JP2003096125A - Addition polymerization catalyst component, production method for addition polymerization catalyst and addition polymer, and use of metallocene transition metal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition polymerization catalyst component and an addition polymerization catalyst, both used for producing an addition polymer having a high melt tension and an excellent processibility; a production method for an addition polymer having a high melt tension and an excellent processibility; and the use of a transition metal compound for producing an addition polymer having a high melt tension and an excellent processibility. SOLUTION: This addition polymerization catalyst component comprises a crosslinked bis-Cp hafnium compound and a noncrosslinked bis-substituted-Cp zirconium or titanium compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for addition polymerization comprising a metallocene-based transition metal compound, a catalyst for addition polymerization, a method for producing an addition polymer, and use of a mixture of metallocene-based transition metal compounds.

[0002]

BACKGROUND OF THE INVENTION 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 of properties and economic efficiency. There is. Conventionally, these addition polymers are obtained by combining a solid catalyst component mainly obtained by using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride with a Group 13 metal compound represented by an organoaluminum compound. Conventional solid catalyst (multi-site catalyst)
Have been produced by polymerizing olefins and the like.

In recent years, olefins and the like are polymerized by using a so-called single-site catalyst, which is a combination of a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) different from a solid catalyst component which has been used for a long time, and an aluminoxane. A method for producing a addition polymer has been proposed. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane.
It has also been reported to combine certain boron compounds with such transition metal compounds. For example, special table 1-5
In 02036, a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate is reported. 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, comonomers are copolymerized more uniformly. Therefore, it is known that a more homogeneous addition polymer can be obtained than in the case of using a conventional solid catalyst.

By the way, the use of addition polymers such as polypropylene and polyethylene is wide-ranging, and various characteristics are required depending on the molding method and use. For example, when an inflation film is to be molded at a high speed, it is preferable to select an addition polymer having a high melt tension in order to perform stable high speed molding. However, in such applications, addition polymers obtained by using conventional single-site catalysts do not have a very high melt tension and are not suitable for use in many cases.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an addition polymerization catalyst component and an addition polymerization catalyst used for producing an addition polymer having a high melt tension and excellent processability, and a high melt tension and a high processability. An object is to provide a method for producing an excellent addition polymer. A further object of the present invention is to provide use of the transition metal compound for producing an addition polymer having high melt tension and excellent processability.

[0006]

The present invention relates to a catalyst component for addition polymerization comprising a transition metal compound of the following (i) and a transition metal compound of the following (ii). The present invention also relates to an addition polymerization catalyst obtained by contacting the addition polymerization catalyst component and an activation co-catalyst component, and a method for producing an addition polymer using the addition polymerization catalyst. Further, the present invention provides the following (i) when producing an addition polymer by homopolymerization of addition-polymerizable monomers or copolymerization of two or more addition-polymerizable monomers.
The present invention relates to the use of a mixture of the transition metal compound (1) and the transition metal compound (ii) below as a catalyst component for addition polymerization. (I): a transition having two groups having a cyclopentadiene type anion skeleton, the groups having the cyclopentadiene type anion skeleton bonded to each other directly or via a cross-linking group, and the central metal being hafnium Metal compound. (Ii): having two groups having a cyclopentadiene type anion skeleton having a substituent, and the groups having this cyclopentadiene type anion skeleton are not bonded to each other,
A transition metal compound whose central metal is zirconium or titanium. Hereinafter, the present invention will be described in more detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The group having a cyclopentadiene type anion skeleton of the transition metal compound (i) or (ii) (hereinafter, may be abbreviated as "Cp group") is η ^5- ( (Substituted) cyclopentadienyl group, η ⁵
Examples thereof include a-(substituted) indenyl group and a η ^5- (substituted) fluorenyl group. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -propylcyclopentadienyl group, η ⁵ -butyl. Cyclopentadienyl group, η ⁵ -hexylcyclopentadienyl group, η ⁵ -octylcyclopentadienyl group, η ⁵ -dimethylcyclopentadienyl group, η ⁵ -butylmethylcyclopentadienyl group, η ⁵ − Methylpropylcyclopentadienyl group, η ⁵ -diethylcyclopentadienyl group, η ⁵ -trimethylcyclopentadienyl group, η ⁵ −
Tetramethylcyclopentadienyl group, η ⁵ -pentamethylcyclopentadienyl group, η ⁵ -indenyl group, η
⁵ -4,5,6,7-tetrahydroindenyl group, eta ⁵
- methylindenyl group, eta ⁵ - butyl indenyl group, eta
⁵ - dimethyl indenyl group, eta ⁵ - trimethyl indenyl group, eta ⁵ - methylpropyl indenyl group, eta ⁵ -4,
5-benzindenyl group, η ⁵ -methyl-4,5-benzindenyl group, η ⁵ -phenylindenyl group, η ⁵ −
Methylphenyl indenyl group, eta ⁵ - methyl naphthyl indenyl group, eta ⁵ - fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - dibutyl fluorenyl group, and substitution products thereof. In this specification, “η ⁵ −” may be omitted as the name of the transition metal compound.

In the above examples, the η ⁵ -cyclopentadienyl group has a di-substituted form and a tri-substituted form, although many combinations exist depending on the positions of the substituents, but all combinations are included. Further, eta ⁵ - include all combinations as well substitutions fluorenyl group - indenyl group and eta ^5. Alkyl groups such as propyl and butyl are n-, i-, sec
Includes isomers such as-and tert-.

The group having a cyclopentadiene type anion skeleton of the transition metal compound of the above (ii) is a group having a substituent. Examples of the group having a cyclopentadiene type anion skeleton having such a substituent include η ⁵ -substituted cyclopentadienyl group, η ^5- (substituted) indenyl group, η ⁵
Examples thereof include a-(substituted) fluorenyl group, and specific examples thereof include those having a cyclopentadiene type anion skeleton other than the η ⁵ -cyclopentadienyl group.

The above transition metal compound (i) or (ii) has two such Cp groups. In the transition metal compound (i), the two Cp groups are bonded to each other directly or via a bridging group, and in the transition metal compound (ii), the two Cp groups are Not connected to each other. In the transition metal compound (i), it is preferable that the two Cp groups are bonded to each other via a bridging group. As such a cross-linking group, many cross-linking groups which cross-link two Cp groups are known, and among them, a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable. Such a residue is preferably a divalent residue in which the atom bonded to the two Cp groups is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 An atom bonded to one Cp group is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and the minimum number of atoms between the atoms bonded to two Cp groups is 3 or less. A residue (this includes a single atom bonded to two Cp groups). Specifically, an ethylene group, an alkylene group such as a propylene group, a substituted alkylene group such as a dimethylmethylene group, a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisilylene group. Or a nitrogen atom, an oxygen atom, a sulfur atom, a hetero atom such as a phosphorus atom, and the like, and 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 base.

The transition metal compound of (i) above includes
The transition metal compound represented by the general formula [4] is preferable. L² ₂HfX¹ ₂                  [4] (Where L is² Has a cyclopentadiene type anion skeleton
Is a group that ² Are the same or different
Well, two L² Is a direct or carbon atom, a silicon atom,
Contains nitrogen, oxygen, sulfur or phosphorus atoms
Are linked via a residue. X¹ Is a halogen atom, charcoal
It represents a hydrogenated group or a hydrocarbon oxy group. )

The group having a cyclopentadiene type anion skeleton in L ² is as described above, and among them,
η ⁵ -Indenyl groups or η ⁵ -alkyl-substituted indenyl groups are preferred. Two L ² in the general formula [4] are
They are linked directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. The residue is as described above, and the transition metal compound represented by the general formula [4] is preferably such that two L ² are carbon atoms, silicon atoms, nitrogen atoms, oxygen atoms, sulfur atoms or phosphorus atoms. Is a transition metal compound linked via a residue containing.

X ¹ in the general formula [4] is a halogen atom, a hydrocarbon group 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. The hydrocarbon group referred to here is an alkyl group,
Examples thereof include an aralkyl group and an aryl group, and preferably
Alkyl group having 1 to 20 carbon atoms, 7 to 20 carbon atoms
Is preferably an aralkyl group or an aryl group having 6 to 20 carbon atoms.

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 and ter.
t-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. Of these, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group or an amyl group is more preferable. 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 thereof include perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group and perbromopropyl group. In addition, all 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-propyl) (Phenyl) 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) Examples thereof include a methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group and anthracenylmethyl group, and more preferably benzyl group. is there. All of these aralkyl groups are fluorine atom, chlorine atom,
It may be partially substituted with a halogen atom such as a bromine atom or an iodine atom, 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 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, 2,5-xylyl group, 2,6-xylyl group, 3,4
-Xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-
Trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,
3,4,6-tetramethylphenyl group, 2,3,5,6
-Tetramethylphenyl group, pentamethylphenyl group,
Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like can be mentioned, and phenyl group is more preferable. All of these aryl groups are fluorine atom, chlorine atom, bromine atom,
It may be partially substituted with a halogen atom such as an iodine atom, 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 hydrocarbon oxy group include an alkoxy group, an aralkyloxy group, an aryloxy group and the like, preferably an alkoxy group having 1 to 20 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms. A group or an aryloxy group having 6 to 20 carbon atoms is preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and n-pentoxy group. , Neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, more preferably methoxy group, ethoxy group, isopropoxy group, or tert-
It is a butoxy group. Each of these alkoxy groups is
Partially substituted with halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, alkoxy group such as methoxy group, ethoxy group, aryloxy group such as phenoxy group or aralkyloxy group such as benzyloxy group. May be.

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 and (2 , 3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group,
(3,4-dimethylphenyl) methoxy group, (3,5-
Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl)
Methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl)
Methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy 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, and more preferably a benzyloxy group. All of these aralkyloxy groups include 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. Part 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-trimethylphenoxy 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, s
Examples thereof include an ec-butylphenoxy group, a tert-butylphenoxy group, an n-hexylphenoxy group, an n-octylphenoxy group, an n-decylphenoxy group, an n-tetradecylphenoxy group, a naphthoxy group and an anthracenoxy group. All of these aryloxy groups include 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. Part may be substituted with a group or the like.

More preferably, X is 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,
It is a 3,5,6-tetrafluoro-4-pentafluorophenylphenoxy group or a benzyl group.

Specific examples of the transition metal compound represented by the above general formula [4] include ethylenebis (cyclopentadienyl) hafnium dichloride, ethylenebis (methylcyclopentadienyl) hafnium dichloride and ethylenebis (ethylcyclo). Pentadienyl) hafnium dichloride, ethylenebis (propylcyclopentadienyl) hafnium dichloride, ethylenebis (butylcyclopentadienyl) hafnium dichloride, ethylenebis (hexylcyclopentadienyl) hafnium dichloride, ethylenebis (octylcyclopentadiene) (Enyl) hafnium dichloride, ethylene bis (dimethylcyclopentadienyl) hafnium dichloride,
Ethylenebis (diethylcyclopentadienyl) hafnium dichloride, ethylenebis (ethylmethylcyclopentadienyl) hafnium dichloride, ethylenebis (butylmethylcyclopentadienyl) hafnium dichloride, ethylenebis (trimethylcyclopentadienyl) hafnium dichloride, Ethylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (methylindenyl) hafnium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, ethylene Bis (phenylindenyl) hafnium dichloride, ethylene bis (fluorenyl) hafnium dichloride,

Ethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, ethylene (cyclopentadienyl) (indenyl)
Hafnium dichloride, ethylene (methylcyclopentadienyl) (indenyl) hafnium dichloride,
Ethylene (ethylcyclopentadienyl) (indenyl) hafnium dichloride, ethylene (propylcyclopentadienyl) (indenyl) hafnium dichloride, ethylene (butylcyclopentadienyl) (indenyl) hafnium dichloride, ethylene (hexylcyclopentadienyl) (Indenyl) hafnium dichloride, ethylene (octylcyclopentadienyl)
(Indenyl) hafnium dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) hafnium dichloride, ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene ( Tetramethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (propylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (butylcyclopentadienyl) ( Fluorenyl) hafnium dichloride, ethylene (hexylcyclopentadienyl) (fluorenyl)
Hafnium dichloride, ethylene (octylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (indenyl) (fluorenyl) hafnium dichloride, etc.,

Compounds in which ethylene of these compounds is changed to isopropylidene, dimethylsilylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl,
Dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, bis (2,6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis ( Examples thereof include pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), and compounds modified to dibenzyl.

In the above example, η^Five -Cyclope
The mono-substituted di-diamine of the diandienyl group has a 2-position and a 3-position.
Disubstituted products include 2,3-position, 2,4-position, 2,
The 5-substitution and 3,5-substitution include the tri-substitution
It includes substitution products at the 2,3,4-position and the 2,3,5-position.
η^Five Similarly, in the substituted indenyl group, the crosslinking group has the 1-position.
In the case of, if it is a mono-substituted product, 2-position, 3-position, 4-position,
The 5-position, the 6-position, and the 7-position are substituted, and the cross-linking position is
Similarly, all combinations other than the 1-position are included. Also, two sets
In the same manner as above, all combinations of substituents and crosslinking positions
including. Also, η ^Five The same applies to substituted fluorenyl groups
Includes all combinations of substituents and bridging positions. Again
And alkyl groups such as butyl are n-, i-, sec
Includes isomers such as-and tert-. There is no particular notation
Alkoxy groups such as propoxy and butoxy are
Includes isomers such as n-, i-, sec-, and tert-
Mu. Further, two or more kinds of these complexes may be used.

As the transition metal compound (ii), a transition metal compound represented by the following general formula [5] is preferable. L ³ ₂ M ² X ² ₂ [5] (In the formula, M ² is a titanium atom or a zirconium atom, L ³ is a group having a cyclopentadiene type anion skeleton having a substituent, and two L ³ are bridges. X ² represents a halogen atom, a hydrocarbon group or a hydrocarbon oxy group.)

The group having a cyclopentadiene type anion skeleton having a substituent in L ³ is as described above, and among them, a η ⁵ -alkyl-substituted cyclopentadienyl group is preferable. Two L ^{3 s} in the general formula [5] are not crosslinked.

X ² in the general formula [5] is a halogen atom, a hydrocarbon group or a hydrocarbon oxy group and is the same as X ¹ in the above general formula [4].

Specific examples of the transition metal compound represented by the above general formula [5] include bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride and bis (propylcyclopentadiene). (Enyl) titanium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (hexylcyclopentadienyl) titanium dichloride, bis (octylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (Diethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (methylbutylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) ) Titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (methylindenyl) titanium dichloride, bis (phenylindenyl) Titanium dichloride, bis (methylfluorenyl) titanium dichloride,

(Methylcyclopentadienyl) (indenyl) titanium dichloride, (ethylcyclopentadienyl) (indenyl) titanium dichloride, (propylcyclopentadienyl) (indenyl) titanium dichloride, (butylcyclopentadienyl) ( Indenyl)
Titanium dichloride, (hexylcyclopentadienyl) (indenyl) titanium dichloride, (octylcyclopentadienyl) (indenyl) titanium dichloride, (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, (methylcyclopentadienyl) (Fluorenyl) titanium dichloride, (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, (ethylcyclopentadienyl) (fluorenyl) titanium dichloride, (propylcyclopentadienyl) (fluorenyl) titanium dichloride, (butylcyclopenta) (Dienyl) (fluorenyl) titanium dichloride, (hexylcyclopentadienyl) (fluorenyl) titanium dichloride, (octylcyclopentadienyl) (fluor Reniru) titanium dichloride,
(Pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, (indenyl) (fluorenyl) titanium dichloride, etc.,

Compounds of these compounds in which titanium is changed to zirconium, and dichloride is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide. , Bis (2,6-di-tert-butylphenoxide), bis (3,4,5)
-Trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), or a compound modified to dibenzyl.

In the above example, the disubstituted product of η ⁵ -cyclopentadienyl group is 1,2-position and 1,3-position.
Position substitutions, tri-substitutions include 1,2,3- and 1,2,4-position substitutions. Similarly, the substituted η ⁵ -indenyl group is a 1-position, a 2-position, and a 4-position if they are mono-substituted.
Includes substitutions at the -position and the 5-position and symmetries thereof, and at least two substitutions and all combinations. Further, the substitution product of the η ⁵ -fluorenyl group also includes all combinations. Alkyl groups such as propyl and butyl are n-, i-, se
Including isomers such as c- and tert-. Further, unless otherwise specified, an alkoxy group such as propoxy and butoxy includes isomers such as n-, i-, sec-, and tert-. Further, two or more kinds of these complexes may be used.

The above-described mixture of transition metal compounds of the present invention is used as a catalyst for addition polymerization when an addition polymer is produced by homopolymerization of addition-polymerizable monomers or copolymerization of two or more addition-polymerizable monomers. Used as an ingredient. As the addition polymerization catalyst, an addition polymerization catalyst obtained by contacting an addition polymerization catalyst component comprising the above-described transition metal compound of the present invention and an activation cocatalyst component is used. The activation co-catalyst component is not particularly limited as long as it activates the addition polymerization catalyst component comprising the transition metal compound of the present invention and enables addition polymerization, but the following (B) and / Alternatively, the following (C) is preferable.
That is, as the addition polymerization catalyst used in the present invention, preferably, the addition polymerization catalyst component (A) composed of the transition metal compound of the present invention is brought into contact with the following (B) and / or the following (C). It is a catalyst for addition polymerization thus obtained.

(B): One or more kinds of aluminum compounds (B1) selected from the following (B1) to (B3) General formula E ¹ _a AlZ _3-a Organoaluminum compound (B2) General formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
_A linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same) Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, c represents an integer of 1 or more.) (C): One or more boron compounds (C1) selected from the following (C1) to (C3): boron represented by the general formula BQ ¹ Q ² Q ^3. A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , and (C3) a general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- A boron compound represented by the formula (provided that B is a boron atom in a trivalent valence state, and Q is
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and they may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (L-H) ⁺ is a Bronsted acid. ) Hereinafter, the addition polymerization catalyst will be described in more detail.

(B) Aluminum Compound The aluminum compound (B) is the following (B1) to (B)
One or more aluminum compounds selected from 3). (B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O-} _b Cyclic aluminoxane (B3) having a structure represented by general formula E ^{3 {-Al (E 3) -O-} } c AlE 3
_A linear aluminoxane having the structure shown by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same) Z may represent a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. , And c represents an integer of 1 or more.) As the hydrocarbon group for E ¹ , E ² , or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like. Trialkyl aluminum; Dialkyl aluminum chloride such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum chloride; methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride, etc. Alkyl aluminum Dichloride; dimethyl aluminum hydride, diethyl aluminum hydride,
Examples thereof include dialkyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, and other dialkyl aluminum hydrides. It is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum or trinormaloctylaluminum, and particularly preferably triisobutylaluminum or trinormaloctylaluminum. is there.

[0037] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include alkyl groups such as isobutyl group, normal pentyl group and neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably E ²
And E ³ is a methyl group or an isobutyl group, b
Is 2 to 40 and c is 1 to 40.

The above aluminoxanes can be made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, it is prepared by bringing a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in a suitable organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) into contact with water. In addition, a method in which a trialkylaluminum (eg, trimethylaluminum) is brought into contact with a metal salt containing crystal water (eg, copper sulfate hydrate) can be exemplified. It is considered that the aluminoxane produced by such a method is usually a mixture of cyclic aluminoxane and linear aluminoxane.

(C) Boron Compound As the boron compound (C), there may be mentioned (C1) the general formula B
Boron compound represented by Q ¹ Q ² Q ³ , (C2) general formula
A boron compound represented by G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C
3) General formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - one or more boron compounds selected from boron compound represented by used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably halogen atoms, hydrocarbon groups containing 1 to 20 carbon atoms, and 1 to 20.
A halogenated hydrocarbon group containing 1 carbon atom, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. , More preferably Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
A halogenated hydrocarbon group containing -20 carbon atoms. More preferably Q ¹ to Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, particularly preferably Q ¹ to Q ⁴ are each at least one fluorine 6 to 2 carbon atoms including atoms
It is a fluorinated aryl group of 0.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane and tris (2,3,3).
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Examples thereof include phenylbis (pentafluorophenyl) borane, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. Atoms, and Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as.

Specific examples of G ⁺ , which is an inorganic cation in the compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , include ferrocenium cations, alkyl-substituted ferrocenium cations, and silver. Examples of G ⁺ , which is an organic cation such as a cation, include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistri) Examples thereof include fluoromethylphenyl) borate.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, but most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In addition, the general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

A Bronsted acid in the compound represented by the general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like,
^{(BQ 1 Q 2 Q 3 Q} 4) - as include the same as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, but most preferably tri (n-butyl) ammonium tetrakis (pentafluoro). Phenyl) borate or N, N-
It is dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the production of the addition polymerization catalyst obtained by contacting the above transition metal compound with the activating cocatalyst component of the present invention, the contact is made between the transition metal compound and the activating cocatalyst component. Any means may be used so long as the catalyst is contacted with the catalyst to form a catalyst, and a method of contacting the transition metal compound and the activating cocatalyst component by mixing them with or without dilution with a solvent in advance, or separately. It is possible to employ a method in which the solution is supplied to the polymerization tank and contacted in the polymerization tank. Here, as the activating co-catalyst component, a plurality of types may be used in combination, but a part of them may be mixed in advance and used, or they may be separately supplied to the polymerization tank for use. It goes without saying that you may do it.

The amount of each component used is usually such that the molar ratio of (B) / transition metal compound (A) is 0.1 to 10000, preferably 5 to 2000, and the molar ratio of (C) / transition metal compound (A) is. It is desirable to use each component so that the ratio is in the range of 0.01 to 100, preferably 0.5 to 10.

The concentration of each component when it is supplied in a solution state or in a state of being suspended or slurried in a solvent depends on conditions such as the performance of the apparatus for supplying each component to the polymerization reactor.
Although appropriately selected, in general, the transition metal compound (A) is
Usually 0.0001 to 1000 mmol / l, more preferably 0.05 to 200 mmol / l,
More preferably, 0.01 to 50 mmol / liter, (B) is usually 0.01 to 500 in terms of Al atom.
0 mmol / liter, more preferably 0.1 to 2
500 mmol / liter, more preferably 0.1
~ 2000 mmol / l, (C) is usually 0.0
01-500 mmol / l, more preferably,
It is desirable to use each component in the range of 0.01 to 250 mmol / liter, more preferably 0.05 to 100 mmol / liter.

The addition polymerization catalyst is an addition polymerization catalyst obtained by contacting the above transition metal compound (A) with the above (B) and / or (C). When the addition polymerization catalyst obtained by contacting A) and (B) is used, (B) is preferably the above cyclic aluminoxane (B2) and / or linear aluminoxane (B3). Further, as other preferable embodiments of the addition polymerization catalyst, the transition metal compounds (A) and (B)
And a catalyst for addition polymerization obtained by bringing (C) into contact with each other. As the (B) in that case, the above-mentioned (B1) is easy to use.

The polymerization method is also not particularly limited, but for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, methylene dichloride and the like. Solvent polymerization using a halogenated hydrocarbon as a solvent, slurry polymerization, gas phase polymerization in a gaseous monomer or the like is possible, and either continuous polymerization or batchwise polymerization is possible.

The polymerization temperature can usually be in the range of -50 ° C to 200 ° C, but in particular, the range of -20 ° C to 100 ° C is preferable, and the polymerization pressure is usually normal pressure to 6 MPa.
The polymerization time is generally determined as appropriate depending on the type of the target polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours. Further, in the present invention, a chain transfer agent such as hydrogen may be added to control the molecular weight of the copolymer.

When the catalyst component for addition polymerization comprising the above-mentioned transition metal compound of the present invention is applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), it is activated. As the co-catalyst component for use, the modified particles of the following (I) or (II) are preferably used.
That is, as the preferable addition polymerization catalyst of the present invention, the addition polymerization catalyst component (A) comprising the above-described transition metal compound of the present invention and the modified particles (D) of the following (I) or (II) The catalyst for addition polymerization obtained by contacting

(I) Modified particles obtained by bringing the following (a), (b), (c) and particles (d) into contact with each other. (A): Compound M ¹ L ¹ _m [1] represented by the following general formula [1] (b): Compound R ¹ _t-1 TH [2] (c) represented by the following general formula [2] : Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3] (In the above general formulas [1] to [3], M ¹ is each of the ^first , second, 12, and 14th periodic tables. Or represents a typical metal atom of Group 15, m represents the valence of M ¹ , L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when plural L ^1's are present, they are the same as each other. It may even be different .R ¹ is a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality may be different even they the same as each other .R ² Represents a hydrocarbon group or a halogenated hydrocarbon group, and each T independently represents an atom of Group 15 or Group 16 of the periodic table. , And t represents the valence of T of each compound.)

(II) Modified particles obtained by contacting aluminoxane (e) with particles (d). Hereinafter, these will be sequentially described.

(I) Modified particles obtained by bringing (a), (b), (c) and particles (d) into contact with each other. M ¹ in the above general formula [1] is the periodic table (I
UPAC Inorganic Chemistry Nomenclature Revised 1989) 1, 2, 1
It represents a typical metal atom of Group 2, 14 or 15. 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 above 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 or different from each other. Specific examples of the halogen atom for 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.

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, such as a 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, n-hexyl group, n-octyl group, n-decyl group Group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an 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, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Examples thereof include perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group and perbromoeicosyl group. In addition, all 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.

The aryl group has 6 to 20 carbon atoms.
Aryl groups are preferred, for example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples thereof include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group and an anthracenyl group, and a phenyl group is more preferable. Each of these aryl groups is a fluorine atom,
Halogen atom such as chlorine atom, bromine atom, iodine atom,
It 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.

The aralkyl group has 7 to 2 carbon atoms.
An aralkyl group of 0 is preferable, and examples thereof include a benzyl group and (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, (3,3
4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,3 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, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include (n-tetradecylphenyl) methyl group, naphthylmethyl group and anthracenylmethyl group, and more preferably benzyl group. All of these aralkyl groups include 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. May be partially substituted with, for example.

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

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 Chemistry Nomenclature Revised 1989). T in the general formula [2] and T in the general formula [3] may be the same or different. First
Specific examples of the group 5 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 general formula [2] or [3], t represents the valence of each T, and when T is a Group 15 atom, t is 3, and when T is a Group 16 atom, t is t.
Is 2.

R ¹ in the above general formula [2] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ¹ are present, they may be the same or different from each other. Good. As an index of the electron-withdrawing property, the Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's rule substituent constant σ can be mentioned as the electron-withdrawing group.

Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group and a phenyl group. Examples of groups containing an electron-withdrawing group include halogenated alkyl groups, halogenated aryl groups, (halogenated alkyl) aryl groups, cyanated aryl groups, nitrated aryl groups, ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups, and Aryloxycarbonyl group) and the like.

Specific examples of the halogenated alkyl group include:
Fluoromethyl group, chloromethyl group, bromomethyl group,
Iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group trifluoromethyl group, trichloromethyl group, tribromomethyl group,
Triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group,
2,2,3,3,3-pentafluoropropyl group, 2,
2,3,3,3-pentachloropropyl group, 2,2
3,3,3-pentabromopropyl group, 2,2,3
3,3-Pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2
-Trichloro-1-trichloromethylethyl group, 2,
2,2-tribromo-1-tribromomethylethyl group,
2,2,2-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 can be mentioned.

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, pentachlorophenyl group, 2,
3,5,6-Tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2-naphthyl group, 2- Bromophenyl group, 3-bromophenyl group, 4-bromophenyl group,
2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 2,4,6-tribromophenyl group, 3,
4,5-tribromophenyl group, 2,3,5,6-tetrabromophenyl 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-diiodophenyl 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, periodo-1-naphthyl group, periodo-2-naphthyl group and the like. To be

Specific examples of the (halogenated alkyl) aryl group include a 2- (trifluoromethyl) phenyl group,
3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4 Examples thereof include a 6-tris (trifluoromethyl) phenyl group and a 3,4,5-tris (trifluoromethyl) phenyl group.

Specific examples of the cyanated aryl group include 2
-Cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like can be mentioned.

Specific examples of the nitrated aryl group include 2
-Nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like can be mentioned.

Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, normal propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group and the like.

R ¹ is preferably a halogenated hydrocarbon group, more 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-
Trifluoro-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, 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
-Pentafluorophenyl phenyl group, perfluoro-
1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl 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 pentachlorophenyl group, particularly preferably fluoroalkyl group or fluoroaryl group, and most preferably Is a trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1
-Bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group, 3,
It is a 4,5-trifluorophenyl group or a pentafluorophenyl group.

R ² in the above 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. Examples of the halogenated hydrocarbon group for R ² include a halogenated alkyl group, a halogenated aryl group, and (halogenated alkyl)
Examples of the aryl group include the same halogenated alkyl groups, halogenated aryl groups and (halogenated alkyl) aryl groups as those mentioned as specific examples of the electron-withdrawing group for R ¹ in the general formula [2]. To be

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

A specific example of the compound (a) is M ¹
When is a zinc atom, specific examples thereof include dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc,
Dialkyl zinc such as diisobutyl zinc and dinormalhexyl 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 zinc chloride, methyl zinc bromide,
Ethyl zinc bromide, propyl zinc bromide, normal butyl zinc bromide, isobutyl zinc bromide, normal hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, normal butyl zinc iodide, iodide Alkyl zinc halides such as isobutyl zinc and normal hexyl zinc iodide; zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide.

The compound (a) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, dinormalbutylzinc, diisobutylzinc, or dinormalhexylzinc, and particularly preferably dimethylzinc. Or it is diethyl zinc.

Illustrating the compound (b) as a specific example, the amines include di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine. 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) 2-triiodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2 2,3,3,3 penta-chloropropyl) amine, bis (2,2,3,3,3-penta-bromopropyl) 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
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) 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- (tri Fluoromethyl) 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) amine, bis (2-cyanophenyl) amine, (3- Cyanophenyl) amine,
Examples thereof include bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine and bis (4-nitrophenyl) amine. Further, a phosphine compound in which a nitrogen atom is replaced with a phosphorus atom can be similarly exemplified. Those phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples into phosphine.

Specific examples of the compound (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, trichloromethanol and trichloromethanol. Bromomethanol, 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-trifluoromethylethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1 -Triiodomethyl ethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1,1
-Bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2,
2,2-tribromoethanol, 1,1-bis (triiodomethyl) -2,2,2-triiodoethanol and the like can be mentioned. Further, a thiol compound in which an oxygen atom is replaced by a sulfur atom can be similarly exemplified. The thiol compounds are compounds represented by rewriting methanol in the above-mentioned specific examples into methanethiol, ethanol into ethanethiol, and propanol into propanethiol.

Specific examples of the compound (b) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol and 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-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-
Dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5
6-tetrachlorophenol, 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-dibromo Phenol, 3,5-dibromophenol, 2,4,6-tribromophenol,
3,4,5-Tribromophenol, 2,3,5,6-
Tetrabromophenol, 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-triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periodo-1-naphthol, periodo-2-naphthol, 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, 3,4,5
-Tris (trifluoromethyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like. Further, a thiophenol compound in which an oxygen atom is replaced by a sulfur atom can be similarly exemplified. Those thiophenol compounds are compounds represented by rewriting the above-mentioned specific examples of phenol into thiophenol.

The compound (b) is preferably amines such as bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine and bis (2,2,3,3,3-). Pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine , Or bis (pentafluorophenyl) amine,
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 include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-
Difluorophenol, 2,4,6-trifluorophenol, 3,4,5-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.
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 (trifluoromethyl) phenol, more preferably 3,5-difluorophenol, 3,4,5-trifluorophenol, pentafluoro Phenol 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, and more preferably Water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, t
ert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine,
n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-
Trilylamine, 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-pentylaniline, neopentylaniline,
n-hexylaniline, n-octylaniline, n-decylaniline, n-dodecylaniline, n-tetradecylaniline, naphthylamine, anthracenylamine,

Benzylamine, (2-methylphenyl)
Methylamine, (3-methylphenyl) methylamine,
(4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (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, anthracenylmethylamine, fluoromethylamine , 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-pentafluoropropylamine, 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-tribromoethylamine, 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-
Dibromoaniline, 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-tribromoaniline,
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. It is 5-tri (trifluoromethyl) aniline.

More preferably, the compound (c) is water,
Hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, se
c-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, per Fluoropentadecylamine, 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, most preferably water or pentafluoroaniline.

As the particles (d), those generally used as a carrier are preferably used, a porous substance having a uniform particle size is preferable, an inorganic substance or an organic polymer is preferably used, and an inorganic substance is more preferable. It is preferably used. From the viewpoint of the particle size distribution of the polymer obtained, the particles (d) preferably have a volume-based geometric standard deviation of the particle diameter of the particles (d) of 2.5 or less, more preferably 2.0 or less,
More preferably, it is 1.7 or less.

Of the inorganic substances which can be used as particles (d)
Examples include inorganic oxides and magnesium compounds.
It is possible to use clay and clay minerals as long as there is no problem.
It These may be mixed and used. Inorganic oxide
As a concrete example of₂, Al₂O₃, MgO, Zr
O₂, TiO ₂, B₂O₃, CaO, ZnO, BaO, Th
O₂Etc. and mixtures thereof, eg SiO.₂-Mg
O, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂−
V₂O _Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-Mg
O and the like can be exemplified. Of these inorganic oxides
Among them, SiO₂And / or Al₂O₃Is preferred,
Silica is particularly preferable. A small amount of the above inorganic oxides
Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na
₂SO_Four, Al₂(SO_Four)₃, BaSO_Four, KNO₃, Mg
(NO₃)₂, Al (NO₃)₃, Na₂O, K₂O, Li₂
Contains carbonates, sulfates, nitrates, oxides such as O
I don't care.

As the magnesium compound, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; magnesium methoxy chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, etc. Alkoxy magnesium halides; phenoxy magnesium chloride, methylphenoxy magnesium chloride and other allyloxy magnesium halides; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium and other alkoxy magnesium; phenoxy magnesium, dimethyl Allyloxy magnesium such as phenoxy magnesium; Lau Magnesium phosphate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Of these, magnesium halide or alkoxy magnesium is preferable, and magnesium chloride or butoxy magnesium is more preferable.

As the clay or clay mineral, kaolin,
Bentonite, kibushi clay, gyrome clay, allophane,
Hissingelite, bilophyllite, talc, ummo group,
Examples include montmorillonite group, vermiculite, ryokdee stone group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Of these, smectite, montmorillonite, hectorite, laponite and saponite are preferable, and montmorillonite and hectorite are more preferable.

Among these inorganic substances, inorganic oxides are preferably used. It is preferable that these inorganic substances are dried to substantially remove water, and those dried by heat treatment are preferable. The heat treatment is usually performed at a temperature of 100 to 100 for inorganic substances whose water content cannot be visually confirmed.
At 1,500 ° C, preferably 100-1,000 ° C,
More preferably, it is carried out at 200 to 800 ° C. 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, a method of reducing the pressure, or the like can be used, but the method is not limited to this.

The average particle diameter of the inorganic substance is preferably
5 to 1000 μm, more preferably 10 to 500
μm, and 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 10
It is 0 to 500 m ² / g.

As the organic polymer which can be used as the particles (d), any organic polymer may be used, and plural kinds 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, and specific examples thereof include primary amino group, secondary amino group, imino group, amide group, hydrazide group and 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,
Examples thereof include piperidyl group, indazolyl group, carbazolyl group and the like. Preferably, a primary amino group, a secondary amino group,
It is an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group. Particularly preferred is a primary amino group, a secondary amino group, an amido group or a hydroxy group. In addition, these groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The aproton donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base moiety having no active hydrogen atom, and specific examples thereof include a pyridyl group and an N-substituted imidazolyl group. N-substituted indazolyl group, nitrile group, azido 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,
Examples thereof include N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. A heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable. Particularly preferred are pyridyl group, N-substituted imidazolyl group and N-substituted indazolyl group, and most preferred is pyridyl group. In addition, 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 preferably 0.01 to 50 mmol / mol of the functional group per gram of the polymer. g, and more preferably 0.1 to 20 mmol / g.

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

As the monomer having such a functional group having active hydrogen or an aproton-donating Lewis basic functional group and at least one polymerizable unsaturated group, the above-mentioned functional group having active hydrogen and at least one Examples thereof include a monomer having a polymerizable unsaturated group, or a monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such a polymerizable unsaturated group include a vinyl group, an alkenyl group such as an allyl group, and an alkynyl group such as an ethyne group. Examples of the monomer having a functional group having active hydrogen and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine,
Vinyl group-containing secondary amine, vinyl group-containing amide compound,
Mention may be made of vinyl group-containing hydroxy compounds.
Specific examples include N- (1-ethenyl) amine and 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 can be mentioned. 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, vinyl (N-substituted) indazole. Can be mentioned.

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

The average particle size of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 5 μm.
It is 00 μm. The pore volume is preferably 0.1 m
It is 1 / 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.

It is preferable that these organic polymers are dried to substantially remove water, and those dried by heat treatment are preferable. The heat treatment is usually performed at a temperature of 30 to 40 for an organic polymer whose water content cannot be visually confirmed.
It is carried out at 0 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. 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, a method of reducing the pressure, or the like can be used, but the method is not limited to this.

The order of bringing (a), (b), (c) and (d) into contact with each other is not particularly limited, and the following order may be mentioned. <1> A contact product obtained by bringing (a) and (b) into contact with (c) is brought into contact with (d). <2> A contact product obtained by bringing (a) and (b) into contact with (d) is brought into contact with (c). <3> A contact product obtained by bringing (a) and (c) into contact with (b) is brought into contact with (d). <4> A contact product of (a) and (c) is contacted with a contact product obtained by contacting (d) with (b). <5> A contact product obtained by bringing (a) and (d) into contact with (b) is brought into contact with (c). <6> The contact product of (a) and (d) is contacted with the contact product obtained by contacting (c) with (b). <7> The contact product of (b) and (c) is contacted with the contact product obtained by contacting (a) with (d). <8> A contact product obtained by bringing (b) and (c) into contact with (d) is brought into contact with (a). <9> The contact product of (b) and (d) is contacted with the contact product obtained by contacting (a) with (c). <10> The contact product of (b) and (d) is contacted with the contact product obtained by contacting (c) with (a). <11> The contact product of (c) and (d) is contacted with the contact product obtained by contacting (a) with (b). <12> A contact product obtained by bringing (c) and (d) into contact with (b) is brought into contact with (a). The contact order is preferably <1>, <2>, <11 above.
> Or <12>.

Such contact treatment is preferably carried out in an inert gas atmosphere. Processing temperature is usually -100 to 3
The temperature is 00 ° C, preferably -80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 1
It is 0 minutes to 100 hours. Further, such a treatment may use a solvent or may directly treat these compounds without using them.

As the solvent, a solvent which does not react with each of the components to be contacted when the solvent is used and the contact product obtained by the contact is usually used. As described above, when the components are brought into contact with each other stepwise, for example, the above (a)
Even if it is a solvent that reacts with, the contact product obtained by contacting (a) with other components may no longer react with the solvent. The solvent can be used as a solvent at the time of the contacting operation with one component. Examples of the solvent are shown below, but the solvent may be appropriately used in this way. Examples of the solvent that can be used are aliphatic hydrocarbon solvents, non-polar solvents such as aromatic hydrocarbon solvents, or halide solvents, ether solvents,
Examples thereof include polar solvents such as alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amine solvents and sulfur compounds.
Specific examples include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane and other aliphatic hydrocarbon solvents, benzene, toluene, xylene and other aromatic hydrocarbon solvents, dichloromethane, dichlorodifluoromethane. Chloroform, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,1,2
-Trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene,
Halide solvents such as o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,
Ether solvent such as 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, triethylene glycol, alcohol solvents such as glycerin, phenol, phenol solvents such as p-cresol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, Ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-
Carbonyl solvents such as methyl-2-pyrrolidone, phosphoric acid derivatives such as hexamethylphosphoric triamide and triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile, nitro such as nitromethane and nitrobenzene. Compound, pyridine,
Examples thereof include amine solvents such as piperidine and morpholine, and sulfur compounds such as dimethyl sulfoxide and sulfolane.

When the contact product (e) obtained by contacting (a), (b) and (c) with the particle (d) is contacted with each other, that is, the above <1>, <3>, <7. In the case of>, the solvent (s1) for producing the contact product (e) is preferably the above-mentioned aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) when the contact substance (e) and the particles (d) are brought into contact with each other.
As an index representing the polarity of the solvent, E _T ^N value (C.Reic
hardt, “Solvents and Solve
nts Effects in Organic Ch
"", 2nd ed., VCH Ve
rlag (1988). ) Etc. are known and 0.8
A solvent satisfying ≧ E _T ^N ≧ 0.1 is particularly preferable. Examples of such polar solvents include 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, cyclohexanol, 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, phosphorus Examples thereof include triethyl acid, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide and sulfolane. Solvent (s2)
More preferably as 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. With 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. And most preferably tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

As the solvent (s2), a mixed solvent of these polar solvent and hydrocarbon solvent can be used. As the hydrocarbon solvent, the above-exemplified aliphatic hydrocarbon solvent or aromatic hydrocarbon solvent is used. Specific examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, 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 etc. can be illustrated.
Preferably 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 /
They are a methanol mixed solvent and a xylene / ethanol mixed solvent. More preferred are hexane / methanol mixed solvent, hexane / ethanol mixed solvent, toluene / methanol mixed solvent or toluene / ethanol mixed solvent. Most preferably, it is a toluene / ethanol mixed solvent. The preferred range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, and more preferably 15 to 30% by volume.

A method of bringing the contact product (e) obtained by bringing (a), (b) and (c) into contact with (d);
That is, in the cases of <1>, <3>, and <7> above,
A hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2), but in this case (a), (b)
After contacting (c) and (c), it is preferable that the time interval between contacting the obtained contact product (e) and particles (d) is short. The time interval is preferably 0 to 5 hours,
More preferably 0 to 3 hours, most preferably 0.
~ 1 hour. The temperature at which the contact product (e) and the particles (d) are contacted is usually -100 ° C to 40 ° C, preferably -20 ° C to 200 ° C, and most preferably -10 ° C to 10 ° C. ℃.

The above <2>, <5>, <6>, <8>,
In the case of <9>, <10>, <11>, and <12>, any of the above nonpolar solvents and polar solvents can be used, but nonpolar solvents are more preferable. This is because the contact product of (a) and (c) or the contact product of (a) and (b) with (c) generally has a solubility in a nonpolar solvent. Since it is low, when (d) is present in the reaction system when these contact products are produced, it is more stable to deposit the produced contact product on the surface of (d) than to exist in the nonpolar solvent. It is preferable because it is considered that the particles are more easily immobilized.

The amount of each compound (a), (b), (c) used is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: When the molar ratio of y: z is satisfied, it is preferable that y and z substantially satisfy the following formula (1). | M−y−2z | ≦ 1 (1) (In the above formula (1), m represents the valence of M ^1. )
As y in the above formula (1), preferably 0.01 to
The number is 1.99, more preferably 0.10 to 1.8.
It is a number of 0, more preferably a number of 0.20 to 1.50, most preferably a number of 0.30 to 1.00, and a similar preferable range of z in the above formula (1) is , M, y and equation (1) above.

In the actual contact treatment of each compound, even if it is attempted to use each compound so as to completely satisfy the above formula (1), the amount used may be slightly changed, and It is common practice to appropriately increase or decrease the amount used in consideration of the amount of the compound remaining in the reaction. As used herein, "substantially satisfying the equation (1)" means that the above equation (1) is not completely satisfied.
It is meant to include when the compound is intended to be obtained by contacting each compound at a molar ratio satisfying

In the preparation of modified particles (I),
As the amount of (d) used with respect to (a), typical metal atoms derived from (a) contained in the particles obtained by contacting (a) and (d) are contained in 1 g of the obtained particles. In terms of the number of moles of the typical metal atom, the amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol. Therefore, it may be appropriately determined to fall within the range.

After the contact treatment as described above, heating is also preferably carried out to further promote the reaction. At the time of heating, it is preferable to use a solvent having a higher boiling point in order to raise the temperature, and therefore the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.

The modified particles (I) are the raw materials (a), (b) and (c) as a result of such contact treatment.
And / or (d) may remain as an unreacted substance. However, in the case of applying the polymerization involving the formation of addition polymer particles, it is preferable to previously perform a washing treatment for removing unreacted substances. The solvent at that time may be the same as or different from the solvent at the time of contact.

After such contact treatment or washing treatment, it is preferable that the solvent is distilled off from the product, and then the product is dried under reduced pressure at a temperature of 25 ° C. or higher for 1 to 24 hours.
More preferably at a temperature of 40 ° C to 200 ° C for 1 hour to 24
Time, more preferably 60 to 200 ° C for 1 to 24 hours, particularly preferably 60 to 160 ° C for 2 to 18 hours, most preferably 80 to 160 ° C.
It is preferable to perform drying at the temperature of 4 hours to 18 hours.

(II) Modified particles obtained by bringing aluminoxane (e) and particles (d) into contact with each other. The aluminoxane (e) to be used to adjust the modified particle (II), the general formula {-Al (E ²⁾ -O-} cyclic having a structure represented by _b of aluminoxane and / or the general formula E ³ {-Al (E ³⁾ -O-} linear aluminoxane having a structure represented by _c AlE ³ ₂ is preferably used. (However, E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ may be the same or different. Z is hydrogen. Represents an atom or a halogen atom, all Zs may be the same or different, a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more, and c is an integer of 1 or more. Represents.)
As the hydrocarbon group for E ¹ , E ² , or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of E ² and E ³ are methyl group, ethyl group, normal propyl group, isopropyl group,
Examples thereof include alkyl groups such as a normal butyl group, an isobutyl group, a normal pentyl group and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are methyl groups or isobutyl groups, b is 2-40 and c is 1-40.

The above aluminoxanes can be made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, it is prepared by bringing a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in a suitable organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) into contact with water. Further, a method can be exemplified in which a trialkylaluminum (eg, trimethylaluminum etc.) is brought into contact with a metal salt containing crystal water (eg, copper sulfate hydrate etc.). The aluminoxane obtained by such a method is usually considered to be a mixture of a cyclic aluminoxane and a linear aluminoxane.

The aluminoxane (e) and the particles (d) can be contacted by any method to produce the modified particles (II). Specifically, it is produced by dispersing the particles (d) in a solvent and adding the aluminoxane (e) thereto. As the solvent in this case, any of the above-mentioned solvents can be used, those which do not react with the aluminoxane (e) are preferable, and the solvent which dissolves the aluminoxane (e) is more preferable. Specifically, benzene, an aromatic hydrocarbon solvent such as toluene and xylene, or an aliphatic hydrocarbon solvent such as hexane, heptane, and octane is preferable, and toluene or xylene is more preferable.

The temperature and time for contact may be set arbitrarily, but the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 12 ° C.
It is 0 ° C. In particular, in the initial stage of the reaction, it is preferable to react at a low temperature in order to suppress heat generation. The amount of contact can be arbitrarily selected, but the aluminoxane (e) is usually 0.01 per unit gram of the particle (d) in terms of aluminum atom.
~ 100 mmol, preferably 0.1-20 mmol,
More preferably, it is 1-10 mmol.

When the modified particles of the above (I) or (II) are used as an activating cocatalyst component, it is preferable to use an organoaluminum compound in combination. That is, as a more preferred addition polymerization catalyst of the present invention, an addition polymerization catalyst component (A) comprising the above-described transition metal compound of the present invention,
An addition polymerization catalyst obtained by bringing the modified particles (D) of the above (I) or (II) into contact with the organoaluminum compound (E) can be mentioned.

(E) Organoaluminum Compound As the component (E) organoaluminum compound, known organoaluminum compounds can be used. Preferably,
It is an organoaluminum compound represented by the following general formula [7]. R ⁴ _c AlY _3-c [7] (In the formula, R ⁴ represents a hydrocarbon group, and all R ⁴ may be the same or different. Y is a hydrogen atom, a halogen atom, an alkoxy group, Represents an aralkyloxy group or an aryloxy group, and all Y's may be the same or different. C represents a number satisfying 0 <c ≦ 3.)

R ⁴ in the general formula [7] representing an organoaluminum compound preferably has 1 to 2 carbon atoms.
A hydrocarbon group having 4 carbon atoms, more preferably 1 to 1 carbon atoms.
24 alkyl groups. As a specific example, a methyl group,
Examples thereof include an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group and a normal octyl group, and preferably an ethyl group, a normal butyl group, an isobutyl group, a normal hexyl group or a normal octyl group. It is a base.

When Y is a halogen atom, specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. 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,
Ethoxy group, n-propoxy group, isopropoxy group, n
-Butoxy group, sec-butoxy group, t-butoxy group,
Examples include n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, and the like, preferably methoxy group, ethoxy group or t-butoxy group. is there.

The aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms, and specific examples include, for example, 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 group, 2,3,5,6-
Tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group,
Isopropylphenoxy group, n-butylphenoxy group,
Examples thereof include sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group.

The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms, and specific examples thereof include a benzyloxy group, a (2-methylphenyl) methoxy group and a (3-methylphenyl) methoxy group. , (4-methylphenyl) methoxy group, (2,3-
Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group,
(3,4-dimethylphenyl) methoxy group, (3,5-
Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl)
Methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-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. , And preferably a benzyloxy group.

Specific examples of the organoaluminum compound represented by the general formula [7] include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum,
Trialkylaluminums such as trinormaloctylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethyl Alkyl aluminum dichlorides such as aluminum dichloride, normal propyl aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride,
Dialkyl aluminum hydrides such as dinormal propyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride and dinormal hexyl aluminum hydride; trialkoxy aluminum such as trimethoxy aluminum, triethoxy aluminum and tri (t-butoxy) aluminum; methyl ( Alkyl (dialkoxy) aluminum such as dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-t-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t
-Butoxy) aluminum and other dialkyl (alkoxy) aluminum; triphenoxy aluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum and other triaryloxy aluminum; methyl (diphenoxy) aluminum, Alkyl (diaryloxy) aluminums such as methylbis (2,6-diisopropylphenoxy) aluminum and methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2 ，
Examples thereof include dialkyl (aryloxy) aluminums such as 6-diphenylphenoxy) aluminum.

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

The amount of component (A) used is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, per 1 g of component (D). is there. The amount of the component (E) used is 0.0 as the molar ratio (E) / (A) of the aluminum atom of the organoaluminum compound of the component (E) to the transition metal atom of the transition metal compound of the component (A).
It is preferably 1 to 10,000, and 0.1 to 5,
It is more preferably 000, most preferably 1 to 2,000.

As the addition polymerization catalyst, a reaction product obtained by contacting the components (A) and (D), and optionally the component (E) in advance, may be used. You may throw in and use separately. When using the components (A), (D) and (E), any two of them may be contacted in advance and then the other component is contacted.

The method of supplying each catalyst component to the reactor is not particularly limited. Method of supplying each component in a solid state, method of supplying in a solution state dissolved in a hydrocarbon solvent in which components that deactivate catalyst components such as water and oxygen are sufficiently removed, or in a state of suspension or slurry Etc.

When each catalyst component is supplied in a solution state or in a suspended or slurry state, the concentration of the component (D) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. Is. The concentration of the component (E) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atom. The concentration of the component (A) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter in terms of transition metal atom.

The polymerization method is not particularly limited, either.
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 butane, pentane, hexane, heptane, octane and other aliphatic hydrocarbon solvents, benzene, toluene and other aromatic hydrocarbon solvents, and methylene chloride and other halogenated hydrocarbon solvents. Alternatively, the olefin itself can be used as a solvent (bulk polymerization). The polymerization method may be either batchwise polymerization or continuous polymerization, and the polymerization may be carried out in two or more stages under different reaction conditions. Generally, the polymerization time is appropriately determined depending on the kind of the desired olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

Slurry polymerization may be carried out according to known slurry polymerization methods and polymerization conditions, but is not limited thereto. As a preferable polymerization method in the slurry method, a continuous reactor in which a monomer (and a comonomer), a feed, a diluent and the like are continuously added as necessary, and a polymer product is continuously or at least periodically taken out is included. Examples of the reactor include a method using a loop reactor, a plurality of stirring reactors having different reaction conditions 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 of the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably 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. The catalyst can be held in suspension, the medium and at least some of the monomers and comonomers can be maintained in the liquid phase, and pressure can be applied to bring the monomers and comonomers into contact. Therefore, the medium, temperature, and pressure may be selected so 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 a monomer (and a comonomer) to the reaction zone, a method of sequentially adding them, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contacting the monomer (and comonomer).

The gas phase polymerization may be carried out according to known gas phase polymerization methods and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction device, a fluidized bed type reaction tank, preferably a fluidized bed type reaction tank having an enlarged portion is used.
There is no problem even with a reaction apparatus in which a stirring blade is installed in the reaction tank. As a method for supplying each component to the polymerization tank, nitrogen, an inert gas such as argon, hydrogen, ethylene or the like is usually used, and the solution is supplied in a water-free state or is dissolved or diluted in a solvent to prepare a solution or slurry. A method such as supplying in the state can be used. Each catalyst component may be supplied individually, or any component may be contacted in advance in any order and supplied.

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

In the present invention, the following prepolymerization may be carried out before such polymerization (main polymerization).

The prepolymerization is carried out in the presence of the addition polymerization catalyst component (A) comprising the above-mentioned transition metal compound of the present invention and the above-mentioned modified particles (D), or in the presence of the organoaluminum compound (E). It is preferably carried out in a slurry state by supplying a small amount of olefin. Examples of the solvent used for forming a slurry include propane, butane, isobutane, pentane, isopentane, hexane,
Inert hydrocarbons such as heptane, octane, cyclohexane, benzene, toluene can be mentioned. Further, when making a slurry, a liquid olefin can be used in place of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound (E) used in the prepolymerization can be selected within a wide range, such as 0.5 to 700 mol, per 1 mol of the catalyst component (A) for addition polymerization, but 0.8 to 500 mol is preferable, 1 to 200
Molar is particularly preferred.

The amount of olefin to be prepolymerized is
Usually 0.01 to 1000 g per 1 g of modified particles,
Preferably 0.05 to 500 g, particularly preferably 0.1
~ 200g.

The slurry concentration at the time of carrying out the prepolymerization is 0.
1-50 g-modified particles / liter-solvents are preferred, especially 0.5-20 g-modified particles / liter-
Solvents are preferred. The prepolymerization temperature is -20 ° C to 100 ° C.
Is preferable, and 0 ° C to 80 ° C is particularly preferable. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.001M.
Pa to 2 MPa is preferable, and 0.01 MPa to 1 M is particularly preferable.
Pa is preferable, but this is not the case for olefins that are liquid at the pressure and temperature of prepolymerization. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is suitable.

When carrying out the prepolymerization, the addition polymerization catalyst component (A), the modified particles (D), the organoaluminum compound (E), and the olefin may be supplied by the addition polymerization catalyst component (A). ) And the modified particles (D) are brought into contact with each other, or, if necessary, the organoaluminum compound (E) is also brought into contact therewith, and then an olefin is supplied, a catalyst component for addition polymerization (A), the modified particles (D) and the olefin are brought into contact with each other, and then the organoaluminum compound (E) is supplied, the organoaluminum compound (E) and the addition polymerization catalyst component (in the presence of the olefin). Any method such as a method of supplying the modified particles (D) after the contact with the A) may be used, but the modified particles (D) and the organoaluminum compound (E) are contacted with each other. Let It is preferable that the olefin is present in advance when. Further, as the olefin supply method, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying all of a predetermined amount of olefin may be used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the obtained polymer.

In the present invention, the thus obtained prepolymerized product is used as a catalyst component or a catalyst. The prepolymerized catalyst component according to the present invention is obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the addition polymerization catalyst component (A) and the modified particles (D). Olefin in the presence of a prepolymerized catalyst component for addition polymerization, or a catalyst component for addition polymerization (A), modified particles (D), and a primary catalyst obtained by contacting with an organoaluminum compound (E) Is a prepolymerized catalyst component for addition polymerization obtained by prepolymerization. The prepolymerized catalyst according to the present invention,
A catalyst for addition polymerization obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the catalyst component (A) for addition polymerization with the modified particles (D), or the above addition A catalyst for addition polymerization obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting a polymerization catalyst component (A), modified particles (D), and an organoaluminum compound (E). is there. The catalyst using the prepolymerized addition polymerization catalyst component according to the present invention is the addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component and the organoaluminum compound (E).

Examples of the monomer used for the polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers and the like, and two or more kinds of monomers should be used at the same time. You can also Specific examples of these include ethylene, propylene, 1-butene, 1-pentene, and 4-methyl-1-.
Pentene, 5-methyl-1-hexene, 1-hexene,
Olefins such as 1-heptene, 1-octene, 1-nonene, 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-
Endomethylene hexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-
Octadiene, 1,3-cyclooctadiene, 1,3-
Diolefins such as cyclohexadiene; norbornene,
5-methylnorbornene, 5-ethylnorbornene, 5
-Butyl norbornene, 5-phenyl norbornene, 5
-Benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5- Acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5
-Ethoxycarbonyl norbornene, 5-methyl-5-
Methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene,
Cyclic olefins such as 8-methyl-8-tetracyclododecene and 8-cyanotetracyclododecene; styrene, 2
-Alkenylbenzene such as phenylpropylene, 2-phenylbutene and 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p
-Ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene , P-tertiary butyl styrene, p-tertiary butyl styrene and other alkyl styrenes, divinylbenzene and other bisalkenylbenzenes, 1-vinylnaphthalene and other alkenylnaphthalene and other alkenyl aromatic hydrocarbons; acrylic acid, methacrylic acid , Fumaric acid, maleic anhydride, itaconic acid,
Α, β-unsaturated carboxylic acids such as itaconic anhydride and bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, and their metals such as sodium, potassium, lithium, zinc, magnesium and calcium Salt, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Α, β-non-adducts such as isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate. Unsaturated dicarboxylic acids such as saturated carboxylic acid esters, maleic acid and itaconic acid,
Vinyl acetate, vinyl propionate, vinyl caproate,
Examples thereof include vinyl esters such as vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate, polar monomers such as glycidyl acrylate, glycidyl methacrylate, unsaturated carboxylic acid glycidyl esters such as itaconic acid monoglycidyl ester. ..

The present invention applies to homopolymerization or copolymerization of these monomers. Specific examples of the monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and ethylene and 1-.
Examples include octene, propylene and 1-butene,
The present invention 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. As such an olefin polymer, a copolymer of ethylene and α-olefin is particularly preferable, and among them, a copolymer of ethylene and α-olefin having a polyethylene crystal structure is preferable. The α-olefin referred to herein preferably has 3 to 8 carbon atoms.
Α-olefin, specifically 1-butene, 1-butene
Examples include hexene and 1-octene.

[0149]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The measured value of each item in the examples was measured by the following method.

(1) The content of the repeating unit derived from α-olefin in the copolymer was measured by using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation) to measure the characteristic absorption of ethylene and α-olefin. The number of short chain branches per 1000 carbon atoms (SC
Represented as B).

(2) Intrinsic viscosity = [η]: Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer (unit: dl / g).

(3) Melt flow rate = MFR: JI
According to the method defined in SK7210-1995, 1
It is a melt flow rate value measured at a load of 21.18 N (2.16 kg) at 90 ° C. (unit: g / 10 minutes).

(4) Swell ratio = SR: Strand diameter obtained during MFR measurement is 2.095 m which is the inner diameter of the die.
It is a value divided by m.

(5) Melt flow rate ratio = MFRR:
According to the method specified in JIS K7210-1995, 190 ° C, load 211.82N (21.60kg)
The melt flow rate value measured by
It is a value divided by the melt flow rate value (MFR) measured by N (2.16 kg). For the above melt flow rate measurement, 1000 pp of antioxidant was previously prepared.
A polymer compounded with m was used.

(6) Molecular weight and molecular weight distribution It was measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was created using standard polystyrene. The molecular weight distribution is the weight average molecular weight (M
It evaluated by the ratio (Mw / Mn) of w) and the number average molecular weight (Mn). Model: Millipore Outers 150C type column: TSK-GEL GMH6-HT 7.5 ×
300 × 3 bottles Measurement temperature: 140 ° C Solvent: Orthodichlorobenzene, Measurement concentration: 5mg / 5ml

(7) Elemental analysis Zn: A sample was thrown 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: A combustion gas generated by burning a sample in a flask filled with oxygen was absorbed in a sodium hydroxide aqueous solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

(8) Melt tension (MT): 150 using a melt tension tester manufactured by Toyo Seiki Seisakusho
With a piston at ℃ and a descent rate of 5.5 mm / min, the diameter is 2.09
The molten resin extruded from an orifice of mmφ and a length of 8 mm was measured at a take-up speed in the range of 10 to 40 rpm / min (unit: g). This melt tension (MT)
The larger the value of, the higher the melt tension.

Example 1 (1) Nitrogen-substituted 5 liter four-necked flask was charged with 2 liters of tetrahydrofuran and 1.35 liters (2.7 mol) of hexane solution of diethylzinc (2M) at -50 ° C. Cooled to. A solution of 251.5 g (1.37 mol) of pentafluorophenol dissolved in 390 ml of tetrahydrofuran was added dropwise to this over 25 minutes. After the dropping, gradually raise the temperature to room temperature, and
Stir for hours. Then, it heated at 45 degreeC and stirred for 1 hour. Reduce the temperature to 20 ° C. with an ice bath and add H ₂ O 37.
72 g (2.09 mol) was added dropwise over 1.4 hours. As a result, it was divided into a yellow transparent liquid material and a yellow gel material.
After completion of dropping, the mixture was stirred for 2 hours, heated to 40 ° C., and further stirred for 1 hour. After standing overnight at room temperature, 72% by weight of the yellow transparent liquid material and the total amount of the yellow gel-like material were divided into separate flasks each purged with nitrogen, and volatile components were distilled off, respectively, and the pressure was reduced. Below, 120
Drying was carried out at 8 ° C for 8 hours. Then, the solid substance derived from the yellow transparent liquid substance was dissolved in 3 liters of tetrahydrofuran, and this was transferred to a 5 liter flask containing the solid substance derived from the yellow gel substance. After standing still at room temperature for 69 hours, it was dried under reduced pressure at 120 ° C. for 8 hours. as a result,
374 g of a solid product was obtained.

(2) Production of modified particles In a nitrogen-substituted 5 liter four-necked flask, 374 g of the solid product synthesized in Example 1 (1) and 3 liters of tetrahydrofuran were placed and stirred. . Silica heat-treated at 300 ° C. under a nitrogen flow (Sylopol 948 manufactured by Devison; average particle size = 61)
μm; Pore volume = 1.61 ml / g; Specific surface area = 296
m ² / g) 282 g was added. After heating to 40 ° C. and stirring for 2 hours, the solid component was allowed to settle, and the upper slurry portion was removed. As a washing operation, 3 liters of tetrahydrofuran was added to this, and after stirring, the solid component was allowed to settle and the slurry portion of the upper layer was removed.
The above washing operation was repeated 5 times in total. After removing the liquid component with a glass filter, 452 g of modified particles was obtained by drying under reduced pressure at 120 ° C. for 8 hours.

(3) Polymerization After drying under reduced pressure, an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been purged with argon, was evacuated, hydrogen was added so that its partial pressure was 0.001 MPa, and butane was added at 680.
70 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 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 = 0.06 mol.
%, 1-butene = 3.22 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.20 ml of a toluene solution of racemic-ethylenebis (1-indenyl) hafnium dichloride adjusted to a concentration of 1 μmol / ml and a concentration of 2 μmol / ml
Solution of bis (n-butylcyclopentadienyl) zirconium dichloride adjusted to 0.60 ml
Then, 14.6 mg of the modified particles obtained in Example 1 (2) above was charged as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding ethylene gas so as to keep the total pressure constant. As a result, 38 g of an olefin polymer having a good particle property was obtained.
Polymerization activity per total transition metal atom is 2.7 × 10 ⁷ g /
Polymerization activity per solid catalyst component was 2600 g / g solid catalyst component / hour in mol transition metal atom / hour. The obtained olefin polymer has SCB = 13.7, M
FR = 1.15, MFRR = 21, [η] = 1.49,
MT = 19.5.

Example 2 (1) Polymerization After drying under reduced pressure, an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been purged with argon, was evacuated, and hydrogen was added so that the partial pressure was 0.002 MPa. 680
70 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 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 = 0.08 mol.
%, 1-butene = 3.97 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.10 ml of a toluene solution of racemic-ethylenebis (1-indenyl) hafnium dichloride adjusted to a concentration of 1 μmol / ml and a concentration of 2 μmol / ml
Toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride adjusted to 0.40 ml
Then, 13.2 mg of the modified particles obtained in Example 1 (2) above was charged as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding ethylene gas so as to keep the total pressure constant. As a result, 33 g of an olefin polymer having a good particle property was obtained.
Polymerization activity per total transition metal atom is 3.7 × 10 ⁷ g /
Polymerization activity per solid catalyst component was 2500 g / g solid catalyst component / hour in mol transition metal atom / hour. The obtained olefin polymer has SCB = 13.9, M
FR = 8.41, MFRR = 19, Mw = 5.86 × 1
0 ⁴ , Mw / Mn = 1.85, [η] = 1.15, MT
= 3.9.

Reference Example 1 (1) Polymerization After drying under reduced pressure, an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been purged with argon, was evacuated, and hydrogen was added so that the partial pressure thereof became 0.012 MPa. To 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 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 = 0.66 mol.
%, 1-butene = 2.23 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and subsequently the modified particles obtained in Example 1 (2) above. 15.0 mg was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.31 mol% of hydrogen so as to keep the total pressure constant. As a result, an olefin polymer with good particle properties
68 g were obtained. The polymerization activity per all zirconium atoms was 1.4 × 10 ⁸ g / mol Zr / hour, and the polymerization activity per solid catalyst component was 4500 g / g solid catalyst component / hour. The obtained olefin polymer is SCB
= 13.7, MFR = 1.53, MFRR = 48, SR
= 1.29, Mw = 1.03 × 10 ⁵ , Mw / Mn =
It was 4.00, [(eta)] = 1.35, MT = 3.4.

Reference Example 2 (1) Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, and hydrogen was added so that the partial pressure thereof became 0.020 MPa. To 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 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 = 1.00 mol
%, 1-butene = 2.11 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and subsequently the modified particles obtained in Example 1 (2) above. 15.4 mg was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.31 mol% of hydrogen so as to keep the total pressure constant. As a result, an olefin polymer with good particle properties
50 g were obtained. The polymerization activity per all zirconium atoms was 1.0 × 10 ⁸ g / mol Zr / hour, and the polymerization activity per solid catalyst component was 3300 g / g solid catalyst component / hour. The obtained olefin polymer is SCB
= 13.1, MFR = 4.06, MFRR = 42, SR
= 1.38, Mw = 8.05 × 10 ⁴ , Mw / Mn =
It was 4.24, [(eta)] = 1.14, MT = 2.0.

[0164]

As described above in detail, according to the present invention, an addition polymerization catalyst component and an addition polymerization catalyst used for producing an addition polymer having a high melt tension and excellent processability, and a high melt tension can be processed. Provided is a method for producing an addition polymer having excellent properties. Further, according to the present invention, there is provided a use of the transition metal compound for producing an addition polymer having high melt tension and excellent processability.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA02A AB00A AB01A AC01A                       AC10A AC28A BA00B BA01B                       BA02B BA03B BA04B BB00B                       BB01B BB02B BC01B BC09B                       BC12B BC15B BC16B BC17B                       BC25B BC27B CB25C CB63C                       CB64C EB02 EB03 GA26

Claims (6)

[Claims] 1. A catalyst component for addition polymerization comprising a transition metal compound of the following (i) and a transition metal compound of the following (ii). (I): a transition having two groups having a cyclopentadiene type anion skeleton, the groups having the cyclopentadiene type anion skeleton bonded to each other directly or via a cross-linking group, and the central metal being hafnium Metal compound. (Ii): having two groups having a cyclopentadiene type anion skeleton having a substituent, and the groups having this cyclopentadiene type anion skeleton are not bonded to each other,
A transition metal compound whose central metal is zirconium or titanium. 2. A catalyst for addition polymerization obtained by contacting the catalyst component for addition polymerization according to claim 1 and a cocatalyst component for activation. 3. A method for producing an addition polymer using the catalyst for addition polymerization according to claim 2. 4. The method for producing an addition polymer according to claim 3, wherein the addition polymer is an olefin polymer. 5. The method for producing an addition polymer according to claim 3, wherein the addition polymer is a copolymer of ethylene and α-olefin. 6. A transition metal compound of the following (i) and a transition of the following (ii) when producing an addition polymer by homopolymerization of addition-polymerizable monomers or copolymerization of two or more addition-polymerizable monomers. Use of a mixture of metal compounds as a catalyst component for addition polymerization. (I): a transition having two groups having a cyclopentadiene type anion skeleton, the groups having the cyclopentadiene type anion skeleton bonded to each other directly or via a cross-linking group, and the central metal being hafnium Metal compound. (Ii): having two groups having a cyclopentadiene type anion skeleton having a substituent, and the groups having this cyclopentadiene type anion skeleton are not bonded to each other,
A transition metal compound whose central metal is zirconium or titanium.