JP2005239910A - Olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst having excellent olefin polymerization ability and to provide a method for producing a functional polyolefin by using the catalyst. <P>SOLUTION: The catalyst for olefin polymerization comprises a transition metal compound (A) represented by general formula (I) (wherein L is a three-seat anion ligand or a neutral ligand represented by RQ(Pz<SP>1</SP>)<SB>i</SB>(Pz<SP>2</SP>)<SB>3-i</SB>; R is a hydrogen atom, a halogen atom, a hydrocarbon group or the like; Q is boron, carbon or the like; at least 3-position of Pz<SP>1</SP>is a pyrazolyl group substituted with an unsubstituted aryl group, a substituted aryl group, a ≥3C alkyl group, cycloalkyl group, amino group, oxyhydrocarbon group or the like; Pz<SP>2</SP>is an unsaturated pyrazolyl group or a saturated pyrazolyl group; i is an integer of 1-3; M is a transition metal atom of the group III to XI of the periodic table; X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group or the like; Y is a neutral ligand having an electron-donating group; m is a number satisfying a valance of M and n is an integer of 0-3). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst comprising a transition metal compound and an olefin polymerization method using the olefin polymerization catalyst.

  As the olefin polymerization catalyst, a Kaminsky catalyst using a so-called cyclopentadienyl group as a ligand is well known. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of transition metal compounds used in such Kaminsky catalysts include bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Laid-Open No. 58-19309) and ethylene bis (4,5,6,7-tetrahydroindene). Nyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) is known.

  It is also known that the olefin polymerization activity and the properties of the resulting polyolefin differ greatly when the transition metal compound used in the polymerization is different. Recently, olefin polymerization catalysts having ligands other than cyclopentadienyl groups have been proposed, and one of them is a transition metal compound having a pyrazolyl group. Examples of using a transition metal compound having a pyrazolyl group as an olefin polymerization catalyst are disclosed in JP-A-1-95110, JP-A-8-127610, JP-A-8-253524, JP-A-9-220476, and JP-A-10-338698. JP, 11-228614, JP 2002-241422, WO9717379, 9929739, EP0482934B1, US6069110, J. Am. Chem. Soc., 1996 (118), 12453, J. Molecular Catalysis A: Chemical, 1998 (132), 33, Mcromol. Rapid. Commun., 2000 (21), 1054, J. Molecular Catalysis A: Chemical, 2001 (176), 65, Mcromol. Chem. Phys., 2001 (202 ), 319, and Organometallics, 2002 (21), 1882, and the like.

  However, among these transition metal compounds having a pyrazolyl group used in the prior art, an unsubstituted pyrazolyl group or a transition metal compound having a pyrazolyl group with a small substituent such as 3,5-dimethylpyrazole is used. In polymerization, none of the catalysts had sufficient polymerization activity of ethylene, and the obtained polymer had a wide molecular weight distribution.

  In contrast, WO9717379, Mcromol. Rapid. Commun., 2000 (21), 1054, Mcromol. Chem. Phys., 2001 (202), 319, Organometallics, 2002 (21), 1882, etc. A titanium or zirconium complex having a trispyrazolyl borate ligand having two or more pyrazolyl groups substituted with an unsubstituted aryl (Aryl) group or a substituted aryl (Aryl) group exhibits high olefin polymerization activity, and has a molecular weight distribution. It gives a wide polyolefin. However, in the synthesis of Group 4 transition metal compounds having a trispirazolylborate ligand, complexation is performed as described in Inorg. Chem., 1993 (32), 3471, Organometallics, 2002 (21), 1882, etc. During the reaction or storage of the product, isomerization of the ligand occurs under various conditions such as substituent structure, central metal species, reaction solvent and temperature. That is, in the synthesis of a Group 4 transition metal compound having a trispirazolylborate ligand, when a complexing reaction is performed according to the above report, in each step of synthesis of a thallium complex as a reactant and further synthesis of a titanium and zirconium complex, Since a mixture of isomers is generated, it is difficult to separate and purify only the desired isomer with high purity and reproducibility, and to obtain only the desired product in large quantities. Therefore, when olefin is polymerized, the molecular weight distribution is greatly affected.

  WO9717379 also describes an example of an attempt to synthesize [hydrotris (5-methyl-3-phenylpyrazol-1-yl)] titanium trichloride, but there is no description of isolating the complex, and the polymerization of ethylene is not described. In addition to the unknown molecular weight distribution, the polymerization activity of ethylene is not sufficient.

  On the other hand, as for the synthesis example of the hafnium complex having a pyrazolyl group, only Trispyrazolyl borate complex having a 3,5 pyrazolyl group has been reported in Bull. Chem. Soc. Jpn., 2000 (73), 1735. However, there is no description about olefin polymerization, and its polymerization performance is unknown.

  As described above, when polymerizing using the catalyst produced by the method described in the above report, the obtained product is not only a mixture of polymers having a non-uniform molecular weight but also a mixture of ethylene and α-olefin. The copolymerization performance is unknown, no method has been found to easily control the molecular weight of the olefin (co) polymer to the desired value, and the terminal without a modifiable functional group is saturated. There is a problem that industrial usefulness cannot be found in commercial production because it is a linear polymer produced.

In general, polyolefins are used in various fields such as for various molded products because they are excellent in mechanical properties. However, in recent years, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. Yes. However, the conventional catalyst as described above has not been sufficient in polymerization performance. Under such circumstances, there has been a demand for the appearance of an olefin polymerization catalyst capable of producing a polyolefin having excellent olefin polymerization performance and excellent properties.
JP 58-19309 A JP-A 61-130314 JP-A-1-95110 JP-A-8-127610 JP-A-8-253524 JP-A-9-220476 Japanese Patent Laid-Open No. 10-338698 Japanese Patent Laid-Open No. 11-228614 JP 2002-241422 A WO9717379 WO 9929739 EP0482934B1 US6069110 J. Am. Chem. Soc., 1996 (118), 12453 J. Molecular Catalysis A: Chemical, 1998 (132), 33 Mcromol. Rapid. Commun., 2000 (21), 1054 J. Molecular Catalysis A: Chemical, 2001 (176), 65 Mcromol. Chem. Phys., 2001 (202), 319 Organometallics, 2002 (21), 1882, Inorg. Chem., 1993 (32), 3471 Bull. Chem. Soc. Jpn., 2000 (73), 1735

  The present inventors diligently studied a transition metal compound having a novel structure for synthesizing an olefin polymer that solves the above problems and a polymerization method using the same, and are represented by the general formula (I). Succeeded in developing a method for synthesizing a transition metal compound (A) containing a pyrazolyl ligand having a specific structure with high purity and good yield, and also by polymerization using the transition metal compound (A). I found that the problem was solved. In other words, by using the transition metal compound (A) obtained efficiently in the present invention as the main catalyst, the (co) polymerization of olefin proceeds with extremely high polymerization activity from low temperature to high temperature. Has found that a polyolefin having a high comonomer content and a narrow molecular weight distribution in both polymerization and copolymerization of the olefin can be easily produced in a wide range from ultrahigh molecular weight to low molecular weight, and the present invention has been completed. In addition, if necessary, a reactive reagent can be added at the end of the polymerization to end-functionalize the polyolefin.

  That is, the present invention provides a pyrazolyl group substituted at least at the 3-position with an unsubstituted aryl group, a substituted aryl group, an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, an oxyhydrocarbon group, or the like. A transition metal compound having one or more of the following, a method for efficiently producing the transition metal compound, an olefin polymerization catalyst containing the transition metal compound, an olefin polymerization method using the olefin polymerization catalyst, and further, It aims at providing the manufacturing method of the functional polyolefin to be used.

  The catalyst for olefin polymerization according to the present invention includes a transition metal compound (A) represented by the following general formula (I).

(Wherein L is a tridentate anion ligand represented by RQ (Pz ¹ ) _i (Pz ² ) _3-i , or a neutral ligand, wherein R is a hydrogen atom, a halogen atom, Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group, and tin-containing Q represents a group selected from the group consisting of groups, Q represents a group selected from the group consisting of boron, carbon, silicon, germanium, tin, and lead, Pz ¹ is an unsubstituted aryl at the 3-position Group, a substituted aryl group, a pyrazolyl group substituted with an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, or an oxyhydrocarbon group, and Pz ² is an unsubstituted pyrazolyl group or a substituted group Represents a pyrazolyl group, i represents an integer of 1-3, M represents a periodic table X represents a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing Group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, Y represents a neutral ligand having an electron-donating group, and m represents the valence of M. When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. And n represents an integer of 0 to 3.)
The olefin polymerization catalyst according to the present invention, if necessary,
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) may contain at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair, or (D) a specific organic compound component, Furthermore, it can carry | support olefin polymerization by carrying | supporting to a support | carrier (C). Moreover, when superposing | polymerizing using the olefin polymerization catalyst which concerns on this invention, the terminal of polyolefin can also be functionalized by adding a reactive reagent at the time of completion | finish of superposition | polymerization. In the following description, a compound that reacts with the transition metal compound (A) to form an ion pair may be referred to as an “ionized ionic compound”.

  The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst, and further functionalizing the terminal of the polyolefin.

  According to the present invention, a pyrazolyl group substituted at least at the 3-position with an unsubstituted aryl group, a substituted aryl group, an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, an oxyhydrocarbon group or the like is represented by 1 A transition metal compound having one or more compounds can be obtained with high purity and high yield. The catalyst obtained in the present invention has a very high polymerization activity and progresses in polymerization of ethylene and the like, and copolymerization such as ethylene / propylene and ethylene / hexene copolymer, and has a narrow molecular weight distribution. A polyolefin having a high Tm and Tg compared to an ethylene / olefin copolymer obtained by a conventional method is high. Moreover, the functional polyolefin by which the end functionalization was carried out as needed can be easily manufactured in the wide range from ultra high molecular weight to low molecular weight. Further, when these polyolefins are produced, the productivity is good even at high temperature polymerization, specifically at a high temperature of 130 ° C., and this is extremely valuable industrially. Since the obtained product has few adhesive oligomers, it has excellent mechanical properties.

   Hereinafter, the olefin polymerization catalyst according to the present invention and the olefin polymerization method using the same will be described in detail. In the present specification, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. Sometimes used in the inclusive sense.

[Transition metal compound (A), an essential component of olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention comprises a transition metal compound (A) represented by the following general formula (I).

  In the above general formula (I), M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, specifically scandium, yttrium, lanthanoids, actinide group 3 metal atoms, titanium, zirconium, Group 4 metal atom of hafnium, Group 5 metal atom of vanadium, niobium, tantalum, Group 6 metal atom of chromium, molybdenum, tungsten, Group 7 metal atom of manganese, technetium, rhenium, iron, ruthenium, osmium Group 8 metal atoms, Group 9 metal atoms of cobalt, rhodium and iridium, Group 10 metal atoms of nickel, palladium and platinum, and Group 11 metal atoms of copper, silver and gold. Of these, Group 3 metal atoms, Group 4 metal atoms, Group 5 metal atoms, and Group 6 metal atoms are preferred, and transition metals such as yttrium, titanium, zirconium, hafnium, vanadium, and chromium are preferred among these. In addition, transition metal atoms of the Group 4 or Group 5 of the periodic table in which the valence state of the transition metal atom M is divalent, trivalent or tetravalent is more preferable, and titanium, zirconium, hafnium, vanadium are particularly preferable. preferable. When the transition metal atom M is titanium or vanadium, it is particularly preferable that it is trivalent.

X is a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, A silicon-containing group, a germanium-containing group or a tin-containing group, Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and m is 2 or more In X, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring, and n is an integer of 0 to 3 Indicates. )
X is a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, A silicon-containing group, a germanium-containing group or a tin-containing group is shown. When X is an oxygen atom, M and X are bonded by a double bond.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl And aryl groups such as phenanthryl. In addition, these hydrocarbon groups include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.

   Specific examples of the oxygen-containing group include an oxy group, a peroxy group, a hydroxy group, a hydroperoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.

  Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate, Sulfonate groups such as p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene Sulfinate groups such as sulfinates; alkylthio groups; arylthio groups; sulfate groups; sulfide groups; polysulfide groups;

  Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. Arylamino groups or alkylarylamino groups such as: trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine Alkyl or arylamine groups such as (tppda).

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Specific examples of phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite, and phenylphosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .

  Specific examples of the heterocyclic compound residue include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and the like. Examples include a group obtained by further substituting a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms in the heterocyclic compound residue.

  Specific examples of silicon-containing groups include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl; Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium. Specific examples of the tin-containing group include groups in which silicon in the silicon-containing group is substituted with tin.

  When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

m is a number that satisfies the valence of M, is determined by the valence of the transition metal atom M and the valence of X, and is such a number that these positive and negative valences are neutralized. Here, when the absolute value of the valence of the transition metal atom M is a and the absolute value of the valence of X is b, the relationship of a−2 = b × n is established. More specifically, for example, if M is Ti ⁴⁺ and X is Cl ⁻ , n is 2.

  In the general formula (I), Y represents a neutral ligand having an electron-donating group, and n representing the number of Y represents an integer of 0 to 3, preferably 1 or 2. . The electron donating group is a group having an unpaired electron that can be donated to a metal, and Y may be any neutral ligand as long as it has an electron donating property. Specific examples of the neutral ligand Y include linear or cyclic saturated or unsaturated ethers such as diethyl ether, dimethyl ether, diisopropyl ether, tetrahydrofuran, furan, dimethylfuran, anisole, diphenyl ether, and methyl-t-butyl ether. Acyclic or cyclic saturated or unsaturated aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde, p-nitrobenzaldehyde, p-tolualdehyde, phenylacetaldehyde, such as acetone, methyl ethyl ketone, methyl-n- Linear or cyclic saturated or unsaturated ketones such as propyl ketone, acetophenone, benzophenone, n-butyrophenone, benzyl methyl ketone, such as formamide, acetamide, benzamide, n- Linear or cyclic saturated or unsaturated amides such as valeramide, stearylamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylpropionamide, N, N-dimethyl-n-butyramide, for example Chain or cyclic saturated or unsaturated anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, etc., chain or cyclic saturated or unsaturated imides such as succinimide and phthalimide, such as methyl acetate, ethyl acetate, acetic acid Linear or cyclic saturated or unsaturated esters such as benzyl, phenyl acetate, ethyl formate, ethyl propionate, ethyl stearate, ethyl benzoate, such as trimethylamine, triethylamine, triphenylamine, dimethylamine, aniline, pyrrolidine, piperidine Linear or cyclic saturation such as morpholine Is an unsaturated amine such as pyridine, α-picoline, β-picoline, quinoline, isoquinoline, 2-methylpyridine, pyrrole, oxazole, imidazole, pyrazole, indole and the like nitrogen-containing heterocyclic compounds such as thiophene and thiazole Sulfur-containing heterocyclic compounds such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, triphenylphosphine and the like phosphines, eg acetotolyl, saturated or unsaturated nitriles such as benzonitrile, Examples thereof include inorganic salts such as lithium chloride, sodium chloride, potassium chloride, magnesium chloride and calcium chloride, inorganic compounds such as carbon monoxide and carbon dioxide, for example, organometallic compounds (B-1) described later. Furthermore, a compound in which a part of these compounds is substituted with a substituent such as an alkyl group, a halogen group, a nitro group, a carbonyl group, or an amino group may be used. As Y in the formula (I), among these neutral ligands, ethers, aldehydes, ketones, nitrogen-containing heterocyclic compounds, and inorganic salts are preferable.

  In the general formula (I), L is a tridentate anion ligand or a neutral ligand represented by the following general formula (IV).

  In the general formula (IV), R is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group. , A group selected from the group consisting of a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. , Halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group Examples of the tin-containing group include the groups exemplified in the description of X in the general formula (I).

  In the general formula (IV), Q represents a tetravalent group selected from the group consisting of boron, carbon, silicon, germanium, tin, and lead, and boron, carbon, and silicon are particularly preferable.

In the general formula (IV), Pz ¹ is an unsubstituted aryl (Aryl) group, a substituted aryl (Aryl) group, an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, Alternatively, it is a pyrazolyl group substituted with an oxyhydrocarbon group or the like. Examples of the unsubstituted aryl group include a phenyl group, a naphthyl group, a fluorenyl group, and the like, and the substituted aryl group is a nucleus of the unsubstituted aryl group. Examples include one or more hydrogens substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. Preferred Pz ¹ is 2,4,6-Trimethylphenyl group, 2,4,6-Triisopropylphenyl group, 2,3,4,5,6-Pentamethylphenyl group, 4-Tert-Butyl-2,6-Dimethylphenyl at the 3-position Particularly preferred are those substituted with a group and substituted at the 3-position with a 2,4,6-trimethylphenyl group.

Pz ² represents an unsubstituted pyrazolyl group or a substituted pyrazolyl group. The substituted pyrazolyl group may be the same as the above-described Pz ^1, and further may be a group in which the group exemplified as the substituent of the substituted aryl group is substituted at any position other than the 3-position.

  In the general formula (IV), i is an integer of 1-3, preferably 2 or 3.

  In the present invention, among the transition metal compounds (A) satisfying the above requirements, [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate zirconium trichloride, [hydrobis (3-mesitylpyrazol -1-yl) (5-mesitylpyrazol-1-yl)] borate titanium (III) dichloride, [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate hafnium trichloride, and [ Hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride is particularly preferred, and [hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride is particularly preferred.

  Moreover, the transition metal compound (A) may form a complex such as a dimer, trimer or oligomer via these neutral ligands, or alternatively, via these neutral ligands, For example, a cross-linked structure such as a μ-oxo compound may be formed.

[Production Method of Transition Metal Compound (A)]
The transition metal compound (A) according to the present invention is produced by reacting a metal salt (a) represented by the following general formula (II) with a transition metal salt (b) represented by the following general formula (III). However, the process of preparing the metal salt (a) includes a purification step of separating the positional isomers of the metal salt (a) using a chromatograph in which the filler is neutral or basic. It is said.

  In the above general formula (II), Z represents a metal atom selected from Group 1, Group 13, and Group 14 of the Periodic Table, preferably potassium element, sodium element, thallium element, tin element, Preferably it is a thallium element. j represents an integer of 0 or 1, and is preferably 1.

  In the general formula (III), M, X, Y, and m and n can be the groups exemplified in the description of the general formula (I).

  In the present invention, the metal salt (a) represented by the general formula (II) and the transition metal salt (b) represented by the general formula (III) are dissolved or suspended in a nonpolar solvent. It is also characterized by reacting. Examples of the nonpolar solvent include petroleum ether, hexane, carbon tetrachloride, carbon disulfide, toluene, benzene and the like, preferably toluene, benzene and the like. Hereinafter, the production method of the transition metal compound (A) according to the present invention will be described in detail with specific examples.

  First, it has a trispirazolylborate ligand having two or more pyrazolyl groups substituted with an unsubstituted aryl (Aryl) group or a substituted aryl (Aryl) group at the 3-position, which is a precursor of a transition metal compound (A) The thallium complex is synthesized by the method described in Inorg. Chem., 1993 (32), 3471, etc., or a method similar thereto. At that time, if a mixture of isomers is obtained, at that stage, only components that can be easily isolated and purified by recrystallization are isolated by recrystallization, and the remaining mixture is neutralized silica gel or alumina. Purify by packed flash column chromatograph to isolate the desired isomer. The method for neutralizing the silica gel is not particularly limited. For example, the silica gel can be stirred in an eluent containing triethylamine. The eluent for performing flash column chromatography is not particularly limited. For example, petroleum ether, hexane, carbon tetrachloride, carbon disulfide, toluene, benzene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether, acetic acid. Examples thereof include ethyl, acetone, ethanol, methanol, or a mixed solution thereof.

  A transition metal salt is added to the pure thallium complex thus obtained, and then a nonpolar solvent is added and reacted with stirring. The liquid temperature during the reaction is in the range of -80 ° C to 120 ° C, preferably -30 to 30 ° C. Examples of the nonpolar solvent to be used include petroleum ether, hexane, carbon tetrachloride, carbon disulfide, toluene, benzene and the like, and preferably toluene, benzene and the like as described above. As a method for purely removing the complex from the reaction solution thus obtained, usual operations used for purifying the transition metal complex such as extraction and recrystallization are used.

  Moreover, as a complex used as the precursor of a transition metal compound (A), the compound which replaced thallium of the thallium complex illustrated above by potassium, sodium, and tin can be illustrated similarly.

  Examples of the specific structure of the transition metal compound (A) represented by the above general formula (I) obtained as described above are shown below. In this specification, the methyl group is Me, the ethyl group is Et, the t-butyl group is t-Bu, the n-butyl group is n-Bu, the trimethylsilyl group is TMS, the phenyl group is Ph, the mesityl group (2, 4,6-trimethylphenyl group) may be abbreviated as Mes.

[Optional components constituting the olefin polymerization catalyst]
The transition metal compound (A) can be used alone or in combination as a catalyst for olefin polymerization, but the olefin polymerization catalyst according to the present invention, if necessary,
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) may contain at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs, and (D) specific organic compound components, It can also be used as a catalyst for olefin polymerization by being supported on a carrier (C). Next, each component of (B) component used as needed is demonstrated.

( B-1) Organometallic Compound Specific examples of the organometallic compound (B-1) include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄
(Wherein, ^{M 2} represents a Li, Na or K, ^{R a} is from 1 to 15 carbon atoms, preferably an. 1-4 hydrocarbon group) complex of Group 1 metal and aluminum represented by Alkylates.

(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by:

Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.
General formula R ^a _m Al (OR ^b ) _3-m
(In the formula, R ^a and R ^b may be the same or different from each other and each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ An organoaluminum compound represented by the following formula:
General formula R ^a _m AlX _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,
General formula R ^a _m AlH _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3),
General formula R ^a _m Al (OR ^b ) _n X _q
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methyl Pentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum Tri-branched alkylaluminums such as tricyclohexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) tri isoprenylaluminum represented by like Trialkenyl aluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide and the like; Average ^{_{R a 2.5 Al (OR b)}} 0.5 represented by like; mini um methoxide, diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide Partially alkoxylated alkylaluminum with composition: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl- Dialkylaluminum aryloxy such as 4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) De; Dialkylaluminum halides such as methylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; including partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. .

A compound similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  In addition, as the organometallic compound (B-1), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used. Of the organometallic compounds (B-1), organoaluminum compounds are preferred. The organometallic compound (B-1) as described above is used singly or in combination of two or more.

( B-2) Organoaluminum oxy compound The organoaluminum oxy compound ( B-2) used as necessary in the present invention may be a conventionally known aluminoxane or exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound. A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
[1] Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
[2] A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
[3] A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (for example, Hydrocarbon solvents such as chlorinated products, brominated products, etc.). Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is, with respect to benzene. Those that are insoluble or sparingly soluble are preferred.

  Examples of the organoaluminum oxy compound also include an organoaluminum oxy compound (G-1) containing boron represented by the following general formula (V).

(In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other. The organoaluminumoxy compound (G-1) containing boron represented by the general formula (V) includes an alkyl boronic acid (G-2) represented by the following general formula (VI):
R ²⁰ -B (OH) ₂ (VI)
(Wherein R ²⁰ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

  Specific examples of the alkyl boronic acid (G-2) represented by the general formula (VI) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, Examples thereof include n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  The (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.

(B-3) Ionized ionic compound The ionized ionic compound (B-3) is a compound that reacts with the transition metal compound (A) to form an ion pair.

  Examples of such compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, US5321106, and the like. Etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group, or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

  Examples of the ionic compound include compounds represented by the following general formula (VII).

In the formula, ^examples of R ²²⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ may be the same as or different from each other, and each represents an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like; N, N-dimethylanilinium cations; N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ²²⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) Ammonia Such as tetra (o- tolyl) boron and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (VIII) or (IX).

(In the formula, Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.

  Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundeborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammo Nitrobromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri ( n-Butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbaound decaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaound decaborate , Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Salts of anions such as decahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl ) Ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III ), Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) goldate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaoundecaborate ) Ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) chromate (III), tri (n-butyl) ammonium bis (Tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III ), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecah Metal carborane anions such as Dride-7-carbaundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, With barium etc. And organic salts such as triphenylethyl salt, and isopoly compounds, and the like. The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

  The ionized ionic compound (B-3) as described above is used singly or in combination of two or more.

(C) Carrier In the present invention, transition metal compound (A) (hereinafter sometimes referred to as “component (A)”), and / or organometallic compound (B-1), organoaluminum oxy compound (B-2) And at least one compound selected from the ionized ionic compound (B-3) (hereinafter sometimes referred to as “component (B)”) may be used by supporting it on the carrier (C) as necessary. . When used, the carrier (C) is an inorganic or organic compound and is a granular or particulate solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitating agent may be used. Clay used as a carrier is usually composed mainly of clay minerals. The ion-exchangeable layered compound used as a carrier is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite , And the like, and examples of the ion-exchangeable layered compound include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 cc / g, as measured by mercury porosimetry. Is particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to 3 × 10 4 angstroms by mercury porosimetry using a mercury porosimeter. When a carrier having a pore volume with a radius of 20 angstroms or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds that intercalate include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Can be mentioned. These compounds are used alone or in combination of two or more.

Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

(D) Organic Compound Component In the present invention, a specific organic compound component (D) as will be described later can be used as necessary during the polymerization. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, carboxylic acid esters, phosphorus compounds, sulfonates, and halogenated hydrocarbons.

As the alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used (where R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms). Represents a hydrocarbon group), and the alcohols are preferably those in which R ³¹ is a halogenated hydrocarbon. Further, as the phenolic compound, those in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms are preferred, and more preferably, the α, α′-position of the hydroxyl group has a tertiary carbon number. The thing substituted by 4-20 hydrocarbon is mentioned.

As the carboxylic acid, one represented by R ³² —COOH is usually used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable. As the carboxylic acid ester, an alkyl or aryl ester of the carboxylic acid represented by R ³² —COOH is used, and among them, for example, a carboxylic acid having a halogenated hydrocarbon group such as n-butyl perchlorocrotonate or ethyl trichloroacetate. These esters are desirable for improving the polymerization activity.

  As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.

  As the sulfonate, those represented by the following general formula (C-6) are used.

In the formula, M is an element of Groups 1 to 14 of the periodic table. R ²⁹ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7. Examples of the halogenated hydrocarbon include chloroform and carbon tetrachloride.

Other transition metal compounds In the present invention, in the polymerization, together with the transition metal compound (A), other transition metal compounds such as known ligands containing heteroatoms such as nitrogen, oxygen, sulfur, boron or phosphorus These transition metal compounds can be used in combination.

[Olefin polymerization method]
Olefin is an unsaturated hydrocarbon composed of carbon and hydrogen atoms, specifically, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. 20 α-olefins; cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene; butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1, 6-octadiene, 1,7-octadiene, Tylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene, etc. Cyclic or linear diene or polyene having 4 to 30 carbon atoms, preferably 4 to 20 and having two or more double bonds; styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, Aromatic vinyl compounds such as p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; vinylcyclohexane and the like.

  The olefin may have a functional group containing atoms such as oxygen, nitrogen, sulfur and the like. For example, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Unsaturated carboxylic acid metal salts such as salts, magnesium salts and calcium salts; unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Products; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Unsaturated cals such as n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate Unsaturated glycidyl esters such as: Halogenated olefins such as vinyl chloride, vinyl fluoride and allyl fluoride; Unsaturated cyano compounds such as acrylonitrile and 2-cyano-bicyclo [2.2.1] -5-heptene; Methyl vinyl ether, ethyl Unsaturated ether compounds such as vinyl ether; unsaturated amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate Hydroxystyrene, o- chlorostyrene, p- chlorostyrene, functional group-containing styrene derivatives such as divinyl benzene; and N- vinylpyrrolidone. As the olefin, α-olefin is preferable, and ethylene is particularly preferable.

In the method for producing an olefin polymer according to the present invention, a catalyst comprising the components (A) and (B) as described above, and optionally a carrier (C), an organic compound component (D), and another transition metal compound. Olefin polymerization in the presence of During the polymerization, the method of adding the component (A) to the polymerization vessel, the usage method of each component, the addition method, and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(2) A method in which a catalyst in which the component (A) and the component (B) are previously contacted is added to the polymerization reactor.
(3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(4) A method in which the component (A) is supported on the carrier (C) and the component (B) is added to the polymerization vessel in any order.
(5) A method in which a catalyst having components (A) and (B) supported on a carrier (C) is added to a polymerization vessel.
(6) A method in which the component (A) and the component (B) supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(7) A method in which the component (B) supported on the carrier (C) and the component (A) are added to the polymerization vessel in any order.
(8) A method in which the catalyst component having component (B) supported on carrier (C), component (A), and component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(9) A method in which a component carrying component (A) on carrier (C) and a component carrying component (B) on carrier (C) are added to the polymerization vessel in any order.
(10) A method of adding the component (A) supported on the carrier (C), the component (B) supported on the carrier (C), and the component (B) to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(11) A method in which component (A), component (B), and organic compound component (D) are added to the polymerization vessel in any order.
(12) A method in which the component (B) and the component (D) are contacted in advance, and the component (A) are added to the polymerization vessel in an arbitrary order.
(13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in an arbitrary order.
(14) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (D) are added to the polymerization vessel in an arbitrary order.
(15) A method in which the component (A) and the component (B) are contacted in advance, and the component (B) and the component (D) are added to the polymerization vessel in any order.
(16) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component in which the component (B) and the component (D) are contacted in advance are added to the polymerization vessel in an arbitrary order.
(17) A method in which the component (A) supported on the carrier (C), the component (B), and the component (D) are added to the polymerization vessel in any order.
(18) A method in which a component having component (A) supported on carrier (C) and a component in which component (B) and component (D) are contacted in advance are added to the polymerization vessel in any order.
(19) A method in which a catalyst component in which component (A), component (B), and component (D) are contacted in advance in an arbitrary order is added to the polymerization reactor.
(20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(21) A method in which a catalyst having components (A), (B) and (D) supported on a carrier (C) is added to a polymerization vessel.
(22) A method in which the component (A), the component (B) and the component (D) supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.

  The solid catalyst component in which the component (A) and, if necessary, the component (B) are supported on the carrier (C) may be prepolymerized with olefin. The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. It can also be used as a solvent.

When the olefin is polymerized using the catalyst as described above, the component (A) is usually 10 ⁻¹³ to 10 ⁻² mol, preferably 10 ⁻¹¹ to 10 ⁻³ mol per liter of the reaction volume. Used in such amounts. Even when the component (A) is used at a relatively low concentration, the olefin can be polymerized with high polymerization activity.

  Component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000.

  Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) usually from 1 to 1. The amount used is 500,000, preferably 10 to 100,000.

  Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5. When component (D is used, when component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0. In the case of component (B-2) in an amount of 1 to 5, the molar ratio of component (D) to aluminum atoms in component (B-2) [(D) / (B-2 )] Is usually 0.001 to 2, preferably 0.005 to 1 in the case of component (B-3), the molar ratio [(D) / (B-3)] is The amount is usually 0.01 to 10, preferably 0.1 to 5.

  There is no restriction | limiting in particular in the quantity of the olefin used for superposition | polymerization, According to the kind of olefin to be used, the copolymerization ratio of the copolymer to obtain, etc., it selects suitably.

The polymerization temperature using such a polymerization catalyst is usually in the range of −50 to 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight and molecular weight distribution of the polyolefin obtained in the present invention can be adjusted by changing the polymerization temperature.

  Further, the molecular weight and molecular weight distribution of the polyolefin obtained in the present invention can be adjusted by changing the amount of the organometallic compound (B-1) or the organoaluminum oxy compound (B-2), or both. it can. In the present invention, the molecular weight of the polyolefin and the amount of the component (B) used for controlling the molecular weight distribution are the ratio of the number of moles of the organoaluminum compound to the number of moles of the transition metal of the transition metal compound (organoaluminum Compound / transition metal) is 0.1 to 10000000, preferably 10 to 1000000. To lower the molecular weight, increase the ratio of (organoaluminum compound / transition metal), and to narrow the molecular weight distribution (mole number of organoaluminum compound / number of moles of polymer produced). Can be done by.

  The molecular weight and molecular weight distribution of the polyolefin obtained in the present invention can also be adjusted by adding the organic compound component (D). In the present invention, the molecular weight of the polyolefin and the amount of the organic compound component (D) used for controlling the molecular weight distribution are based on the total number of moles of aluminum used in (B-1) and (B-2). The ratio (organic compound / aluminum) to the number of moles of the organic compound component (D) is 0.000001 to 10, preferably 0.01 to 0.1, and more preferably 0.05 to 0.5.

  The molecular weight and molecular weight distribution of the polyolefin obtained in the present invention can also be adjusted by changing the polymer concentration in the polymerization solution. In the present invention, the molecular weight of the polyolefin and the polymer concentration in the polymerization solution used for controlling the molecular weight distribution are 0.01 to 500 g / L, preferably 0.1 to 100 g / L, and more preferably 1 to 100 g / L. 20 g / L. By reducing the polymer concentration in the polymerization solution, the molecular weight can be increased and the molecular weight distribution can be narrowed.

  In the present invention, at the end of the polymerization, a specific reactive reagent (E) as shown below can be further used to functionalize the terminal of the polyolefin. Any method for terminal functionalization may be used, and the method is not particularly limited. For example, Prog. Polym. Sci., 2002 (27), 1347, Macromol. Chem. Phys , 2001 (202), 1757, etc., or a similar method, and the reagent (E) used in this case is the reagent described in the above report, for example, air, oxygen, etc. And sodium hydroxide / hydrogen peroxide, chlorine / carbon tetrachloride, bromine / carbon tetrabromide, iodine / carbon tetraiodide and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The molecular weight and molecular weight distribution of the obtained polymer were determined by high temperature GPC (polyethylene conversion). The hexene content of the obtained ethylene / hexene copolymer was measured by ¹³ C-NMR according to the method of Macromolecules., 1982 (15), 1402. The propylene content of the ethylene / propylene copolymer was measured by ¹ H-NMR.
In this example, [hydrotris (pyrazol-1-yl)] borate is Tp,
[hydrotris (3,5-dimetylpyrazol-1-yl)] borate as Tp *,
[hydrotris (3-mesitylpyrazol-1-yl)] borate is abbreviated as Tp ^Ms , and [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate is abbreviated as Tp ^{Ms *} .

[Synthesis Example 1] <Synthesis of TlTp ^Ms and TlTp ^{Ms *} >
Chlorination of a TlTp ^Ms / TlTp ^{Ms *} mixture using 3-mesitylpyrazole (4.00 g, 21.5 mmol) and potassiumborohydride (0.294 g, 5.45 mmol) according to the method described in Inorg. Chem., 1993 (32), 3471. A methylene solution was obtained. By concentrating this solution, TlTp ^Ms was obtained as colorless crystals in a yield of 21% (0.96 g). The filtrate was concentrated under reduced pressure and dried, and the precipitated solid was washed with methanol, and 3-mesitylpyrazole (1.27 g, 6.82 mmol) was collected as colorless needle crystals from the washed solution. Unnecessary components in methanol were recrystallized in toluene, and TlTp ^Ms was obtained as colorless crystals in a yield of 3% (0.15 g). The filtrate was concentrated under reduced pressure and dried to obtain a mixture of TlTp ^Ms / TlTp ^{Ms *} = 7/93 (ratio is a value by 1H-NMR) (1.27 g, 35%).

Hereinafter, a method for isolating pure TlTp ^{Ms *} using a neutralized silica gel packed flash column chromatograph will be described. After stirring the silica gel in a 1% triethylamine / toluene solution, the slurry was loaded onto a column and the silica gel was then washed with pure toluene to remove excess triethylamine. The mixture of TlTp ^Ms / TlTp ^{Ms *} obtained by the above operation (= 7/93, ratio is a value by ¹ H-NMR, 1.92 g) was suspended in 40 ml of toluene and applied to the column. TlTp ^{Ms *} is eluted as first fraction was obtained which was concentrated under reduced pressure, and dried pure TlTp ^{Ms *} containing no TlTp ^Ms by (1.81 g, 100% recovery). After elution of TlTp ^{Ms *} , the eluent was replaced with methylene chloride to elute a mixture of TlTp ^Ms and impurities.

[Synthesis Example 2] <Synthesis of Tp ^{Ms *} Ti (III) Cl ₂ KCl>
Put a rotor in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and Tp ^{Ms *} TiCl ₃ obtained by the method described in Metallic Potassium (27 g, 0.69 mmol) and Organometallics, 2002 (21), 1882. (500 mg, 0.69 mmol) was charged, and 80 ml of toluene was added at room temperature. The obtained suspension solution was reacted at room temperature for 10 days with stirring to obtain a suspension containing light blue powder. When this reaction solution was concentrated to 5 ml and allowed to stand at -37 ° C, blue crystals were precipitated. After removing the supernatant, the blue crystals were dried under reduced pressure, and a light blue powder was obtained with a yield of 95% (498 mg). The results of analyzing the obtained crystals by elemental analysis, UV / vis and FD-MS were as follows.
Elemental analysis: Calcd: C, 56.83; H, 5.30; N, 11.04. Found: C, 56.92; H, 5.22; N, 10.73.
Visible spectrum (toluene); 615 nm, ε 24.
FD-MS: 685 (M +, Tp ^{Ms *} Ti (III) Cl ₂ ).

[Synthesis Example 3] <Synthesis of Tp ^Ms Zr (IV) Cl ₃ >
A rotor is placed in a Schlenk-type reaction vessel that has been sufficiently dried and substituted with nitrogen, and TlTp ^Ms (300 mg, 0.389 mmol) and ZrCl4 (91 mg, 0.389 mmol, CERAC) obtained by the method described in Synthesis Example 1 are added thereto. And 30 ml of toluene was added at room temperature. The obtained suspension solution is reacted at room temperature for 62 hours with stirring, and a toluene suspension containing a Tp ^Ms ZrCl ₃ / Tp ^{Ms *} ZrCl ₃ mixture (= 72/28, ratio is a value by ¹ H-NMR) is obtained. Obtained. After filtering this suspension with a glass filter, the obtained white solid was further washed with 30 ml of toluene, and the washing was mixed with the filtrate. The transparent solution thus obtained was concentrated to 3 ml and allowed to stand at −37 ° C., whereby colorless crystals were precipitated. The crystals were filtered off with a glass filter, washed with toluene, and dried under reduced pressure to obtain a colorless powder with a yield of 35% (105 mg).

The obtained crystals were analyzed by elemental analysis, NMR, and FD-MS. The results were as follows. Elemental analysis: C, 56.51; H, 5.27; N, 10.98. Found: C, 57.31; H, 5.59; N, 10.27. ¹ H NMR (CD ₂ Cl ₂ ): d 7.98 (d, ³ J _HH = 2.2, 3H, pz 5-H), 6.84 (s, 6H, Ms meta-H), 6.14 (d, ³ J _HH = 2.2, 3H, pz 4-H), 2.29 (s, 9H, Ms para-Me), 1.93 (s, 18H, Ms ortho-Me) ¹³ C { ¹ H} NMR (CDCl ₃ ): d 158.3 (pz C-3), 138.9 (Ms C-4), 138.7 (Ms C-2 and C-6 ), 138.6 (pz C-5), 129.2 (Ms C-1), 127.9 (Ms C-3 and C-5), 108.4 (pz C-4), 21.3 (Ms ortho- and para-Me) .FD -MS: 764 (M +).

[Synthesis Example 4] <Synthesis of Tp ^{Ms *} Zr (IV) Cl ₃ >
A rotor is placed in a Schlenk-type reaction vessel sufficiently dried and substituted with nitrogen, and TlTp ^{Ms *} (1.00 g, 1.30 mmol) and ZrCl ₄ (0.302 mg, 1.30 mmol) obtained by the method described in Synthesis Example 1 are added thereto. CERAC) and 40 ml of toluene were added at room temperature. The obtained suspension solution was allowed to react at room temperature for 15 hours with stirring, and then the by-product TlCl was removed by filtration through a glass filter, and the resulting clear solution was concentrated under reduced pressure and dried to give white. A solid was obtained. When 40 ml of benzene was added and dissolved, and 60 ml of hexane was further added in layers and allowed to stand, colorless crystals were precipitated. The crystals were filtered off with a glass filter, washed with benzene, and dried under reduced pressure to obtain a colorless powder with a yield of 60% (597 mg).

The obtained crystals were analyzed by elemental analysis, NMR, and FD-MS. The results were as follows. Elemental analysis: C, 56.51; H, 5.27; N, 10.98. Found: C, 55.90; H, 5.24; N, 10.73. ¹ H NMR (CD ₂ Cl ₂ ): d 8.23 (d, ³ J _HH = 2.2, ¹ H, pz 3-H), 7.73 (d; ³ J _HH = 2.1, 2H, pz 5-H), 7.02 (s; 2H, Ms meta-H), 6.88 (s; 2H, Ms meta-H) , 6.86 (s; 2H, Ms meta-H), 6.24 (d; ³ J _HH = 2.2, 1H, pz 4-H), 6.11 (d; ³ J _HH = 2.1, 2H, pz 4-H), 2.39 (s; 3H, Ms para-Me), 2.32 (s; 6H, Ms para-Me), 1.95 (s; 6H, Ms ortho-Me), 1.93 (s; 6H, Ms ortho-Me), 1.88 (s ; 6H, Ms ortho-Me). ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): d 158.0 (pz C-3), 148.3 (pz C-3), 145.9, 139.5, 139.1, 138.9 (2C overlapped ), 138.7, 137.9, 128.7, 128.4, 128.1, 128.0, 127.6, 108.1 (pz C-4), 107.2 (pz C-4), 21.4 (2C overlapped), 21.3, 21.2, 19.9.FD-MS: 764 ( M +).

[Synthesis Example 5] <Synthesis of Tp ^{Ms *} Hf (IV) Cl ₃ >
A rotor is placed in a Schlenk-type reaction vessel that has been thoroughly dried and substituted with nitrogen, and TlTp ^{Ms *} (730 mg, 0.95 mmol) and HfCl4 (0.303 mg, 0.95 mmol, CERAC) obtained by the method described in Synthesis Example 1 are added thereto. And 50 ml of toluene was added at room temperature. The obtained suspension solution was reacted at room temperature for 55 hours with stirring, and then the by-product TlCl was removed by filtration through a glass filter. The obtained transparent solution was concentrated under reduced pressure and allowed to stand at -37 ° C. As a result, colorless crystals were precipitated. The crystals were filtered off with a glass filter, washed with toluene, and dried under reduced pressure to obtain a colorless powder with a yield of 64% (519 mg). The obtained crystals were analyzed by elemental analysis, NMR, and FD-MS. The results were as follows. Elemental analysis (C ₃₆ H ₄₀ BCl ₃ N ₆ Hf · 0.12 C ₇ H ₈ ): C, 51.25; H, 4.78; N, 9.73. Found: C, 51.64; H, 4.16; N, 9.79. ¹ H NMR ( CD ₂ Cl ₂ ): d 8.27 (d, ³ J _HH = 2.3, 1H, pz 3-H), 7.77 (d; ³ J _HH = 2.0, 2H, pz 5-H), 7.05 (s; 2H, Ms meta-H), 6.90 (s; 2H, Ms meta-H), 6.88 (s; 2H, Ms meta-H), 6.28 (d; ³ J _HH = 2.4, 1H, pz 4-H), 6.15 (d ; ³ J _HH = 2.3, 2H, pz 4-H), 2.41 (s; 3H, Ms para-Me), 2.33 (s; 6H, Ms para-Me), 1.97 (s; 6H, Ms ortho-Me) , 1.95 (s; 6H, Ms ortho-Me), 1.90 (s; 6H, Ms ortho-Me). ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): d 158.5 (pz C-3), 148.5 ( pz C-3), 146.3, 139.5, 139.1, 139.0, 138.8, 138.7, 137.8, 128.6, 128.4, 128.1, 127.9, 127.4, 108.5 (pz C-4), 107.5 (pz C-4), 21.4, 21.2, 19.9 (Ms Me). FD-MS: 852 (M +).

[Synthesis Example 6] <Synthesis of Tp ^{Ms *} TiCl2 (O-2,4,6-tBu ₃ -Ph)>
A rotor was placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and K (O-2,4,6-tBu ₃ -Ph) (0.419 g, 1.39 mmol) and Organometallics, 2002 (21), 1882, Tp ^{Ms *} TiCl3 (1.00 g, 1.39 mmol) obtained by the method described in 1882 was charged, and 150 ml of toluene was added at room temperature. The resulting solution was allowed to react at room temperature with stirring for 9 days, and then by-product KCl was removed by filtration through a glass filter. The resulting brown solution was concentrated to 20 ml under reduced pressure and allowed to stand at -37 ° C. As a result, brown crystals were precipitated. The crystals were filtered off with a glass filter, washed with hexane, and dried under reduced pressure to obtain a brown powder in a yield of 73% (956 mg). The results of analyzing the obtained crystals by elemental analysis and NMR were as follows. Elemental analysis: C, 68.34; H, 7.34; N, 8.87. Found: C, 67.92; H, 7.36; N, 7.93. ¹ H NMR (CD ₂ Cl ₂ ): d 7.92 (d; 1H; ³ J _HH = 1.8, pz3-H), 7.59 (d; 1H; ³ J _HH = 1.8, pz5-H), 7.46 (d; 1H; ³ J _HH = 1.8, pz5-H), 7.29 (d; 1H; ³ J _HH = 2.3, Ph meta-H), 7.15 (d; 1H; ³ J _HH = 2.4, Ph meta-H), 7.05 (s; 1H; mesityl meta-H), 6.96 (s; 1H; mesityl meta-H) , 6.74 (s; 2H; mesityl meta-H), 6.69 (s; 1H; mesityl meta-H), 6.62 (s; 1H; mesityl meta-H), 6.11 (d; 1H; ³ J _HH = 1.8, pz 4-H), 6.09 (d; 1H; ³ J _HH = 1.8, pz 4-H), 5.91 (d; 1H; ³ J _HH = 1.8, pz 4-H), 2.37 (s; 3H; mesityl para- H), 2.32 (s; 3H; mesityl para-H), 2.25 (s; 3H; mesityl para-H), 2.23 (s; 3H; mesityl ortho-H), 2.19 (s; 3H; mesityl ortho-H) , 2.14 (s; 3H; mesityl ortho-H), 1.68 (s; 3H; mesityl ortho-H), 1.65 (s; 3H; mesityl ortho-H), 1.53 (s; 3H; mesityl ortho-H), 1.35 (s; 9H; Ph ortho- ^t Bu), 1.29 (s; 9H; Ph ortho- ^t Bu), 0.81 (s; 9H; Ph para- ^t Bu), ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): d 172.3 (OCPh), 158.0 (pz 3-C), 157.3 (pz 3-C), 146.9, 146.6, 145.3, 140.7, 140.0, 139.5, 139.3, 138.6, 138.5, 138.2, 138.0, 137.6, 137.2, 136.4, 136.3, 131.9, 131.3, 129.0, 128.84, 128.75, 128.5, 128.0, 127.9, 124.6, 122.9 (pz 5-C , mesityl carbons and Ph), 108.7, 107.1, 106.9 (pz 4-C), 38.6, 37.8, 35.1 (C (CH ₃ ) ₃ ), 33.9, 33.2, 31.8 (C (CH ₃ ) ₃ ), 23.5, 21.9 , 21.38, 21.35, 21.32, 21.25, 21.19, 19.8 (mesityl Me).

<Ethylene polymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
70 ml of a toluene solution containing 0.05 mmol of methylaluminoxane in terms of aluminum atom was charged into a glass reactor having an internal volume of 200 ml sufficiently purged with nitrogen to saturate 4.2 atmospheres of ethylene. Thereafter, 10 ml of a toluene solution (0.1 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl obtained in Example 2 was added to initiate polymerization. The reaction was carried out at 60 ° C. for 6 minutes while maintaining an ethylene pressure of 4.2 atm, and then the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was sufficiently washed with methanol and then dried under reduced pressure at 80 ° C. for 12 hours to obtain polyethylene. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
In Example 1, except that methylaluminoxane was changed to 1.00 mmol in terms of aluminum atom and the polymerization temperature was changed to 80 ° C., polymerization and post-treatment were performed in the same manner as in Example 1 to obtain polyethylene. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
In Example 2, except that the polymerization temperature was changed to 130 ° C., polymerization and post-treatment were performed in the same manner as in Example 2 to obtain polyethylene. The results are shown in Table 1.

<Polymerization and terminal functionalization of ethylene using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
In Example 1, polymerization was carried out in the same manner as in Example 1 except that methylaluminoxane was changed to 5.00 mmol in terms of aluminum atoms. After completion of the polymerization, oxygen was gradually inserted into a 336 ml reaction vessel while stirring at 40 ° C., and allowed to react for 1 hour. After the reaction, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 80 ° C. for 12 hours to obtain terminal hydroxylated polyethylene with a terminal hydroxylation rate of 71%. The results are shown in Table 1 and FIG.

<Ethylene polymerization using Tp ^{Ms *} TiCl2 (O-2-4-6-tBu ₃ -Ph)>
In Example 1, Tp ^{Ms *} TiCl ₂ (O-2-4-6-tBu ₃ -Ph synthesized in Synthesis Example 6 was used instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, and methylaluminoxane was converted to an aluminum atom. Except for changing to 0.20 mmol in terms of conversion, polymerization and post-treatment were performed in the same manner as in Example 1 to obtain polyethylene, and the results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} TiCl ₂ (O-2-4-6-tBu ₃ -Ph)>
In Example 4, except that methylaluminoxane was changed to 1.00 mmol in terms of aluminum atom, polymerization and post-treatment were performed in the same manner as in Example 4 to obtain polyethylene. The results are shown in Table 1.

<Polymerization of ethylene using Tp ^Ms Zr (IV) Cl ₃ >
In Example 1, instead of the toluene solution (0.1 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl, the toluene solution (0.001 mmol / liter) of Tp ^Ms Zr (IV) Cl ₃ synthesized in Synthesis Example 3 was used. 1), except that methylaluminoxane was changed to 0.10 mmol in terms of aluminum atom and the ethylene pressure was changed to 1.4 atm, polymerization and post-treatment were performed in the same manner as in Example 1 to obtain polyethylene. The results are shown in Table 1.

<Polymerization of ethylene using Tp ^Ms Zr (IV) Cl ₃ >
In Example 6, polymerization and post-treatment were performed in the same manner as in Example 6 except that methylaluminoxane was changed to 0.20 mmol in terms of aluminum atom and the reaction time was changed to 0.55 minutes to obtain polyethylene. The results are shown in Table 1.

<Polymerization of ethylene using Tp ^Ms Zr (IV) Cl ₃ >
In Example 6, the toluene solution (0.05 mmol / l) of Tp ^Ms Zr (IV) Cl ₃ synthesized in Synthesis Example 3 was used, methylaluminoxane was changed to 0.50 mmol in terms of aluminum atom, and the reaction time was changed to 1 minute. Except for the above, polymerization and post-treatment were performed in the same manner as in Example 6 to obtain polyethylene. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 8, instead of the toluene solution (0.05 mmol / l) of Tp ^Ms Zr (IV) Cl ₃ , the toluene solution (0.05 mmol / l) of Tp ^{Ms *} Zr (IV) Cl ₃ synthesized in Synthesis Example 3 was used. ), And polymerization and post-treatment were performed in the same manner as in Example 8, except that methylaluminoxane was changed to 0.10 mmol in terms of aluminum atom, ethylene pressure was changed to 4.2 atm, and reaction time was changed to 0.67 minutes. Polyethylene was obtained. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 9, using the ^{Tp Ms * Zr (IV) Cl} 3 of a toluene solution (0.1 mmol / l) instead of Tp ^Ms Zr (IV) Cl ₃ in toluene (0.05 mmol / l), methylaluminoxane Except that 1.00 mmol in terms of aluminum atom and the reaction time was changed to 5 minutes, polymerization and post-treatment were performed in the same manner as in Example 9 to obtain polyethylene. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 1, instead of the toluene solution (0.1 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl, the toluene solution (0.1 mmol) of Tp ^{Ms *} Hf (IV) Cl ₃ synthesized in Synthesis Example 5 was used. / L), except that methylaluminoxane was changed to 0.05 mmol in terms of aluminum atom, polymerization and post-treatment were performed in the same manner as in Example 1 to obtain polyethylene. The results are shown in Table 1.

<Ethylene polymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 11, except that methylaluminoxane was changed to 0.20 mmol in terms of aluminum atom, polymerization and post-treatment were performed in the same manner as in Example 11 to obtain polyethylene. The results are shown in Table 1.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of a toluene solution, and the liquid phase and the gas phase were saturated with an ethylene / propylene mixed gas (= 100/100 liter / hr). Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom was added, followed by 10 ml of a toluene solution (0.5 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl synthesized in Synthesis Example 2 to initiate polymerization. After reacting for 5 minutes at 25 ° C. in an atmosphere of an ethylene / propylene mixed gas (= 100/100 liter / hr) at normal pressure, the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
In Example 14, instead of methylaluminoxane, 0.25 mmol of triisobutylaluminum and 1.2 equivalent of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to Ti to initiate polymerization, and the reaction time was 15 minutes. Except for the change, polymerization and post-treatment were performed in the same manner as in Example 14 to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Copolymerization of ethylene / norbornene using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of a toluene solution and 1 g of norbornene, and the liquid phase and the gas phase were saturated with ethylene gas (50 l / hr). Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom was added, followed by 10 ml of a toluene solution (0.5 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl synthesized in Synthesis Example 2 to initiate polymerization. After reacting at 25 ° C. for 5 minutes in an atmosphere of normal pressure ethylene gas (50 liters / hr), the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
In Example 16, instead of methylaluminoxane, 0.25 mmol of triisobutylaluminum and 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate to Ti were added to initiate polymerization, and the reaction time was 3 minutes. Except having changed, it superposed | polymerized and worked up like Example 16, and obtained the ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Ti (IV) Cl ₃ >
In Example 14, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, a toluene solution of Tp ^{Ms *} Ti (IV) Cl ₃ synthesized according to the method described in Organometallics, 2002 (21), 1882 (0.5 mmol) Polymerization and post-treatment were carried out in the same manner as in Example 14 except that 10 ml of / l) was added and polymerization was started to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Ti (IV) Cl ₃ >
Example 18 was the same as Example 18 except that 0.25 mmol of triisobutylaluminum instead of methylaluminoxane and 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate relative to Ti were added to initiate polymerization. Then, polymerization and post-treatment were performed to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Ti (IV) Cl ₃ >
In Example 16, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, a toluene solution of Tp ^{Ms *} Ti (IV) Cl ₃ synthesized according to the method described in Organometallics, 2002 (21), 1882 (0.5 mmol / Polymerization and post-treatment were carried out in the same manner as in Example 16 except that 10 ml of l) was added and polymerization was started to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Ti (IV) Cl ₃ >
In Example 17, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, a toluene solution of Tp ^{Ms *} Ti (IV) Cl ₃ synthesized according to the method described in Organometallics, 2002 (21), 1882 (0.5 mmol / Polymerization and post-treatment were performed in the same manner as in Example 17 except that 10 ml of l) was added and polymerization was started to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 14, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, 10 ml of a toluene solution (0.2 mmol / l) of Tp ^{Ms *} Zr (IV) Cl ₃ synthesized in Synthesis Example 4 was added to initiate polymerization. Polymerization and post-treatment were performed in the same manner as in Example 14 except that the reaction time was changed to 1 minute to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 22, instead of methylaluminoxane, 0.25 mmol of triisobutylaluminum and 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate with respect to Ti were added, and Tp ^{Ms *} Zr (IV) Cl _{3 was} added. 10 ml of a toluene solution (0.1 mmol / l) was added to initiate the polymerization, and the polymerization and post-treatment were carried out in the same manner as in Example 22 except that the polymerization was carried out while changing the reaction time to 5 minutes. Got. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 16, 10 ml of a toluene solution (0.1 mmol / l) of Tp ^{Ms *} Zr (IV) Cl ₃ synthesized in Synthesis Example 4 was added in place of Tp ^{Ms *} Ti (III) Cl ₂ KCl to initiate polymerization. The polymerization and the post-treatment were performed in the same manner as in Example 16 except that the polymerization was performed while changing the reaction time to 10 minutes to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
In Example 17, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, 10 ml of the toluene solution (0.2 mmol / l) of Tp ^{Ms *} Zr (IV) Cl ₃ synthesized in Synthesis Example 4 was added to initiate polymerization. Polymerization and post-treatment were performed in the same manner as in Example 17 except that the polymerization was performed while changing the reaction time to 10 minutes to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / propylene / dimethyldecatriene copolymerization using Tp ^{Ms *} Zr (IV) Cl ₃ >
A glass reactor with an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene solution and 1 ml of dimethyldecatriene, and the liquid phase and gas phase were saturated with ethylene / propylene mixed gas (= 100/100 liter / hr). It was. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom was added, followed by 10 ml of a toluene solution (0.1 mmol / l) of Tp ^{Ms *} Zr (IV) Cl ₃ synthesized in Synthesis Example 4 to initiate polymerization. After reacting at 25 ° C. for 3 minutes in an atmosphere of normal pressure ethylene / propylene mixed gas (= 100/100 liter / hr), the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain an ethylene / propylene / dimethyldecatriene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 14, an ethylene / propylene mixture using a gas (= 100/150 l ^{/ hr), Tp Ms * Ti} (III) Cl 2 was changed to synthesized in Synthesis Example 5 of ^{KCl Tp Ms * Hf (IV)} Cl Polymerization and post-treatment were performed in the same manner as in Example 14 except that 10 ml of ₃ toluene solution (0.2 mmol / l) was added and polymerization was started to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / propylene copolymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 27, instead of methylaluminoxane, 0.25 mmol of triisobutylaluminum and 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to Ti to initiate polymerization, and the reaction time was 3 minutes. Polymerization and post-treatment were performed in the same manner as in Example 27 except that the polymerization was carried out to obtain an ethylene / propylene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 16, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, 10 ml of the toluene solution (0.2 mmol / l) of Tp ^{Ms *} Hf (IV) Cl ₃ synthesized in Synthesis Example 5 was added to initiate polymerization. Except for the above, polymerization and post-treatment were performed in the same manner as in Example 16 to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / norbornene copolymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 17, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl, 10 ml of a toluene solution (0.2 mmol / l) of Tp ^{Ms *} Hf (IV) Cl ₃ synthesized in Synthesis Example 5 was added to initiate polymerization. The polymerization and post-treatment were carried out in the same manner as in Example 17 except that the polymerization was carried out while changing the reaction time to 10 minutes to obtain an ethylene / norbornene copolymer. The results are shown in Table 2.

<Ethylene / propylene / dimethyldecatriene copolymerization using Tp ^{Ms *} Hf (IV) Cl ₃ >
In Example 26, an ethylene / propylene mixture using a gas (= 500/150 l ^{/ hr), Tp Ms * Zr} Tp synthesized in changes to Synthesis Example 5 ^{_{(IV) Cl 3 Ms * Hf}} (IV) Cl 3 10 ml of a toluene solution (0.2 mmol / l) was added to start the polymerization, and the polymerization and post-treatment were carried out in the same manner as in Example 26 except that the polymerization was carried out while changing the reaction time to 3 minutes. A triene copolymer was obtained. The results are shown in Table 2.

<Ethylene / 1-hexene copolymerization using Tp ^{Ms *} Ti (III) Cl ₂ KCl>
20 ml of toluene solution containing 1.00 mmol of methylaluminoxane in terms of aluminum atoms was charged into a 200 ml glass reactor sufficiently purged with nitrogen, followed by addition of 50 ml of 1-hexene, and 1.4 atmospheres of ethylene. Was saturated. Thereafter, 10 ml of a toluene solution (0.1 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl obtained in Synthesis Example 2 was added to initiate polymerization. The reaction was carried out at 60 ° C. for 6 minutes while maintaining an ethylene pressure of 1.4 atm. After completion of the polymerization, the reaction product was extracted with hexane, washed with dilute hydrochloric acid, concentrated, and dried to obtain an ethylene / hexene copolymer with few hexene-hexene chains. The monomer reactivity ratio measured by 13 C-NMR was r _E · r _H = 0.52. The results are shown in Table 2.

<Ethylene / 1-hexene copolymerization using Tp ^Ms Zr (IV) Cl ₃ >
In Example 14, instead of the toluene solution (0.1 mmol / l) of Tp ^{Ms *} Ti (III) Cl ₂ KCl, the toluene solution (0.001 mmol / l) of Tp ^Ms Zr (IV) Cl ₃ synthesized in Synthesis Example 3 was used. 1), except that methylaluminoxane was changed to 0.10 mmol in terms of aluminum atom, polymerization and post-treatment were performed in the same manner as in Example 14 to obtain an ethylene / 1-hexene copolymer having a small number of hexene-hexene chains. Obtained. ^The monomer reactivity ratio measured by ¹³ C-NMR was r _E · r _H = 0.31. The results are shown in Table 2 and FIG.

Comparative Example 1 <Ethylene polymerization with TpTi (IV) Cl _3>
In Example 1, instead of Tp ^{Ms *} Ti (III) Cl ₂ KCl in toluene (0.1 mmol / l), TpTiCl ₃ in toluene obtained by the method described in Organometallics, 2002 (21), 1882 Polymerization and post-treatment were carried out in the same manner as in Example 1 except that (0.1 mmol / l) was used and methylaluminoxane was changed to 1.00 mmol in terms of aluminum atoms and the reaction time was changed to 23 minutes to obtain polyethylene. . The results are shown in Table 1.

  Catalysts with extremely high olefin (co) polymerization activity can be obtained with high purity and high yield, and by using this, stable industrial production of various high-quality functional polyolefins is enabled.

¹ H-NMR spectrum of terminal hydroxylated polyethylene (o-dichlorobenzene, 110 ° C.). Example 4 ¹³ C-NMR spectrum (o-dichlorobenzene, 110 ° C.) of ethylene / 1-hexene copolymer. (Example 33)

Claims (16)

An olefin polymerization catalyst comprising a transition metal compound (A) represented by the following general formula (I):

(Wherein L is a tridentate anion ligand represented by RQ (Pz ¹ ) _i (Pz ² ) _3-i , or a neutral ligand, wherein R is a hydrogen atom, a halogen atom, Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group, and tin-containing Q represents a group selected from the group consisting of groups, Q represents a group selected from the group consisting of boron, carbon, silicon, germanium, tin, and lead, Pz ¹ is an unsubstituted aryl at the 3-position Group, a substituted aryl group, a pyrazolyl group substituted with an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, or an oxyhydrocarbon group, and Pz ² is an unsubstituted pyrazolyl group or a substituted group Represents a pyrazolyl group, i represents an integer of 1-3, M represents a periodic table X represents a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing Group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, Y represents a neutral ligand having an electron-donating group, and m represents the valence of M. When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. And n represents an integer of 0 to 3.)   2. The olefin polymerization catalyst according to claim 1, wherein i is 2 or 3 in the transition metal compound (A) represented by the general formula (I). In the transition metal compound (A) represented by the general formula (I), Pz ¹ is a pyrazole having a substituted aryl group at least at the 3-position. The catalyst for olefin polymerization as described.   In the transition metal compound (A) represented by the general formula (I), a transition of group 4 or 5 of the periodic table in which the valence state of the transition metal atom M is divalent, trivalent or tetravalent The catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the catalyst is a metal atom.   The catalyst for olefin polymerization according to claim 4, wherein the transition metal atom M is trivalent.   The catalyst for olefin polymerization according to claim 4, wherein the transition metal atom M is hafnium.   The transition metal compound (A) is [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate zirconium trichloride or [hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride The olefin polymerization catalyst according to claim 4. The transition metal compound (A) according to any one of claims 1 to 7,
(B) (B-1) Organometallic compound
(B-2) an organoaluminum oxy compound, and
(B-3) An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs.   The catalyst for olefin polymerization characterized by including a support | carrier (C) in addition to the catalyst for olefin polymerization in any one of Claims 1-8. A method for producing a transition metal compound (A) using a metal salt (a) represented by the following general formula (II) as a raw material, and using a chromatograph in which the filler is neutral or basic, A method for producing a transition metal compound (A), comprising a purification step for separating the positional isomer of a).

(In the formula, Z represents a metal atom selected from Group 1, Group 13, and Group 14 of the Periodic Table, and j represents an integer of 0 or 1.) The metal salt (a) represented by the general formula (II) is reacted with the transition metal salt (b) represented by the following general formula (III) while being dissolved or suspended in a nonpolar solvent. A process for producing a transition metal compound (A).

  A method for polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 9, wherein an organometallic compound (B-1), an organoaluminum oxy compound (B-2), or both A method for polymerizing olefins, characterized in that the molecular weight and molecular weight distribution of the polyolefin are controlled by changing the amount used.   The method for polymerizing olefins in the presence of the olefin polymerization catalyst according to any one of claims 1 to 9, wherein the molecular weight and molecular weight distribution of the polyolefin are controlled by adding a specific organic compound component (D). A process for polymerizing olefins.   The method for polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9, wherein the molecular weight of the polyolefin and the molecular weight distribution are controlled by changing the polymer concentration in the polymerization solution. An olefin polymerization method.   A method for polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9, wherein two or more kinds of olefins are copolymerized.   The method for polymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9, wherein the terminal of the polyolefin is functionalized by adding a reactive reagent (E) at the end of the polymerization. A method for polymerizing olefins.

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