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    • 专利摘要:
    The present invention is obtained by contacting the dried particles (a) with an organometallic compound (b), followed by contacting a functional group having active hydrogen or a compound (c) having a Lewis basic functional group with an aprotic donor with an electron withdrawing group. For stereoregular polymerization of α-olefins obtained by a process comprising contacting a transition metal compound (B) and an organometallic compound (C) having a stereoregular polymerization capacity of the modified particles (A) with an α-olefin. A method for producing a stereoregular α-olefin polymer comprising a catalyst and polymerizing α-olefins using the catalyst.
    公开号:KR20010086047A
    申请号:KR1020017006472
    申请日:2000-09-25
    公开日:2001-09-07
    发明作者:마사유키 후지타；다쿠야 오가네；요시노리 세키；야스키 후지와라；겐이치로 야다；마사타다 다사카
    申请人:고오사이 아끼오；스미또모 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Catalyst for stereoregular α-olefin polymerization and process for producing stereoregular α-olefin polymer {Catalyst for stereoregular polymerization of α-olefin and process for producing stereoregular α-olefin polymer}
    [2] Mainly stereoregular α-olefin polymers have been conventionally produced using multi-site catalysts such as solid catalysts, but recently single-site obtained using metallocene complexes having a specific structure. It is known that stereoregular α-olefin polymers can also be produced by site catalysts.
    [3] For example, a preparation example of a high stereoregular isotactic propylene polymer using a metallocene complex in which two 1 to 3 substituted η 5 -cyclopentadienyl groups are crosslinked (see Japanese Patent No. 2587251, 2627669 specification and 2668732 specification) and the like are known. It has also been reported that syndiotactic propylene polymers are obtained by using isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride or the like with an aluminumoxy compound, which is a Cs symmetric metallocene complex [J: Am. Chem. Soc., 1988, 110, 6255. Also, Japanese Unexamined Patent Application Publication No. 9-510745 uses (2-phenylindenyl) zirconium dichloride and methylaluminoxane to have stereo isotactic segments and atactic segments in one molecular chain. A method for producing block polypropylene is disclosed.
    [4] However, since these known single site catalysts are soluble in the reaction system, when used for polymerization (e.g., slurry polymerization, gas phase polymerization, bulk polymerization, etc.) according to the formation of the α-olefin polymer particles, the resulting α-olefin polymer is hardened. There was a problem in that it could not be taken out or in the continuous polymerization process, the catalyst was scattered together with the fine particles of the α-olefin polymer, and the growth of the polymer may occur in the piping of the subsequent process.
    [5] In addition, in the known method of using a single-site catalyst, the method for producing the α-olefin polymer was not sufficiently efficient.
    [6] In addition, the stereoregularity of the stereoregular α-olefin polymers obtained using these known single site catalysts is not necessarily high enough, and the stereoregularity of the stereoblock polypropylene obtained according to the above-described method is particularly isotactic. Development of a method for obtaining stereoblock polypropylene having a higher stiffness and higher rigidity in the range of 6-33% pentad fraction has been required.
    [7] Disclosure of the Invention
    [8] It is an object of the present invention to provide a stereoregularity that provides a polymer with uniform polymer particle diameters when a single site catalyst is applied to polymerization (eg, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) according to the formation of α-olefin polymer particles. A polymer having a uniform polymer particle diameter when applied to a single site catalyst for α-olefin polymerization and to polymerization (e.g., slurry polymerization, gas phase polymerization, bulk polymerization, etc.) according to formation of α-olefin polymer particles using the catalyst. It is to provide a method for producing a stereoregular α-olefin polymer that provides.
    [9] It is a further object of the present invention to provide a more efficient process for the preparation of stereoregular α-olefin polymers using single site catalysts.
    [10] Another object of the present invention is to provide a method for producing an isotactic α-olefin polymer having improved stereoregularity using a single site catalyst.
    [11] In addition, another object of the present invention is to provide a catalyst for olefin polymerization capable of producing stereoblock polypropylene having a higher isotactic pentad fraction and an olefin polymer using the catalyst [including stereoblock poly (α-olefins). )] To provide a method of manufacturing.
    [12] Other objects and advantages of the present invention will become apparent from the following description.
    [13] The present invention is obtained by contacting dried particles (a) with an organometallic compound (b), followed by contacting a functional group having active hydrogen or a compound (c) having a Lewis basic functional group with an unprotonated donor with an electron withdrawing group. Stereoregular α-olefins obtained by contacting the modified particles (A) with a transition metal compound (B) having a stereoregular polymerization capacity of the α-olefin or by further contact with an organometallic compound (C). The present invention relates to a catalyst for polymerization, and also to a method for producing a stereoregular α-olefin polymer using the catalyst.
    [14] In addition, the present invention provides a transition metal compound (B) and an organometallic compound (C) having contact with the modified particles (A) and an α-olefin, and then having a stereoregular polymerization capability of the obtained contact with the α-olefin. A method for producing a stereoregular α-olefin polymer, comprising polymerizing an α-olefin by contacting it. This provides a more efficient manufacturing method.
    [15] In addition, the present invention is for stereoregular α-olefin polymerization obtained by contacting the modified particles (A) and the transition metal compound (B) of formula (I) or by further contacting an organometallic compound (C) thereto. The present invention relates to a catalyst and to a method for producing a stereoregular α-olefin polymer using the catalyst for α-olefin polymerization. This provides a process for producing isotactic α-olefin polymers having improved stereoregularity.
    [16]
    [17] In Formula I above,
    [18] M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    [19] L is a substituted η 5 -cyclopentadienyl group, η 5 -indenyl group, or substituted η 5 -indenyl group, wherein two Ls may be the same or different from each other,
    [20] Y is a bridging group connecting two L,
    [21] Two X's are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group.
    [22] The present invention also relates to a catalyst for α-olefin polymerization obtained by contacting a modified particle (A) and a transition metal compound (B) of formula (II), and also comprising polymerizing α-olefin using the same. It relates to a method for producing a stereo block poly (α-olefin). Thereby, the manufacturing method of the olefin polymer using the catalyst for olefin polymerization which can manufacture stereo block polypropylene with a higher isotactic pentad fraction is provided.
    [23]
    [24] In Formula II above,
    [25] R 1 to R 22 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or a substituted silyl group, and R 1 to R 22 may be the same as or different from each other, and any two adjacent R 1 to the same ring may be used. R 22 may form a ring of 5 to 8 carbon atoms,
    [26] M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    [27] X is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkoxy group, and two X's may be the same or different.
    [1] The present invention relates to a process for the preparation of stereoregular α-olefin polymers. In particular, the present invention relates to a method for producing a stereoregular α-olefin polymer having a uniform polymer particle diameter using the catalyst for stereoregular α-olefin polymerization and the catalyst for α-olefin polymerization.
    [28] 1 is a flowchart to help understand the present invention. This flowchart is a typical example of embodiment of this invention, and this invention is not limited to this at all.
    [29] Best Mode for Carrying Out the Invention
    [30] Hereinafter, the present invention will be described in more detail.
    [31] (a) dried particles
    [32] The modified particles used in the present invention contact the dried particles (a) with the organometallic compounds (b), and then have a functional group having active hydrogen or a compound having an aprotic donor Lewis basic functional group and an electron withdrawing group (c). (A) used herein is a dried particle and is substantially free of moisture and does not substantially produce aluminoxane in contact with trialkylaluminum. The fact that aluminoxane is not substantially produced by contact with trialkylaluminum is obtained by using the solid component obtained using the particles under the same conditions as in Example 1 (1) without the treatment of Example 1 (2). It can be confirmed that no polymer was produced when the polymerization was carried out under the same conditions as in Example 1 (3).
    [33] As the particle (a), those generally used as carriers are preferably used. A porous material having a uniform particle diameter is preferable, and an inorganic material or an organic polymer is suitably used.
    [34] The particle (a) is preferably 2.5 or less, more preferably 2.0 or less, further preferably 1.7 or less as a geometric standard deviation based on the volume of the particle diameter of the particle (a) in terms of the particle diameter distribution of the polymer obtained. .
    [35] Examples of the inorganic material that can be used for the particle (a) of the present invention include inorganic oxides, magnesium compounds, and the like, and clays, clay minerals, and the like can be used if they do not interfere. You may mix and use these.
    [36] Specific examples of the inorganic oxides include SiO 2 , Al 2 0 3 , Mg0, Zr0 2 , Ti0 2 , B 2 0 3 , Ca0, Zn0, BaO, ThO 2 , and mixtures thereof, for example, SiO 2 -Mg0, SiO 2 -Al 2 0 3 , SiO 2 -TiO 2 , SiO 2 -V 2 0 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO, and the like. Among these inorganic oxides, SiO 2 and / or Al 2 O 3 are preferred. In addition, a small amount of Na 2 CO 3 , K 2 CO 3 , CaC0 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 0, it does not matter even if containing a carbonate, sulfate, nitrate and oxide components, such as K 2 O, Li 2 O.
    [37] Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; Alkoxy magnesium halides, such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and ocoxy magnesium chloride; Aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxy magnesium, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethyl hexa hexamagnesium; Aryloxy magnesium, such as phenoxy magnesium and dimethylphenoxy magnesium; Carboxylic acid salts of magnesium, such as magnesium laurate and magnesium stearate, can be illustrated.
    [38] Among them, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxy magnesium is more preferable.
    [39] Clays or clay minerals include kaolin, bentonite, kibushi clay, frog eye clay, allophan, hisingerite, pyrophyllite, talc, mica groups , Montmorillonite group, vermiculite, chlorite group, palygorskite, kaolinite, nacrite, decite, halosite and the like.
    [40] Of these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.
    [41] These inorganic materials need to be dried to substantially remove moisture and are preferably dried by heat treatment. The heat treatment is usually performed at an temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C., of an inorganic substance in which moisture cannot be confirmed with the naked eye. Although the heating time is not specifically limited, Preferably it is about 10 minutes-about 50 hours, More preferably, it is 1 hour-about 30 hours. Further, for example, a method of circulating a dried inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure may be mentioned, but is not limited to such a method.
    [42] As average particle diameter of an inorganic substance, it is preferably 5-1000 micrometers, More preferably, it is 10-500 micrometers, More preferably, it is 10-100 micrometers. As a micropore capacity, Preferably it is 0.1 ml / g or more, More preferably, it is 0.3-10 ml / g. The specific surface area is preferably 10 to 1000 m 2 / g, more preferably 100 to 500 m 2 / g.
    [43] In addition, in this invention, any organic polymer can be used as particle | grain (a), and the mixture of several types of organic polymer can also be used. It is preferable that it is an organic polymer which has a functional group which has the reactivity with an organometallic compound (b) as an organic polymer. Examples of such functional groups include functional groups having active hydrogens, Lewis basic functional groups of aprotic donors, and the like, and organic polymers that can be used in the particles (a) include functional groups having active hydrogens or Lewis basic functional groups of aprotic donors. Polymers are preferred.
    [44] There is no restriction | limiting in particular as long as it has active hydrogen as a functional group which has active hydrogen, As a specific example, a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group, a hydroxyl group, a hydroperoxy group, Carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, and carbazoyl group. . Preferably, they are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group. Especially preferably, they are a primary amino group, a secondary amino group, an amide group, or a hydroxyl group. In addition, these groups may be substituted with halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.
    [45] The Lewis basic functional group of the apron donor is not particularly limited as long as it is a functional group having a Lewis base moiety having no active hydrogen atom, and specific examples thereof include pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, Azide group, N-substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, Carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group, etc. are mentioned. Preferably it is a heterocyclic group, More preferably, it is an aromatic heterocyclic group which has an oxygen atom and / or a nitrogen atom in a ring. Especially preferably, they are a pyridyl group, N-substituted imidazolyl group, or N-substituted indazolyl group, Most preferably, it is a pyridyl group. In addition, these groups may be substituted with halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.
    [46] The amount of a functional group having such active hydrogen or a Lewis basic functional group of an apron donor is not particularly limited, but is preferably 0.01 to 50 mmol / g as molar amount of functional group per gram of polymer, more preferably 0.1 to 20 mmol / g to be.
    [47] The polymer having such a functional group may be, for example, homopolymerizing a functional group having an active hydrogen or a monomer having at least one polymerizable unsaturated group with a Lewis basic functional group having an unprotonated donor, or other having one polymerizable unsaturated group. It can be obtained by copolymerizing other monomers of. At this time, it is preferable to copolymerize the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups together.
    [48] As a monomer having such a functional group having an active hydrogen or an unprotonated Lewis basic functional group and at least one polymerizable unsaturated group, a monomer having an active hydrogen and at least one polymerizable unsaturated group or a Lewis without having an active hydrogen atom And monomers having a functional moiety having a base moiety and at least one polymerizable unsaturated group. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethine groups.
    [49] Examples of the monomer having a functional group having active hydrogen and at least one polymerizable unsaturated group include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene -1-ol etc. are mentioned.
    [50] Specific examples of the monomer having a Lewis base moiety without an active hydrogen atom and a monomer having at least one polymerizable unsaturated group include vinylpyridine, vinyl (N-substituted) imidazole and vinyl (N-substituted) indazole. .
    [51] Examples of the other monomer having one polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound, and the like, and specific examples thereof include ethylene, propylene, butene-1, hexene-1,4-methyl-pentene-1, styrene, and the like. Can be. Preferably ethylene or styrene. These monomers can use two or more types. Moreover, divinylbenzene etc. are mentioned as a specific example of the crosslinkable polymerizable monomer which has two or more polymerizable unsaturated groups.
    [52] As average particle diameter of an organic polymer, Preferably it is 5-1000 micrometers, More preferably, it is 10-500 micrometers. As micropore capacity, Preferably it is 0.1 ml / g or more, More preferably, it is 0.3-10 ml / g. The specific surface area is preferably 10 to 1000 m 2 / g, more preferably 50 to 500 m 2 / g.
    [53] These organic polymers need to be dried to substantially remove moisture and are preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 30 to 400 ° C, preferably 50 to 200 ° C, more preferably 70 to 150 ° C of an organic polymer which cannot be visually identified as moisture. The heating time thereof is not particularly limited, but is preferably about 30 minutes to about 50 hours, more preferably 1 hour to about 30 hours. In addition, a method of circulating a dry inert gas (for example, nitrogen or argon, etc.) at a constant flow rate or a method of reducing the pressure during heating may be mentioned, but is not limited to such a method.
    [54] (b) organometallic compounds
    [55] The organometallic compound (b) used in the present invention is preferably a compound of formula (1).
    [56] R a n AX 1 qn
    [57] In Formula 1 above,
    [58] A is a Group 2, 12 or 13 metal atom of the Periodic Table of Elements (IUPAC, 1993)
    [59] R a is a C1-C20 hydrocarbon group or a C1-C20 hydrocarbonoxy group,
    [60] X 1 is a halogen atom or a hydrogen atom,
    [61] n is a number satisfying 0 <n≤q,
    [62] q is the valence of the metal atom A.
    [63] In Chemical Formula 1, A is a metal atom of Group 2, 12 or 13 of the Periodic Table of Elements (IUPAC, 1993), and preferably A is a boron atom, aluminum atom, magnesium atom or zinc atom. When A is a boron atom or an aluminum atom, the valence is 3 (q = 3), and when A is a magnesium atom or a zinc atom, the valence is 2 (q = 2).
    [64] When A is a boron atom, R a is a hydrocarbon group, and specific examples thereof include trialkylboranes such as trimethylborane, triethylborane, tripropylborane, tributylborane and triphenylborane, dimethylchloroborane, diethylchloroborane and di Dialkyl halide boranes such as propylchloroborane, dibutylchloroborane, diphenylchloroborane, dimethyl hydride borane, diethyl hydride borane, dipropyl hydride borane, dibutyl hydride borane and diphenyl hydride borane Alkyl dihalide borane, such as a dialkyl hydride borane, methyldichloroborane, ethyldichloroborane, propyldichloroborane, butyl dichloroborane, and phenyldichloroborane, etc. are mentioned.
    [65] When A is an aluminum atom, R a is preferably a hydrocarbon group, and specific examples thereof include trialkylaluminum, dimethylaluminum chloride, such as trimethylaluminum, triethylaluminum, tripropylaluminum, trinormalylaluminum, triisobutylaluminum, and trinormalamxylaluminum. , Dialkylaluminum halides such as diethylaluminum chloride, dipropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propyl Alkyl aluminum dihalide, such as aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl alu Titanium hydride, di -n- butyl may be mentioned aluminum hydride, diisobutylaluminum hydride, di -n- hexyl aluminum hydride, such as dialkylaluminum hydride. It is preferably trialkylaluminum and more preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum and tri-n-hexylaluminum. Especially preferably, they are trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
    [66] When A is a magnesium atom, R a is preferably a hydrocarbon group, and specific examples thereof include diethylmagnesium, di-n-butylmagnesium, and the like, and di-n-butoxymagnesium, which is a hydrocarbonoxy group, is also exemplified. In addition, when A is a zinc atom, R a is preferably a hydrocarbon group, and diethyl zinc and the like are exemplified.
    [67] The organometallic compound (b) is more preferably an organoaluminum compound or an organoborane compound, most preferably an organoaluminum compound.
    [68] (c) a compound having a functional group having active hydrogen or an aproton-donating Lewis basic functional group and an electron withdrawing group
    [69] The functional group which has active hydrogen, or the Lewis basic functional group of an aprotic donor which compound (c) used by this invention has reacts with an organometallic compound normally.
    [70] The functional group which has active hydrogen here, and the Lewis basic functional group of aproton donor are the same as that of what was already described, respectively.
    [71] In addition, although compound (c) has an electron withdrawing group, as a parameter | index of an electron withdrawing group, the substituent constant (sigma) of a Hammet side, etc. can be used, and the functional group with a positive substituent constant (sigma) of a Hammet side is equivalent to an electron withdrawing group. .
    [72] Specific examples of the electron withdrawing group include fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, phenyl group, acetyl group, carbonyl group, thionyl group, sulfone group and carboxyl group.
    [73] In the compound (c), a plurality of types and / or plural kinds of functional groups having active hydrogens or non-protonated Lewis basic functional groups and electron withdrawing groups may be provided.
    [74] In the compound (c), the Lewis basic functional group and the electron withdrawing group may be the same. In this case, the compound (c) may have only one such functional group.
    [75] As such a compound (c), the compound which has a functional group which has active hydrogen, and an electron withdrawing group is preferable, The amine, phosphine, alcohol, phenol, thiol, thiophenol, carboxylic acid, sulfonic acid which have an electron withdrawing group as an example of this is preferable. Etc. can be mentioned.
    [76] As compound (c), More preferably, it is a compound of following General formula (2).
    [77] R b m ZH zm
    [78] In Formula 2 above,
    [79] R b is a group containing an electron withdrawing group or an electron withdrawing group,
    [80] Z is a group 15 or 16 atom of the periodic table of elements,
    [81] z is 2 or 3 as valency of Z,
    [82] m is 1 when z is 2, and m is 1 or 2 when z is 3.
    [83] Examples of the group containing an electron withdrawing group in R b of the formula (2) include a halogenated alkyl group, a halogenated aryl group, a cyanoylated aryl group, a nitrated aryl group, an ester group and the like.
    [84] Specific examples of the halogenated alkyl group include fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group, trifluoromethyl group, trichloromethyl group, and tribromomethyl group. , Triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2 , 2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2, 3,3,3-pentaiopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 2,2,2 -Tribromo-1-tribromomethylethyl group, 2,2,2-triiode-triiodomethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethyl Propyl group, 1,1,1,3,3,3-hexachloro-2-trichloromethylpropyl group, 1,1,1,3,3,3 -Hexabromo-2-tribromomethylpropyl group, a 1,1,1,3,3,3-hexaiodo-2- triiodomethylpropyl group, etc. are mentioned.
    [85] As a specific example of a halogenated aryl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group , 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-tri Fluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, Pentaiodophenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-di (trifluoromethyl) phenyl group, 3, 5-di (trifluoromethyl) phenyl group, 2,4,6-t There may be mentioned (trifluoromethyl) phenyl group and the like.
    [86] Specific examples of the cyanoylated aryl group include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, and the like.
    [87] As a specific example of a nitrated aryl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, etc. are mentioned.
    [88] Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, pentafluorophenyloxycarbonyl group and the like.
    [89] R b in the formula (2) is preferably a halogenated alkyl group or a halogenated aryl group, more preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 2, 2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2- Trifluoromethylpropyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3.5-difluorophenyl group, 2,4,6-trifluorophenyl group or pentafluorophenyl group, more preferably Trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group or pentafluoro It is a rophenyl group.
    [90] In formula (2), Z is a group 15 or 16 atom of the periodic table of elements, and H represents a hydrogen atom. Specific examples of Z include a nitrogen atom, a person atom, an oxygen atom, a sulfur atom, and the like, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.
    [91] z is the valence of Z. For example, z is 3 when Z is a nitrogen atom or a person atom, and z is 2 when Z is an oxygen atom or a sulfur atom. And when z is 2, m is 1, and when z is 3, m is 1 or 2.
    [92] Specific examples of the compound (c) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine and di (difluoromethyl). Amine, di (dichloromethyl) amine, di (dibromomethyl) amine, di (diiodomethyl) amine, di (trifluoromethyl) amine, di (trichloromethyl) amine, di (tribromomethyl ) Amine, di (triiodomethyl) amine, di (2,2,2-trifluoroethyl) amine, di (2,2,2-trichloroethyl) amine, di (2,2,2-trit Ribomoethyl) amine, di (2,2,2-triiodoethyl) amine, di (2,2,3,3,3-pentafluoropropyl) amine, di (2,2,3,3, 3-pentachloropropyl) amine, di (2,2,3,3,3-pentabromopropyl) amine, di (2,2,3,3,3-pentaiodopropyl) amine, di (2, 2,2-trifluoro-1-trifluoromethylethyl) amine, di (2,2,2-trichloro-1-trichloromethylethyl) amine, di (2,2,2-tribromo- 1-tribromomethylethyl) amine, Di (2,2,2-triiodine-1-triiodomethylethyl) amine, di (1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl) amine, di (1,1,1,3,3,3-hexachloro-2-trichloromethylpropyl) amine, di (1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl ) Amine, di (1,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl) amine, di (2-fluorophenyl) amine, di (3-fluorophenyl) amine , Di (4-fluorophenyl) amine, di (2-chlorophenyl) amine, di (3-chlorophenyl) amine, di (4-chlorophenyl) amine, di (2-bromophenyl) amine, di ( 3-bromophenyl) amine, di (4-bromophenyl) amine, di (2-iodophenyl) amine, di (3-iodophenyl) amine, di (4-iodophenyl) amine, di ( 2,6-difluorophenyl) amine, di (3,5-difluorophenyl) amine, di (2,6-dichlorophenyl) amine, di (3,5-dichlorophenyl) amine, di (2, 6-dibromophenyl) amine, di (3,5-dibromophenyl) amine, di (2,6-diiodophenyl) amine, di (3,5-diio Phenyl) amine, di (2,4,6-trifluorophenyl) amine, di (2,4,6-trichlorophenyl) amine, di (2,4,6-tribromophenyl) amine, di ( 2,4,6-triiodophenyl) amine, di (pentafluorophenyl) amine, di (pentachlorophenyl) amine, di (pentabromophenyl) amine, di (pentaoodophenyl) amine, di ( 2- (trifluoromethyl) phenyl) amine, di (3- (trifluoromethyl) phenyl) amine, di (4- (trifluoromethyl) phenyl) amine, di (2,6-di (trifluoro) Rhomethyl) phenyl) amine, di (3,5-di (trifluoromethyl) phenyl) amine, di (2,4,6-tri (trifluoromethyl) phenyl) amine, di (2-cyanophenyl ) Amine, (3-cyanophenyl) amine, di (4-cyanophenyl) amine, di (2-nitrophenyl) amine, di (3-nitrophenyl) amine, di (4-nitrophenyl) amine, and the like. Can be mentioned. Moreover, the phosphine compound in which nitrogen atom was substituted by the person can also be illustrated similarly. These phosphine compounds are compounds etc. which are shown by changing the amine of the specific example mentioned above into phosphine.
    [93] As specific examples of the compound (c), alcohols include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, Trichloromethanol, tribromomethanol, triiodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2, 2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol , 2,2,3,3,3-pentaiopropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2 , 2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1,1,3,3,3-hexafluoro 2-trifluoromethylpropanol, 1,1,1,3,3,3-hexachloro-2-trichloromethylpro Ol, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropanol, 1,1,1,3,3,3-hexaiod-2-triiodomethylpropanol, etc. Can be mentioned. Moreover, the thiol compound in which the oxygen atom was substituted by the sulfur atom can also be illustrated by the same formula. These thiol compounds are compounds represented by replacing methanethiol with methanol, ethanol with ethanol, and propanol with propanethiol.
    [94] As specific examples of the compound (c), phenols include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3 Bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6 -Dichlorophenol, 3,5-dichlorophenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4 , 6-trifluorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, penta Bromophenol, pentaiodophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) Phenol, 3,5-di (trifluoromethyl) phenol, 2,4,6-tri (trifluoromethyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, etc. are mentioned. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can also be illustrated by the same formula. These thiophenol compounds are compounds etc. which are represented by substituting the phenol of the specific example mentioned above with thiophenol.
    [95] As specific examples of the compound (c), as carboxylic acids, 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2, 5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2 , 4,5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, pentafluoro Benzoic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoroethylcarboxylic acid, heptafluoropropylcarboxylic acid, 1,1,1,3,3,3-hexafluoro-2- Propylcarboxylic acid, and the like.
    [96] As a specific example of the compound (c), sulfonic acids include fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1 And 3,3,3-hexafluoro-2-propanesulfonic acid.
    [97] As the compound (c), preferably, as amines, di (trifluoromethyl) amine, di (2,2,2-trifluoroethyl) amine, di (2,2,3,3,3-pentafluoropropyl ) Amine, di (2,2,2-trifluoro-1-trifluoromethylethyl) amine, di (1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl ) Amines, di (pentafluorophenyl) amines and alcohols are trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2 Trifluoro-1-trifluoromethylethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, and phenols as 2-fluorophenol and 3-fluoro Phenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) Phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 3,5-di (triflu Examples of oromethyl) phenol, 2,4,6-tri (trifluoromethyl) phenol and carboxylic acids include pentafluorobenzoic acid, trifluoroacetic acid, and sulfonic acids.
    [98] More preferably, as the compound (c), di (trifluoromethyl) amine, di (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6-trifluorophenol, Pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 2,4,6-tri (trifluoromethyl) phenol, and more preferably Pentafluorophenol or 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol (common name: perfluoro-tert-butanol).
    [99] (A) modified particles
    [100] The modified particles are obtained by contacting the dried particles (a) with the organometallic compound (b), followed by contacting the functional group having active hydrogen or the compound (c) having an electron aspirating group with a Lewis basic functional group having an unprotonated donor. do.
    [101] The contact treatment between (a) and (b) and the subsequent contact treatment with (c) are preferably carried out in an inert gas atmosphere. The treatment temperature is usually -80 ° C to 200 ° C, preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The treatment time is not particularly limited but is usually 1 minute to 48 hours, preferably 10 minutes to 24 hours. Although it is preferable to use a solvent, it is preferable that the solvent to be used is an aliphatic or aromatic hydrocarbon solvent which is inert to (a), (b) and (c). Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane and octane. Examples of the aromatic hydrocarbon solvent include benzene, toluene and xylene. Alternatively, materials in which these hydrocarbon solvents are optionally mixed may be used.
    [102] The contact method of (a) and (b) and the contact method with (c) performed after this contact may be the same or different.
    [103] In addition, although the contact treated particle does not need to be performed even if it performs an isolation operation in each contacting step, it is preferable to isolate the processed particle after contacting in each contacting step. As the isolation method, a method of decanting the supernatant of the treatment liquid, a method of washing the treated particles with an inert solvent after filtration, a method of washing the treated particles with an inert solvent after filtration and drying them under reduced pressure or under an inert gas flow, a solvent at the time of contact treatment And distillation off under reduced pressure or inert gas flow. In addition, when the process operation which isolates the obtained process particle | grains is not performed, it can use for the polymerization reaction in the state which suspended the particle | grains obtained in the process liquid in the inert solvent.
    [104] As an amount of (b) used with respect to (a) in preparation of modified particle | grains, the metal atom of the organometallic compound (b) contained in the particle | grains obtained by the contact of (a) and (b) is 1 g of particle | grains of a dry state It is preferable to be 0.1 mmol or more as molar number of the metal atom contained in, and since it is more preferable that it is 0.5-20 mmol, what is necessary is just to determine suitably so that it may become the said range. As the usage-amount of (c), the compound (c) which has a functional group which has active hydrogen with respect to the metal atom derived from the organometallic compound (b) contained in 1 g of dry particles, or a Lewis basic functional group of an aprotic donor and an electron withdrawing group (c) It is preferable that it is 0.01-100 as molar ratio (c) / (b) of (), It is more preferable that it is 0.05-5, It is most preferable that it is 0.1-2.
    [105] (B) a transition metal compound having stereoregular polymerization capacity of α-olefin
    [106] The transition metal compound used in the catalyst for α-olefin polymerization of the present invention may be a transition metal compound that forms a single-site catalyst capable of producing a stereoregular α-olefin polymer such as an isotactic propylene polymer or a syndiotactic propylene polymer. Although not particularly limited, transition metal compounds having transition metal atoms of the Group 4 to Group 10 and lanthanoid series of the Periodic Table of Elements (IUPAC 1985) are preferable. As such a transition metal atom, for example, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, samarium Atom, a ytterbium atom, etc. are mentioned, A titanium atom, a zirconium atom, or a hafnium atom is preferable.
    [107] Preferred transition metal compounds (B) are transition metal compounds represented by the following formula (I) or (III).
    [108] Formula I
    [109]
    [110]
    [111] In the above formulas (I) and (III),
    [112] M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    [113] L is a substituted η 5 -cyclopentadienyl group, η 5 -indenyl group, or substituted η 5 -indenyl group, and two L's may be the same or different from each other,
    [114] Y is a bridging group connecting two L,
    [115] Two X's are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group.
    [116] The transition metal atom represented by M in the formula (I) or (III) is the transition metal atom described above, and preferably a titanium atom, a zirconium atom, a hafnium atom, and more preferably a titanium atom or a zirconium atom.
    [117] In formula (III), L is a substituted η 5 -cyclopentadienyl group, η 5 -indenyl group or substituted η 5 -indenyl group, and two L's may be the same or different from each other. Substituted η 5 - cyclopentadienyl Specific examples of the group include η 5 -2- methyl cyclopentadienyl group (hereinafter, η 5 - there is a case to omit a), 2-ethyl cyclopentadienyl group, 2-n- propyl-cyclopenten Pentadienyl group, 2-isopropylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2-isobutylcyclopentadienyl group, 2-tert-butylcyclopentadienyl group, 2-n-hexylcyclopentadiene Neyl group, 3-methylcyclopentadienyl group, 3-ethylcyclopentadienyl group, 3-n-propylcyclopentadienyl group, 3-isopropylcyclopentadienyl group, 3-n-butylcyclopentadienyl group, 3-iso Butylcyclopentadienyl group, 3-tert-butylcyclopentadienyl group, 3-n-hexylcyclopentadienyl group, 2,3-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3 -Di-n-propylcyclopentadienyl group, 2,3-diisopropylcyclophene Dienyl group, 2,3-di-n-butylcyclopentadienyl group, 2,3-diisobutylcyclopentadienyl group, 2,3-di-tert-butylcyclopentadienyl group, 2,3-di-n -Hexylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,4-diethylcyclopentadienyl group, 2,4-di-n-propylcyclopentadienyl group, 2,4-diisopropylcyclo Pentadienyl group, 2,4-di-n-butylcyclopentadienyl group, 2,4-diisobutylcyclopentadienyl group, 2,4-di-tert-butylcyclopentadienyl group, 2,4-di- n-hexylcyclopentadienyl group, 3,5-dimethylcyclopentadienyl group, 3,5-diethylcyclopentadienyl group, 3,5-di-n-propylcyclopentadienyl group, 3,5-diisopropyl Cyclopentadienyl group, 3,5-di-n-butylcyclopentadienyl group, 3,5-diisobutylcyclopentadienyl group, 3,5-di-tert-butylcyclopentadienyl group, 3,5-di -n-hexylcyclopentadienyl group, 2- Ethyl-3-methylcyclopentadienyl group, 2-methyl-3-ethylcyclopentadienyl group, 2-methyl-3-n-propylcyclopentadienyl group, 2-methyl-3-isopropylcyclopentadienyl group, 2 -Ethyl-3-isopropylcyclopentadienyl group, 2-methyl-3-n-butylcyclopentadienyl group, 2-methyl-3-isobutylcyclopentadienyl group, 2-methyl-3-tert-butylcyclopenta Dienyl group, 2-methyl-3-n-hexylcyclopentadienyl group, 2-ethyl-4-methylcyclopentadienyl group, 2-methyl-4-ethylcyclopentadienyl group, 2-methyl-4-n-propyl Cyclopentadienyl group, 2-methyl-4-isopropylcyclopentadienyl group, 2-ethyl-4-isopropylcyclopentadienyl group, 2-methyl-4-n-butylcyclopentadienyl group, 2-methyl-4 -Isobutylcyclopentadienyl group, 2-methyl-4-tert-butylcyclopentadienyl group, 2-methyl-4-n-hexylcyclopentadienyl group, 3-ethyl-5-methylcyclopentadienyl Group, 3-methyl-5-ethylcyclopentadienyl group, 3-methyl-5-n-propylcyclopentadienyl group, 3-methyl-5-isopropylcyclopentadienyl group, 3-ethyl-5-isopropylcyclo Pentadienyl group, 3-methyl-5-n-butylcyclopentadienyl group, 3-methyl-5-isobutylcyclopentadienyl group, 3-methyl-5-tert-butylcyclopentadienyl group, 3-methyl-5 -n-hexylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,4,5-trimethylcyclopentadienyl group, 2- (2-furyl) -3,5-dimethylcyclopentadienyl group And 2- (2-furyl) -4,5-dimethylcyclopentadienyl group. η 5 - substituted inde group as η 5 - inde methyl group, η 5 - dimethyl inde group, η 5 -n- propyl inde group, η 5 - inde isopropyl group, η 5 -n- butyl inde group, η 5 - tert-butyl indenyl group, (eta) 5 -phenylindenyl group, (eta) 5 -methylphenyl indenyl group, (eta) 5 -naphthyl indenyl group, (eta) 5 -trimethylsilyl indenyl group, (eta) 5 -tetrahydroindenyl group, etc. are mentioned.
    [118] In formula (I), Y is a bridging group connecting two Ls. Examples of the crosslinking group include a divalent crosslinking group containing a Group 14 atom of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Rev. 1989), and preferably a divalent crosslinking containing a carbon atom, a silicon atom, a germanium atom or a tin atom. Qi. More preferably, it is a bivalent bridging group which is a valent carbon atom, silicon atom, germanium atom, and / or tin atom couple | bonded with two L, More preferably, the valent carbon atom, silicon atom, germanium atom couple | bonded with two L is more preferable. And / or a divalent bridging group having a tin atom and a minimum number of atoms between three L-bonding atoms (including a single atom bonding to two L's). Specifically, methylene group, ethylene group, propylene group, dimethyl methylene group (isopropylidene group), diphenylmethylene group, tetramethylethylene group, silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, tetra The methyl disilylene group, the dimethoxy silylene group, etc. are mentioned, Especially preferably, they are a methylene group, an ethylene group, a dimethyl methylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group, or a diphenylsilylene group.
    [119] In the formula (III), two X's are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group.
    [120] As a halogen atom here, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is illustrated, Preferably it is a chlorine atom or a bromine atom, More preferably, it is a chlorine atom.
    [121] Moreover, as an alkyl group, a C1-C20 alkyl group is preferable, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, isobutyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like. Preferably, they are methyl group, ethyl group, isopropyl group, tert-butyl group, isobutyl group, or isoamyl group.
    [122] These alkyl groups may all be substituted with halogen atoms which are fluorine, chlorine, bromine or iodine atoms. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, fluoroethyl group, pentafluoroethyl group, perfluoropropyl group, and perfluoro Butyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group, perbromopropyl group and the like.
    [123] In addition, all of these alkyl groups may be partially substituted by an alkoxy group such as methoxy group, ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group.
    [124] As an aralkyl group, a C7-20 aralkyl group is preferable, For example, a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) Methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetra Methylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert- Butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octyl pe ) Methyl group, (n- decyl and phenyl) may be made of methyl group, (n- dodecylphenyl) methyl group, naphthylmethyl group, anthracenyl group, etc., more preferably benzyl group.
    [125] All of these aralkyl groups include a fluorine atom, chlorine atom, bromine atom or halogen atom of iodine atom, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group, etc. May be substituted.
    [126] As an aryl group, a C6-C20 aryl group is preferable, For example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2, 3- xylyl group, 2, 4- xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group , 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neo A pentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. are mentioned, More preferably, it is a phenyl group.
    [127] All of these aryl groups are partially substituted with fluorine, chlorine, bromine or halogen atoms of iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups or aralkyloxy groups such as benzyloxy groups. Can be substituted.
    [128] The substituted silyl group is a silyl group substituted with a hydrocarbon group, and as the hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group and aryl groups such as alkyl groups having 1 to 10 carbon atoms, such as n-pentyl groups, n-hexyl groups, and cyclohexyl groups, and phenyl groups. As such a C1-C20 substituted silyl group, C1-C20 monocyclic silyl groups, such as a methyl silyl group, an ethyl silyl group, a phenyl silyl group, a dimethyl silyl group, a diethyl silyl group, a diphenyl silyl, for example C2-C20 disubstituted silyl groups, trimethylsilyl groups, triethylsilyl groups, tri-n-propylsilyl groups, triisopropylsilyl groups, tri-n-butylsilyl groups, and tri-sec-butylsilyl groups such as groups , Tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group C3-C20 trisubstituted silyl group etc. are mentioned, Preferably, they are a trimethylsilyl group, tert- butyl dimethyl silyl group, or a triphenyl silyl group.
    [129] All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom or a halogen atom of an iodine atom, an alkoxy group such as methoxy group or ethoxy group, an aryloxy group such as phenoxy group or an aralkyloxy group such as benzyloxy group Etc., some of which may be substituted.
    [130] As an alkoxy group, a C1-C20 alkoxy group is preferable, For example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n -Pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodec group, n-pentadex group, n-ecoxoxy group, etc. are mentioned, More preferably, a methoxy group and an ethoxy group are mentioned. , Isopropoxy group or tert-butoxy group.
    [131] All of these alkoxy groups include a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group. May be substituted.
    [132] As an aralkyloxy group, a C7-20 aralkyloxy group is preferable, For example, a benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, ( 2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl ) Methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl ) Methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4, 5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy Period, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, ( tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthyl methoxy group, anthracenyl methoxy group, etc. are mentioned, More preferably, it is a benzyloxy group.
    [133] These aralkyloxy groups are all alkoxy groups such as fluorine atom, chlorine atom, bromine atom or iodine atom, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group, etc. Some may be substituted.
    [134] As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms is preferable. For example, a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2, 4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-tert-butyl-3-methylphenoxy, 2-tert-butyl-4-methylphenoxy, 2-tert-butyl-5-methylphenoxy, 2-tert-butyl-6-methylphenoxy, 2,3,4-trimethylphenoxy, 2,3, 5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 2-tert-butyl-3,4-dimethylphenoxy, 2-tert-butyl-3,5-dimethylphenoxy, 2-tert-butyl-3,6-dimethylphenoxy, 2,6-di-tert-butyl-3-methylphenoxy, 2-tert-butyl- 4,5-dimethylphenoxy, 2,6-di-tert-butyl-4-methylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2-tert -Butyl-3,4,5-trimethylphene Period, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2 , 3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group , Ethyl phenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy A time period, n-tetradecyl phenoxy group, a naphthoxy group, anthraceneoxy group, etc. are mentioned.
    [135] All of these aryloxy groups include fluorine, chlorine, bromine or halogen atoms of iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups or aralkyloxy groups such as benzyloxy groups. May be substituted.
    [136] The heterocyclic group is a group having a heterocycle, preferably a group having a 4 to 8 membered ring heterocyclic group, and more preferably a group having a 4 to 8 membered ring aromatic heterocycle. As a hetero atom contained in a heterocycle, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. As a specific example of such a heterocyclic group, an indolyl group, a furyl group, a thienyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, etc. are mentioned, for example, A more preferable example of such a heterocyclic group is more preferable. Is a furyl group.
    [137] All of these heterocyclic groups include a fluorine atom, chlorine atom, bromine atom or halogen atom of iodine atom, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group, etc. May be substituted.
    [138] As the metallocene compound of the formula (III), bis (2-methylindenyl) zirconium dichloride, bis (2-ethylindenyl) zirconium dichloride, bis (2-t-butylinyl) zirconium dichloride, Bis (2-phenylindenyl) zirconium dichloride, bis (2-phenylindenyl) zirconium dimethyl, bis [2- (3,5-dimethylphenyl) indenyl] zirconium dichloride, bis [2- (3,5 -Bis-trifluoromethylphenyl) indenyl] zirconium dichloride, bis [2- (4-fluorophenyl) indenyl] zirconium dichloride, bis [2- (2,3,4,5-tetrafluorophenyl ) Indenyl] zirconium dichloride, bis [2- (2,3,4,5,6-pentafluorophenyl) indenyl] zirconium dichloride, (2-phenylindenyl) [2- (3,5- Bis-trifluorophenyl) indenyl] zirconium dichloride, bis [2- (4-trimethylsilyl) indenyl] zirconium dichloride or bis [2- (3,5-tert-butyl-4-methoxy) Carbonyl] zirconium dichloride gamyeo chloride, (2-phenyl-inde carbonyl) most preferably bis go zirconium dichloride.
    [139] In addition, specific examples of the transition metal compound in which L in Formula I is an indenyl group or a substituted indenyl group include methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium di Chloride, dimethylsilylenebis (indenyl) zirconium dichloride, diphenylmethylenebis (indenyl) zirconium dichloride, methylenebis (2-methylindenyl) zirconium dichloride, methylenebis (2-n-propylinyl) Zirconium dichloride, methylenebis (2-n-butylindenyl) zirconium dichloride, methylenebis (2-n-hexylindenyl) zirconium dichloride, methylenebis (2-isopropylinyl) zirconium dichloride, methylenebis (2-isobutyl indenyl) zirconium dichloride, methylenebis (2-tert-butylinyl) zirconium dichloride, methylenebis (2-phenylindenyl) zirconium dicle Ride, methylenebis (2-trimethylsilylindenyl) zirconium dichloride, methylenebis (2,4-dimethylindenyl) zirconium dichloride, methylenebis (2,4,7-trimethylindenyl) zirconium dichloride, methylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, methylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, methylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride , Methylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, methylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium Dichloride, Ethylenebis (2-n-propylindenyl) zirconium dichloride, Ethylenebis (2-n-butylindenyl) zirconium dichloride, Ethylenebis (2-n-hexylindenyl) zirconium dichloride, Ethylenebis (2-isopropylindenyl) zirconium dichloride, Ethylenebis (2-isobutylinyl) zirconium dichloride, ethylenebis (2-tert-butylinyl) zirconium dichloride, ethylenebis (2-phenylindenyl) zirconium dichloride, ethylenebis (2-trimethylsilyl Nile) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-isopropyl Nil) zirconium dichloride, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, ethylenebis (2-methyl-4, 5-benzoindenyl) zirconium dichloride, ethylenebis (4,5.6,7-tetrahydroindenyl) zirconium dichloride, isopropylidenebis (2-methylindenyl) zirconium dichloride, isopropylidenebis (2- n-propylindenyl) zirconium dichloro Ide, Isopropylidenebis (2-n-butylindenyl) zirconium dichloride, Isopropylidenebis (2-n-hexylindenyl) zirconium dichloride, Isopropylidenebis (2-isopropylinyl) zirconium di Chloride, isopropylidenebis (2-isobutylindenyl) zirconium dichloride, isopropylidenebis (2-tert-butylindenyl) zirconium dichloride, isopropylidenebis (2-phenylindenyl) zirconium dichloride, Isopropylidenebis (2-trimethylsilylindenyl) zirconium dichloride, isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, isopropylidenebis (2,4,7-trimethylidenyl) zirconium di Chloride, isopropylidenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4-phenylindenyl) zirconium dichloride, isopropylidenebis (2-methyl- 4-me Tildeinyl) zirconium dichloride, isopropylidenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride Dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-propylinyl) zirconium dichloride, dimethylsilylenebis (2-n-butylindenyl) zirconium dichloride, Dimethylsilylenebis (2-n-hexylindenyl) zirconium dichloride, dimethylsilylenebis (2-isopropylinyl) zirconium dichloride, dimethylsilylenebis (2-isobutylinyl) zirconium dichloride, dimethyl Silylenebis (2-tert-butylindenyl) zirconium dichloride, dimethylsilylenebis (2-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, dimethylsilylene Bis (2,4-dime Indenyl) zirconium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-isopropylinyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylinyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzo Nil) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, diphenylmethylenebis (2-methylindenyl) zirconium dichloride, diphenylmethylenebis (2- n-propylindenyl) zirconium dichloride, diphenylmethylenebis (2-n-butylindenyl) zirconium dichloride, diphenylmethylenebis (2-n-hexylindenyl) zirconium dichloride, diphenylmethylenebis (2 Isopropylindenyl) zirconium dichloride, diphenylmethylene ratio (2-isobutyl indenyl) zirconium dichloride, diphenylmethylene bis (2-tert-butyl indenyl) zirconium dichloride, diphenylmethylene bis (2-phenylindenyl) zirconium dichloride, diphenylmethylene bis ( 2-trimethylsilylindenyl) zirconium dichloride, diphenylmethylenebis (2,4-dimethylindenyl) zirconium dichloride, diphenylmethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, diphenylmethylene Bis (2-methyl-4-isopropylindenyl) zirconium dichloride, diphenylmethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylmethylenebis (2-methyl-4-naphthyl Nil) zirconium dichloride, diphenylmethylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylmethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, di Phenylsilylenebis (2-methylindenyl) zirconium dichloride, Phenylsilylenebis (2-n-propylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-butylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-hexylindenyl) zirconium Dichloride, diphenylsilylenebis (2-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-isobutylindenyl) zirconium dichloride, diphenylsilylenebis (2-tert-butylindenyl Zirconium dichloride, diphenylsilylenebis (2-phenylindenyl) zirconium dichloride, diphenylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, diphenylsilylenebis (2,4-dimethyl Nil) zirconium dichloride, diphenylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4-isopropylinyl) zirconium dichloride, diphenylsilyl Lenbis (2-methyl-4-phenylindenyl) zirconium dichloride, dipe Nylsilylenebis (2-methyl4-naphthylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylsilylenebis (4,5 , 6,7-tetrahydroindenyl) zirconium dichloride and the like. Moreover, the compound which substituted the zirconium atom by the titanium atom or the hafnium atom in the above zirconium compound can also be illustrated similarly.
    [140] Among them, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-n-propylinyl) zirconium dichloride, dimethylsilylenebis (2-n-butylindenyl) zirconium dichloride Dimethylsilylenebis (2-n-hexylindenyl) zirconium dichloride, dimethylsilylenebis (2-isopropylinyl) zirconium dichloride, dimethylsilylenebis (2-isobutylinyl) zirconium dichloride, Dimethylsilylenebis (2-tert-butylindenyl) zirconium dichloride, dimethylsilylenebis (2-phenylinyl) zirconium dichloride, dimethylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, dimethylsilyl Lenbis (2,4-dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-isopropylinyl) Zirconium dichloride , Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylinyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4 , 5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, diphenylsilylenebis (2-methylindenyl) zirconium dichloride, di Phenylsilylenebis (2-n-propylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-butylindenyl) zirconium dichloride, diphenylsilylenebis (2-n-hexylindenyl) zirconium Dichloride, diphenylsilylenebis (2-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-isobutylindenyl) zirconium dichloride, diphenylsilylenebis (2-tert-butylindenyl Zirconium dichloride, diphenylsilylenebis (2-phenylindenyl) zirconium dichloride, di Nylsilylenebis (2-trimethylsilylindenyl) zirconium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, diphenylsilylenebis (2,4,7-trimethylindenyl) Zirconium dichloride, diphenylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, diphenylsilylenebis (4,5,6, Preferred are compounds in which the crosslinking group Y in the formula (I), such as 7-tetrahydroindenyl) zirconium dichloride, is a disubstituted silicon atom.
    [141] Specific examples of the transition metal compound wherein L is a substituted cyclopentadienyl group in formula (I) include dimethylsilylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3 -tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3 , 5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl) (4-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-tert-butylcyclopentadiene Nil) (4-tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3,5-dimethylsilylenecyclopentadienyl) zirconium dichlora Id, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3-methylcyclopentadienyl Zirconium dichloride, methylene (cyclopentadienyl) (3-tert-butylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (Cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (4-methylcyclopentadienyl) zirconium dichloride, methylene (3- tert-butylcyclopentadienyl) (4-tert-butylcyclopentadienyl) zirconium dichloride, methylene (2,4-dimethylcyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, Methylene (2,3,5-trime Cyclopentadienyl) (2,4,5-trimethyl cyclopentadienyl) zirconium dichloride.
    [142] Moreover, the compound which substituted the zirconium atom by the titanium atom or the hafnium atom in the said zirconium compound can also be illustrated by the same method.
    [143] In the case where L in the formula (I) is a substituted cyclopentadienyl group, particularly preferred are transition metal compounds of the formula (IV).
    [144]
    [145] In Formula IV above,
    [146] (R 23 n -C 5 H 4-n ) and (R 23 q -C 5 H 4-q ) are each a substituted η 5 -cyclopentadienyl group,
    [147] n and q are integers of 1 to 3,
    [148] Each R 23 may be the same or different and represents a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, but is substituted η 5 -cyclo In the pentadienyl group the position and / or type of R 23 is chosen such that there is no symmetry plane comprising M,
    [149] R 24 and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, and R 24 and X may be the same as or different from each other. And
    [150] Y 2 is a carbon atom, a silicon atom, a germanium atom or a tin atom.
    [151] R 23 , R 24 and X as used herein are each selected from a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a heterocyclic group. Specifically, it is as described in the general formula (IV). In the general formula (IV), the position and / or type of R 23 in the substituted η 5 -cyclopentadienyl group needs to be selected such that there is no symmetry plane including M, but preferably the two substituted η 5 -cyclopentadienyl groups It is a compound of different origin. R 23 is preferably an alkyl group or a heterocyclic group.
    [152] Specific examples of (R 23 n -C 5 H 4-n ) or (R 23 q -C 5 H 4-q ) include a substituted η 5 -cyclopentadienyl group described in the description of Formula (I).
    [153] Y 2 in formula (IV) is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom.
    [154] Specific examples of the formula (IV) may be selected from specific examples of the transition metal compound in which the L in the formula (I) is a substituted cyclopentadienyl group. These transition metal compounds may be used in one kind or in combination of two or more kinds.
    [155] Moreover, when using the transition metal compound of Formula (II) among the transition metal compound of Formula (III), since stereo block poly ((alpha) -olefin) with a high isotactic pentad fraction can be obtained, it is preferable.
    [156] Formula II
    [157]
    [158] In Formula II above,
    [159] R 1 to R 22 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or a substituted silyl group, and R 1 to R 22 may be the same or different from each other and are the same cyclic two adjacent R 1 to R 22 may form a ring of 5 to 8 carbon atoms,
    [160] M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    [161] X is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkoxy group, and two X's may be the same or different.
    [162] M is the same as in formula (III) and is preferably a titanium atom, a zirconium atom or a hafnium atom, particularly preferably a zirconium atom.
    [163] R 1 to R 22 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or a substituted silyl group, which are exemplified by the formulas (I) and (III), and R 1 to R 22 may be the same or different from each other. Any two adjacent R 1 to R 22 of the same ring may form a ring of 5 to 8 carbon atoms. In addition, with regard to X, the same ones as X in the formulas (I) and (III) are exemplified and the two Xs may be the same or different.
    [164] Examples of the halogen atom in the substituents R 1 to R 22 or X include a fluorine atom, a chlorine atom and an iodine atom, and R 1 to R 22 are fluorine atoms and X is particularly preferably a chlorine atom.
    [165] Particularly preferred as R 1 to R 12 in formula (II) is a hydrogen atom.
    [166] Preferred as R 13 to R 22 are each independently a hydrogen atom, a halogen atom or an alkyl group, more preferably each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom.
    [167] Moreover, what is preferable as X is a halogen atom, an alkyl group, or an alkoxy group.
    [168] Examples of the metallocene compound of the formula (II) include those included in the definition of the formula (II) from the specific compounds described in the description of the compound of the formula (III).
    [169] One type of these metallocene compounds may be used, and two or more types may be combined.
    [170] It is also preferable to use a transition metal compound in which L is a substituted indenyl group in the transition compound of the formula (I), since an α-olefin polymer having higher stereoregularity can be obtained.
    [171] (C) organometallic compounds
    [172] Examples of the organometallic compound as the component (C) include a compound of the formula (I), and it is preferable to use one or two or more thereof. More preferably, it is an organoaluminum compound of the following general formula (3).
    [173] R c b AlY 3-b
    [174] In Formula 3 above,
    [175] R c is a hydrocarbon group having 1 to 8 carbon atoms,
    [176] Al is an aluminum atom,
    [177] Y is a hydrogen atom and / or a halogen atom,
    [178] b is a number which satisfy | fills 0 <b <= 3.
    [179] Specific examples of R c in the general formula (3) representing the organoaluminum compound include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like. And an ethyl group, n-butyl group, isobutyl group, n-hexyl group. Specific examples of the case where Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom.
    [180] Specific examples of the organoaluminum compound of formula (3) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Dialkylaluminum chlorides such as trialkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride and di-n-hexylaluminum chloride, methyl Alkyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum, such as aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butylaluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride Hydride, di-n-propylal Dialkyl aluminum hydride, such as a luminium hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n-hexyl aluminum hydride, etc. can be illustrated. Among them, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum or tri-n-hexylaluminum, and more preferably triisobutylaluminum or tri -n-hexyl aluminum.
    [181] These organoaluminum compounds may be used in one kind or in combination of two or more kinds.
    [182] The catalyst for α-olefin polymerization of the present invention is obtained by contacting a modified particle (A) with a transition metal compound (B) having a stereoregular polymerization ability of the α-olefin or modified particles (A), α- Although what is obtained by contacting the transition metal compound (B) and organometallic compound (C) which have the stereoregular polymerization ability of an olefin is mentioned, It is preferable because the latter is more highly active.
    [183] The catalyst for α-olefin polymerization of the present invention is a catalyst for stereoregular α-olefin polymerization which provides a polymer having a matching polymer particle diameter when applied to polymerization involving formation of α-olefin polymer particles. As the catalyst for α-olefin polymerization of the present invention, the geometric standard deviation based on the volume diameter of the particle diameter of the polymer obtained when applied to polymerization involving the formation of α-olefin polymer particles is preferably 2.5 or less, and more preferably 2.0. Hereinafter, it is the catalyst for stereoregular alpha-olefin polymerization which provides the alpha-olefin polymer which is most preferably 1.7 or less. In addition, the method for producing the α-olefin polymer of the present invention preferably has a geometric standard deviation of 2.5 or less (more preferred) based on the volume diameter of the obtained polymer when applied to polymerization involving the formation of α-olefin polymer particles. Preferably a less than 2.0, most preferably less than 1.7).
    [184] When the catalyst for α-olefin polymerization of the present invention is obtained by contacting a modified particle (A) with a transition metal compound (B) or by adding an organometallic compound (C) thereto, the amount of the component (B) is used as a component ( A) It is 1 * 10 <-6> -1 * 10 <-3> mol normally with respect to 1g, Preferably it is 5 * 10 <-6> -1 * 10 <-4> mol. In addition, the usage-amount of the organometallic compound of component (C) is 0.01 as molar ratio (C) / (B) of the metal atom of the organometallic compound of component (C) with respect to the transition metal atom of the transition metal compound of component (B). It is preferably from 10,000 to 10,000, more preferably from 0.1 to 5,000, most preferably from 1 to 2,000.
    [185] In the present invention, component (A) and component (B) or component (C) may be used in any order in the reactor at the time of polymerization, and may also be added to the reactor after contacting these optional components in any combination in advance. In particular, after contacting component (A) with α-olefin, the obtained contact with component (B) and component (C) is contacted to polymerize α-olefin to produce α-olefin polymer. desirable.
    [186] In this case, the contact conditions of the component (A) and the α-olefin are not particularly limited, but the contact temperature is preferably -5 to 90 ° C, more preferably 5 to 50 ° C. The contact may be carried out in the presence of aliphatic hydrocarbon solvents such as butane, pentane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene or halogenated hydrocarbons such as methylene chloride. The α-olefin used for the contact may be the same as or different from the monomer of the α-olefin polymer to be produced, and two or more kinds of α-olefins may also be used.
    [187] In the present invention, the monomer used for the polymerization may be an α-olefin having 3 to 20 carbon atoms, and two or more kinds of monomers may be used at the same time. Although such a monomer is illustrated below, this invention is not limited to these. Specific examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, vinylcyclohexane, and the like. Is illustrated.
    [188] In the present invention, copolymerization of these α-olefins with comonomers copolymerizable with the α-olefins is also suitably carried out. Ethylene, a diolefin compound, etc. are mentioned as a comonomer copolymerizable with the said alpha olefin. Examples of the diolefin compound include conjugated dienes and nonconjugated dienes. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, and 1,7-octane as nonconjugated dienes. Dienes, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5 Ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, etc. are illustrated, and as a conjugated diene, 1, 3- butadiene, isoprene, 1, 3- hexadiene, 1, 3-octadiene, 1, 3 -Cyclooctadiene, 1,3-cyclohexadiene, etc. can be illustrated.
    [189] The method for producing the α-olefin polymer of the present invention is suitable as a method for producing an isotactic stereoregular α-olefin polymer and is particularly suitable as a method for producing an isotactic stereoregular propylene polymer.
    [190] Specific examples of such isotactic stereoregular propylene polymers include homopolymers of propylene; Random copolymers of propylene with comonomers such as ethylene and / or α-olefins having 4 to 12 carbon atoms in an amount of not losing crystallinity; Or homopolymerization of propylene or copolymerization of propylene with ethylene or an α-olefin having 4 to 12 carbon atoms (this is referred to as "shear polymerization"), and then the α-olefin having 3 to 12 carbon atoms and ethylene in one or multiple stages. Block copolymers etc. which superpose | polymerize (it calls this "post-stage polymerization") are mentioned. The amount that does not lose crystallinity with a random copolymer depends on the type of comonomer, but, for example, in the case of ethylene, the amount of repeating units derived from ethylene in the copolymer is usually 10% by weight or less, 1-butene, or the like. For other α-olefins, the amount of repeating units derived from the α-olefins in the copolymer is usually 30% by weight or less, preferably 10% by weight or less. In the case of shear polymerization in a block copolymer, for example, the polymerization amount of ethylene is usually 10% by weight or less, preferably 3% by weight or less, more preferably 0.5% by weight or less, and the polymerization amount of α-olefin is It is usually 15% by weight or less, preferably 10% by weight or less, and in the case of post-stage polymerization, the polymerization amount of ethylene is usually 20 to 80% by weight, preferably 30 to 50% by weight.
    [191] Specific examples of the monomer combination constituting the copolymer include a combination of propylene and ethylene, propylene and 1-butene, propylene and 1-hexene, but the present invention is not limited thereto.
    [192] In addition, an isotactic pentad fraction is used as a measure of isotactic stereoregularity.
    [193] The isotactic pentad fraction referred to herein is a crystalline polypropylene measured using the method disclosed in A. Zambelli et al., Macromolecules, 6, 925 (1973), i.e. 13 C-NMR. The isotactic chain in the pentad unit in a molecular chain, in other words, it is the fraction of the propylene monomer unit in the center of the chain which meso bonded five consecutive propylene monomer units. However, the attribution of an NMR absorption peak is performed based on the literature published after that (Macromolecules, 8, 687 (1975)). The isotactic pentad fraction may be abbreviated as "mmmm%". The upper limit of theoretical mmmm% is 1.000.
    [194] In the present invention, an isotactic stereoregular α-olefin polymer having a mmmm% of 0.800 or more and more preferably an isotactic stereoregular α-olefin polymer of 0.900 or more (more preferably 0.940 or more, even more preferably 0.955 or more) It can be manufactured highly.
    [195] In addition, in the present invention, by selecting the transition metal compound (B) component of the catalyst as described above, it is possible to produce stereo block poly (α-olefin) having a higher isotactic pentad fraction than the conventional one. . As alpha-olefin, it is as having mentioned above, but propylene is especially preferable.
    [196] In addition, a stereo block poly (α-olefin) has isotactic and atactic segments in one molecular chain, and when viewed as a whole, it shows relatively low stereoregularity (isotactic pentad fraction) and high melting point. It is a polymer and is a polymer different from the conventional isotactic crystalline poly (α-olefin) and atactic poly (α-olefin).
    [197] According to the present invention, stereoblock poly (α-olefin) having higher stereoregularity expressed in isotactic pentad fraction and higher melting point can also be obtained.
    [198] The polymerization method is also not particularly limited, and gas phase polymerization in a known gas monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. As a solvent used for solution polymerization or slurry polymerization, aliphatic hydrocarbon solvents, such as butane, pentane, heptane, and octane, aromatic hydrocarbon solvents, such as benzene and toluene, or halogenated hydrocarbon solvents, such as methylene chloride, are mentioned, or olefin itself is added to a solvent It is also possible to use (bulk polymerization). Among them, it is particularly suitably applied to polymerization (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) involving the formation of the α-olefin polymer particles. The polymerization type may be any of batch polymerization and continuous polymerization, and the polymerization may be performed by dividing the polymerization into two or more stages having different reaction conditions.
    [199] The polymerization time is generally appropriately determined depending on the kind of the olefin polymer desired and the reaction apparatus, but can be in the range of 1 minute to 20 hours.
    [200] The slurry polymerization may be carried out in accordance with a known slurry polymerization method or polymerization conditions, but is not limited thereto. Preferred polymerization methods in the slurry method include a continuous reactor in which monomers (and comonomers), feeds, diluents and the like are continuously added as necessary and the polymer product is taken out continuously or at least periodically. As a reactor, the method of using a loop reactor, the method of using a plurality of stirring reactors in which a different reactor or different reaction conditions are used in series or in parallel, or combined them etc. can be illustrated.
    [201] As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature of the polymerization reactor or reaction zone may usually be in the range of about 0 to about 150 ° C, preferably 30 to 100 ° C. The pressure can typically be varied from about 0.1 to about 10 MPa, preferably 0.5 to 5 MPa. Pressure may be taken to keep the catalyst in suspension, to keep the medium and at least some monomers and comonomers in the liquid phase and to contact the monomers and comonomers. Thus, the medium, temperature and pressure may be chosen such that the α-olefin polymer is produced as solid particles and recovered in this form.
    [202] The gas phase polymerization may be carried out according to known gas phase polymerization methods and polymerization conditions, but is not necessarily limited thereto. As the gas phase polymerization reactor, a fluidized bed reactor, preferably a fluidized bed reactor having an enlarged portion is used. There is no problem in the reaction apparatus provided with the stirring blade in the reaction tank.
    [203] As a method of supplying each component to a polymerization tank, methods, such as supplying in the absence of moisture using inert gas, such as nitrogen and argon, hydrogen, etc., or dissolving or diluting in a solvent and supplying it in the form of a solution or a slurry, can be used.
    [204] Each catalyst component can be supplied separately and can be supplied by contacting any component in advance in any order.
    [205] As polymerization conditions the temperature is in the range below the temperature at which the resulting polymer melts, preferably 0 to 150 ° C, particularly preferably 30 to 100 ° C. In addition, hydrogen may be added as a molecular weight regulator for the purpose of controlling the melt flowability of the final product. In addition, you may make an inert gas coexist in mixed gas in superposition | polymerization.
    [206] The molecular weight of the α-olefin polymer can be controlled by various known means such as adjusting the temperature of the reaction zone, introducing hydrogen, and the like.
    [207] Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, the method of adding each catalyst component, monomer (and comonomer) to a reaction zone simultaneously, the method of adding in order, etc. can be used. If desired, each catalyst component may be precontacted in an inert atmosphere prior to contacting the monomer (and comonomer).
    [208] In addition, especially when using a transition metal compound of the formula (I), a higher molecular weight α-olefin polymer can also be prepared, and preferably a weight average molecular weight of 350,000 to 600,000 (more preferably 380,000 to 600,000) , More preferably 400,000 to 600,000).
    [209] Example
    [210] The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto. The properties of the olefin polymer in the examples were measured by the following method.
    [211] (1) Molecular weight and molecular weight distribution: It calculated | required on the following conditions using gel permeation chromatography (150, C by Waters). In addition, molecular weight distribution (Mw / Mn) was shown by the ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn).
    [212] Column: Shodex AT806-M / S
    [213] Measurement temperature: 145 ℃ set
    [214] Measuring Concentration: 8mg / 8ml O-Dichlorobenzene
    [215] (2-1) 13 C-NMR measurement (Examples 1, 2 and 4 to 7, Comparative Examples 1, 3 and 4)
    [216] 200 mg of the polymer was dissolved in 3 ml of a mixed solvent of orthodichlorobenzene / orthodichlorobenzene (orthodichlorobenzene / orthodichlorobenzene = 4/1 (volume ratio)) and manufactured by JNM-EX270 manufactured by JEOL Ltd. Measured using.
    [217] (2-2) 13 C-NMR Measurement (Example 3 and Comparative Example 2)
    [218] A 200 mg sample was measured by dissolving in 3 ml of o-dichlorobenzene / benzene in mixed solvent (o-dichlorobenzene / benzene in 3 = 1/1).
    [219] (3) Melting | fusing point of a polymer: It calculated | required on condition of the following using Seiko SSC-5200.
    [220] Temperature rise: It is hold | maintained for 5 minutes from 25 degreeC to 200 degreeC (20 degreeC / min)
    [221] Cooling: 200 ° C to -50 ° C (20 ° C / min), hold for 5 minutes
    [222] Measurements: -50 ° C to 300 ° C (20 ° C / min)
    [223] (4) Intrinsic Viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C and set in a bath of water maintained at 135 ° C using a Uberode-type viscometer, and this sample was used. It calculated | required from the falling speed of this dissolved tetralin solution.
    [224] (5) Measurement of particle size distribution of polymer
    [225] It measured using the laser diffraction type particle size distribution measuring apparatus (The HELOS made from Nippon Denshi Corporation). From the measurement results, the geometric standard deviation (σg) based on the volume of the particle diameter of the polymer was calculated by the following equation.
    [226] σg = D 50% / D 15.87%
    [227] (Wherein D 50% is the polymer particle diameter of 50% cumulative volume fraction and D 15.87% represents the polymer particle diameter of 15.87% cumulative volume fraction).
    [228] A large geometric standard deviation ( G) indicates that the polymer particle diameter distribution is wide and a small one is narrow.
    [229] Example 1
    [230] (1) Contact treatment of particles (a) and organometallic compounds (b)
    [231] A 5 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then nitrogen-substituted. Silica (Davison Corporation # 948; average particle diameter = 55.0 μm; geometric standard deviation based on volume of particle diameter = 1.52; pore capacity = 1.60 ml / g; heat treated at 300 ° C. under nitrogen flow in this flask; Specific surface area = 310 m2 / g) 366 g were collected. 3.3L of toluene was added thereto to make a slurry, and after cooling to 5 degreeC using an ice bath, 366 ml of toluene solutions of the trimethylaluminum which adjusted the density | concentration to 2 mmol / ml are dripped gradually. At this time, gas generation is seen. After stirring for 30 minutes at 5 ° C and 2 hours at 80 ° C, the supernatant was filtered and washed four times with 3.3 L of toluene at 80 ° C for the remaining solid components.
    [232] (2) compound (c) treatment
    [233] After the treatment in (1) above, 3.3L of toluene was added thereto to make a slurry, cooled to 5 ° C using an ice bath, and then 400ml of toluene solution of pentafluorophenol having a concentration adjusted to 2mmol / ml was slowly added thereto. At this time, gas generation is seen. After stirring for 30 minutes at 5 ° C. and 2 hours at 80 ° C., the supernatant was filtered and washed four times with 3.3 L of toluene at 80 ° C. for twice the solid component remaining, and twice with 3.3 L of hexane at room temperature. Conduct. The solid component is then dried under reduced pressure to give 489 g of a flowable solid component.
    [234] (3) propylene polymerization
    [235] After drying under reduced pressure, 1 L of toluene was added to a stainless autoclave with an internal volume of 3 L, which was substituted with argon, and then 29.7 mg of the solid component (catalyst component (A)) and 100 g of propylene obtained in (2) above were added. Then, it heats up to 40 degreeC. Then, in a separate stainless container, 1.4 ml of toluene solution of triisobutylaluminum adjusted to 1 mmol / ml as the catalyst component (C) and dimethylsilylbis (2) adjusted to 2 µmol / ml as the catalyst component (B). 1.05 ml of a toluene solution of -methyl-1-indenyl) zirconium dichloride was contacted, and then put into an autoclave to carry out polymerization at 40 ° C. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 20 minutes, 10 ml of isobutanol is added to terminate the polymerization, and then unreacted monomers are purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 5 hours to yield 62 g of polypropylene powder.
    [236] Thus, 1 mol of the transition metal compound and the yield of polypropylene per hour of polymerization (hereinafter abbreviated as g-PP / mol-Zr hr) are g-PP / mol-Zr hr = 8.9 × 10 7 and the propylene obtained The stereoregularity of the polymer is mmmm% = 0.964%. The polymerization results are shown in Table 1.
    [237] Example 2
    [238] (1) Polymerization of propylene
    [239] Propylene was polymerized in the same manner as in Example 1 (3) except that the amount of the solid component (catalyst component (A)) was changed to 76.4 mg and the polymerization time was changed to 60 minutes. The polymerization results are shown in Table 1.
    [240] Example 3
    [241] (1) Polymerization of propylene
    [242] After drying under reduced pressure, made of stainless steel with agitator of internal volume 3L substituted with argon
    [243] 1 L of toluene was added to the autoclave, 100 g of propylene was added, and the temperature was raised to 40 ° C. Next, in a separate stainless steel container, 31.5 mg of the solid component obtained in Example 1 (2) as the catalyst component (A) and 2.1 ml of the toluene solution of triisobutylaluminum with the concentration adjusted to 1 mmol / ml as the catalyst component (C) And 1.05 ml of a toluene solution of dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride whose concentration was adjusted to 2 μmol / ml as catalyst component (B) was contacted, and then charged into an autoclave to carry out polymerization at 40 ° C. Conduct. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 60 minutes, 10 ml of isobutanol is added to terminate the polymerization, and then the unreacted monomer is purged. The resulting polymer is dried under reduced pressure at 60 ° C. for 5 hours to yield 31 g of polypropylene powder. The polymerization results are shown in Table 1.
    [244] Example 4
    [245] (1) Polymerization of propylene
    [246] After drying under reduced pressure, 1 L of toluene was introduced into a stainless autoclave with an internal volume of 3 L replaced with argon, and then 100 g of propylene was added thereto, followed by heating up to 40 ° C. Next, in a separate stainless steel container, 2.1 ml of toluene solution of triisobutylaluminum having a concentration of 1 mmol / ml as the catalyst component (C) and dimethylsilylbis (2) having a concentration of 2 μmol / ml as the catalyst component (B) 1.05 ml of a toluene solution of -methyl-1-indenyl) zirconium dichloride was contacted and placed in an autoclave, and then 31.1 mg of the solid component obtained in Example 1 (2) was added to 10 ml of toluene as a catalyst component (A). The added toluene slurry was put into an autoclave and superposed | polymerized at 40 degreeC. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 60 minutes, 10 ml of isobutanol is added to terminate the polymerization, and then the unreacted monomer is purged. The resulting polymer is dried under reduced pressure at 60 ° C. for 5 hours to yield 0.25 g of polypropylene powder. The polymerization results are shown in Table 1.
    [247] Comparative Example 1
    [248] (1) Polymerization of propylene
    [249] 1.3 ml of toluene solution of triisobutylaluminum with concentration adjusted to 1 mmol / ml as catalyst component (C) and dimethylsilylbis (2-methyl-1-indenyl with concentration adjusted to 2 μmol / ml as catalyst component (B) 0.65 ml of toluene solution of zirconium dichloride was contacted in advance, and then charged into an autoclave, and a solution in which 1.2 mg of triphenylmethyltetrakis (pentafluorophenyl) borate was dissolved in 0.58 ml of toluene was added and polymerized at 40 ° C. Is carried out. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 60 minutes, 20 ml of isobutanol is added to terminate the polymerization, and then unreacted monomers are removed. The resulting polymer is dried under reduced pressure at 60 ° C. for 5 hours to yield 140 g of polypropylene powder. The polymerization results are shown in Table 1. The obtained polymer has low stereoregularity or molecular weight.
    [250]
    [251] Example 5
    [252] (1) Polymerization of propylene
    [253] 1 L of toluene was introduced into a stainless autoclave with an internal volume of 3 liters substituted with argon, 100 g of propylene was added, and the temperature was raised to 40 ° C. Next, in a separate stainless steel container, 2.4 ml of toluene solution of triisobutylaluminum having a concentration of 1 mmol / ml as the catalyst component (C) and ethylene bis (indenyl) having a concentration of 2 µmol / ml as the catalyst component (B) ) 1.2 ml of a toluene solution of zirconium dichloride and 170 mg of the solid component obtained in Example 1 (2) were contacted as catalyst component (A), and then charged into the autoclave to carry out polymerization at 40 ° C. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 1 hour, 10 ml of isobutanol is added to terminate the polymerization, and then unreacted monomers are removed. The resulting polymer is dried under reduced pressure at 60 ° C. for 5 hours to yield 14.5 g of polypropylene powder.
    [254] Thus, 1 mol of the transition metal compound and the yield of polypropylene per hour of polymerization (hereinafter abbreviated as g-PP / mol-Zr hr) are g-PP / mol-Zr hr = 6.0 × 10 6 , and the resulting propylene Stereoregularity of the polymer is mmmm% = 0.872%. The polymerization results are shown in Table 2. Polymer particles having a small sigma value and matching particle diameters are obtained.
    [255] Example 6
    [256] (1) Contact treatment of particles (a) and organometallic compounds (b)
    [257] Heat-treated silica had an average particle diameter of 6.60 µm; a geometric standard deviation of a particle diameter based on volume = 1.43; Pore volume = 1.62 ml / g; Contact treatment was carried out in the same manner as in Example 1 (1), except that 382 g of silica (# 948, manufactured by Davidson) having a specific surface area of 312 m 2 / g was changed to 382 ml of the amount of trimethylaluminum toluene adjusted to 2 mmol / ml. Is carried out.
    [258] (2) compound (c) treatment
    [259] After the treatment in (1) above, 3.3L of toluene was added thereto to make a slurry, cooled to 5 ° C using an ice bath, and then 420ml of a toluene solution of pentafluorophenol having a concentration adjusted to 2mmol / ml was slowly added thereto. At this time, gas generation is seen. After stirring for 30 minutes at 5 ° C. for 2 hours at 80 ° C., the supernatant was filtered and washed four times with 3.3 L of toluene at 80 ° C. with respect to the remaining solid components. Conduct it twice. The solid component is then dried under reduced pressure to give 434 g of a flowable solid component.
    [260] (3) Polymerization of propylene
    [261] After drying under reduced pressure, 0.9 ml of toluene solution of triisobutylaluminum adjusted to 1 mmol / ml as the catalyst component (C) in an internal 0.1 L autoclave containing a stirrer substituted with nitrogen, and the concentration as the catalyst component (B) 1 ml of toluene solution of ethylenebis (indenyl) zirconium dichloride adjusted to 2 mol / ml and 27 mg of the solid component obtained in (2) as the catalyst component (A) were added. The temperature is raised to ℃. After 1 hour, the unreacted monomer is removed. The resulting polymer is dried under reduced pressure at 60 ° C. for 2 hours to afford 7.0 g of polypropylene powder.
    [262] The polymerization results are shown in Table 2. Polymer particles having a small sigma value and a uniform particle diameter are obtained.
    [263] Comparative Example 2
    [264] (1) Polymerization of propylene
    [265] After drying under reduced pressure, 1 liter of toluene was introduced into a stainless autoclave with an internal volume of 3 liters substituted with argon and 100 g of propylene was added, followed by raising the temperature to 40 ° C. Next, in a separate stainless steel container, 1.4 ml of toluene solution of triisobutylaluminum having the concentration adjusted to 1 mmol / ml as the catalyst component (C) and ethylene bis (indenyl) having the concentration adjusted to 2 µmol / ml as the catalyst component (B) 0.7 ml of toluene solution of zirconium dichloride was brought into contact with the autoclave, and a solution of 1.25 g of triphenylmethyltetrakis (pentafluorophenyl) borate dissolved in 1.25 ml of toluene was added to the autoclave. And polymerization at 40 ° C. Propylene is fed continuously during the polymerization and the total pressure is maintained at 0.6 MPa. After 1 hour, 20 ml of isobutanol is added to terminate the polymerization, and then unreacted monomers are removed. The resulting polymer is dried under reduced pressure at 60 ° C. for 5 hours to yield 94.3 g of polypropylene powder. The polymerization results are shown in Table 2. The value of sigma g is large and many fine powders are present in the polymer particles.
    [266]
    [267] Example 7
    [268] (1) Contact treatment of particles (a) and organometallic compounds (b)
    [269] Heat-treated silica had an average particle diameter of 6.60 mu m; Geometric standard deviation = 1.43 based on volume of particle diameter; Pore volume = 1.62 ml / g; Contact treatment was carried out in the same manner as in Example 1 (1), except that the amount of toluene solution of trimethylaluminum, which was changed to 382 g of silica (# 948) manufactured by Debson Corporation with a specific surface area of 312 m 2 / g, was changed to 382 ml Is carried out.
    [270] (2) compound (c) treatment
    [271] After the treatment of (1), 3.3L of toluene was added thereto to make a slurry, cooled to 5 ° C using an ice bath, and then slowly added 413 ml of a toluene solution of pentafluorophenol having a concentration adjusted to 2 mmol / ml. At this time, gas generation is seen. After stirring for 30 minutes at 5 ° C. for 2 hours at 80 ° C., the supernatant was filtered and washed four times with 3.3 L of toluene at 80 ° C. with respect to the remaining solid components, and further washed with 3.3 L of hexane at room temperature. Conduct it twice. The solid component is then dried under reduced pressure to give 475 g of a flowable solid component.
    [272] (3) Polymerization of propylene
    [273] After drying under reduced pressure, 280 g of propylene was charged into an autoclave with an internal volume of 1 L of stirrer substituted with argon, and then heated up to 40 ° C. Next, 1 ml of toluene solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 5 ml of a toluene solution of bis (2-phenylindenyl) zirconium dichloride whose concentration was adjusted to 2 µmol / ml was added thereto, and then 303 mg of the solid component obtained in (2) was added as a solid catalyst component to 60 at 40 ° C. The polymerization is carried out for a minute. 2.9 g of propylene polymer are obtained. The propylene polymer thus obtained was a polymer particle having a particle diameter of 148.2 DEG C, [ ] = 1.48 dl / g, Mw / Mn = 2.6, mmmm% = 49.5% and matching the particle diameter.
    [274] Comparative Example 3
    [275] (1) propylene polymerization
    [276] After drying under reduced pressure, 280 g of propylene was charged into an autoclave with an internal volume of 1 L of stirrer substituted with argon, and then heated up to 40 ° C. Methyl aluminoxane [MMAO-3A, toluene solution, Al concentration: 5.6 wt%; 10 mmol (in terms of Al atoms) was added to Toso-Akzo Company. Next, 5 ml of a toluene solution of bis (2-phenylindenyl) zirconium dichloride whose concentration was adjusted to 2 mol / ml was added thereto, and polymerization was carried out at 40 ° C. for 60 minutes. As a result, 68 g of propylene polymer is obtained. In addition, the obtained propylene polymer was obtained in a state in which a polymer having a melting point of 144.1 占 폚, [η] = 1.60 dl / g, Mw / Mn = 2.7, mmmm% = 32.0 was agglomerated and lumped.
    [277] According to the present invention there is provided a more efficient method for producing an α-olefin polymer using a single site catalyst. In addition, a method for producing a stereoblock regular α-olefin polymer and a stereo block polypropylene having a high isotactic pentad fraction is provided. In particular, when applied to the polymerization (for example, slurry polymerization, gas phase polymerization, etc.) involving the formation of polymer particles, a method for efficiently producing a stereoregular α-olefin polymer having a matching polymer particle diameter is provided.
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] Modified particles obtained by contacting the dried particles (a) with an organometallic compound (b), followed by contacting a functional group with active hydrogen or a compound (c) with a Lewis basic functional group with an unprotonated donor with an electron withdrawing group A catalyst for α-olefin stereoregular polymerization obtained by a method comprising contacting (A) with a transition metal compound (B) and an organometallic compound (C) having a stereoregular polymerization ability of the α-olefin.
    [2" claim-type="Currently amended] The catalyst for stereoregular polymerization of α-olefin according to claim 1, wherein the compound (c) having a functional group having an active hydrogen or an aprotic donor Lewis basic functional group and an electron withdrawing group is a compound of the formula (2).
    Formula 2
    R b m ZH zm
    In Formula 2 above,
    R b is a group containing an electron withdrawing group or an electron withdrawing group,
    Z is a group 15 or 16 atom of the periodic table of elements,
    H represents a hydrogen atom,
    z is 2 or 3 as valency of Z,
    m is 1 when z is 2, and m is 1 or 2 when z is 3.
    [3" claim-type="Currently amended] The catalyst for stereoregular polymerization of α-olefins according to claim 1, wherein the transition metal compound (B) is selected from the group consisting of transition metal compounds of the formulas (I) and (III).
    Formula I

    Formula III

    In the above formulas (I) and (III),
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    L is a substituted η 5 -cyclopentadienyl group, η 5 -indenyl group, or substituted η 5 -indenyl group, wherein two Ls may be the same or different from each other,
    Y is a bridging group connecting two L,
    Two X's are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group.
    [4" claim-type="Currently amended] The catalyst for stereoregular polymerization of α-olefin according to claim 1, wherein the transition metal compound (B) is selected from the group consisting of transition metal compounds of the formula (IV) and (I).
    Formula I

    Formula IV

    In Formula I and Formula IV above,
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    L is an η 5 -indenyl group or a substituted η 5 -indenyl group, and two L's may be the same as or different from each other,
    Y is a bridging group connecting two L,
    Each X is independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group,
    ((R 23 n -C 5 H 4-n ) and (R 23 q -C 5 H 4-q ) are each a substituted η 5 -cyclopentadienyl group,
    n and q are integers of 1 to 3,
    Each R 23 may be the same or different from each other and is a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, but is substituted η 5 -cyclopentadie The position and / or type of R 23 in the nil group is chosen such that there is no symmetry plane comprising M,
    R 24 is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group,
    R 24 and X may be the same or different from each other,
    Y 2 is a carbon atom, a silicon atom, a germanium atom or a tin atom.
    [5" claim-type="Currently amended] The catalyst for stereoregular polymerization of α-olefin according to claim 3, wherein the transition metal compound (B) is a transition metal compound of the formula (II).
    Formula II

    In Formula II above,
    R 1 to R 22 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or a substituted silyl group, and R 1 to R 22 may be the same as or different from each other, and any two adjacent R 1 to the same ring may be used. R 22 may form a ring of 5 to 8 carbon atoms,
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    X is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkoxy group, and two X's may be the same or different.
    [6" claim-type="Currently amended] A method for producing a stereoregular α-olefin polymer, characterized in that the α-olefin is polymerized using the catalyst for stereoregular polymerization of α-olefin according to any one of claims 1 to 5.
    [7" claim-type="Currently amended] Modified particles obtained by contacting the dried particles (a) with an organometallic compound (b), followed by contacting a functional group with active hydrogen or a compound (c) with a Lewis basic functional group with an unprotonated donor with an electron withdrawing group (A) is brought into contact with the α-olefin, followed by contacting the obtained contact material, a transition metal compound (B) having a stereoregular polymerization capacity of the α-olefin, and an organometallic compound (C) to polymerize the α-olefin. A process for producing a stereoregular α-olefin polymer, characterized in that.
    [8" claim-type="Currently amended] The method for producing a stereoregular α-olefin polymer according to claim 7, wherein the compound (c) having a functional group having an active hydrogen or an aprotic donor Lewis basic functional group and an electron withdrawing group is a compound of the formula (2).
    Formula 2
    R b m ZH zm
    In Formula 2 above,
    R b is a group containing an electron withdrawing group or an electron withdrawing group,
    Z is a group 15 or 16 atom of the periodic table of elements,
    H represents a hydrogen atom,
    z is 2 or 3 as valency of Z,
    m is 1 when z is 2, and m is 1 or 2 when z is 3.
    [9" claim-type="Currently amended] The process for producing a stereoregular α-olefin polymer according to claim 7, wherein the transition metal compound (B) is selected from the group consisting of transition metal compounds of the formulas (I) and (III).
    Formula I

    Formula III

    In the above formulas (I) and (III),
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    L is a substituted η 5 -cyclopentadienyl group, η 5 -indenyl group, or substituted η 5 -indenyl group, wherein two Ls may be the same or different from each other,
    Y is a bridging group connecting two L,
    Two X's are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group.
    [10" claim-type="Currently amended] The process for producing a stereoregular α-olefin polymer according to claim 7, wherein the transition metal compound (B) is selected from the group consisting of transition metal compounds of the formulas (I) and (IV).
    Formula I

    Formula IV

    In Formula I and Formula IV above,
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    L is an η 5 -indenyl group or a substituted η 5 -indenyl group, and two L's may be the same or different from each other,
    Y is a bridging group connecting two L,
    Each X is independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group,
    (R 23 n -C 5 H 4-n ) and (R 23 q -C 5 H 4-q ) are each a substituted η 5 -cyclopentadienyl group,
    n and q are integers from 1 to 3,
    Each R 23 may be the same or different from one another and is a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, but is substituted η 5 -cyclo In the pentadienyl group the position and / or type of R 23 is chosen such that there is no symmetry plane comprising M,
    R 24 is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group,
    R 24 and X may be the same or different from each other,
    Y 2 is a carbon atom, a silicon atom, a germanium atom or a tin atom.
    [11" claim-type="Currently amended] The process for producing a stereoregular α-olefin polymer according to claim 9, wherein the transition metal compound (B) is a transition metal compound of formula II.
    Formula II

    In Formula II above,
    R 1 to R 22 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or a substituted silyl group, and R 1 to R 22 may be the same as or different from each other, and any two adjacent R 1 to the same ring may be used. R 22 may form a ring of 5 to 8 carbon atoms,
    M is a Group 4 transition metal atom of the Periodic Table of the Elements,
    X is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkoxy group, and two X's may be the same or different.
    [12" claim-type="Currently amended] The process for producing the stereoregular α-olefin polymer according to any one of claims 7 to 11, wherein the α-olefin is propylene.
    [13" claim-type="Currently amended] The process for producing a stereoregular α-olefin polymer according to claim 6, wherein the α-olefin is propylene.
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    同族专利:
    公开号 | 公开日
    EP1153938A1|2001-11-14|
    EP1153938A4|2004-03-17|
    WO2001023436A1|2001-04-05|
    CN1339040A|2002-03-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-09-29|Priority to JP99-276372
    1999-09-29|Priority to JP27637299
    2000-09-25|Application filed by 고오사이 아끼오, 스미또모 가가꾸 고교 가부시끼가이샤
    2000-09-25|Priority to PCT/JP2000/006591
    2001-09-07|Publication of KR20010086047A
    优先权:
    申请号 | 申请日 | 专利标题
    JP99-276372|1999-09-29|
    JP27637299|1999-09-29|
    PCT/JP2000/006591|WO2001023436A1|1999-09-29|2000-09-25|CATALYST FOR STEREOREGULAR POLYMERIZATION OF α-OLEFIN AND PROCESS FOR PRODUCING STEREOREGULAR α-OLEFIN POLYMER|
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