JP5228265B2 - Modified particles, carrier, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

Description

  The present invention relates to a modified particle useful as a carrier and a catalyst component for addition polymerization, a catalyst for addition polymerization obtained using the same, and a method for producing an addition polymer.

Addition polymers such as polypropylene and polyethylene are widely used in various molding fields due to their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy.
These addition polymers are conventionally a combination of a solid catalyst component obtained mainly using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride and a Group 13 metal compound typified by an organoaluminum compound. The conventional solid catalyst (multisite catalyst) is used to polymerize olefins and the like.

  In recent years, an addition polymer that polymerizes olefins using a so-called single-site catalyst in which a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) different from a solid catalyst component that has been used for a long time and an aluminoxane or the like are combined. Manufacturing methods have been proposed. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported that certain boron compounds are combined with such transition metal compounds. For example, JP-A-1-502036 discloses a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Addition polymers obtained using these single-site catalysts generally have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomer is copolymerized more uniformly. Therefore, it is known that an addition polymer more homogeneous than that obtained when a conventional solid catalyst is used can be obtained.

  However, since such a single-site catalyst is soluble in the reaction system, when it is applied to polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), Indeterminate shape, resulting in the formation of coarse addition polymer particles, bulk addition polymer, fine powder addition polymer, etc., decrease in bulk density of addition polymer, adhesion of addition polymer to polymerization reactor wall, etc. It might be. These factors contribute to heat transfer failure and heat removal failure in the reactor, leading to a problem in that stable operation is difficult and productivity is reduced. Japanese Patent Laid-Open No. 11-193306 discloses a method for solving such a problem.

Problems to be solved by the invention

  However, the solution described in the publication is still insufficient in terms of polymerization activity. The object of the present invention is to provide particles, supports and additions useful for the preparation of highly active single-site catalysts suitably applied to polymerizations involving the formation of addition polymer particles (eg slurry polymerization, gas phase polymerization, bulk polymerization, etc.). An object of the present invention is to provide a polymerization catalyst component, a highly active addition polymerization catalyst, and an efficient method for producing an addition polymer.

Means for solving the problem

[Means for Solving the Problems]
The present invention was obtained by bringing the following (a), (b), (c) and inorganic oxide particles (d) into contact with each other, and was modified to satisfy the following formula [4] and the following formula [5]. It depends on the particles. Moreover, this invention is obtained by making the following (a), following (b), following (c), and inorganic oxide particle (d) contact, and addition polymerization which satisfy | fills following formula [4] and following formula [6] It relates to the modified particles used in the process.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(Respectively in the general formula [1] ~ [3], M 1 represents a Zn atom, m is .L ¹ representing a 2 represents a hydrocarbon group, be L ¹ is optionally substituted by one or more identical to each other R ¹ represents a halogenated hydrocarbon group, and when a plurality of R ¹ are present, they may be the same or different from each other, and R ² represents a hydrocarbon group or a halogenated hydrocarbon group. Each T independently represents a Group 15 or Group 16 atom of the Periodic Table, and t represents the T valence of each compound.)
N / M> 0.9 [4]
(In the formula, N represents the amount of halogen atoms contained in the modified particles, and M represents the amount of Zn contained in the modified particles.)
A / B ≧ 0.1 [5]
(In the formula, A represents the integrated intensity of a halo whose apex is at a Bragg angle (2θ) of 33 ° to 37 ° in a diffraction intensity profile obtained by wide-angle X-ray measurement, and B represents a Bragg angle (2θ) of 18 ° to 22 (Indicates the integrated intensity of the halo at the apex at °.)
D / C ≧ 0.5 [6]
(In the formula, C represents the peak intensity of the maximum peak in the range of 1 to 2 nm in the radial distribution function obtained by measuring particles modified by the X-ray absorption fine structure analysis method, and D represents the radial diameter. This represents the peak intensity of the maximum peak in the range of 2.5 to 3.5 nm in the distribution function, which is obtained by measuring the modified particles by an X-ray absorption fine structure (XAFS) analysis method. The wide X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of Zn is obtained from the obtained X-ray absorption spectrum, and is obtained by Fourier transform.)

The present invention relates to a carrier composed of any one of the above modified particles, and to a catalyst component for addition polymerization composed of any one of the above modified particles. The present invention also relates to an addition polymerization catalyst obtained by contacting any of the above modified particles (A) and a group 3-11 or lanthanoid series transition metal compound (B), And it applies to the catalyst for addition polymerization obtained by contacting any one of the modified particles (A), the group 3-11 or lanthanoid series transition metal compound (B), and the organoaluminum compound (C). Is. Furthermore, the present invention relates to a method for producing an addition polymer using any of the above addition polymerization catalysts.
Hereinafter, the present invention will be described in more detail.

M in the above formula [4] represents the amount of substance of the typical metal atom M ¹ of Group ¹ , 2, 12, 14 or 15 of the periodic table contained in the modified particles. M is generally determined by a method generally used in analytical chemistry (for example, “4th edition, Experimental Chemistry Course 15 Analysis” edited by The Chemical Society of Japan, Maruzen Co., Ltd., pages 2 and 3). Spectroscopy (spectroscopy) is preferred. Spectroscopy is more preferred because of its simple operation. Among these, atomic absorption analysis (AAS analysis) or inductively coupled plasma emission analysis (ICP analysis) is particularly preferred for analysis of trace metal elements.

  N in the above formula [4] represents the amount of halogen atoms contained in the modified particles. The amount of the halogen atom is determined by the gravimetric method, the spectrophotometric method, and the ion electrode method as described in “Chemical Analysis Course 4 of the 4th edition” published by The Chemical Society of Japan, Maruzen Co., Ltd., pages 218 to 231. be able to.

In the modified particles of the present invention, as shown in the above formula [4], the ratio of the typical metal atom M ¹ contained in the modified particles and the amount of halogen atoms exceeds 0.9. There are many halogen atoms. The ratio (N / M) is preferably in the range exceeding 0.90.

The wide-angle X-ray measurement performed in the present invention is measured under the following conditions using, for example, a vertical rotor flex ultraX18 (manufactured by Rigaku Corporation) as an X-ray diffractometer.
Load: 50kV-100mA
Focus: Line Scan mode: 2θ / θ (2 ° / min.)
Measuring range: 5 ° ~ 70 ° Slit: Divergence slit 1 ° Receiving slit 0.15mm
Scatter slit 1 ° Detector: Scintillation counter Monochromator: Graphite In the present invention, this wide-angle X-ray measurement is usually performed under the condition that the measurement sample does not touch the atmosphere.

In the diffraction intensity profile obtained by wide-angle X-ray measurement, the integrated intensity A of the halo showing the apex from the Bragg angle (2θ) 33 ° to 37 ° and the halo showing the apex from the Bragg angle (2θ) 18 ° to 22 ° The integrated intensity B is obtained and the ratio A / B is calculated.
The halo whose apex is from 33 ° to 37 ° with the Bragg angle (2θ) is considered to be a halo based on the contact material of the compounds (a), (b) and (c), while the Bragg angle (2θ) 18 A halo whose apex is from 22 ° to 22 ° is considered a halo based on particle (d). When the integrated intensity ratio A / B is at or above a certain level, the activity of the addition polymerization catalyst obtained using the modified particles becomes high, which is preferable. In the present invention, the integrated intensity ratio A / B is 0.1 or more, preferably 0.15-1, more preferably 0.2-0.8, and particularly preferably 0.25-0. 7.

The above formula [6] is a formula using a wide area X-ray absorption fine structure (EXAFS) analysis method. Hereinafter, a general X-ray absorption fine structure (XAFS) analysis will be described. The principle and analysis method thereof are, for example, “The Spectroscopical Society of Japan Measurement Method Series 26 X-ray absorption fine structure Yasuo Udagawa (1993)”. It is familiar with books such as.
When a substance is placed on the X-ray beam line, the X-ray intensity irradiated to the substance (incident X-ray intensity: I0) and the X-ray intensity transmitted through the substance (transmitted X-ray intensity: It) The X-ray absorbance of the material is calculated. When X-ray energy is changed while monitoring the increase or decrease in X-ray absorbance and the X-ray absorption spectrum is measured, a sharp rise (absorption edge) of the X-ray absorbance is observed at a certain X-ray energy. The X-ray energy at the absorption edge corresponds to the energy required for the inner-shell electrons of atoms (absorbing atoms) that absorb X-rays to jump out as photoelectrons. There are various types of inner shells such as K shell, L shell, and M shell, and there is an absorption edge corresponding to each inner shell electron. A K-shell electron is an innermost electron, and a corresponding absorption edge is called a K absorption edge. In the X-ray absorption spectrum, a fine vibration structure that appears in a high energy side region of about 30 to 1000 eV from the absorption edge is called a wide-area X-ray absorption fine structure (EXAFS). These fine vibration structures appearing on the spectrum are the result of interference effects between the photoelectron wave emitted from the absorbing atom by X-ray absorption and the photoelectron wave that is scattered back by the surrounding atoms (scattering atoms). Caused. Therefore, by analyzing this in detail, information on the local structure near the absorbing atom can be obtained.

  Subtracting the background from the X-ray absorption spectrum, and subtracting the absorption coefficient without the vibration structure when the absorbing atom is isolated, subtracting the absorption coefficient without the vibration structure, the Fourier transform is performed in an appropriate region. The radial distribution function centered on the atom is obtained. By examining this radial distribution function in detail, it is possible to obtain information on the distance between the absorbing atom and the scattering atom from the position of the maximum value of this function, and the number of scattering atoms from the intensity, and pay attention to it. The structural information in the vicinity of absorbing atoms can be clarified.

In the present invention, the peak intensity of the maximum peak in the range of 1 to 2 nm in the radial distribution function is C, the peak intensity of the maximum peak in the range of 2.5 to 3.5 nm is D, and the ratio D / C is calculated. A peak in the range of ¹ to 2 nm in the radial distribution function is considered to be a peak based on the presence of the atom (1) bonded to the typical metal atom M ^1. The peak in the range of ˜3.5 nm is considered to be a peak based on the presence of the atom (2) bonded to the atom (1). An increase in the peak intensity D of the peak based on the presence of the atom (2) means that the number of the atoms (2) existing in the vicinity of the typical metal atom M ¹ increases, which means that the typical metal atom M ^1. It is considered that the structure including the atom (1) and the atom (2) is a more ordered structure. When the ratio D / C of these peak intensities is above a certain level, the activity of the addition polymerization catalyst obtained using the modified particles becomes high, which is preferable. In the present invention, the peak intensity ratio D / C is 0.5 or more, preferably 0.55 to 1.2, and more preferably 0.6 to 0.9.

  In the present invention, the XAFS measurement is usually performed under the condition that the measurement sample does not touch the atmosphere.

M ¹ in the general formula [1] represents a typical metal atom of Group 1, 2, 12, 14 or 15 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples thereof include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, mercury atom, germanium atom, tin atom. , Lead atom, antimony atom, bismuth atom and the like. M ¹ is particularly preferably a Group 12 atom, and most preferably a zinc atom.
M in the general formula [1] represents a valence of M ^1, for example, when M ¹ is a zinc atom and m is 2.

L ¹ in the general formula [1] represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ¹ are present, they may be the same as or different from each other. Specific examples of the halogen atom in L ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group.

  As an alkyl group here, a C1-C20 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, An isobutyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-pentadecyl group, an n-eicosyl group, and the like, more preferably a methyl group , Ethyl group, isopropyl group, tert-butyl group or isobutyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, --Fluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2, 3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetra Methylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl Group, anthracenyl group, etc. are mentioned, More preferably, it is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2 , 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) Methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) Methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl Group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group And anthracenylmethyl group, and the like, more preferably a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

L ¹ in the general formula [1] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

T in the above general formula [2] or [3] each independently represents an atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). T in the general formula [2] and T in the general formula [3] may be the same or different. Specific examples of the Group 15 atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 atom include an oxygen atom and a sulfur atom. T is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the above general formula [2] or [3], t represents the valence of each T. When T is a Group 15 atom, t is 3, and when T is a Group 16 atom, t is 2. is there.

R ¹ in the single-stage formula [2] represents a halogenated hydrocarbon group, and when a plurality of R ¹ are present, they may be the same or different from each other.
Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the halogenated hydrocarbon group include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group.

  Specific examples of the halogenated alkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. Group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3 , 3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethyl Ethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1 , 1-bis (triiodomethyl) -2,2,2-triiodoethyl group and the like.

  Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl. Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6 Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, penta Chlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2- Naphtyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromo Phenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromide Phenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group Perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodo Phenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl Group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, A do-1-naphthyl group, a periodo-2-naphthyl group, etc. are mentioned.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, etc. Can be mentioned.

R ¹ is preferably a halogenated alkyl group or a halogenated aryl group. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, 2,4,6-tri Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Tylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloronutyl group 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group or A pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, most preferably a trif Olomethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group, A 3,4,5-trifluorophenyl group or a pentafluorophenyl group.

R ² in the general formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group for R ² is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbon group as described for L ¹ in the general formula [1] is used. The halogenated hydrocarbon group in R ^2, a halogenated alkyl group, halogenated aryl group, (halogenated alkyl) aryl group and the like, similar halogenated and described as R ¹ in the general formula [2] Hydrocarbon groups are used.

R ² in the general formula [3] is preferably a halogenated hydrocarbon group, and more preferably a fluorinated hydrocarbon group.

Specific examples of the compound (a) include, when M ¹ is a zinc atom, dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl zinc; Diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, normal butyl zinc chloride , Isobutyl zinc chloride, normal hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, normal butyl zinc bromide, isobutyl zinc bromide, normal hexyl bromide zinc, methyl zinc iodide, ethyl iodide Zinc, propylzinc iodide, normal butene iodide Zinc iodide isobutyl zinc, halogenated alkyl zinc such as iodide-hexyl zinc, zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.

  The compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, or dinormal hexyl zinc, particularly preferably dimethyl zinc or diethyl zinc. It is.

  Specific examples of the compound (b) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (Dichloromethyl) amine, bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, Bis (2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-trimethyl) Iodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3) 3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2, 2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1 -Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1 Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2, 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) Enyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) ) Amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (3,4, 5-trifluorophenyl) amine, bis (3,4,5-trichlorophenyl) amine, bis (3,4,5-tribromophenyl) amine, bis (3,4,5-triiodophenyl) amine, bis (Pentafluorophenyl) amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- ( Trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) amine, Bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (3,4,5-tri (trifluoromethyl) phenyl) An amine etc. are mentioned. Moreover, the phosphine compound by which the nitrogen atom was substituted by the phosphorus atom can be illustrated similarly. These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.

  Specific examples of the compound (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, tribromomethanol, Triiodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3 , 3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2, , 2,2-trifluoro-1-trifluorome Ethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1 -Bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1,1-bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2, Examples include 2,2-tribromoethanol and 1,1-bis (triiodomethyl) -2,2,2-triiodoethanol. Moreover, the thiol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiol compounds are compounds represented by rewriting methanol in the above specific examples to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.

  Specific examples of the compound (b) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3 , 5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6- Tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 2-chlorophenol, 3-chloro Phenol, 4-chlorophenol, 2,4-dichloropheno 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5,6-tetrachloro Phenol, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1-naphthol, perchloro-2- Naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6 -Tribromophenol, 3,4,5-tribromophenol, 2,3,5,6- Trabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo- 2-naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-tri Iodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol , Period-1-naphthol, period-2-naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) Examples include phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 3,4,5-tris (trifluoromethyl) phenol, and the like. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiophenol compounds are compounds represented by rewriting phenol of the above-mentioned specific examples with thiophenol.

  The compound (b) is preferably a bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine. ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, or bis (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, phenols Are 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol , Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis ( Trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol or 3,4,5-tris (trifluoromethyl) phenol.

  More preferably, the compound (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis. (Trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6 -Trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6-tris (tri Fluoromethyl) phenol, more preferably 3,5- Fluoro phenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.

  The compound (c) is preferably water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine, more preferably water, sulfurized. Hydrogen, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, n- Octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tolylamine, 4-tolylamine 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5 -Trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6 -Tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, tert-butylaniline, n-pentyl Aniline, neopentylaniline, n-hexylaniline, n-octylaniline, n-de Ruanirin, n- dodecyl aniline, n- tetradecyl aniline, naphthylamine, anthracenyl amine,

Benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methyl Amine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine, (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3 , 4-Trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2 , 4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamine , (2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n -Propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (Neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthra Cenylmethylamine, fluorome Ruamine, chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3,3-penta Fluoropropylamine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-pentaiodopropylamine, 2 , 2,2-trifluoro-1-trifluoromethylethylamine, 2,2 , 2-trichloro-1-trichloromethylethylamine, 2,2,2-tribromo-1-tribromomethylethylamine, 2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl) ) -2,2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2,2-tribromo Ethylamine, 1,1-bis (triiodomethyl) -2,2,2-triiodoethylamine,

2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3,5-dibromo Aniline, 2,6-diiodoaniline, 3,5-diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4 , 6-triiodoaniline, 3,4,5-trifluoroaniline, 3,4,5-trichloroaniline, 3,4,5- Ribromoaniline, 3,4,5-triiodoaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline, pentaiodoaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (Trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline or 3,4,5 -Tri (trifluoromethyl) aniline.

  More preferably, the compound (c) is water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2 , 6-Xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine , Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4 Fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris ( Trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2- Fluoroaniline, 3-fluoroaniline, 4-fluoroaniline 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3, -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris (tri Fluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, most preferably water or pentafluoroaniline.

As the particles (d), those generally used as carriers are preferably used, porous materials having a uniform particle size are preferable, inorganic materials or organic polymers are preferably used, and inorganic materials are more preferably used. Is done.
The particle (d) is preferably 2.5 or less, more preferably 2.0 or less, more preferably 2.0 or less as a volume-based geometric standard deviation of the particle size of the particle (d) from the viewpoint of the particle size distribution of the obtained polymer. Is 1.7 or less.

Examples of inorganic substances used as the particles (d) include inorganic oxides and magnesium compounds, and clays and clay minerals can be used as long as they do not hinder. These may be mixed and used.
Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof such as SiO ₂ — Examples thereof include 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. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and silica is particularly preferable. For the upper inorganic oxide, a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride Allyoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxymagnesium, dimethylphenoxymagnesium, etc. Allyloxymagnesium; Magne Laurate Um, and the like can be exemplified carboxylates of magnesium such as magnesium stearate.
Among these, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.

Examples of clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite and the like.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

Of these inorganic substances, inorganic oxides are preferably used.
These inorganic substances are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

The average particle diameter of the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  As the organic polymer that can be used as the particles (d), any organic polymer may be used, and a plurality of types of organic polymers may be used as a mixture. As the organic polymer, a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group is preferable.

  The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group. , Hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group, etc. . A primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group is preferred. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion that does not have an active hydrogen atom. Specific examples include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. Indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group , Furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the boundary. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The amount of the functional group having active hydrogen or the non-proton donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol / g as the molar amount of the functional group per unit gram of the polymer. Yes, more preferably from 0.1 to 20 mmol / g.

  The polymer having such a functional group is obtained by, for example, homopolymerizing a monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or It can be obtained by copolymerizing this and another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

Such a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include the above-described functional group having active hydrogen and one or more polymerizable groups. A monomer having a saturated group, or a monomer having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups may be used. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethyne groups.
Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, 1 -Ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like .
Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Can be mentioned.

Examples of other monomers having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compounds and the like. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1- Examples include pentene and styrene. Preferred is ethylene or styrene. Two or more of these monomers may be used.
Specific examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle diameter of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

  These organic polymers are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 30 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

The modified particles of the present invention are modified particles obtained by bringing the above (a), (b), (c) and (d) into contact with each other. The order in which (a), (b), (c), and (d) are brought into contact is not particularly limited, and examples include the following order.
<1> A contact object obtained by contacting (a) and (b) with (c) and a contact object obtained by bringing (c) into contact with each other.
<2> A contact object obtained by bringing (a) and (b) into contact with each other and a contact object obtained by bringing (d) into contact with each other.
<3> A contact object obtained by bringing (a) and (c) a contact object into contact with (b) is brought into contact with (d).
<4> A contact object obtained by bringing (a) and (c) into contact with each other and (d) in contact with (b).
<5> A contact product obtained by contacting (b) with a contact product between (a) and (d) and (c) are brought into contact with each other.
<6> A contact object obtained by bringing (a) and (d) into contact with each other and (c) with the contact object obtained in contact with (b).
<7> A contact product obtained by contacting (b) with the contact product between (b) and (c) is brought into contact with (d).
<8> A contact product obtained by contacting (b) with the contact product between (b) and (c) and (a) are brought into contact with each other.
<9> A contact product obtained by contacting (b) with the contact product between (b) and (d) and (c) are brought into contact with each other.
<10> The contact product obtained by bringing (b) and (d) into contact with each other and (c) with the contact product are brought into contact with each other.
<11> A contact product obtained by contacting (a) with a contact product between (c) and (d) and (b) are brought into contact with each other.
<12> A contact product obtained by contacting (b) with a contact product between (c) and (d) and (a) are brought into contact with each other.

  As the contact order, it is preferable to contact the contact (e) obtained by bringing (a), (b) and (c) into contact with (d), and more preferably <1> or < 3>. That is, the modified particles of the present invention are preferably modified particles obtained by bringing (a), (b) and (c) into contact with each other and (d) a contact product (e) obtained by contacting them. More preferably, the modified particles obtained by contacting (d) with the contact product obtained by contacting (a) with the contact product between (a) and (b), and (c). Or a modified particle obtained by contacting (d) with a contact product obtained by contacting (b) with a contact product between (a) and (c).

  Such contact treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, such treatment may use a solvent, or these compounds may be directly treated without using them.

  As the solvent, a solvent that does not react with each of the components to be contacted when the solvent is used and the contact product obtained by contact is usually used. As described above, when each component is brought into contact stepwise, for example, even if the solvent reacts with (a), contact obtained by contacting (a) with other components The product may no longer react with the solvent, and in such a case, the solvent can be used as a solvent in the contact operation using the contact product as one component. Solvents are exemplified below, but they may be properly used as described above. Examples of solvents that can be used include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, or halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, Examples include polar solvents such as nitrile solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane and cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, dichloromethane and dichlorodifluoromethane. Halide solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, promobenzene, o-dichlorobenzene, Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydroph Ether solvents such as tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl Alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, alcohol solvents such as glycerin, phenol solvents such as phenol and p-cresol, acetone, ethyl methyl ketone, cyclohexanone, Carbonyl-based solutions such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone , Phosphoric acid derivatives such as hexamethylphosphoric triamide and triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, amines such as pyridine, piperidine and morpholine Sulfur compounds such as system solvents, dimethyl sulfoxide, sulfolane and the like.

  When the contact (e) obtained by bringing (a), (b) and (c) into contact with the particles (d), that is, in the case of <1>, <3> and <7> above In the above, the solvent (s1) for producing the contact product (e) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) for bringing the contact product (e) into contact with the particles (d). As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying E _TN ≧ 0.1 is particularly preferred. Examples of such polar solvents are dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene. O-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, Tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cycl Hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, ethylenediamine Pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane and the like. More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene Glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol Most preferably, it is tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

Moreover, as said solvent (s2), the mixed solvent of these polar solvents and hydrocarbon solvents can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent exemplified above are used. Specific examples of a mixed solvent of a polar solvent and a hydrocarbon solvent include a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a hexane / 1-propanol mixed solvent, a hexane / 2-propanol mixed solvent, and a heptane / methanol mixed solvent. , Heptane / ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent , Xylene / methanol mixed solvent, xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, xylene / 2-propanol mixed solvent, and the like. Preferably in hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent is there. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent or a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent.
The preferable range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.

  In the method of contacting (a), (b) and (c) with the contact product (e) obtained by contacting (d), that is, in the case of <1>, <3> and <7> above A hydrocarbon solvent can be used as the solvent (s1) and the solvent (s2). In this case, the contact product (e) obtained after contacting (a), (b) and (c). It is preferable that the time interval until the particles (d) are brought into contact with each other is short. The time interval is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature at the time of contacting a contact thing (e) and particle | grains (d) is -100 degreeC-40 degreeC normally, Preferably it is -20 degreeC-200 degreeC, Most preferably, it is -10 degreeC-10. ° C.

The modified particles of the present invention can be obtained, for example, by adjusting the ratio of the amount of each compound (a), (b), (c) used within a specific range. Specifically, when the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z, the y and z are represented by the following formulas (1) and ( The modified particles of the present invention are produced under conditions that substantially satisfy 2).
| M−y−2z | ≦ 1 (1)
(In the above formula (1), m represents the valence of M ^1. )
2 ≦ z / y <3 (2)

Y in the above formula (1) is preferably a number of 0.20 to 0.42, more preferably a number of 0.30 to 0.41, and even more preferably a number of 0.20 to 1.50. And most preferably a number from 0.35 to 0.40, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1) and the above formula (2). The
The ratio of y to z (z / y) is preferably a number from 2.2 to 2.8.

  In actual contact treatment of each compound, even if the use of each compound is intended to completely satisfy the above formula (1) or the above formula (2), the amount used may slightly vary. In addition, taking into consideration the amount of the compound that remains unreacted, etc., it is usual to slightly increase or decrease the amount used as appropriate. Here, “substantially satisfying the formula (1) and the formula (2)” means that the formula (1) and the formula (2) are satisfied even if the formula (1) and the formula (2) are not completely satisfied. This means that it is included when an attempt is made to obtain a target product obtained by bringing each compound into contact at a molar ratio satisfying (2).

  The amount of (d) used for (a) in the preparation of the modified particles of the present invention is derived from (a) contained in the particles obtained by contacting (a) and (d). The amount of typical metal atoms in terms of the number of moles of typical metal atoms contained in 1 g of the obtained particles is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol. What is necessary is just to determine suitably so that it may become this range.

  Heating is also preferably performed after the contact treatment as described above in order to further advance the reaction. In heating, it is preferable to use a solvent having a higher boiling point in order to obtain a higher temperature. For this purpose, the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.

  In the modified particles of the present invention, as a result of such contact treatment, the raw materials (a), (b), (c) and / or (d) may remain as unreacted substances. . However, when applied to polymerization involving the formation of addition polymer particles, it is preferable to perform a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact.

  Further, after such contact treatment or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 25 ° C. or higher. More preferably, it is 1 hour to 24 hours at a temperature of 40 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 60 ° C. to 200 ° C., particularly preferably 2 hours to 18 hours at a temperature of 60 ° C. to 160 ° C. Most preferably, drying is performed at a temperature of 80 to 160 ° C. for 4 to 18 hours.

The modified particles of the present invention can be used as a support for supporting a catalyst component for addition polymerization composed of a transition metal compound that forms a single site catalyst, and is suitably used for polymerization accompanied by formation of addition polymer particles. The modified particles of the present invention are useful as addition polymerization catalyst components (especially olefin polymerization catalyst components). Specific examples of the addition polymerization catalyst of the present invention include the above-mentioned modified particles (A) and the addition polymerization obtained by bringing the Group 3-11 or lanthanoid series transition metal compound (B) into contact with each other. And addition polymerization obtained by contacting the modified particles (A), a group 3-11 or lanthanoid series transition metal compound (B), and an organoaluminum compound (C). The latter is preferred because the latter is more active.
Hereinafter, these addition polymerization catalysts will be described in more detail.

(B) Group 3-11 or lanthanoid series transition metal compound Group 3-11 or lanthanoid series transition metal compound (B) used in the addition polymerization catalyst of the present invention is a transition metal forming a single site catalyst. Group 3-11 or lanthanoid series transitions that exhibit addition polymerization activity by using a compound and using the modified particles (A) (or further organoaluminum compound (C)) as a promoter component for activation If it is a metal compound, there will be no restriction | limiting in particular. In addition, the single site catalyst here is a concept distinguished from the conventional solid catalyst, and in the case of copolymerization, not only a single site catalyst in a narrow sense that can provide an addition polymer having a narrow molecular weight distribution and a narrow composition distribution. In addition, a catalyst obtained by an adjustment method similar to such a single-site catalyst in a narrow sense includes an addition polymer having a broad molecular weight distribution and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization. .

The transition metal compound (B) is preferably a transition metal compound represented by the following general formula [6] or a μ-oxo type transition metal compound dimer thereof.
L ² _a M ² X _b [6]
(In the formula, M ² is a transition metal atom of Groups 3 to 11 of the periodic table or a lanthanoid series. L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² May be linked directly or through a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X is a halogen atom, a hydrocarbon group (provided that the cyclopentadiene anion (Excluding a group having a skeleton), or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.

In the general formula [6], M ² is a transition metal atom of Group 3 to 11 of the periodic table (IUPAC 1989) or a lanthanoid series. Specific examples include scandium atoms, yttrium atoms, titanium atoms, zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, iron atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms. , Samarium atoms, ytterbium atoms, and the like. M ² in the general formula [6] is preferably a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, particularly preferably a titanium atom, zirconium atom or hafnium atom. is there.

In the general formula [6], L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² may be the same or different. A plurality of L ² may be linked directly or through a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl Group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methylcyclopentadienyl Group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ Tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-5-Mechiruinde} Nyl group, η ⁵ -6-methylindenyl group, η ⁵ -7-methylindenyl group, η ⁵ -2-tert-butylindenyl group, η ⁵ -3-tert-butylindenyl group, η ^5- 4-tert-butyl indenyl group, η ⁵ -5-tert-butyl indenyl group, η ⁵ -6-tert-butyl indenyl group, η ⁵ -7-tert-butyl indenyl group, η ⁵ -2, 3-dimethyl-indenyl group, eta ^{5-4,7-dimethyl-indenyl} group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ⁵ - 4,5 benzindenyl group, eta ^5-2-methyl - , 5-benzindenyl group, eta ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^5-2-methyl 4-naphthyl indenyl group, eta ⁵ - fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl fluorenyl groups, and their substitution products Is mentioned.
In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, and an alkyl group. Amino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic heterocyclic group having an oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom in the ring Is preferred.

  Specific examples of groups containing heteroatoms include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethyl. Phenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6 -Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5 -Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophene Xy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, Diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4- Isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2 ′ -Dihydroxy-6,6'-dimethylbiphenyl group, 4,4 ', 6,6'-te La -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.

Moreover, as group containing the said hetero atom, group represented by following General formula [7] can also be illustrated.
R ₃ P = N− [7]
(Wherein R represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, they may be the same or different from each other, and two or more of them may be bonded to each other, May be formed.)

  Specific examples of R in the general formula [5] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert. Examples include, but are not limited to, -butyl group, cyclopropyl group, cyclobutyl group, cycloheptyl group, cyclohexyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, benzyl group and the like.

（式中、Ｒはそれぞれの場合に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、それらは互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。）Further, examples of the group containing a hetero atom include a group represented by the following general formula [8].

(Wherein R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group in each case, and they may be the same or different from each other. Or two or more of them may be bonded to each other or may form a ring.)

  Specific examples of R in the general formula [8] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2, 6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group , Triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group, etc., but are not limited thereto. Absent.

  The chelating ligand refers to a ligand having a plurality of coordination sites. Specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, Porphyrin, crown ether, cryptate and the like can be mentioned.

  Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, preferably a pyridyl group.

A group having a cyclopentadiene type anion skeleton, a group having a cyclopentadiene type anion skeleton and a group containing a hetero atom, or a group containing a hetero atom may be directly connected to each other, such as a carbon atom, silicon It may be linked via a residue containing an atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Such a residue is preferably a divalent residue in which the atoms bonded to two L ² are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 one of L ² and the atoms connecting the carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, the minimum number of atoms between the atoms connecting the two L ² is a divalent of 3 or less Residue (this includes the case where there is a single atom bound to two L ² ). Specifically, an alkylene group such as an ethylene group or a propylene group, a substituted alkylene group such as a dimethylmethylene group or a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisylylene group. Or a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, particularly preferably a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene. It is a group.

  X in the general formula [6] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, and an aryl group, and preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 6 to 20 carbon atoms. Are preferred.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples include perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group, perbromopropyl group, and the like.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3 , 5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4) 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, ( Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. More preferred is a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl group Nyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group More preferred is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

  The hydrocarbon oxy group herein includes an alkoxy group, an aralkyloxy group, an aryloxy group, and the like, and preferably an alkoxy group having 1 to 20 carbon atoms, a dearalkyloxy group having 7 to 20 carbon atoms, or a carbon atom. A number 6 to 20 aryloxy group is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and a neopentoxy group. , N-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, etc., more preferably methoxy group, ethoxy group, isopropoxy group, or tert-butoxy group. .
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Phenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. More preferably, it is a benzyloxy group.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl -4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Phenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di -Tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3 , 4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, Anthracenoxy group etc. are mentioned.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

  X is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, trifluoromethoxy. Group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-penta A fluorophenylphenoxy group or a benzyl group;

  In the general formula [6], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M.

  Among the transition metal compounds represented by the general formula [6], specific examples of the compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclohexane). Pentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (n-butylmethylcyclo) Pentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indeni ) Titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride, bis [2- (bis-3,5- Trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4 -Methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride,

Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride, pentamethylcyclopentadienyl (indenyl) ) Titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindenyl) titanium dichloride,

Ethylenebis (cyclopentadienyl) titanium dichloride, ethylenebis (2-methylcyclopentadienyl) titanium dichloride, ethylenebis (3-methylcyclopentadienyl) titanium dichloride, ethylenebis (2-n-butylcyclopentadi) Enyl) titanium dichloride, ethylenebis (3-n-butylcyclopentadienyl) titanium dichloride, ethylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) Titanium dichloride, ethylene bis (2,5-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (3,4-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,3-ethylmethylcyclopentadiene) L) Titanium dichloride, ethylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylene bis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylene bis (3,5-ethylmethylcyclopenta) Dienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (tetramethylcyclopentadi) Enyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-phenylindenyl) titanium dichloride, ethylenebi (Fluorenyl) titanium dichloride,

Ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentadienyl) (indenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (n-butyl) Cyclopentadienyl) (indenyl) dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) titanium Dichloride, ethylene (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride Id, ethylene (tetramethyl cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (indenyl) (fluorenyl) titanium dichloride,

Isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (2-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-n- Butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, isopropylidenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, isopropylidenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropyl Piridenbisu (4,5,6,7-tetrahydroindenyl) titanium dichloride, isopropylidene-bis (2-phenyl indenyl) titanium dichloride, isopropylidene-bis (fluorenyl) titanium dichloride,

Isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (N-butylcyclopentadienyl) (indenyl) dichloride, isopropylidene (tetramethylcyclopentadienyl) (indenyl) dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadi) Enyl) (fluorenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylide (Tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (indenyl) titanium dichloride, dimethyl Shirirenbisu (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl Down (indenyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride,

Cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride , Cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) ) Titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) titanium dichloride, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl ( , 6-diisopropylphenyl) titanium dichloride,

Methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl- 5-methoxy-2-fu Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadi Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) ( -tert- butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) ) Tandichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5- Chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methyl (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) ) Titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) Tandichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl -2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) ( -tert- butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopente) Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Id, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2) -Phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3 Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5- Til-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3 Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) ( 3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenyl) Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethyle (Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) Tandichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadi) Nyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethyl Ril-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadi) Nyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dilaenylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-methyl) Carboxymethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- - phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Rushiriren (tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Rushiriren (trimethylsilyl cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride ,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dimethyl, (tert-Butylamide) tetramethylcyclo Pentadienyl-1,2-ethanediyltitanium dibenzyl, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium Dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dimethyl, (tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl, ( Benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl,

(Tert-Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-Butylamido) indenyl-1,2-ethanediyltitanium dimethyl, (tert-Butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (Tert-Butylamide) tetrahydroindenyl-1,2-ethanediyltitanium dimethyl, (tert-Butylamide) fluorenyl-1,2-ethanediyltitanium dichloride, (tert-Butylamido) fluorenyl-1,2-ethanediyltitanium dimethyl,
(Tert-Butylamide) indenyldimethylsilane titanium dichloride, (tert-Butylamide) indenyldimethylsilane titanium dimethyl, (tert-Butylamido) tetrahydroindenyldimethylsilane titanium dichloride, (tert-Butylamide) tetrahydroindenyldimethylsilane titanium dimethyl, (Tert-Butylamide) fluorenyldimethylsilane titanium dichloride, (tert-Butylamide) fluorenyldimethylsilane titanium dimethyl,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride , (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride,
(B-dimethylaminoborabenzene) cyclopentadienylzirconium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) zirconium dichloride,

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride,

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride, [bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis ( tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1 , 3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] titanium dichloride,
[Bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [Bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [Bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [Bis (tert-butyldimethylsilyl) naphthalenediamide ] Titanium dibromide,

[Hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium triiodide, [ Hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-diethylpyrazolyl) borate] titanium triiodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-di-t rt-butylpyrazolyl) borate] titanium triiodide, [tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-dimethylpyrazolyl) methyl] titanium tribromide, [tris (3,5 -Dimethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium tribromide, [tris (3,5- Diethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium tribromide, [Tris (3,5-di-tert-butyl (Lupyrazolyl) methyl] titanium triiodide and the like, compounds obtained by changing titanium of these compounds to zirconium or hafnium, (2-phenoxy) to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy) Or a compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), a compound changed from dimethylsilylene to diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride to difluoride, dibromide, diiodide, dimethyl, diethyl, Diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), di (n-butoxide), di (trifluoromethoxide), diphenoxide, di (2, 6-di-tert-butylphenoxide), di (3,4,5-trifluorophenoxide), di (pentafluorophenoxide), or di (2,3,5,6-tetrafluoro-4-pentafluoro) Examples thereof include compounds changed to phenylphenoxide).

  Among the transition metal compounds represented by the general formula [6], specific examples of the compound in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Dimethyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5, 5'-diethyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5'-di-n-propyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl- , 5′-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diisopropyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R ) -4-phenyl-5,5′-diisopropyloxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5′-dicyclohexyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dicyclohexyloxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethoxyoxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethoxy Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5, 5′-diethoxyoxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5′-diphenyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diphenyloxazoline] nickel Dibromide, methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3- Methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5 -Di- (2-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5 , 5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,
Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclobutane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclopentane}] nickel dibromide , Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel di bromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline] nickeldi Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5, -Di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,3'-methylenebis [(4R) -4-isopropyl-5,5- Di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibro Ido,
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] nickel dibromide 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5- Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl- 5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Sobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel Dibromide,
2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyl Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel di Romide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- tert-butyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) ) Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [( 4R) -4-tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebi [(4R) -4-tert-butyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5 , 1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [Spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1 ′ -Cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Id, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline- 5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-phenyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzene Dil-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Id, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline- 5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-benzyloxazoline-5,1'-cycloheptane}] nickel dibromide, and enantiomers of the above compounds. In addition, a compound in which the configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline type compound is reversed, or dibromide of these compounds is converted to dichloride, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide. , Di (n-propoxide), di (isopropoxide), di (n-butoxide), di (trifluoromethoxide), diphenoxide, di (2,6-di-tert-butylphenoxide), di ( Examples thereof include compounds changed to 3,4,5-trifluorophenoxide), di (pentafluorophenoxide), or di (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide). .

Specific examples of the nickel compound include [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-dimethylpyrazolyl) borate. ] Nickel iodide, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickelethyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel allyl, [Hydrotris (3,5-dimethylpyrazolyl) borate] nickel methallyl,
[Hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-diethylpyrazolyl) borate] nickel iodide, [hydrotris (3 , 5-diethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickelethyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickel allyl, [hydrotris (3,5-diethylpyrazolyl) ) Borate] nickel methallyl,
[Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-di-tert-butyl) Pyrazolyl) borate] nickel iodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickelmethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickelethyl, [hydrotris (3 , 5-di-tert-butylpyrazolyl) borate] nickel allyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel methallyl,

（式中、Ｒ⁷とＲ⁸はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｘ、Ｒ⁹およびＲ¹⁰は下記の表１に表わされる置換基の組み合わせのいずれかである。）

また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。Examples include compounds represented by the following structural formulas.

(Wherein R ⁷ and R ⁸ are each a 2,6-diisopropylphenyl group, and X, R ⁹ and R ¹⁰ are any combination of substituents shown in Table 1 below.)

In addition, in the above nickel compound, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium can be exemplified as well.

Among the transition metal compounds represented by the general formula [6], specific examples of compounds in which the transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine. Iron dichloride, 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron Dichloride,
[Hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-dimethylpyrazolyl) borate] iron iodide, [hydrotris (3,3 5-dimethylpyrazolyl) borate] methyl iron, [hydrotris (3,5-dimethylpyrazolyl) borate] ethyl iron, [hydrotris (3,5-dimethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-dimethylpyrazolyl) Borate] iron metalyl,
[Hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-diethylpyrazolyl) borate] iron iodide, [hydrotris (3,3 5-diethylpyrazolyl) borate] methyl iron, [hydrotris (3,5-diethylpyrazolyl) borate] ethyl ethyl, [hydrotris (3,5-diethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-diethylpyrazolyl) Borate] iron metalyl,
[Hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3,5-di-tert-butyl) Pyrazolyl) borate] iron iodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] methyl methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] ethyl ethyl, [hydrotris (3 5-di-tert-butylpyrazolyl) borate] iron allyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methallyl, and the like.
In addition, in the above iron compound, a compound in which iron is replaced with cobalt or nickel can also be exemplified.

Specific examples of the transition metal compound of the transition metal compound represented by the general formula [6] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopuropiriden (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride],
μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride ], Μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2- Phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methyl-2- Phenoxy) titanium chloride], and the like. Further, the chlorides of these compounds are fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, trifluoromethoxide, phenoxide, 2, Illustrate compounds such as 6-di-tert-butylphenoxide, 3,4,5-trifluorophenoxide, pentafluorophenoxide, or 2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide Can do.

  In addition to the transition metal compound represented by the general formula [6] and the μ-oxo type transition metal compound exemplified above, a compound used as the transition metal compound (B) is exemplified. As compounds that are nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, nickel cyanide, nickel oxalate, nickel acetylacetonate, bis (allyl) Nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis ( Triethylphosph Nickel), diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] Nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenylphosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, nickel Examples include phthalocyanine.

Similarly, specific examples of the compound in which the transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride and the like.
Specific examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
Specific examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

  These transition metal compounds may be used alone or in combination of two or more.

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above general formula [6]. Among these, a transition metal compound in which M ² in the general formula [6] is a Group 4 atom is preferable, and in particular, a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton as L ² in the general formula [6]. Is preferred.

(C) Organoaluminum compound As the organoaluminum compound (C) used in the addition polymerization catalyst of the present invention, a known organoaluminum compound can be used. An organoaluminum compound represented by the following general formula [9] is preferable.
R ⁴ _c AlY _3-c [9]
(Wherein R ⁴ represents a hydrocarbon group, and all R ⁴ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group; All Y may be the same or different, and c represents a number satisfying 0 <c ≦ 3.)

R ⁴ in the general formula [9] representing the organoaluminum compound is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a normal octyl group, and the like, preferably an ethyl group, a normal butyl group, and an isobutyl group. A group, a normal hexyl group or a normal octyl group.

Specific examples when Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
The alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms, and specific examples include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, t -Butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadexoxy group, n-icosoxy group, etc., preferably methoxy group, ethoxy group or t -Butoxy group.

  The aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms. Specific examples thereof include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3 -Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5 -Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group N-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

  The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Specific examples include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6- Limethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group , Anthracenylmethoxy group and the like, preferably a benzyloxy group That.

  Specific examples of the organoaluminum compound represented by the general formula [9] include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum and the like. Dimethylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride , Alkyl aluminum dichlorides such as normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride, etc. Dialkylaluminum hydrides; trialkoxynalminiums such as trimethoxyaluminum, triethoxyaluminum and tri (t-butoxy) aluminum; alkyls such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum and methyl (di-t-butoxy) aluminum (The (Lucoxy) aluminum; Dialkyl (alkoxy) aluminum such as dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2, Triaryloxyaluminum such as 6-diphenylphenoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (Phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2,6-diphenylphenoxy) Ii) Dialkyl (aryloxy) aluminum such as aluminum can be exemplified.

Of these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum or trinormaloctylaluminum is particularly preferable, and triisobutylaluminum or trialkylaluminum is particularly preferable. Normal octyl aluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

The usage-amount of a component (B) is 1 * 10 < ^-6 > -1 * 10 < ^-3 > mol normally with respect to 1g of a component (A), Preferably it is 5 * 10 < ^-6 > -5 * 10 <^-4> mol. Moreover, the usage-amount of a component (C) is 0.01-10 as molar ratio (C) / (B) of the aluminum atom of a component (C) organoaluminum compound with respect to the transition metal atom of a component (B) transition metal compound. 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by bringing the component (A) and the component (B), and optionally the component (C) into contact with each other in advance may be used. It may be used after being put in. When the components (A), (B) and (C) are used, any two of them may be contacted in advance, and then the other component may be contacted.

  The method for supplying each catalyst component to the reactor is not particularly limited. A method of supplying each component in a solid state, a method of supplying a solution dissolved in a hydrocarbon solvent from which components for deactivating catalyst components such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state Etc.

  When supplying each catalyst component in a solution state or in a suspended or slurried state, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of the component (C) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atoms. The concentration of the component (B) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter in terms of transition metal atoms.

  The polymerization method is not particularly limited, and gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, or halogenated hydrocarbon solvents such as methylene chloride. It is also possible to use olefin itself as a solvent (bulk polymerization). The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

The present invention is particularly suitably applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.).
The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. A preferred polymerization method in the slurry process is a continuous reactor in which monomers (and comonomers), feeds, diluents, etc. are continuously added as required, and the polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor, a plurality of stirred reactors having different reactors or different reaction conditions in series or in parallel, or a combination thereof.

  As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature in the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably from 30 ° C to 100 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. A pressure can be applied to maintain the catalyst in suspension, maintain the medium and at least some of the monomer and comonomer in a liquid phase, and allow the monomer and comonomer to contact. Accordingly, the medium, temperature, and pressure may be selected such that the addition polymer is produced as solid particles and recovered in that form.

The molecular weight of the addition polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and monomer (and comonomer) to the reaction zone, a method of adding them sequentially, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction apparatus, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even in a reactor equipped with a stirring blade in the reaction vessel.
As a method for supplying each component to the polymerization tank, a solution or a slurry is usually supplied using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in the absence of moisture, or dissolved or diluted in a solvent. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

  As polymerization conditions, the temperature is less than the temperature at which the polymer melts, preferably 0 ° C. to 150 ° C., particularly preferably 30 ° C. to 100 ° C. Furthermore, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In the polymerization, an inert gas may coexist in the mixed gas.

  In the present invention, the prepolymerization described below may be performed before such polymerization (main polymerization).

  The prepolymerization is carried out by supplying a small amount of olefin in the presence of the modified particles (A) and the transition metal compound (B) or further in the presence of the organoaluminum compound (C). It is preferable to do so. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound (C) used during the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per mol of the transition metal compound (B), preferably 0.8 to 500 mol, 1 to 200 mol is particularly preferred.

  The amount of the prepolymerized olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the modified particles.

  The slurry concentration at the time of prepolymerization is preferably 0.1 to 50 g-modified particle / liter-solvent, particularly 0.5 to 20 g-modified particle / liter-solvent is preferable. . The prepolymerization temperature is preferably -20 ° C to 100 ° C, particularly preferably 0 ° C to 80 ° C. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is preferably 0.001 MPa to 2 MPa, and particularly preferably 0.01 MPa to 1 MPa. For olefins that are liquid at the prepolymerization pressure and temperature, Not as long. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

  As a method of supplying the modified particles (A), the transition metal compound (B), the organoaluminum compound (C), and the olefin, when the prepolymerization is performed, the modified particles (A) And a transition metal compound (B), or a method of supplying an olefin after contact with an organoaluminum compound (C), if necessary, the above modified particles ( A), a method of supplying an organoaluminum compound (C) after contacting a transition metal compound (B) and an olefin, an organoaluminum compound (C) and a transition metal compound (B) in the presence of an olefin After contacting, any method such as a method of supplying the modified particles (A) may be used, but the modified particles (A) and the organoaluminum compound (C) are combined. Contact It is preferable that the olefin is present in advance when to. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  In the present invention, the prepolymerized product is used as a catalyst component or a catalyst. The prepolymerized catalyst component according to the present invention is obtained in the presence of a primary catalyst obtained by bringing the modified particles (A) and the Group 3-11 or lanthanoid series transition metal compound (B) into contact with each other. In addition, a prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin, or the above modified particles (A), a group 3-11 or lanthanoid series transition metal compound (B), and organic It is a prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the aluminum compound (C). Further, the prepolymerized catalyst according to the present invention is the presence of a primary catalyst obtained by contacting the modified particles (A) and a group 3-11 or lanthanoid series transition metal compound (B). In addition, a catalyst for addition polymerization obtained by prepolymerization of olefin, or the above modified particles (A), group 3-11 or lanthanoid series transition metal compounds (B), and organoaluminum compounds (C ) Is a catalyst for addition polymerization obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained. The catalyst using the prepolymerized addition polymerization catalyst component according to the present invention is an addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C).

Examples of the monomer used for polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like, and two or more monomers can be used at the same time.
Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Olefins such as 1-decene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2 -Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphth Diolefins such as len, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5- Ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8 -Ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbo Cyclic olefins such as nene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene Alkenylbenzene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3 , 4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-5-ethyl styrene, p-practical tertiary butyl styrene, p-secondary butyl styrene and other alkyl styrenes, divinyl benzene and other bisalkenyl benzenes, Alkene such as alkenylnaphthalene such as 1-vinylnaphthalene Nyl aromatic hydrocarbons; α, β such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid -Unsaturated carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic acid Such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, α, β-unsaturated carboxylic acid esters, maleic acid, itaconic acid, etc. Unsaturated dicarboxylic acid, vinyl acetate, vinyl propionate, capro Polar monomers such as vinyl esters such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Is mentioned.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, and propylene and 1-butene. It should not be limited to these.

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is preferably used in a method for producing an olefin polymer. Such an olefin polymer is particularly preferably a copolymer of ethylene and an α-olefin, and among them, a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is preferable. The α-olefin herein is preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 1-octene and the like.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. The measured value of each item in an Example was measured with the following method.

(1) Elemental analysis Zn: The sample was poured into a sulfuric acid aqueous solution (1M), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
F: Combustion gas generated by burning a sample in a flask filled with oxygen was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified using an ion electrode method.

(2) Wide-angle X-ray measurement After putting the cell which stuck the sample and the Kapton film into the nitrogen bag, nitrogen substitution was carried out. After the sample was packed in the cell, it was sealed and the cell was taken out and attached to the X-ray measurement apparatus. Wide-angle X-ray measurement was performed as follows.
X-ray diffractometer: Vertical rotor flex ultraX18 (manufactured by Rigaku Corporation)
Load: 50kV-100mA
Focus: Line Scan mode: 2θ / θ (2 ° / min.)
Measuring range: 5 ° ~ 70 °
Slit: Divergence slit 1 °
Receiving slit 0.15mm
Scatter slit 1 °
Detector: Scintillation counter Monochromator: Graphite

(3) XAFS measurement method {circle around (1)} Preparation of measurement sample (i) The central part of the polyester sheet was cut out and a Kapton film was attached.
(Ii) The polyester sheet which cut out and removed the center part similarly on this was affixed.
(Iii) A sample was spread over the cut out portion.
(Iv) A sample obtained by pasting a Kapton film on a polyester sheet obtained by cutting out the central portion from the top was pasted to obtain a measurement sample.
Of the above operations, (iii) and (iv) were performed in a nitrogen gas atmosphere.

(2) Measurement The X-AFS measurement of the K absorption edge of Zn atoms in the sample was carried out with the XAFS measurement apparatus of the beam line 10B (BL-10B) of the Synchrotron Radiation Research Facility, Institute for Materials Structure Science, High Energy Accelerator Research Organization. Si (311) channel cut crystal is used, incident X-ray intensity (I0) is 17 cm ion chamber using nitrogen as detection gas, and transmission X-ray intensity (It) is 50% nitrogen and 50% argon in detection gas. Using a 31 cm ion chamber using a mixed gas of The measurement area, measurement point interval, and integration time per measurement point are set as follows.

・ Accumulation of incident X-ray energy (E) from 9160 eV to 9610 eV at intervals of 6.43 eV for 1 second each point (number of measurement points is 70 points)
・ Integrated X-ray energy (E) from 9610 eV to 9760 eV at 1 eV intervals for 1 second each point (number of measurement points is 150)
・ A section where incident X-ray energy (E) is from 9760eV to 10160eV is integrated for 2 seconds at 2.5eV intervals (160 measurement points)
-Integration of incident X-ray energy (E) from 10160 eV to 10760 eV for 2 seconds at 6 eV intervals (number of measurement points is 101 points). The energy calibration is performed by setting the angle of the spectroscopic crystal to 24.934 degrees at the position of the energy value (8980.3 eV) of the pre-edge peak appearing in the X-ray absorption near-edge structure (XANES) spectrum of the K absorption edge of metallic copper. Went as.

EXAFS Analysis Method The K absorption edge energy E0 of Zn atoms in the sample was 9663 eV. Note that E0 is an energy value at which the first-order differential coefficient is maximum in the XANES spectrum.
Back determined by applying the Victorien equation (Aλ ³ −Bλ ⁴ + C; λ is the wavelength of the incident X-ray, A, B, and C are arbitrary constants) to the absorption coefficient in the energy range lower than the absorption edge by the least square method. The ground was subtracted, and then the absorbance of isolated atoms was estimated by the weighted Cubic Spline method, and the EXAFS function χ (k) was extracted. Note that k is a photoelectron wave number defined by 0.5123 × (E−E0) ^1/2 , and the unit of k at this time is ⁻¹ .
Finally, EXAFS function weighted by k ³ k ³ χ a (k), k is called for radial distribution function with the Fourier transform in the range 15.7A ^-1 from 2.5 Å ^-1. A Hanning function was used as the window function for Fourier transform, and 0.05Å- ¹ was used as the window width.

(4) The content of the repeating unit derived from α-olefin in the copolymer is a calibration curve from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation). And expressed as the number of short chain branches per 1000 carbon atoms (SCB).

(5) Melt flow rate = MFR: Melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) according to the method defined in JIS K7210-1995 (unit: g / 10 minutes) .

(6) Swell ratio = SR: A value obtained by dividing the strand diameter obtained at the time of MFR measurement by the die inner diameter of 2.095 mm.

(7) Melt flow rate ratio = MFRR: According to the method defined in JIS K7210-1995, the melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) was calculated as a load of 21.18 N (2. It is a value divided by the melt flow rate value (MFR) measured at 16 kg).
For all the melt flow rate measurements, a polymer containing 1000 ppm of an antioxidant in advance was used.

[Example 1]
(1) Synthesis of contact product (e) In a 5-liter four-necked flask purged with nitrogen, 1.5 liters of tetrahydrofuran and 1.35 liters of diethylzinc hexane solution (2.00 M) (2.7 mol) were placed. Cooled in an ice bath. A solution prepared by dissolving 199.8 g (1.09 mol) of pentafluorophenol in 340 ml of tetrahydrofuran was added dropwise thereto over 65 minutes. It stirred for 1 hour after completion | finish of dripping. The temperature was raised to 45 ° C. in 0.5 hours, and stirring was performed at the same temperature for 1 hour. The temperature was lowered to 20 ° C. in a water bath, and 45.09 g (2.51 mol) of H ₂ O was added dropwise over 1.5 hours. Then, after stirring at 20 ° C. for 1 hour, the temperature was raised to 45 ° C. and stirred at the same temperature for 1 hour. After cooling to room temperature, volatile components were distilled off, and drying was performed at 120 ° C. under reduced pressure for 8 hours. As a result, 425.5 g of a solid product was obtained.

(2) Synthesis of component (A) 3 liters of tetrahydrofuran was added to the flask of the above (1) and stirred. This was charged with 327.4 g of silica (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.61 ml / g; specific surface area = 296 m ² / g) heated at 300 ° C. under nitrogen flow. After heating to 40 ° C. and stirring for 2 hours, the solid component was allowed to settle and then filtered. As a washing operation, 3 liters of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and then filtered. The above washing operation was repeated 5 times in total. The component (A) 510.0g was obtained by drying at 120 degreeC under pressure reduction for 8 hours. As a result of elemental analysis, Zn = 2.5 mmol / g and F = 2.4 mmol / g. Therefore, F / Zn = 0.96 (molar ratio). In addition, as a result of wide-angle X-ray measurement, the integrated intensity of the halo that shows the apex from the Bragg angle (2θ) 33 ° to 37 ° in the diffraction intensity profile is A, and the halo that shows the apex from the Bragg angle (2θ) 18 ° to 22 °. The A / B calculated with the integrated intensity as B was 0.274.

(3) Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.012 MPa, 700 g of butane and 50 g of 1-butene. The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.45 mol%. To this, 0.9 ml of a heptane solution of triisobutylaluminum having a concentration adjusted to 1 mmol / ml was added. Next, 14.3 mg of the component (A) obtained in the above (2) was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding an ethylene / hydrogen mixed gas (hydrogen 0.2 vol%) so as to keep the total pressure constant. As a result, 77.4 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Example 1 (2) above) was 5,410 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 15.5, MFR = 0.35, MFRR = 118, SR = 1.15.

[Example 2]
(1) Synthesis of contact product (e) 106 ml of tetrahydrofuran and 40 ml (80 mmol) of hexane solution (2.0 M) of diethylzinc were placed in a nitrogen-substituted 300 ml four-necked flask and cooled in a water bath. To this, 14.5 ml (32.0 mmol) of a tetrahydrofuran solution (2.21 M) of pentafluorophenol was added dropwise over 50 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Thereafter, the temperature was raised to 20 ° C., and 8.9 ml (88.1 mmol) of a tetrahydrofuran solution (9.9 M) of H ₂ O was added dropwise over 1 hour. Then, after stirring for 2 hours, it left still at room temperature for 15.3 hours. This was refluxed at 63 ° C. and then cooled to room temperature to obtain 146 ml of a yellow solution.

(2) Synthesis of component (A) Silica (Dyson SYLOPOL 948; average particle size = 55 μm; pore volume = 1.66 ml) heat treated at 300 ° C. under nitrogen flow in a nitrogen-substituted 50 ml four-necked flask / G; 3.12 g of specific surface area = 309 m ² / g) was added, and 50 ml of the yellow solution synthesized in Example 2 (1) was added. After heating to 40 ° C. and stirring for 2 hours, the solid component was precipitated and filtered. As a washing operation, 30 ml of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and filtered. The above washing operation was repeated 5 times in total. By drying at 120 ° C. for 8 hours under reduced pressure, 5.60 g of component (A) was obtained. As a result of elemental analysis, Zn = 3.7 mmol / g and F = 4.1 mmol / g. Therefore, F / Zn = 1.1 (molar ratio). As a result of the wide-angle X-ray measurement, the integrated intensity of the halo showing the apex from the Bragg angle (2θ) 33 ° to 37 ° in the diffraction intensity profile is A, and the integrated intensity of the halo showing the apex from the Bragg angle (2θ) 18 ° to 22 °. A / B calculated as B was 0.696. As a result of EXAFS analysis, the peak intensity C of the maximum peak in the range of 1 to 2 nm in the radial distribution function obtained by Fourier transform is 14.2 and the maximum peak in the range of 2.5 to 3.5 nm. The peak intensity D was 10.1 and the peak intensity ratio D / C = 0.71.

(3) Polymerization The solid catalyst component was changed to 14.6 mg of the component (A) obtained in (2) above, and the hydrogen concentration of the ethylene / hydrogen mixed gas to keep the total pressure of the autoclave constant was changed to 0.199 vol%. Except that described above, the same procedure as in Example 1 (3) was performed. As a result, 72.3 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Example 2 (2) above) was 5,320 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 15.5, MFR = 1.57, MFRR = 58.2, SR = 1.30.

[Example 3]
(1) Synthesis of contact product (e) In a 5-liter four-necked flask purged with nitrogen, 1.5 liters of tetrahydrofuran and 1.35 liters of diethylzinc hexane solution (2.00 M) (2.7 mol) were placed. Cooled in an ice bath. A solution prepared by dissolving 197.3 g (1.07 mol) of pentafluorophenol in 380 ml of tetrahydrofuran was added dropwise thereto over 65 minutes. It stirred for 1 hour after completion | finish of dripping. The temperature was raised to 45 ° C. in 0.5 hours, and the mixture was stirred at the same temperature for 1 hour. The temperature was lowered to 20 ° C. in a water bath, and 44.0 g (2.44 mol) of H ₂ O was added dropwise over 1.5 hours. Then, after stirring at 20 ° C. for 1 hour, the temperature was raised to 45 ° C. and stirred at the same temperature for 1 hour. After cooling to room temperature, volatile components were distilled off, and drying was performed at 120 ° C. under reduced pressure for 8 hours. As a result, 423.3 g of a solid product was obtained.

(2) Synthesis of component (A) 3 liters of tetrahydrofuran was added to the flask of the above (1) and stirred. Thereto was added 324.6 g of silica (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.61 ml / g; specific surface area = 296 m ² / g) manufactured at 300 ° C. under a nitrogen flow. After heating to 40 ° C. and stirring for 2 hours, the solid component was allowed to settle and then filtered. As a washing operation, 3 liters of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and then filtered. The above washing operation was repeated 5 times in total. By drying at 120 ° C. for 8 hours under reduced pressure, 515.6 g of component (A) was obtained. As a result of elemental analysis, they were Zn = 2.6 mmol / g and F = 3.2 mmol / g. Therefore, F / Zn = 1.2 (molar ratio). As a result of the EXAFS analysis, the peak intensity C of the maximum peak in the range of 1 to 2 nm in the radial distribution function obtained by Fourier transform is 13.3, the peak of the maximum peak in the range of 2.5 to 3.5 nm The intensity D was 8.51 and the peak intensity ratio D / C = 0.64.

(3) Polymerization The solid catalyst component was changed to 13.1 mg of the component (A) obtained in (2) above, and the hydrogen concentration of the ethylene / hydrogen mixed gas to keep the total pressure of the autoclave constant was changed to 0.199 vol%. Except that described above, the same procedure as in Example 1 (3) was performed. As a result, 71.5 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Example 3 (2) above) was 5,460 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 14.3, MFR = 0.13, MFRR = 126, SR = 1.10.

[Comparative Example 1]
(1) Synthesis of contact product (e) In a 200 ml four-necked flask purged with nitrogen, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of a diethylzinc hexane solution (2.00 M) were placed and cooled with greed. To this, 17.2 ml (40 mmol) of pentafluorophenol in tetrahydrofuran (2.33 M) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred for 2.6 hours. The temperature was raised to 20 ° C., and 1.08 ml (60 mmol) of H ₂ O was added dropwise over 2 hours. Then, after stirring at room temperature for 3.2 hours, volatile components were distilled off, and drying was performed at 120 ° C. under reduced pressure for 8 hours. As a result, 14.2 g of a solid product was obtained.

(2) Synthesis of Component (A) To a 50 ml four-necked flask purged with nitrogen, 4.34 g of the solid product obtained in (1) above and 30 ml of tetrahydrofuran were added and stirred. To this, 2.87 g of heat-treated silica in the same lot as used in Example 2 was added, the temperature was raised to 40 ° C., and the mixture was stirred at the same temperature for 2 hours. Thereafter, the solid component was precipitated and filtered. As a washing operation, 30 ml of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and filtered. The above washing operation was repeated 5 times in total. By drying at 120 ° C. for 8 hours under reduced pressure, 3.21 g of the component (A) was obtained. As a result of elemental analysis, Zn = 1.5 mmol / g and F = 2.5 mmol / g. Therefore, F / Zn = 1.7 (molar ratio). As a result of wide-angle X-ray measurement, A / B was 0.034. As a result of EXAFS analysis, the peak intensity C was 13.2, the peak intensity D was 4.76, and the peak intensity ratio D / C = 0.36.

(3) Polymerization The solid catalyst component was changed to 15.1 mg of the component (A) obtained in (2) above, and the hydrogen concentration of the ethylene / hydrogen mixed gas to keep the total pressure of the autoclave constant was changed to 0.187 vol%. Except that described above, the same procedure as in Example 1 (3) was performed. As a result, 25.7 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Comparative Example 1 (2) above) was 1,700 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 14.6, MFR = 0.17, MFRR = 116, SR = 1.10.

[Comparative Example 2]
(1) Synthesis of contact (e) 100 ml of tetrahydrofuran and 39.6 ml (80 mmol) of diethylzinc in hexane (2.02 M) were placed in a nitrogen-substituted 300 ml four-necked flask and cooled in an ice bath. To this, 14.5 ml (32.0 mmol) of a tetrahydrofuran solution (2.21 M) of pentafluorophenol was added dropwise over 50 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Thereafter, the temperature was raised to 20 ° C., and 9.7 ml (96.0 mmol) of H ₂ O in tetrahydrofuran (9.9 M) was added dropwise over 1 hour. Then, after stirring for 2 hours, it left still at room temperature for 15.3 hours. This was refluxed at 63 ° C. and then cooled to room temperature to obtain a yellowish white slurry.

(2) Synthesis of Component (A) In a 50 ml four-necked flask purged with nitrogen, 2.88 g of heat-treated silica of the same lot as used in Example 2 was placed, and the yellowish white color synthesized in (1) above 50 ml of the slurry was added. After heating to 40 ° C. and stirring for 2 hours, the solid component was precipitated and filtered. As a washing operation, 30 ml of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and filtered. The above washing operation was repeated 5 times in total. By drying at 120 ° C. for 8 hours under reduced pressure, 3.00 g of component (A) was obtained. As a result of elemental analysis, they were Zn = 2.8 mmol / g and F = 1.9 mmol / g. Therefore, F / Zn = 0.68 (molar ratio). As a result of wide-angle X-ray measurement, A / B was 0.472. As a result of EXAFS analysis, the peak intensity C was 14.0, the peak intensity D was 14.4, and the peak intensity ratio D / C = 1.03.

(3) Polymerization The solid catalyst component was changed to 12.4 mg of the component (A) obtained in (2) above, and the hydrogen concentration of the ethylene / hydrogen mixed gas to keep the total pressure of the autoclave constant was changed to 0.186 vol%. The same procedure as in Example 1 (3) was performed except that. As a result, 29.4 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Comparative Example 2 (2) above) was 2,370 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 14.7, MFR = 1.63, MFRR = 52.1, SR = 1.26.

[Comparative Example 3]
(1) Synthesis of contact product (e) In a 200 ml four-necked flask purged with nitrogen, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of a diethylzinc hexane solution (2.00 M) were placed and cooled with greed. To this, 8.6 ml (20 mmol) of pentafluorophenol in tetrahydrofuran (2.33 M) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred for 2.6 hours. The temperature was raised to 20 ° C., and 1.26 ml (69.9 mmol) of H ₂ O was added dropwise over 2 hours. Thereafter, after stirring at room temperature for 3.2 hours, volatile components were distilled off, and drying was performed at 120 ° C. under reduced pressure for 8 hours to obtain a solid product.

(2) Synthesis of Component (A) To a 50 ml four-necked flask purged with nitrogen, 3.21 g of the solid product obtained in (1) above and 30 ml of tetrahydrofuran were added and stirred. Here, 3.02 g of the same lot of heat-treated silica as used in Example 2 was added, the temperature was raised to 40 ° C., and the mixture was stirred at the same temperature for 2 hours. Thereafter, the solid component was precipitated and filtered. As a washing operation, 30 ml of tetrahydrofuran was added thereto and stirred, and then the solid component was precipitated and filtered. The above washing operation was repeated 5 times in total. By drying at 120 ° C. for 8 hours under reduced pressure, 4.16 g of component (A) was obtained. As a result of elemental analysis, Zn = 2.6 mmol / g and F = 2.2 mmol / g. Therefore, F / Zn = 0.85 (molar ratio). As a result of wide-angle X-ray measurement, A / B = 0.212. As a result of EXAFS analysis, the peak intensity C was 13.1, the peak intensity D was 5.74, and the peak intensity ratio D / C = 0.44.

(3) Polymerization Polymerization was carried out in the same manner as in Example 1 (3) except that the solid catalyst component was changed to 16.3 mg of the component (A) obtained in (2) above. As a result, 20.5 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Comparative Example 3 (2) above) was 1,260 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 12.7, MFR = 0.17, MFRR = 108, SR = 1.10.

Effect of the invention

  As described in detail above, according to the present invention, it is useful for preparing a highly active single-site catalyst suitably applied to polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.). Particles, a carrier and an addition polymerization catalyst component, a highly active addition polymerization catalyst, and an efficient method for producing an addition polymer are provided. Further, according to the present invention, an addition polymerization catalyst that gives an addition polymer having excellent particle properties when applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.). Particles useful for preparation, support and catalyst component for addition polymerization, addition polymer excellent in particle properties when applied to polymerization accompanying formation of addition polymer particles (eg slurry polymerization, gas phase polymerization, bulk polymerization, etc.) And an addition weight excellent in particle properties when applied to polymerization involving formation of addition polymer particles using the addition polymerization catalyst (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) A method for producing a coalescence is also provided.

Claims (11)

Modification used for addition polymerization, obtained by contacting the following (a), (b), (c) and inorganic oxide particles (d), and satisfying the following formula [4] and the following formula [5] Particles.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(Respectively in the general formula [1] ~ [3], M 1 represents a Zn atom, m is .L ¹ representing a 2 represents a hydrocarbon group, be L ¹ is optionally substituted by one or more identical to each other R ¹ represents a halogenated hydrocarbon group, and when a plurality of R ¹ are present, they may be the same or different from each other, and R ² represents a hydrocarbon group or a halogenated hydrocarbon group. Each T independently represents a Group 15 or Group 16 atom of the Periodic Table, and t represents the T valence of each compound.)
N / M> 0.9 [4]
(In the formula, N represents the amount of halogen atoms contained in the modified particles, and M represents the amount of Zn contained in the modified particles.)
A / B ≧ 0.1 [5]
(In the formula, A represents the integrated intensity of a halo whose apex is at a Bragg angle (2θ) of 33 ° to 37 ° in a diffraction intensity profile obtained by wide-angle X-ray measurement, and B represents a Bragg angle (2θ) of 18 ° to 22 (Indicates the integrated intensity of the halo at the apex at °.)
Modification used for addition polymerization, obtained by contacting the following (a), (b), (c) and inorganic oxide particles (d), and satisfying the following formula [4] and the following formula [6] Particles.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(Respectively in the general formula [1] ~ [3], M 1 represents a Zn atom, m is .L ¹ representing a 2 represents a hydrocarbon group, be L ¹ is optionally substituted by one or more identical to each other R ¹ represents a halogenated hydrocarbon group, and when a plurality of R ¹ are present, they may be the same or different from each other, and R ² represents a hydrocarbon group or a halogenated hydrocarbon group. Each T independently represents a Group 15 or Group 16 atom of the Periodic Table, and t represents the T valence of each compound.)
N / M> 0.9 [4]
(In the formula, N represents the amount of halogen atoms contained in the modified particles, and M represents the amount of Zn contained in the modified particles.)
D / C ≧ 0.5 [6]
(In the formula, C represents the peak intensity of the maximum peak in the range of 1 to 2 nm in the radial distribution function obtained by measuring particles modified by the X-ray absorption fine structure analysis method, and D represents the radial diameter. This represents the peak intensity of the maximum peak in the range of 2.5 to 3.5 nm in the distribution function, which is obtained by measuring the modified particles by an X-ray absorption fine structure (XAFS) analysis method. The wide X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of Zn is obtained from the obtained X-ray absorption spectrum, and is obtained by Fourier transform.)
The modified particles according to claim 1 or 2, obtained by bringing the contact (e) obtained by bringing (a), (b) and (c) into contact with the inorganic oxide particles (d). .
The contact product (e) is a contact product obtained by bringing the contact product of (a) and (b) into contact with (c), or the contact product of (a) and (c); and (b) The modified particle according to claim 3, which is a contact product obtained by contacting with.
The modified particles according to any one of claims 1 to 4, wherein the amount of each compound (a), (b), (c) used satisfies the following formulas (1) and (2).
| M−y−2z | ≦ 1 (1)
2 ≦ z / y <3 (2)
(In the above formula (1), m represents 2. Also, in the above formulas (1) and (2), y and z are the amounts of the respective compounds used in (a), (b), and (c), respectively. (Y and z are expressed when the molar ratio is expressed as (a) :( b) :( c) = 1: y: z molar ratio).
A carrier comprising the modified particles according to claim 1.
The modified particles (A) according to any one of claims 1 to 4, and a transition metal compound represented by the following general formula [6] or a μ-oxo type transition metal compound dimer (B) catalyst for addition polymerization obtained by contacting and.

L ² _a M ² X _b [6]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² are directly or carbon atoms. , A silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and at least one of the plurality of L ² is a group having a cyclopentadiene type anion skeleton. X is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), or a hydrocarbon oxy group, a is a number satisfying 0 <a ≦ 8, and b is 0 <b Represents a number satisfying ≦ 8.)

The modified particles (A) according to any one of claims 1 to 4, and a transition metal compound represented by the following general formula [6] or a μ-oxo type transition metal compound dimer (B) When the organoaluminum compound (C) and is contacted with by addition polymerization catalyst is obtained.

L ² _a M ² X _b [6]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² are directly or carbon atoms. , A silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and at least one of the plurality of L ² is a group having a cyclopentadiene type anion skeleton. X is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), or a hydrocarbon oxy group, a is a number satisfying 0 <a ≦ 8, and b is 0 <b Represents a number satisfying ≦ 8.)
A method for producing an addition polymer using the addition polymerization catalyst according to claim 7 or 8 .
The method for producing an addition polymer according to claim 9, wherein the addition polymer is an olefin polymer.
The method for producing an addition polymer according to claim 9, wherein the addition polymer is a copolymer of ethylene and an α-olefin.