (CDCl 3 ):
    [458] 1.47 (s, 9H), 1.77-1.94 (m, 2H), 2.16-2.33 (m, 2H), 2.35-2.41 (m, 2H), 4.04-4.16 (m, 1H), 6.79 (t, 1H), 7.06-7.32 (m, 2H), 8.23 (s, 1H), 14.2 (s, 1H)
    [459] [Synthesis result of ligand L-4]
    [460] 1 H NMR (CDCl 3 ):
    [461] 1.44 (s, 9H), 1.65-1.98 (m, 8H), 3.73-3.78 (m, 1H), 6.79 (t, 1H), 7.06-7.31 (m, 2H), 8.33 (s, 1H), 14.1 ( s, 1H)
    [462] [Synthesis result of ligand L-5]
    [463] 1 H NMR (CDCl 3 ):
    [464] 1.18-1.29 (m, 3H), 1.48 (s, 9H), 1.52-1.62 (m, 2H), 1.69-1.79 (m, 1H), 1.82-1.89 (m, 1H), 2.22-2.39 (m, 2H ), 3.29-3.32 (m, 1H), 6.79 (t, 1H), 7.08-7.32 (m, 2H), 8.29 (s, 1H), 14.1 (s, 1H)
    [465]
    [466] [Synthesis of Ligand L-6]
    [467] Synthesis Example
    [468] Into a 100 ml reactor sufficiently dried and nitrogen-substituted, 3.89 g (15.0 mmol) of 3-cumyl-5-methylsalicylaldehyde, 30 ml of toluene, and 1.75 g (40% aqueous solution, 22.5 mmol) of methylamine were injected, Stirred for 5 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 3.87 g (yield 97%) of a yellow oil represented by the following formula L-6.
    [469] 1 H NMR (CDCl 3 ):
    [470] 1.69 (s, 6H), 2,34 (s, 3H), 3.33 (s, 3H), 6.93-7.29 (m, 7H), 8.21 (s.1H), 13.5 (s, 1H)
    [471]
    [472] The ligands L-7 to L-10 were synthesized from the corresponding phenol compounds and alkylamine compounds in the same manner.
    [473] [Synthesis result of ligand L-7]
    [474] 1 H NMR (CDCl 3 ):
    [475] 1,79 (s, 6H), 3.38 (s.3H), 7.15 (t.1H), 7.20-7.40 (m.4H), 7.43 (t, 2H), 7.61 (d, 2H), 7.76 (d, 1H), 8.37 (s, 1H), 13.9 (s, 1H)
    [476] [Synthesis result of ligand L-8]
    [477] 1 H NMR (CDCl 3 ):
    [478] 1.59-2.35 (m, 8H), 1.73 (s, 6H), 2.35 (5,3H), 3.62-3.67 (m, 1H), 6.92-7.27 (m, 7H), 8.23 (s, 1H), 13.3 ( s, 1H)
    [479] [Synthesis result of ligand L-9]
    [480] 1 H NMR (CDCl 3 ):
    [481] 1.12-2.26 (m, 17H), 2.32 (s, 3H), 3.19-3.23 (m, 1H), 6.91-7.25 (m, 7H), 8.18 (s, 1H), 13.1 (s, 1H)
    [482] [Synthesis result of ligand L-I0]
    [483] 1 H NMR (CDCl 3 ):
    [484] 1.66 (s, 6H), 1.70 (s.6H), 3.31 (s.3H), 6.98-7.34 (m, 12H), 8.2l (s, 1H), 13.6 (s, 1H)
    [485]
    [486] (2) Synthesis of transition metal compound
    [487] Synthesis Example 1
    [488] 1.52 g (7.79 mmol) of compound L-1 and 30 ml of diethyl ether were poured into a 100 ml reactor sufficiently dried and argon-substituted, and cooled to -78 ° C and stirred. To this, n-butyllithium 5.0 ml (n-hexane solution, 1.56 M, 7.80 mmol) was added dropwise over 5 minutes, stirred at the same temperature for 3 hours, then slowly raised to room temperature, and further stirred at room temperature for 2 hours. To prepare a lithium salt. The solution was added dropwise to 30 ml of a tetrahydrofuran solution containing 1.48 g (3.92 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 30 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 1.54 g (yield 72%) of a compound of yellow powder represented by the following formula (1).
    [489] 1 H NMR (CDCl 3 ):
    [490] 1.54 (s, 18H), 3.37 (s, 6H), 6.92 (t, 2H), 7.18-7.58 (m, 4H), 8.15 (s, 2H)
    [491] FD-mass spectrometry: 542
    [492]
    [493] Synthesis Example 2
    [494] 1.25 g (4.00 mmol) of compound L-2 and 20 mL of diethyl ether were introduced into a 100 mL reactor sufficiently dried and argon-substituted, and cooled to -78 ° C and stirred. 2.50 mL (n-hexane solution, 1.6 M, 4.00 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.76 g (2.00 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 100 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane and dried under reduced pressure to obtain 0.88 g (yield 56%) of a compound of yellow powder represented by the following formula (2).
    [495] 1 H NMR (CDCl 3 ):
    [496] 0.48-0.98 (m, 8H), 1.41 (s, 18H), 3.25 (m, 2H), 6.90 (t, 2H), 7.19-7.55 (m, 4H), 8.49 (s, 2H)
    [497] FD-mass spectrometry: 594
    [498]
    [499] Synthesis Example 3
    [500] 1.26 g (5.34 mmol) of Compound L-3 and 25 mL of diethyl ether were introduced into a 100 mL reactor sufficiently dried and argon-substituted, and cooled to -78 ° C and stirred. 3.5 ml of n-butyllithium (n-hexane solution, 1.56 M, 5.46 mmol) were dripped at 5 minutes over this, and after stirring for 3 hours at the temperature as it is, it heated up slowly to room temperature and stirred further at room temperature for 2 hours. To prepare a lithium salt. This solution was added dropwise to 25 ml of a tetrahydrofuran solution of 1.00 g (2.66 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of the dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 20 ml of methylene chloride, and the insolubles were removed by a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane and dried under reduced pressure to obtain 0.18 g (yield 11%) of a compound of yellow powder represented by the following formula (3).
    [501] 1 H NMR (CDCl 3 ):
    [502] 1.43-2.22 (m, 30H), 4.52 (bs, 2H), 6.93 (t, 2H), 7.25-7,64 (m, 4H), 8,27 (s, 2H)
    [503] FD-mass spectrometry: 622
    [504]
    [505] Synthesis Example 4
    [506] 0.99 g (4.00 mmol) of compound L-4 and 20 mL of diethyl ether were poured into a 50 mL reactor sufficiently dried and argon-substituted, and cooled to -78 ° C and stirred. 2.63 mL (n-hexane solution, 1.52 M, 4.00 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.76 g (2,00 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 40 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.97 g (yield 75%) of a compound of yellow powder represented by the following formula (4).
    [507] 1 H NMR (CDCl 3 ):
    [508] 1.18-1.65 (m, 34H), 2.16 (bs, 2H), 6.91 (t, 2H), 7.18-7.57 (m, 4H), 8.28 (s, 2H)
    [509] FD-mass spectrometry: 650
    [510]
    [511] Synthesis Example 5
    [512] Into a 50 ml reactor sufficiently dried and argon-substituted, 1.10 g (4.00 mmol) of Compound L-6 and 20 ml of diethyl ether were charged, and cooled to -78 ° C and stirred. 2.50 mL (n-hexane solution, 1.6 M, 4.00 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.76 g (2.00 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 20 ml of methylene chloride, and the insolubles were removed by a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid portion was reprecipitated with diethyl ether and hexane and dried under reduced pressure to obtain 1.13 g (yield 81%) of a compound of yellow powder represented by the following formula (5).
    [513] 1 H NMR (CDCl 3 ):
    [514] 0.85-1.87 (m, 34H), 2.16-2.28 (m, 4H), 3.85-4.12 (m, 2H), 6.92 (t, 2H), 7.19-7.59 (m, 4H), 8.32-8.41 (m, 2H )
    [515] FD-mass spectrometry: 702
    [516]
    [517] Synthesis Example 6
    [518] Into a 100 mL reactor sufficiently dried and argon-substituted, 1.12 g (4.0 mmol) of compound L-6 and 25 mL of diethyl ether were charged, and cooled to -78 ° C and stirred. 2.58 ml (n-hexane solution, 1.55 M, 4.00 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was dripped at 25 ml of tetrahydrofuran solutions containing 0.76 g (2.0 mol) of ZrCl 4 (THF) 2 complexes cooled to -78 deg. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 50 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with n-hexane and dried under reduced pressure to obtain 1.10 g (yield 79%) of a compound of yellow powder represented by the following formula (11).
    [519] 1 H NMR (CDCl 3 ):
    [520] 0.86-1.91 (m, 18H), 2.35 (s, 6H), 6.92-7.52 (m, 14H), 7.78 (s, 2H)
    [521] FD-mass spectrometry: 694
    [522]
    [523] Synthesis Example 7
    [524] Into a 50 ml reactor sufficiently dried and argon-substituted, 1.38 g (4.19 mmol) of Compound L-7 and 20 ml of diethyl ether were charged, and cooled to -78 ° C and stirred. 2.64 ml (n-hexane solution, 1.59 M, 4.19 mmol) n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.79 g (2.09 mmol) of ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 60 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 1.12 g (yield 65%) of a compound of yellow powder represented by the following formula (12).
    [525] 1 H NMR (CDCl 3 ):
    [526] 1.79 (s, 12H), 2.40 (s, 6H), 6.90-7.80 (m.24H), 7.98 (s, 2H)
    [527] FD-mass spectrometry: 818
    [528]
    [529] Synthesis Example 8
    [530] 1.35 g (4.00 mmol) of compound L-8 and 20 ml of diethyl ether were introduced into a 50 ml reactor sufficiently dried and argon-substituted, and cooled to -78 ° C and stirred. 2.56 ml (n-hexane solution, 1.56 M, 5.46 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.76 g (2.00 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 40 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl chloride and n-hexane and dried under reduced pressure to obtain 1.14 g (yield 71%) of a compound of yellow powder represented by the following formula (13).
    [531] 1 H NMR (CDCl 3 ):
    [532] 0.95-1.81 (m, 16H), 1.69 (s, 6H), 1.90 (s, 6H), 2.36 (s, 6H), 3.54-3.62 (m, 2H), 6.95-7.46 (m, 14H), 8.02 ( s, 2H)
    [533] FD-mass spectrometry: 802
    [534]
    [535] Synthesis Example 9
    [536] Into a 50 ml reactor sufficiently dried and argon-substituted, 1.39 g (4.00 mmol) of Compound L-9 and 20 ml of diethyl ether were charged, and cooled to -78 ° C and stirred. 2.56 ml (n-hexane solution, 1.56 M, 4.00 mmol) of n-butyllithium was dripped at 5 minutes over this, and after stirring for 2 hours at the temperature as it is, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. The solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.76 g (2.0 mmol) of ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 12 hours, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 40 ml of methylene chloride, and the insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and n-hexane and dried under reduced pressure to obtain 1.16 g (yield 68%) of a compound of yellow powder represented by the following formula (14).
    [537] 1 H NMR (CDCl 3 ):
    [538] 0.80-2.41 (m, 40H), 3.27-3.32 (m, 2H), 6.96-7.45 (m, 14H), 8.12 (s, 2H)
    [539] FD-mass spectrometry: 854
    [540]
    [541] Synthesis Example 10
    [542] Into a 100 mL reactor sufficiently dried and argon-substituted, 1.31 g (3.50 mmol) of Compound 10 and 20 mL of diethyl ether were charged, and cooled to -78 ° C and stirred. 2.38 ml (n-hexane solution, 1.59 M, 3.78 mmol) n-butyllithium was dripped at 5 minutes over this, and after stirring at the temperature as it is for 2 hours, it heated up slowly to room temperature and stirred further at room temperature for 3 hours. To prepare a lithium salt. This solution was added dropwise to 20 ml of a tetrahydrofuran solution of 0.66 g (1.75 mmol) of a ZrCl 4 (THF) 2 complex cooled to -78 ° C. After completion of dropping, stirring was continued while the temperature was slowly raised to room temperature. After stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 20 ml of methylene chloride, and the insolubles were removed by a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and n-hexane and dried under reduced pressure to obtain 0.22 g (yield 14%) of a compound of yellow powder represented by the following formula (15).
    [543] 1 H NMR (CDCl 3 ): 1.57-2.32 (m, 30H), 6.94-7.57 (m.24H), 7.77 (s, 2H)
    [544] FD-mass spectrometry: 902
    [545]
    [546] Example 1
    [547] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.00025 mmol of the following zirconium compound (1) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, the polymerization was carried out at atmospheric pressure at 25 ° C. for 5 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polyethylene was 1.31 g, the polymerization activity was 62.9 kg / mmol-Zr hr, Mw = 2,750, Mw / Mn = 1.65, the intrinsic viscosity [η] was 0.12 dl / g, and the single terminal vinylation ratio was 90.5 mol%. .
    [548]
    [549] Example 2
    [550] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.0002 mmol of the following zirconium compound (2) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, polymerization was carried out at 25 캜 for 5 minutes at atmospheric pressure, and then a small amount of isobutanol was added to terminate the polymerization. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene obtained was 0.64 g and the intrinsic viscosity [η] was 0.19 dl / g.
    [551]
    [552] Example 3
    [553] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.0001 mmol of the following zirconium compound (3) were added to initiate polymerization. Ethylene was continuously supplied at 100 l / hr, and polymerized at 25 ° C for 5 minutes under atmospheric pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene obtained was 0.25 g and the intrinsic viscosity [η] was 0.10 dl / g.
    [554]
    [555] Example 4
    [556] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atoms) of methylaluminoxane and then 0.0001 mmol of the following zirconium compound (4) were added to initiate polymerization. Ethylene was continuously supplied at 100 l / hr, polymerization was carried out at atmospheric pressure at 25 ° C. for 5 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polyethylene was 0.97 g, the polymerization activity was 116.4 kg / mmol-Zr.hr, Mw = 3,800, Mw / Mn = 1.75, the intrinsic viscosity [eta] was 0.15 dl / g, and the single terminal vinylation ratio was 92 mol%.
    [557]
    [558] Example 5
    [559] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.0002 mmol of the following zirconium compound (5) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, the polymerization was carried out at atmospheric pressure at 25 ° C. for 5 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polyethylene was 1.39 g and the intrinsic viscosity [η] was 0.17 dl / g.
    [560]
    [561] Comparative Example 1
    [562] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.0005 mmol of the following zirconium compound (6) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, the polymerization was carried out at atmospheric pressure at 25 ° C. for 5 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene was 1.85 g, the polymerization activity was 44.4 kg / mmol-Zr hr, Mw = 9,500, Mw / Mn = 1.85, intrinsic viscosity [ ] Was 0.41 dl / g, and one-terminal vinylation ratio was 88 mol%.
    [563]
    [564] Comparative Example 2
    [565] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.005 mmol of the following zirconium compound (7) were added to initiate polymerization. Ethylene was continuously supplied at 100 l / hr, and the polymerization was carried out at 25 캜 for 30 minutes at atmospheric pressure, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene obtained was 2.15 g and the intrinsic viscosity [η] was 0.40 dl / g.
    [566]
    [567] Comparative Example 3
    [568] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 125 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.0005 mmol of the following zirconium compound (8) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, polymerized at normal pressure at 25 ° C. for 30 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene was 2.07 g and the intrinsic viscosity [η] was 0.48 dl / g.
    [569]
    [570] Comparative Example 4
    [571] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, l.25 mmol of methylaluminoxane in terms of aluminum atoms, and then 0.0002 mmol of the following zirconium compound (9) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, polymerized at normal pressure at 25 degreeC for 30 minutes, and superposition | polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polyethylene was 1.09 g, the polymerization activity was 65.4 kg / mmol-Zr hr, Mw = 13,800, Mw / Mn = 1.87, intrinsic viscosity [eta] was 0.44 dl / g, and the single terminal vinylation ratio was 84 mol%.
    [572]
    [573] Comparative Example 5
    [574] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.005 mmol of the following zirconium compound (10) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, the polymerization was carried out at 25 캜 for 15 minutes at atmospheric pressure, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene obtained was 2.47 g and the intrinsic viscosity [n] was 0.61 dl / g.
    [575]
    [576] Example 6
    [577] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atom) of methylaluminoxane and then 0.000005 mmol of the following zirconium compound (11) were added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, polymerization was carried out at 25 ° C for 5 minutes at atmospheric pressure, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polyethylene was 0.40 g, the polymerization activity was 960 kg / mmol-Zr hr, Mw = 2,880, Mw / Mn = 1.65, [η] = 0.15 dl / g, and single terminal vinylation ratio = 94.3 mol%.
    [578] Example 7
    [579] 500 mL of heptanes were injected into a 100 mL stainless steel autoclave sufficiently substituted with nitrogen, and the liquid phase and the gas phase were saturated at 100 liters / hr for 15 minutes at room temperature. Then, after heating up at 80 degreeC, it heated up by ethylene 8kg / cm <2> -G, and maintained the temperature. 0.5 ml (0.5 mmol) of a hexane solution (1.00 mmol / ml in terms of aluminum atoms) of MMAO (manufactured by Toso Finechem Co., Ltd.) was press-fitted, followed by 1 ml (0.00003 mmol) of a toluene solution (0.00003 mmol / ml) of Compound (11). It pressed in and started superposition | polymerization. The pressure was maintained while supplying ethylene gas, polymerization was performed at 80 ° C. for 15 minutes, and then polymerization was stopped by injecting 5 ml of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained ethylene polymer was 9.73 g, the polymerization activity was 1,297 kg / mmol-Zr * hr, Mw = 2,720, Mw / Mn = 1.60, [(eta)] = 0.14dl / g, and single terminal vinylation ratio = 94.Omol%. .
    [580] Example 8
    [581] 1000 mL of heptanes were poured into the 2000 mL stainless steel autoclave substituted with nitrogen sufficiently at room temperature, and it heated up at 150 degreeC. The autoclave was then pressurized with 30 kg / cm 2 G in ethylene to maintain the temperature. 0.5 ml (0.5 mmol) of a hexane solution (1.00 mmol / ml in terms of aluminum atoms) of MMAO (manufactured by Touso Finecam Co., Ltd.) was press-fitted, followed by 0.5 ml (0.0001 mmol / ml) of a toluene solution (0.0002 mmol / ml) of compound (11). mmol) was pressed in to initiate polymerization. After the polymerization was conducted at 150 DEG C for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by indenting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained ethylene polymer was 18.8 g, the polymerization activity was 376 kg / mmol-Zr.hr, Mw = 2,230, Mw / Mn = 1.52, [(eta)] = 0.12 dl / g, single-ended vinylation ratio = 94.2 mol%.
    [582]
    [583] Example 9
    [584] Polymerization was carried out in the same manner as in Example 6 except that the following zirconium compound (12) was added at 0.00002 mmol. Obtained polyethylene was 1.98 g, the polymerization activity was 1,185 kg / mmol-Zr.hr, Mw = 2,430, Mw / Mn = 1.63, intrinsic viscosity [η] was 0.11 dl / g, single-ended vinylation ratio = 94.1 mol%. .
    [585] Example 10
    [586] Polymerization was carried out in the same manner as in Example 7, except that the following zirconium compound (12) was added 0.000003 mmol. Obtained polyethylene was 11.2g, the polymerization activity was 1,490kg / mmol-Zr * hr, Mw = 2,350, Mw / Mn = 1.63, the intrinsic viscosity [(eta)] was 0.12 dl / g, single terminal vinylation ratio = 96.0 mol%. .
    [587] Example 11
    [588] Polymerization was carried out in the same manner as in Example 8, except that 0.0001 mmol of the following zirconium compound (12) was added. The obtained polyethylene was 18.9 g, the polymerization activity was 378 kg / mm01-Zr hr, Mw = 2,050, Mw / Mn = 1.52, intrinsic viscosity [η] was 0.10 dl / g, single-ended vinylation ratio = 94.6 mol%.
    [589]
    [590] Example 12
    [591] Polymerization was carried out in the same manner as in Example 6 except that the following zirconium compound (13) was added 0.000005 mmol. The polyethylene was 0.86 g, the polymerization activity was 2,069 kg / mmol-Zr hr, Mw was 3,120, Mw / Mn was 1.68, the intrinsic viscosity [η] was 0.19 dl / g, and the one-end vinylation ratio was 94.0 mol%. .
    [592]
    [593] Example 13
    [594] Polymerization was carried out in the same manner as in Example 6 except that 0.00005 mmol of the following zirconium compound (14) was added. The obtained polyethylene was 0.75 g, the polymerization activity was 1,793 kg / mmol-Zr hr, Mw = 2,850, Mw / Mn = 1.78, intrinsic viscosity [η] was 0.15 dl / g, single-ended vinylation ratio = 94.5 mol% .
    [595]
    [596] Example 14
    [597] Polymerization was carried out in the same manner as in Example 6 except that the following zirconium compound (15) was added 0.0002 mmol. Obtained polyethylene was 0.16g, the polymerization activity was 97 kg / mmol-Zr * hr, Mw = 2,850, Mw / Mn = 1.78, the intrinsic viscosity [(eta)] was 0.13 dl / g, single-ended vinylation ratio = 96.2 mol%.
    [598]
    [599] Comparative Example 6
    [600] 250 ml of toluene was injected into the 500 ml glass reactor with sufficient nitrogen substitution, and the liquid phase and the gas phase were saturated at 100 liters / hr of ethylene. Thereafter, 1.25 mmol (in terms of aluminum atoms) of methylaluminoxane was added, followed by addition of 0.9 mmol of the following zirconium compound (16) to initiate polymerization. Ethylene was continuously fed at 100 liters / hr, and polymerized at atmospheric pressure at 25 ° C. for 5 minutes, and then polymerization was stopped by adding a small amount of isobutanol. After the completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The polyethylene was 1.71 g, the polymerization activity was 2,057 kg / mmol-Zr hr, Mw = 9,600, Mw / Mn = 2.11, the intrinsic viscosity [η] was 0.48 dl / g, and the single terminal vinylation ratio was 86.2 mol%. .
    [601] Example 15
    [602] To a 200 ml glass flask, 0.5 g of polyethylene obtained in Example 4, 90 ml of n-decane and 1.19 ml (1.09 mmol) of heptane solution (1.0 mmol / ml) of diisobutylaluminum hydride were added, and 100 ° C. Stirred for 7 hours. Subsequently, dry air was passed through at 100 liters / hr for 6 hours, maintaining 100 degreeC. The reaction product was added to a methanol / acetone mixed solution (1.5 liters / 1.5 liters) containing a small amount of hydrochloric acid to precipitate the product. After wash | cleaning with methanol, it dried under reduced pressure at 80 degreeC for 10 hours, and obtained terminal hydroxylated polyethylene.
    [603] Example 16
    [604] 5 g of the ethylene polymer obtained in Example 7 and 100 ml of toluene were added to a 300 ml glass flask, and it heated up at 110 degreeC in nitrogen atmosphere. Then 0.34 g of m-chloro and benzoic acid were added and stirred for 3 hours. After the reaction, the product was added to 800 ml of methanol to precipitate the product. After wash | cleaning with methanol, it dried under reduced pressure at 80 degreeC for 10 hours, and obtained terminal hydroxylated polyethylene.
    [605] Example 17
    [606] 15 g of the ethylene polymer obtained in Example 8 and 2.7 g of maleic anhydride were added to a 300 ml glass flask, and the reaction was carried out at 200 ° C. for 6 hours under a nitrogen atmosphere. Excess unreacted maleic anhydride was left to remove for 1 hour under reduced pressure (10 mmHg) to obtain terminal maleic anhydride polyethylene.
    [607] Example 18
    [608] To a 300 ml glass flask, 5 g of polyethylene obtained in Example 11, 100 ml of xylene, 1.47 g of sulfuric acid, and 3.79 g of acetic anhydride were added and reacted at 100 ° C for 3 hours. After the reaction, the product was added to 800 ml of methanol to precipitate the product. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C. for 10 hours to obtain terminal sulfonated polyethylene.
    [609] Example 19
    [610] 250 ml of dimethylene and 4.5 g of polyethylene obtained in Example 12 were added to the glass reactor of the inner volume of 500 ml with sufficient nitrogen substitution, and it heated up at 140 degreeC at normal pressure, circulating ethylene at 100 liter / hr. Thereafter, 2.5 mmol of methylaluminoxane in terms of aluminum atoms, dimethylsilyl (1- (2-methyl-4,5-benzinyl)) (9- (2,7-di-tert-butylfluorenyl) The polymerization was initiated by addition of 0.OO5 mmol of zirconium dichloride 15 minutes later, the polymerization was stopped by addition of a small amount of isobutanol The product was then added to 2 liters of methanol to precipitate the polymer. Then, it dried under reduced pressure at 80 degreeC for 10 hours. The obtained polyethylene was 10.5g, and 1.10 long-chain branches of 1,000 carbon were contained by 13 C-NMR analysis.
    [611] Comparative Example 7
    [612] The polymerization was carried out in the same manner as in Example 19 except that 4.5 g of polyethylene was not used. The polymer obtained was 4.9 g and did not contain long chain branching of 1000 carbons by 13 C-NMR analysis.
    [613]
    [614] Since the low molecular weight ethylene polymer of the present invention has a vinyl- or vinylidene-type unsaturated bond having reactivity at one end of the polymer chain, any functional group can be given by various modification methods. Such a low molecular weight ethylene polymer and its modified body can provide a toner releasing agent excellent in high temperature release property and excellent in low temperature fixability. In addition, the low molecular weight ethylene polymer and its modified body can provide a pigment dispersant having excellent pigment dispersibility and a lubricant for polyvinyl chloride resin having excellent initial activity. In addition, many useful compositions can be provided, such as paint modifiers, varnishes, and the like.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] (A) An olefin polymerization catalyst comprising a transition metal compound represented by the following general formula (I).

    Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    m represents an integer of 1 to 4,
    R 1 represents a straight chain hydrocarbon group having 1 to 5 carbon atoms (C n ′ H 2n ′ + 1 , n ′ = 1 to 5) or a hydrogen atom,
    R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    n is a number satisfying the valence of M,
    X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a heterocyclic compound residue, a silicon group, a germanium group , Or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be combined with each other to form a ring.)
    [2" claim-type="Currently amended] (A) A catalyst for olefin polymerization, comprising a transition metal compound represented by the following formula (II).

    Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    m represents an integer of 1 to 4,
    R 1 is a 3 to 5 membered alicyclic hydrocarbon group which may have one or a plurality of substituents,
    R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    n is a number satisfying the valence of M,
    X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a heterocyclic compound residue, a silicon group, a germanium group , Or a tin-containing group, when n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may combine with each other to form a ring.)
    [3" claim-type="Currently amended] (A) A catalyst for olefin polymerization, characterized by comprising a transition metal compound represented by the following general formula (III).

    Wherein M represents a transition metal atom of Groups 4 to 5 of the periodic table,
    m represents an integer of 1 to 4,
    R 1 represents a bicyclic hydrocarbon group which shares at least one carbon having 4 to 20 carbon atoms which may have one or a plurality of substituents,
    R 2 to R 6 may be the same as or different from each other, and hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups and germanium A containing group or a tin-containing group, two or more of them may be linked to each other to form a ring,
    Moreover, when m is two or more, two groups may be connected among the groups represented by R <2> -R <6> ,
    n is a number satisfying the valence of M,
    X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen group, a sulfur group, a nitrogen group, a boron group, an aluminum group, a phosphorus group, a halogen group, a heterocyclic compound residue, a silicon group, a germanium group , Or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be combined with each other to form a ring.)
    [4" claim-type="Currently amended] The transition metal compound (A) according to claims 1 to 3, (B) (B-1) organic metal compound, (B-2) organic aluminum oxy compound, and (B-3) transition metal compound (A A catalyst for olefin polymerization, characterized in that it comprises at least one compound selected from compounds which react with to form ion pairs.
    [5" claim-type="Currently amended] An olefin polymerization method characterized by polymerizing or copolymerizing olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 4.
    [6" claim-type="Currently amended] In the presence of the catalyst for olefin polymerization according to any one of claims 1 to 4, ethylene is obtained by homopolymerization or by copolymerizing ethylene with an α-olefin having 3 to 10 carbon atoms,
    (1) The structural unit derived from ethylene is 81-100 mol%, the structural unit derived from an alpha olefin is 0-19 mol%,
    (2) the weight average molecular weight (Mw) measured by GPC is 7,000 or less,
    (3) the molecular weight distribution (Mw / Mn) is 1.1 ≦ Mw / Mn ≦ 2.5,
    (4) Having vinyl or vinylidene groups at the polymer main chain ends, and the content of these groups measured by 1 H-NMR is not less than 90% of the total length of the whole pieces;
    Low molecular weight ethylene polymer, characterized in that.
    [7" claim-type="Currently amended] At least one vinyl or vinylidene group in the low molecular weight ethylene polymer according to claim 6 selected from an epoxidizing agent, a sulfonating agent, maleic anhydride and its derivatives, a hydroborating agent, an organoaluminum hydride, a silylating agent, and a halogenating agent A low molecular weight ethylene polymer having an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a halogen-containing group or a tin-containing group obtained by treating with a compound of the above.
    [8" claim-type="Currently amended] A paint modifier containing a low molecular weight ethylene polymer according to claim 6 or 7, a gloss agent, a mold release agent for resin molding, a rubber processing aid, a lipid improver, an abrasion resistance improver for ink, a fiber processing aid, a hot melt additive, an electric Insulation agent, compounding agent for natural wax, antifog additive for polyolefin film.
    [9" claim-type="Currently amended] A releasing agent for toner, a pigment dispersant, and a lubricant for vinyl chloride resin containing the low molecular weight ethylene polymer according to claim 6 or 7.
    [10" claim-type="Currently amended] The olefin polymer obtained by copolymerizing with the low molecular weight ethylene polymer of Claim 6 or 7 as a macromonomer, or homopolymerization or at least 1 sort (s) of olefin selected from ethylene and the C3-C10 alpha-olefin.
    [11" claim-type="Currently amended] The resin composition containing the olefin polymer of Claim 10.
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    同族专利:
    公开号 | 公开日
    CN1212339C|2005-07-27|
    KR100533055B1|2005-12-02|
    CN1699434A|2005-11-23|
    EP1270603A2|2003-01-02|
    US20030027955A1|2003-02-06|
    EP1270603B1|2014-04-09|
    US7109284B2|2006-09-19|
    EP1270603A3|2003-05-14|
    CN1396188A|2003-02-12|
    CN100335510C|2007-09-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-06-20|Priority to JPJP-P-2001-00186459
    2001-06-20|Priority to JP2001186459
    2002-06-20|Application filed by 미쓰이 가가쿠 가부시키가이샤
    2002-12-31|Publication of KR20020097026A
    2005-12-02|Application granted
    2005-12-02|Publication of KR100533055B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2001-00186459|2001-06-20|
    JP2001186459|2001-06-20|
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