JP2002338573A - Phthalocyanine complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phthalocyanine complex capable of forming a catalyst for olefin polymerization exhibiting high polymerization activity by using the complex as a cocatalyst component. SOLUTION: This phthalocyanine complex comprises a compound represented by general formula [1] (wherein M represents an atom of the group 8-10; T represents an atom of the group 14 or 15; R<1> and R<2> represent each independently hydrogen atom, a halogen atom, a hydrocarbon group or a halogenated hydrocarbon group; X represents hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbonoxy group; m represents a valence of M) and exhibits a strongest diffraction peak to CuKα-characteristic X ray at a position larger than 15 deg. of Bragg angle (2θ±0.2 deg.) in X-ray diffraction spectrum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phthalocyanine complex useful as a catalyst component for olefin polymerization.

[0002]

2. Description of the Related Art Olefin polymers such as polypropylene and polyethylene are widely used in various molding fields because of their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economic efficiency. I have. Conventionally, these olefin polymers are obtained by combining a solid catalyst component mainly obtained using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride with a Group 13 metal compound represented by an organoaluminum compound. It has been produced by polymerizing olefins using a conventional solid catalyst (multi-site catalyst).

In recent years, transition metal compounds (eg, metallocene complexes) different from solid catalyst components that have been used for a long time
There has been proposed a method for producing an olefin polymer in which olefin is polymerized using a so-called single-site catalyst in which olefin is combined with aluminoxane or the like. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported to combine certain boron compounds with such transition metal compounds. For example, Japanese Patent Application Laid-Open No. 1-502036 discloses a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Olefin polymers obtained with these single-site catalysts have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomers are copolymerized more uniformly. Therefore, it is known that a more homogeneous olefin polymer can be obtained than when a conventional solid catalyst is used.

[0004] Improvements in such olefin polymerization catalysts have been studied diligently, and the types of metals used as main catalyst components have been widely reported in each group of the periodic table. For example, Angew. Chem. Int. Ed. 3
8 , 428 (1999) reports that a metallocene complex of a Group 3 to 13 metal or a nonmetallocene compound is effective as a main catalyst component. On the other hand, as the co-catalyst component for activation to be combined with a metallocene complex or a non-metallocene compound, aluminoxane or boron compound belonging to Group 13 compounds occupies the center of its development.

On the other hand, phthalocyanine complexes are widely used in the field of electrophotographic photoreceptors and the like, but no examples have been used in the field of olefin polymerization.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phthalocyanine complex which can be used as an activating co-catalyst component to form an olefin polymerization catalyst having high polymerization activity.

[0007]

The present invention comprises a compound represented by the following general formula [1], and in the X-ray diffraction spectrum, the strongest diffraction peak for CuKα characteristic X-ray is represented by the Bragg angle (2θ ± 2). (0.2 °) of the phthalocyanine complex appearing at a position larger than 15 °. (Wherein, M represents an atom of Groups 8 to 10 of the periodic table, T represents an atom of Groups 14 or 15 of the periodic table, and all Ts are the same or different from each other. R ¹
And R ² are each independently a hydrogen atom, a halogen atom,
It is a hydrocarbon group or a halogenated hydrocarbon group, and all R ¹ and all R ² may be the same or different from each other, and may form a ring with each other. Note that T
Is a Group 15 atom, there is no R ² attached to it. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon oxy group. When a plurality of Xs are present, they may be the same or different. m represents the valence of M. Hereinafter, the present invention will be described in more detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION M in the above general formula [1] is
Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 19)
89) represents an atom belonging to Groups 8 to 10. Specific examples thereof include an iron atom, a ruthenium atom, an osmium atom, a cobalt atom, a rhodium atom, an iridium atom, a nickel atom, a palladium atom, and a platinum atom. M is particularly preferably a Group 9 atom, and most preferably a cobalt atom. In the general formula [1], m represents a valence of M. For example, when M is a cobalt atom, 2 or 3 is preferable.

T in the general formula [1] represents an atom belonging to Group 14 or Group 15 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989), and all T are the same as each other. May also be different. Specific examples of the group 14 atom include a carbon atom and a silicon atom.
Specific examples of the group atom include a nitrogen atom and a phosphorus atom. T is preferably a carbon atom or a nitrogen atom, and particularly preferably T is a nitrogen atom.

In the general formula [1], R ¹ and R ²
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and all R ¹ and all R ² may be the same or different, and form a ring with each other It may be. R ¹ and R ²
Is preferably an electron-withdrawing group, and the electron-withdrawing group is preferably a halogen atom or a halogenated hydrocarbon group.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably it is a fluorine atom. As the hydrocarbon group, an alkyl group, an aryl group or an aralkyl group is preferable.

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl Groups, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group or isobutyl group.

The aryl group has 6 to 20 carbon atoms.
Are preferred, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples thereof include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable.

The aralkyl group may have 7 to 2 carbon atoms.
An aralkyl group of 0 is preferred, 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, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include a (n-tetradecylphenyl) methyl group, a naphthylmethyl group and an anthracenylmethyl group, and more preferably a benzyl group.

The halogenated hydrocarbon group is preferably a halogenated alkyl group, a halogenated aryl group or a (halogenated alkyl) aryl group.

The halogenated alkyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms, for example, a fluoromethyl group, a chloromethyl group, a bromomethyl group,
Iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group trifluoromethyl group, trichloromethyl group, tribromomethyl group,
Triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group,
2,2,3,3,3-pentafluoropropyl group, 2,
2,3,3,3-pentachloropropyl group, 2,2
3,3,3-pentabromopropyl group, 2,2,3
3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2
A trichloro-1-trichloromethylethyl group, 2,
2,2-tribromo-1-tribromomethylethyl group,
2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2
-Trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1, 1-bis (triiodomethyl) -2,2,2
-A triiodoethyl group and the like.

The halogenated aryl group is preferably a halogenated aryl group having 6 to 20 carbon atoms, such as 2-fluorophenyl group, 3-fluorophenyl group,
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4
-Iodophenyl group, 2,6-difluorophenyl group,
3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-
Diiodophenyl group, 3,5-diiodophenyl group,
2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl Group, pentabromophenyl group, pentaiodophenyl group and the like.

The (halogenated alkyl) aryl group is preferably a (halogenated alkyl) aryl group having 7 to 20 carbon atoms, for example, 2- (trifluoromethyl) aryl.
A phenyl group, a 3- (trifluoromethyl) phenyl group,
4- (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group And the like.

X in the general formula [1] is a hydrogen atom,
Represents a halogen atom, a hydrocarbon group, or a hydrocarbon oxy group, and when a plurality of Xs are present, they may be the same or different. Specific examples of such a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Further, as the hydrocarbon group here, an alkyl group, an aryl group or an aralkyl group is preferable.

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl Groups, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group or isobutyl group.

The aryl group has 6 to 20 carbon atoms.
Are preferred, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples thereof include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable.

The aralkyl group may have 7 to 2 carbon atoms.
An aralkyl group of 0 is preferred, 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, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include a (n-tetradecylphenyl) methyl group, a naphthylmethyl group and an anthracenylmethyl group, and more preferably a benzyl group.

The hydrocarbon oxy group in X in the above formula is preferably an alkoxy group, an aryloxy group or an aralkyloxy group. The alkoxy group referred to here is preferably an alkoxy group having 1 to 24 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a t-butoxy group. , N-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-
Examples thereof include a dodeoxy group, an n-pentadeoxy group, and an n-icosoxy group, and a methoxy group, an ethoxy group, or a t-butoxy group is preferable.

The aryloxy group is preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and 2,3-dimethyl. Phenoxy group, 2,4-dimethylphenoxy group, 2,5-
Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group 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 is preferably an aralkyloxy group having 7 to 24 carbon atoms, for example, a benzyloxy group, a (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) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n- Propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-
(Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl)
Examples include a methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group and an anthracenylmethoxy group, and a benzyloxy group is preferable.

Hereinafter, specific examples of the compound represented by the general formula [1] will be shown, but the invention is not limited thereto. In the following specific examples, M represents an atom of Groups 8 to 10 of the periodic table, X represents a hydrogen atom, a halogen atom, a hydrocarbon group,
Or, m represents a valence of M.

[0027]

The phthalocyanine complex of the present invention is more preferably a phthalocyanine complex represented by the following general formula [2]. (Wherein, M represents an atom of Groups 8 to 10 of the periodic table, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbonoxy group, and when there are a plurality of Xs, they are the same as each other. M represents the valence of M.) M, X and m in the general formula [2] are the same as in the general formula [1].

The phthalocyanine complex of the present invention preferably has a high Lewis acidity. When the Lewis acidity is defined by a numerical value obtained by a density functional method, which is a kind of quantum chemical calculation, the phthalocyanine complex of the present invention is preferably the phthalocyanine complex described above and represented by the general formula [1] or [2]. P of the valence orbit of M in
The lowest orbital level of the empty molecular orbital whose atomic orbital is the main component (the coefficient represented by linear combination is 0.4 or more) is 0.00
A phthalocyanine complex having 8 atomic units (Hartley) or less. However, the orbital level is determined by calculation by the density functional theory (B3LYP / 3-21G level).

The calculation of the density functional method is based on Gaussian
Inc. It is calculated by a high-speed computer such as IBM SP2 using the Gaussian 94 program manufactured by the company. The calculation level can be selected according to the model to be calculated and the calculation function. The combination of basis functions representing the atomic orbitals of each atom is Gaussia
Many types are built in the n94 program, and these can also be selected according to the model to be calculated and the calculation function. In particular, a plurality of basis functions are often used for an atomic orbital suitable for expressing a valence orbital or a polarization state. Further, as for the structural parameters to be input at the time of calculation, it is also possible to input experimental data or coordinates obtained by other theoretical and chemical methods, and it is also possible to obtain by structural optimization calculation by the above-mentioned program. The other theoretical chemical methods mentioned here include not only quantum chemical methods but also molecular mechanical methods. The calculation of the molecular mechanical method can be performed by using a CAChe system sold by Fujitsu Limited.

The orbital level is preferably from -0.1 to
0.007 atomic units, more preferably 0-0.1 atomic units.
006 atomic units, particularly preferably 0.001 to
The range is 0.005 atomic units.

The compound represented by the general formula [1] can be synthesized by a known method. For example, Inorga
nic Chemistry, 19 , 3131-313
5 (1980). Many of these compounds are generally commercially available.

The phthalocyanine complex of the present invention is composed of the compound represented by the above general formula [1], and in the X-ray diffraction spectrum, the strongest diffraction peak with respect to CuKα characteristic X-ray has a Bragg angle (2θ ± 0.2). Phthalocyanine complex appearing at a position larger than 15 ° in (°). When the X-ray diffraction spectrum of a commercially available product is measured, the largest diffraction peak appears at a position smaller than the Bragg angle of 15 °. By subjecting such a phthalocyanine complex to crystal transition or the like, the phthalocyanine complex of the present invention in which the strongest diffraction peak appears at a position larger than 15 ° of the Bragg angle is produced.

Examples of the method of crystal transition include a method of applying a mechanical shearing force such as grinding, and an acid treatment such as an acid pasting treatment. The method of producing the phthalocyanine complex of the present invention is preferably a method of grinding or acid pasting the above-mentioned phthalocyanine complex.

In grinding, a ball mill, a planetary mill,
Devices such as a sand grinder, a vibration mill, and an attritor are used. At this time, dry grinding, grinding only with solids,
Any method of wet milling in which a liquid is added and milled can be used. In addition, a water-soluble inorganic salt such as sodium chloride or sodium sulfate can be used as a grinding aid. The grinding temperature is preferably in the range of 0 to 200 ° C, more preferably 10 to 100 ° C, and particularly preferably 20 to 8 ° C.
0 ° C. As for the grinding time, it is preferable to grind until saturation of crystal transition is confirmed. The saturation of the crystal transition can be determined by X-ray diffraction, infrared spectrum, or the like.

The acid pasting means that an object compound is first dissolved or slurried in an acid to form an acid paste solution, which is then poured into a liquid such as water to precipitate (hereinafter, referred to as "reprecipitation"). In this method, a solid is recovered as a target compound. Examples of the acid used for the acid pasting include sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid and the like. Concentrated sulfuric acid is preferable because of its high solubility and easy handling. In the case of concentrated sulfuric acid, it is preferably used in an amount of 5 to 100 times by weight, more preferably 15 to 40 times by weight, based on the above compound. In reprecipitation, neutral water or alkaline water, or a mixture of these water and an organic solvent can be used. Examples of the alkali used for the alkaline water include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Ammonia and various ammonium hydroxide salts can be exemplified. Examples of the organic solvent include alcohols such as methanol, glycols such as ethylene glycol, glycerin and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and halogenated compounds such as dichloromethane and chloroform. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene. The amount of the organic solvent is usually 1 to water.
It is used in a range of 0 times by weight or less, preferably 5 times by weight or less. The neutral water, the alkaline water, or the mixed solution is 1 to 100 times by weight, preferably 3 to 100 times the acid paste solution.
Use in the range of 20 weight times. Acid pasting is usually performed at a processing temperature in the range of -15 ° C to 100 ° C,
When using a mixed solvent, it is preferable to carry out the reaction at a temperature lower than the boiling point.

The phthalocyanine complex of the present invention described in detail above is used as an activating co-catalyst component in olefin polymerization. Examples of the olefin polymerization catalyst prepared using the phthalocyanine complex of the present invention include a transition metal compound that forms a single-site catalyst, organoaluminum, and a catalyst obtained by contacting the phthalocyanine complex of the present invention. Examples of the transition metal compound that forms the single-site catalyst include known metallocene complexes and non-metallocene compounds, and specific examples include ethylenebis (indenyl) zirconium dichloride.
Examples of the organoaluminum include known trialkylaluminums, and specifically, triisobutylaluminum and the like. With respect to the use conditions and the like, the conditions of the embodiments described below can be exemplified.

[0038]

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

(1) The α-olefin unit content in the copolymer was measured by an infrared spectrophotometer (FT, manufactured by JASCO Corporation).
-IR7300), using a calibration curve from the characteristic absorptions of ethylene and α-olefins, and expressed as the number of short-chain branches per 1,000 carbon atoms (SCB).

(2) Molecular weight and molecular weight distribution: Measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was created 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: 150C type manufactured by Millipore Waters Co., Ltd. Column: TSK-GEL GMH-HT 7.5 × 600 × 2 tubes Measurement temperature: 140 ° C. Solvent: orthodichlorobenzene, measurement concentration: 5 mg / 5 ml

(3) Calculation of density functional method: A high-speed computer SP2 manufactured by IBM Corporation and Gaussian Inc.
B3LY using Gaussian94 program
Using a calculation method called P, the atomic orbital of each atom is calculated by a density functional theory method using a planar structure calculated by molecular mechanics calculation using a combination of basis functions called 3-21G built in the program. did.

(4) Measurement of X-ray diffraction: Apparatus: RINT 2500V (vertical goniometer) manufactured by Rigaku Denki Co. X-ray output: 50 kV-100 mA X-ray tube: Cu monochromator: Curved monochromator (graphite) Detector: Scintillation counter Scan speed: 20 / min (2θ) Scan angle: 5-70 deg. (2θ)

(5) Measurement of Specific Surface Area Using ASAP2000 manufactured by Shimadzu Corporation, the adsorption and desorption of nitrogen gas was measured at the temperature of liquid nitrogen and determined by the BET method. The pretreatment of the sample was performed by evacuating at 110 ° C.

Example 1 (1) Grinding of Complex A 10.45 g of Complex A having the following structure was placed in a zirconia pot (capacity: 45 ml), and seven zirconia balls (diameter: 15 mm) were put into a planetary mill. Grinding was started at room temperature using a P-7 (manufactured by Fritsch Japan) at a rotation speed of the disk of 360 rpm. After that, one every eight hours
Each g was sampled, and the X-ray diffraction pattern was measured.
Grinding was performed for up to 40 hours. The temperature of the sample in the pot at the time of sampling was 34 ° C.

(Complex A): manufactured by Aldrich In this complex A, the orbital coefficient of the p-orbital in the lowest orbital order of the empty molecular orbital whose main component is the p-orbital of the valence electron orbital of the Co atom is 0.879, and the orbital level is 0.0035 atom. It was a unit (Hartley). In the case of the milling treatment 0 hour, that is, the complex A before milling, in the X-ray diffraction pattern using the X-ray corresponding to the wavelength of CuKα as a radiation source, the Bragg angles 2θ = 6.3 °, 9.2 °, and 12.
6 °, 13.3 °, 15.0 °, 15.8 °, 17.7
°, 18.4 °, 18.9 °, 22.7 °, 28.5
°, 29.0 °, 30.2 °, 31.9 °, 33.9
°, 34.9 °, 39.0 °, 43.2 °, 45.4
± 0.2 ° to °, 46.6 °, 51.9 °, 58.9 °
A specific diffraction peak was observed within the error range of. Also,
The main peak was at 6.3 °. FIG. 1 shows an X-ray diffraction pattern.

After 8 hours of grinding, the sample reached X
In the line diffraction pattern, the Bragg angle 2θ = 6.1 °, 8.
9 °, 12.3 °, 17.9 °, 22.2 °, 24.1
°, 28.3 °, 33.2 °, 33.9 °, 34.9
°, 39.1 °, 43.1 °, 52.1 °, 58.5 °
A specific diffraction peak was observed within an error range of ± 0.2 °. The main peak is at 28.3 °, and 28.
The ratio of the peak intensity at 3 ° to the peak intensity at 6.1 ° (6.
(1 ° peak intensity / 28.3 ° peak intensity) is 0.7
It was one. FIG. 2 shows an X-ray diffraction pattern. In Table 1,
The grinding time and the ratio of the peak intensity at 28.3 ° to the peak intensity at 6.1 ° (peak intensity at 6.1 ° / peak intensity at 28.3 °) were shown.

[Table 1] By performing the grinding treatment for 40 hours, the specific surface area becomes 3
It decreased from 0.0 m ² / g to 2.03 m ² / g. FIG. 3 shows an X-ray diffraction pattern of the sample 40 hours after the grinding treatment. 4 and 5 show TEM photographs of the sample before the grinding treatment and 40 hours after the grinding treatment.

(2) Polymerization An autoclave with a stirrer having an internal volume of 400 ml was vacuum-dried and purged with argon, and hexane was used as a solvent.
0 ml and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 m
mol, followed by 0.2 μmol of ethylenebis (indenyl) zirconium dichloride, and 83.5 mg (97.2 μmol) of the complex A ground for 40 hours in Example 1 (1) to initiate polymerization. Started. Polymerization was performed for 30 minutes. 6.92 g as a result of polymerization
Of ethylene / 1-hexene copolymer was obtained. Polymerization activity = 6.9 × 10 ⁷ g / mol / h, SCB = 11.9
It was 0. Mw = 88000, Mw / Mn = 2.5.

Reference Example 1 In Example 1 (2), 4
Unmilled complex A80 in place of 0 hour milled complex A80.
Example 1 except that 4 mg (93.6 μmol) was used.
Polymerization was performed as in (2). As a result, 1.08 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity was 1.1 × 10 ⁷ g / mol / h. Mw = 78
000, Mw / Mn = 2.3.

Example 2 (1) Acid Pasting Treatment of Complex A 1.04 g of the above-mentioned Complex A was placed in a 100 ml one-necked flask and cooled in an ice bath. 20 ml of concentrated sulfuric acid was gradually added dropwise thereto. As a result, the content became a dark green paste. After dropping, the mixture was stirred in an ice bath for 1 hour,
The contents were poured into 400 ml of water. The precipitate was filtered through a glass filter (G4) and washed with water until the washing became neutral. Then, it dried at 50 degreeC under reduced pressure for 8 hours. As a result, 0.74 g of the compound of the present invention was obtained.

The X-ray diffraction pattern of the complex A which has not been subjected to the acid pasting treatment is the same as that of the complex A before grinding, that is, the grinding time of 0 hours described in Example 1 (1). On the other hand, in the complex A after the acid pasting treatment, the Bragg angle 2θ = 6.0 in the X-ray diffraction pattern.
°, 6.2 °, 8.5 °, 9.1 °, 12.4 °, 1
8.2 °, 22.5 °, 28.3 °, 34.9 °, 4
Specific diffraction peaks were observed at 3.2 °, 46.2 °, and 58.9 ° within an error range of ± 0.2 °. The main peak is 28.3 °, and the ratio of the peak intensity at 28.3 ° to the peak intensity at 6.2 ° (peak intensity at 6.2 ° / peak intensity / 6.2 °).
Peak intensity at 28.3 °) was 0.74. FIG. 6 shows an X-ray diffraction pattern. FIG. 7 shows a TEM photograph after the acid pasting process.

(2) Polymerization A 400 ml-volume autoclave with a stirrer was vacuum-dried and purged with argon.
0 ml and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 m
mol, followed by 0.2 μmol of ethylenebis (indenyl) zirconium dichloride, and 82.1 mg (95.5 μmol) of the complex A subjected to the acid pasting treatment in the above (1) to initiate polymerization. . Polymerization was performed for 30 minutes. As a result of polymerization,
3.15 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity = 3.2 × 10 ⁷ g / mol / h, SCB
= 10.91. Mw = 72000, Mw / Mn
= 2.1.

Comparative Example 1 (Xylene Reflux Treatment) (1) Xylene Reflux Treatment of Complex A 1.10 g of the above-mentioned complex A was dispersed in 100 ml of xylene (o, m, p mixture) and refluxed for 8 hours. Was.
Thereafter, the solvent was distilled off under reduced pressure, and drying was performed at 50 ° C. for 8 hours under reduced pressure. In the X-ray diffraction pattern of complex A after this treatment, Bragg angles 2θ = 6.3 °, 9.1 °, 9.4 °, 1
2.5 °, 13.2 °, 14.9 °, 15.7 °, 1
7.6 °, 18.4 °, 18.9 °, 22.6 °, 2
3.0 °, 24.2 °, 25.3 °, 26.5 °, 2
7.6 °, 28.3 °, 29.0 °, 30.2 °, 3
1.5 °, 31.8 °, 33.8 °, 43.1 °, 4
Specific diffraction peaks were observed at 5.3 °, 46.6 °, and 51.8 ° within an error range of ± 0.2 °. The main peak is 6.3 °, and the ratio of the peak intensity at 28.3 ° to the peak intensity at 6.3 ° (peak intensity at 6.3 ° / peak intensity / 6.3 °).
Peak intensity at 28.3 °) was 10.0. FIG. 8 shows an X-ray diffraction pattern. FIG. 9 shows a TEM photograph.

(2) Polymerization A 400 ml internal volume autoclave with a stirrer was vacuum-dried and purged with argon.
0 ml and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 m
mol, then 0.2 μmol of ethylenebis (indenyl) zirconium dichloride was added, and 83.5 mg (97.2 μmol) of the complex A subjected to the xylene reflux treatment in the above (1) was added to initiate polymerization. Polymerization was performed for 30 minutes. As a result of polymerization, 0.398
g of ethylene / 1-hexene copolymer was obtained. Polymerization activity was 4.0 × 10 ⁶ g / mol / h. Mw =
69000, Mw / Mn = 2.4.

FIG. 10 shows the peak intensity at 28.3 ° and 6.
Ratio to peak intensity at 3 ° (peak intensity at 6.3 ° / 2
8.3 ° peak intensity) and the polymerization activity.

[0055]

As described above in detail, according to the present invention, there is provided a novel phthalocyanine complex capable of forming an olefin polymerization catalyst having high polymerization activity by using it as an activating co-catalyst component.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of a complex A used in Examples before grinding treatment (when not treated).

FIG. 2 is an X-ray diffraction pattern of complex A after 8 hours of grinding.

FIG. 3 is an X-ray diffraction pattern of a complex A 40 hours after a grinding treatment.

FIG. 4 shows T of complex A before grinding (when not treated).
It is an EM photograph.

FIG. 5 is a TEM of complex A 40 hours after grinding.
It is a photograph.

FIG. 6 is an X-ray diffraction pattern of complex A after acid pasting treatment performed in Example 2 (1).

FIG. 7 is a TEM photograph of complex A after the acid pasting treatment performed in Example 2 (1).

FIG. 8 is an X-ray diffraction pattern of complex A after the xylene reflux treatment performed in Comparative Example 1.

FIG. 9 is a TEM photograph of complex A after the xylene reflux treatment performed in Comparative Example 1.

FIG. 10 shows the ratio of the peak intensity at 28.3 ° to the peak intensity at 6.3 ° in the X-ray diffraction pattern of complex A (peak intensity at 6.3 ° / peak intensity at 28.3 °). )
FIG. 3 is a diagram showing a correlation between the polymerization activity and the polymerization activity.

Continued on the front page (72) Inventor Tatsuya Miyatake 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture F-term (reference) in Sumitomo Chemical Co., Ltd. 4C050 PA13 4J028 AA01A AB01A AC27A BA00A BA01B BB00A BB01B BC15B CB72C EB02 EB09 4J128 AA01 AB BA00A BA01B BB00A BB01B BC15B CB72C EB02 EB09

Claims (5)

[Claims] An X-ray diffraction spectrum comprising a compound represented by the following general formula [1], wherein the strongest diffraction peak with respect to CuKα characteristic X-rays is the Bragg angle (2θ ±
Phthalocyanine complex appearing at a position larger than 15 ° (0.2 °). (Wherein, M represents an atom of Groups 8 to 10 of the periodic table, T represents an atom of Groups 14 or 15 of the periodic table, and all Ts are the same or different from each other. R ¹
And R ² are each independently a hydrogen atom, a halogen atom,
It is a hydrocarbon group or a halogenated hydrocarbon group, and all R ¹ and all R ² may be the same or different from each other, and may form a ring with each other. Note that T
Is a Group 15 atom, there is no R ² attached to it. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon oxy group. When a plurality of Xs are present, they may be the same or different. m represents the valence of M. ) 2. The phthalocyanine complex according to claim 1, wherein at least one of R ¹ and R ² in the general formula [1] is an electron-withdrawing group. 3. The compound according to claim 1, wherein at least one of R ¹ and R ² in the general formula [1] is a halogenated hydrocarbon group.
The phthalocyanine complex according to the above. 4. The X-ray diffraction spectrum of the compound represented by the following general formula [2], wherein the strongest diffraction peak for CuKα characteristic X-rays is the Bragg angle (2θ ±
Phthalocyanine complex appearing at a position larger than 15 ° (0.2 °). (Wherein, M represents an atom of Groups 8 to 10 of the periodic table, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbonoxy group, and when there are a plurality of Xs, they are the same as each other. And m represents the valence of M.) 5. The lowest orbital level of an empty molecular orbital whose main component is a p atomic orbital of the valence orbital of M (coefficient represented by linear combination is 0.4 or more) is 0.008 atomic unit ( Hartley) The phthalocyanine complex according to any one of claims 1 to 4, wherein