JP2012057174A - Polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition polymerization catalyst component and an addition polymerization catalyst, used in manufacturing an addition polymer high in melt tension and excellent in processability; and to provide a method for manufacturing an addition polymer high in melt tension and excellent in processability.SOLUTION: The polymerization catalyst for ethylene and α-olefin is prepared by bringing an olefin polymerization catalyst component including a transition metal compound of (i) and a transition metal compound of (ii) into contact with an activating cocatalyst component and an organoaluminum compound: (i) A transition metal compound which has two groups having a cyclopentadienic anion skeleton, the two groups being bonded to each other directly or through a crosslinking group, and has hafnium as a central metal; (ii) A transition metal compound which has two groups having a cyclopentadienic anion skeleton having a substituent, the two groups not being bonded to each other, and has zirconium as a central metal.

Description

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

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

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

  By the way, there are various uses of addition polymers such as polypropylene and polyethylene, and various properties are required depending on the molding method and use. For example, when an inflation film is to be molded at 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, the addition polymers obtained using conventional single-site catalysts have many melt tensions that are not so high and are not suitable for use.

JP 58-19309 A Japanese translation of PCT publication No. 1-502036

  The object of the present invention is to provide an addition polymerization catalyst component and an addition polymerization catalyst used for the production of an addition polymer having a high melt tension and excellent processability, and a method for producing an addition polymer having a high melt tension and excellent processability. There is to do. A further object of the present invention is to provide a use of a transition metal compound for producing an addition polymer having a high melt tension and excellent workability.

The present invention provides an olefin polymerization catalyst component comprising the transition metal compound of the following (i) and the transition metal compound of the following (ii), an activation co-catalyst component, and ethylene obtained by contacting an organoaluminum compound with α -It relates to a catalyst for polymerization with olefins.
(I): a transition having two groups having a cyclopentadiene-type anion skeleton, the groups having this cyclopentadiene-type anion skeleton being bonded to each other directly or via a bridging group, and the central metal being hafnium Metal compound.
(Ii): a transition metal compound having two groups having a cyclopentadiene-type anion skeleton having a substituent, the groups having this cyclopentadiene-type anion skeleton are not bonded to each other, and the central metal is zirconium .
The present invention also relates to a method for producing a copolymer of ethylene and α-olefin using the above-described catalyst for polymerization of ethylene and α-olefin.
Hereinafter, the present invention will be described in more detail.

  According to the present invention, there are provided an addition polymerization catalyst component and an addition polymerization catalyst used for the production of an addition polymer having a high melt tension and excellent processability, and a method for producing an addition polymer having a high melt tension and excellent processability. Is done. Furthermore, according to this invention, the use of the transition metal compound for manufacturing the addition polymer which has high melt tension and is excellent in workability is provided.

The group having a cyclopentadiene-type anion skeleton of the transition metal compound (i) or (ii) (hereinafter, may be abbreviated as “Cp group”) is a η ^5- (substituted) cyclopentadienyl group. Η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group, and the like. Specific examples include 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- methylpropyl cyclopentadienyl group, eta ⁵ - diethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, eta ⁵ - methylindenyl group, eta ⁵ - butyl indenyl group, ⁵ - dimethyl indenyl group, eta ⁵ - trimethyl indenyl group, eta ⁵ - methylpropyl indenyl group, eta ^5-4,5 benzindenyl group, eta ⁵ - methyl-4,5-benzindenyl group, eta ⁵ - phenyl indenyl group, eta 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 substituted thereof Examples include the body.
In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

In the above examples, there are many combinations of di- and tri-substituted η ⁵ -cyclopentadienyl groups depending on the position of the substituent, but all of these 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 include isomers such as n-, i-, sec- and tert-.

The group having a cyclopentadiene type anion skeleton of the transition metal compound (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- (substituted) fluorenyl group, and the like. As examples of the group having a cyclopentadiene-type anion skeleton other than the η ⁵ -cyclopentadienyl group.

  The 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. In the transition metal compound (ii), the two Cp groups are Are not connected to each other. In the transition metal compound (i), the two Cp groups are preferably bonded to each other via a bridging group. As such a bridging group, many bridging groups that bridge 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 atoms bonded to two Cp groups are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 A divalent atom having a minimum number of atoms of 3 or less between the atoms bonded to two Cp groups, wherein the atoms bonded to one Cp group are carbon atoms, silicon atoms, nitrogen atoms, oxygen atoms, sulfur atoms and / or phosphorus atoms. Residue (this includes the case where there is a single atom attached to two Cp groups). Specifically, an alkylene group such as an ethylene group or a propylene group, a substituted alkylene group such as a dimethylmethylene group or a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisylylene group. Or a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, particularly preferably a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene. It is a group.

The transition metal compound (i) is preferably a transition metal compound represented by the following general formula [4].
L ² ₂ HfX ¹ ₂ [4]
(In the formula, L ² is a group having a cyclopentadiene type anion skeleton, and two L ² may be the same or different, and two L ² may be directly or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom. X ¹ represents a halogen atom, a hydrocarbon 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 group or η ⁵ -alkyl-substituted indenyl group is preferable.
Two L ² in the general formula [4] 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. Such a residue is as described above, and preferably, as the transition metal compound represented by the general formula [4], two L ² are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. 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. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, and an aryl group, and preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 6 to 20 carbon atoms. Are preferred.

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

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

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

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

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

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

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

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

  Specific examples of the transition metal compound represented by the general formula [4] include ethylene bis (cyclopentadienyl) hafnium dichloride, ethylene bis (methylcyclopentadienyl) hafnium dichloride, and ethylene bis (ethylcyclopentadienyl). ) Hafnium dichloride, ethylenebis (propylcyclopentadienyl) hafnium dichloride, ethylenebis (butylcyclopentadienyl) hafnium dichloride, ethylenebis (hexylcyclopentadienyl) hafnium dichloride, ethylenebis (octylcyclopentadienyl) hafnium Dichloride, ethylenebis (dimethylcyclopentadienyl) hafnium dichloride, ethylenebis (diethylcyclopentadienyl) hafnium dichloride, ethylenebi (Ethylmethylcyclopentadienyl) hafnium dichloride, ethylenebis (butylmethylcyclopentadienyl) hafnium dichloride, ethylenebis (trimethylcyclopentadienyl) hafnium dichloride, ethylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylene Bis (indenyl) hafnium dichloride, ethylenebis (methylindenyl) hafnium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, ethylenebis (phenylindenyl) hafnium dichloride, ethylenebis (fluorenyl) Hafnium dichloride,

Ethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, ethylene (cyclopentadienyl) (indenyl) hafnium dichloride, ethylene (methylcyclopentadienyl) (indenyl) hafnium dichloride, ethylene (ethylcyclopentadiene) Dienyl) (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 dichlori , And ethylene (indenyl) (fluorenyl) hafnium dichloride,

Compounds in which ethylene 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 (pentafluorophenoxide), bis (2, 3,5,6-tetrafluoro-4-pentafluorophenyl phenoxide), or a compound changed to dibenzyl.

In the above examples, the mono-substituted product of the η ⁵ -cyclopentadienyl group includes 2-position and 3-position substituents, and the di-substituted product is 2,3-position, 2,4-position, 2 , 5- and 3,5-position substitutions, and tri-substitutions include 2,3,4-position and 2,3,5-position substitutions. Similarly, in the case of a substituted η ⁵ -indenyl group, when the bridging group is in the 1-position, if it is a mono-substituted product, the 2-position, the 3-position, the 4-position, the 5-position, the 6-position and the 7-position In the same manner, all combinations are included even when the cross-linked position is other than the 1-position. Similarly, di-substituted compounds or more also include all combinations of substituents and crosslinking positions. Similarly, the substitution product of the η ⁵ -fluorenyl group includes all combinations of substituents and crosslinking positions. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-. Unless otherwise indicated, alkoxy groups such as propoxy and butoxy include isomers such as n-, i-, sec- and tert-. Two or more of these complexes may be used.

The transition metal compound (ii) is preferably a transition metal compound represented by the following general formula [5].
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 not crosslinked. X ² is a halogen atom, carbonized Represents a hydrogen 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, an η ⁵ -alkyl-substituted cyclopentadienyl group is preferable. Two L ³ 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 general formula [4].

  Specific examples of the transition metal compound represented by the general formula [5] include bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, and bis (propylcyclopentadienyl) titanium. Dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (hexylcyclopentadienyl) titanium dichloride, bis (octylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (diethylcyclo Pentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (methylbutylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride Rholide, 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, ( (Lopylcyclopentadienyl) (fluorenyl) titanium dichloride, (butylcyclopentadienyl) (fluorenyl) titanium dichloride, (hexylcyclopentadienyl) (fluorenyl) titanium dichloride, (octylcyclopentadienyl) (fluorenyl) titanium Dichloride, (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, (indenyl) (fluorenyl) titanium dichloride,

Compounds in which titanium is changed to zirconium, 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-pentafluorophenyl) Phenoxide) or a compound changed to dibenzyl can be exemplified.

In the above example, the disubstituted η ⁵ -cyclopentadienyl group includes 1,2-position and 1,3-position substituents, and the trisubstituted body includes 1,2,3-positions, 1, Includes substitutions at the 2,4-position. Similarly, a substituted form of η ⁵ -indenyl group includes a substituted form of 1-position, 2-position, 4-position and 5-position and a symmetric form thereof as long as it is a mono-substituted form. Includes combinations.
Similarly, the substitution product of η ⁵ -fluorenyl group includes all combinations. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-. Unless otherwise indicated, alkoxy groups such as propoxy and butoxy include isomers such as n-, i-, sec- and tert-. Two or more of these complexes may be used.

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

(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ 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 may be the same or different, Z is a hydrogen atom or a halogen atom And all Z's may be the same or different, a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
(C): one or more boron compounds selected from the following (C1) to (C3) (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, substituted silyl groups, alkoxy groups or disubstituted amino groups, which may be the same or different, G ⁺ is an inorganic or organic cation. Yes, 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 at least one aluminum compound selected from the following (B1) to (B3).
(B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O—} Cyclic aluminoxane (B3) having the structure represented by _b General formula E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane having a structure represented by AlE ³ ₂ (where 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 represents a hydrogen atom or a halogen atom, and all Z may be the same or different. (A number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
As the hydrocarbon group in E ^1, E ² or E ^3,, preferably a hydrocarbon group having 1 to 8 carbon atoms, the alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminums such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Dichloride Examples thereof include dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.
Preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum or trinormaloctylaluminum, and particularly preferred is triisobutylaluminum or trinormaloctylaluminum. is there.

Cyclic aluminoxane (B2) having a structure represented by the general formula {-Al (E ² ) —O—} _b , a structure represented by the general formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Specific examples of E ² and E ^{3 in} the linear aluminoxane (B3) having a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, a neopentyl group, etc. An alkyl group can be illustrated. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.
The aluminoxane produced by such a method is usually considered to be a mixture of a cyclic aluminoxane and a linear aluminoxane.

(C) Boron Compound As the boron compound (C), (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (C3) One or more boron compounds selected from boron compounds represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ are used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups, halogenated hydrocarbons. A 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 a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substitution containing 1 to 20 carbon atoms A silyl group, 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 halogen atoms, carbonization containing 1 to 20 carbon atoms A hydrogen group or a halogenated hydrocarbon group containing 1 to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms each containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q ⁴ are each at least one fluorine atom. It is a fluorinated aryl group having 6 to 20 carbon atoms including atoms.

  Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, Examples include tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and most preferably tris (pentafluoro). Phenyl) 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 a boron atom in a trivalent valence state. , Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

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 cation, alkyl-substituted ferrocenium cation, silver cation, etc. However, examples of G ⁺ that is an organic 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 ) ⁻ includes 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) Fluoromethylphenyl) borate and the like.

  Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (Pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In the boron compound (C3) represented by the general formula (L—H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L is a neutral Lewis base, and (L—H) ⁺ is a slashed.nsted acid, B is a 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).

Specific examples of (LH) ⁺ which is a Bronsted acid in the compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include trialkyl-substituted ammonium, N, N - dialkylanilinium, dialkylammonium and triarylphosphonium ^{mentioned, (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 (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, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate.

  In the present invention, the contact at the time of producing the addition polymerization catalyst obtained by bringing the transition metal compound and the activation promoter component into contact with each other is such that the transition metal compound and the activation promoter component are in contact with each other. As long as the catalyst is formed, any means may be used. A method in which the transition metal compound and the activating co-catalyst component are mixed and brought into contact with each other by diluting with a solvent in advance or not, or separately in a polymerization tank. The method of supplying and contacting in a polymerization tank can be taken. Here, the co-catalyst component for activation may be used in combination of a plurality of types, but some of them may be mixed in advance and used separately or supplied to the polymerization tank Needless to say.

  The amount of each component used is usually a molar ratio of (B) / transition metal compound (A) of 0.1 to 10,000, preferably 5 to 2000, and a molar ratio of (C) / transition metal compound (A) of 0. It is desirable to use each component so that it is in the range of 0.01 to 100, preferably 0.5 to 10.

  The concentration in the case of supplying each component in a solution state or in a state suspended or slurried in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. The compound (A) is usually 0.0001 to 1000 mmol / liter, more preferably 0.05 to 200 mmol / liter, still more preferably 0.01 to 50 mmol / liter, and (B) is an Al atom. In terms of conversion, it is usually 0.01 to 5000 mmol / liter, more preferably 0.1 to 2500 mmol / liter, more preferably 0.1 to 2000 mmol / liter, and (C) is usually 0.001 to 0.001 mmol / liter. 500 mmol / liter, more preferably 0.01 to 250 mmol / liter, still more preferably 0.05 to 100 mmol / liter. It is desirable to use each component to be in the range of liters.

  The addition polymerization catalyst is an addition polymerization catalyst obtained by bringing the transition metal compound (A) into contact with the above (B) and / or the above (C). The transition metal compound (A) and When the addition polymerization catalyst obtained by contacting with (B) is used, the above cyclic aluminoxane (B2) and / or linear aluminoxane (B3) is preferable as (B). Other preferred addition polymerization catalysts include addition polymerization catalysts obtained by bringing transition metal compounds (A), (B) and (C) into contact with each other. The above (B1) is easy to use.

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

  The polymerization temperature can usually be in the range of −50 ° C. to 200 ° C., but the range of −20 ° C. to 100 ° C. is particularly preferable, and the polymerization pressure is usually preferably normal pressure to 6 MPa. In general, the polymerization time is appropriately determined 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. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

  When the addition polymerization catalyst component comprising the above transition metal compound of the present invention is applied to polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), an activation cocatalyst is used. The following modified particles (I) or (II) are preferably used as the component. That is, as a preferred addition polymerization catalyst of the present invention, the above addition polymerization catalyst component (A) comprising the transition metal compound of the present invention, and the modified particles (D) of (I) or (II) below: The catalyst for addition polymerization obtained by contacting is mentioned.

(I) Modified particles obtained by bringing the following (a), (b), (c) and particles (d) into contact with each other.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(In the above general formulas [1] to [3], M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table, and m represents a valence of M ^1. L 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, and R ¹ contains an electron-withdrawing group or an electron-withdrawing group In the case where a plurality of R ¹ are present, they may be the same or different from each other, R ² represents a hydrocarbon group or a halogenated hydrocarbon group, and each T independently represents a group in the periodic table. Represents an atom of Group 15 or Group 16, and t represents the valence of T of each compound.)

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

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

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

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

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

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

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

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

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

R ¹ in the 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 as or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule constant σ are listed as electron withdrawing groups.

  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 the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group) and the like.

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

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

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

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

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

  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-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-tri Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Methylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl 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 a pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, and most preferably a trialkyl group. Fluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group , 3,4,5-trifluorophenyl group or pentafluorophenyl group.

R ² in the general formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group for R ² is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbon group as described for L ¹ in the general formula [1] is used. Examples of the halogenated hydrocarbon group for R ² include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group for R ¹ in the general formula [2] The same halogenated alkyl group, halogenated aryl group and (halogenated alkyl) aryl group as those mentioned above are used.

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

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

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

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

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

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

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

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

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

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

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

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

Examples of inorganic substances that can be used as the particles (d) include inorganic oxides and magnesium compounds, and clays and clay minerals can be used as long as they do not hinder. These may be mixed and used.
Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof such as SiO ₂ — Examples thereof include MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and silica is particularly preferable. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO _3.
, Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents may be used. A nonpolar solvent is more preferred. This is because the contact product between (a) and (c) or the contact product between (a) and (b) and (c) is generally soluble 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 that the produced contact product is deposited on the surface of (d) than in a nonpolar solvent. It is preferable because it is considered that the fixation becomes easier.

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: y: z 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. )
In the above formula (1), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1).

  In the actual contact treatment of each compound, even if the use of each compound is intended to completely satisfy the above formula (1), the amount used may fluctuate slightly and remain unreacted. In consideration of the amount of the compound to be used, etc., it is usual to slightly increase or decrease the amount used as appropriate. Here, “substantially satisfying the formula (1)” is obtained by bringing each compound into contact with each other at a molar ratio satisfying the above formula (1) without completely satisfying the above formula (1). It is meant to be included when attempting to obtain such objects.

  In the preparation of modified particles (I), the amount of (d) used relative to (a) is derived from (a) contained in the particles obtained by contacting (a) and (d). It is preferable that the amount of the typical metal atom to be converted is 0.1 mmol or more in terms of the number of moles of the typical metal atom contained in 1 g of the obtained particles, and more preferably 0.5 to 20 mmol. And may be determined as appropriate within the range.

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

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

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

(II) Modified particles obtained by contacting aluminoxane (e) and particles (d).
As the aluminoxane (e) used for the preparation of the modified particles (II), a cyclic aluminoxane having a structure represented by the general formula {-Al (E ² ) —O—} _b and / or the general formula E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane having a structure represented by 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, and 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. To express.)
As the hydrocarbon group in E ^1, E ² or E ^3,, preferably a hydrocarbon group having 1 to 8 carbon atoms, the alkyl group is more preferable.

Specific examples of E ² and E ³ include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, 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 are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making the metal salt (for example, copper sulfate hydrate etc.) containing crystal water contact the trialkylaluminum (for example, trimethylaluminum etc.) can be illustrated. The aluminoxane obtained by such a method is usually considered to be a mixture of a cyclic aluminoxane and a linear aluminoxane.

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

  Although the temperature and time to contact can be taken arbitrarily, the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C. In particular, the reaction is preferably performed at a low temperature in order to suppress heat generation at the initial stage of the reaction. The amount of contact can be arbitrarily selected, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol, preferably 0.1 to 20 mmol, more preferably 1 to 20 in terms of aluminum atom. 10 mmol.

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

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

R ⁴ in the general formula [7] representing the organoaluminum compound is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms.
Specific examples include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a normal octyl group, and the like, preferably an ethyl group, a normal butyl group, and an isobutyl group. A group, a normal hexyl group or a normal octyl group.

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

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

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

  Specific examples of the organoaluminum compound represented by the general formula [7] include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum and the like. Dimethylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride , Alkyl aluminum dichlorides such as normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride Dialkylaluminum hydrides; trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum and tri (t-butoxy) aluminum; alkyls such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum and methyl (di-t-butoxy) aluminum ( The (Lucoxy) aluminum; Dialkyl (alkoxy) aluminum such as dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2, Triaryloxyaluminum such as 6-diphenylphenoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (Phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2,6-diphenylphenoxy) Ii) Dialkyl (aryloxy) aluminum such as aluminum can be exemplified.

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

The amount of component (A) used is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, relative to 1 g of component (D). Moreover, the usage-amount of a component (E) is 0.01-10 as molar ratio (E) / (A) of the aluminum atom of a component (E) organoaluminum compound with respect to the transition metal atom of a component (A) transition metal compound. 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As such an addition polymerization catalyst, components (A) and (D), and in some cases, a reaction product obtained by previously contacting component (E) may be used, and they are charged separately into the polymerization reactor. May be used. When components (A), (D) and (E) are used, any two of them may be contacted in advance, and then another component may be contacted.

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

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

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

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

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

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

The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction apparatus, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even in a reactor equipped with a stirring blade in the reaction vessel.
As a method for supplying each component to the polymerization tank, a solution or a slurry is usually supplied by using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like without supplying moisture, or by dissolving or diluting in a solvent. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

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

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

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

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

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

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

  When the prepolymerization is carried out, the addition polymerization catalyst component (A), the modified particles (D), the organoaluminum compound (E), and the method of supplying the olefin include the addition polymerization catalyst component (A), A method for supplying an olefin after contact with the modified particles (D) or after contact with an organoaluminum compound (E) as necessary, catalyst component for addition polymerization (A) , A method of supplying the organoaluminum compound (E) after contacting the modified particles (D) and the olefin, and the organoaluminum compound (E) and the catalyst component for addition polymerization (A) in the presence of the olefin. Any method such as a method of supplying the modified particles (D) after contact may be used, but when the modified particles (D) and the organoaluminum compound (E) are brought into contact with each other. Is me It is preferable that fin is present in advance. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

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

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

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

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

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

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

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

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

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

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

(6) Molecular weight and molecular weight distribution It measured on the following conditions by gel permeation chromatography (GPC).
A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Model 150C manufactured by Millipore Waters Inc .: TSK-GEL GMH6-HT 7.5 × 300 × 3 Measurement temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5 mg / 5 ml

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

(8) Melt tension (MT): Made of Toyo Seiki Seisakusho, using a melt tension tester, a molten resin extruded from an orifice with a diameter of 2.09 mmφ and a length of 8 mm with a piston at 150 ° C. and a descending speed of 5.5 mm / min. , Measured at a winding up speed in the range of 10 to 40 rpm / min (unit: g). It shows that melt tension is so high that the value of this melt tension (MT) is large.

[Example 1]
(1)
A 5-liter four-necked flask purged with nitrogen was charged with 2 liters of tetrahydrofuran and 1.35 liters (2.7 mol) of diethylzinc in hexane (2M) and cooled to -50 ° C. A solution prepared by dissolving 251.5 g (1.37 mol) of pentafluorophenol in 390 ml of tetrahydrofuran was added dropwise thereto over 25 minutes. After completion of the dropping, the temperature was gradually raised to room temperature and stirred for 3 hours. Then, it heated at 45 degreeC and stirred for 1 hour. The temperature was lowered to 20 ° C. in an ice bath, and 37.72 g (2.09 mol) of H ₂ O was added dropwise over 1.4 hours. As a result, it was separated into a yellow transparent liquid and a yellow gel. After completion of the dropping, the mixture was stirred for 2 hours, heated to 40 ° C., and further stirred for 1 hour. After standing at room temperature overnight, 72% by weight of the yellow transparent liquid and the total amount of the yellow gel were separated into separate flasks each purged with nitrogen, and each volatile component was distilled off under reduced pressure. Then, drying was performed at 120 ° C. for 8 hours. Thereafter, the solid derived from the yellow transparent liquid was dissolved in 3 liters of tetrahydrofuran, and transferred to a 5 liter flask containing the solid derived from the yellow gel. After leaving still at room temperature for 69 hours, it dried under reduced pressure at 120 degreeC for 8 hours. As a result, 374 g of a solid product was obtained.

(2) Production of modified particles In a 5-liter four-necked flask purged with nitrogen, 374 g of the solid product synthesized in Example 1 (1) and 3 liters of tetrahydrofuran were placed and stirred. To this was added 282 g of silica (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.61 ml / g; specific surface area = 296 m ² / g) manufactured at 300 ° C. under nitrogen flow. 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 thereto and stirred, and then the solid component was allowed to settle, and the upper slurry portion was removed. The above washing operation was repeated 5 times in total. After removing the liquid component with a glass filter, drying was performed at 120 ° C. for 8 hours under reduced pressure to obtain 452 g of modified particles.

(3) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.001 MPa, 680 g of butane and 70 g of 1-butene. The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.06 mol% and 1-butene = 3.22 mol%. To this, 0.9 ml of a heptane solution of triisobutylaluminum having a concentration 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 bis (n-butylcyclopentadienyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml 0.60 ml of a toluene solution of was added, followed by 14.6 mg of the modified particles obtained in Example 1 (2) 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. The polymerization activity per total transition metal atom was 2.7 × 10 ⁷ g / mol transition metal atom / hour, and the polymerization activity per solid catalyst component was 2600 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 13.7, MFR = 1.15, MFRR = 21, [η] = 1.49, and MT = 19.5.

[Example 2]
(1) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.002 MPa, 680 g of butane and 70 g of 1-butene. The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.08 mol% and 1-butene = 3.97 mol%. To this, 0.9 ml of a heptane solution of triisobutylaluminum having a concentration 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 bis (n-butylcyclopentadienyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml 0.40 ml of a toluene solution of was added, followed by 13.2 mg of the modified particles obtained in Example 1 (2) 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. The polymerization activity per total transition metal atom was 3.7 × 10 ⁷ g / mol transition metal atom / hour, and the polymerization activity per solid catalyst component was 2500 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 13.9, MFR = 8.41, MFRR = 19, Mw = 5.86 × 10 ⁴ , Mw / Mn = 1.85, [η] = 1.15, MT = 3.9.

[Reference Example 1]
(1) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.012 MPa, 700 g of butane and 50 g of 1-butene. The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.66 mol% and 1-butene = 2.23 mol%. To this, 0.9 ml of a heptane solution of triisobutylaluminum having a concentration adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic ethylene bis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then 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, 68 g of an olefin polymer having a good particle property was obtained. The polymerization activity per total zirconium atom was 1.4 × 10 ⁸ g / molZr / hour, and the polymerization activity per solid catalyst component was 4500 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 13.7, MFR = 1.53, MFRR = 48, SR = 1.29, Mw = 1.03 × 10 ⁵ , Mw / Mn = 4.00, [η ] = 1.35, MT = 3.4.

[Reference Example 2]
(1) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.020 MPa, 700 g of butane and 50 g of 1-butene. The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.00 mol% and 1-butene = 2.11 mol%. To this, 0.9 ml of a heptane solution of triisobutylaluminum having a concentration adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic ethylene bis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then the modified particles obtained in Example 1 (2) above. 15.4 mg was charged 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, 50 g of an olefin polymer having a good particle property was obtained. The polymerization activity per total zirconium atom 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 had SCB = 13.1, MFR = 4.06, MFRR = 42, SR = 1.38, Mw = 8.05 × 10 ⁴ , Mw / Mn = 4.24, [η ] = 1.14, MT = 2.0.

Claims (4)

A catalyst component for olefin polymerization comprising the transition metal compound of the following (i) and the transition metal compound of the following (ii):
A catalyst for polymerization of ethylene and α-olefin obtained by contacting an activating co-catalyst component and an organoaluminum compound.
(I): a transition having two groups having a cyclopentadiene-type anion skeleton, the groups having this cyclopentadiene-type anion skeleton being bonded to each other directly or via a bridging group, and the central metal being hafnium Metal compound.
(Ii): a transition metal compound having two groups having a cyclopentadiene-type anion skeleton having a substituent, the groups having this cyclopentadiene-type anion skeleton are not bonded to each other, and the central metal is zirconium . The polymerization catalyst according to claim 1, wherein the transition metal compound of (i) is represented by the following formula [4].
L ² ₂ HfX ¹ ₂ [4]
(Wherein L ² is a η ⁵ -indenyl group or a η ⁵ -alkyl-substituted indenyl group, the two L ^{2 s} may be the same or different, and the two L ² represent a residue containing a carbon atom. X ¹ represents a halogen atom, a hydrocarbon group or a hydrocarbon oxy group.) The polymerization catalyst according to claim 1 or 2, wherein the transition metal compound of (ii) is represented by the following formula [5].
L ³ ₂ ZrX ² ₂ [5]
(In the formula, L ³ is an η ⁵ -alkyl-substituted cyclopentadienyl group, and two L ³ are not crosslinked. X ² represents a halogen atom, a hydrocarbon group, or a hydrocarbon oxy group.) The manufacturing method of the copolymer of ethylene and an alpha olefin using the catalyst for polymerization in any one of Claims 1-3.