JP3352242B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an olefin polymer having excellent physical properties and a polymer thereof, and more particularly, it comprises a transition metal compound and an inorganic solid component carrying an organic aluminum oxy compound. By combining a method using a catalyst, a multi-stage polymerization method and a polymerization method using at least two kinds of transition metal compounds, and controlling the structure at each structural level such as the molecular structure, micro structure, and macro structure of the polymer, The present invention relates to a method for producing an olefin polymer having significantly superior physical properties,
The present invention also relates to a polymer obtained by the production method.

[0002]

2. Description of the Related Art A so-called Ziegler-Natta type catalyst comprising a titanium compound and an organoaluminum compound has been known as a catalyst for producing an olefin polymer. On the other hand, in recent years, ethylene or ethylene and other 1-olefins have a high polymerization activity, and are composed of a soluble halogen-containing transition metal compound such as bis (cyclopentadienyl) zirconium dichloride and alumoxane which is one kind of an organic aluminum oxy compound. A technique for polymerizing with high activity by using a catalyst has been found.
No. 09 became publicly known.

Further, as a method of utilizing a catalyst system comprising the above transition metal compound and an organoaluminum oxy compound,
Japanese Patent Application Laid-Open No. 60-35007 discloses that a transition metal according to a purpose is selected from various types of transition metal compounds including the above-mentioned transition metal compounds, not by a conventional method depending on control of hydrogen concentration or polymerization temperature. A method of adjusting the molecular weight and comonomer content of the olefin polymer by selecting a compound has also been proposed.

The catalyst system comprising such a transition metal compound and an organoaluminum oxy compound is capable of polymerizing a polymer having a narrow molecular weight distribution as compared with a so-called Ziegler-Natta type catalyst, and is also excellent in copolymerizability and contains comonomer. Since it is possible to obtain a large amount of a polymer or a uniform polymer having a comonomer distribution, it has a feature that a polymer having excellent physical properties such as impact resistance and solvent resistance can be obtained. .

However, recent industrial progress has been remarkable, and the demand for polyolefins has been drastically increased to a broader and higher level in view of environmental problems. Simply using a catalyst system comprising a metal compound and an organoaluminum oxy compound has not yet met such required performances, and there is a strong demand for further performance improvements.

[0006] Further, since such a catalyst system is soluble in a solvent, when applied to a suspension polymerization method or a gas phase polymerization method, the properties of the obtained polymer are extremely poor. There is a problem that it adheres and cannot be used industrially as it is. In addition, although the narrow molecular weight distribution of the polymer is advantageous for obtaining the excellent physical properties as described above, there is also a serious practical problem that the molding processability is reduced. Due to these problems, a catalyst system comprising a transition metal compound and an organoaluminum oxy compound,
At present, it has not yet reached full-scale industrialization by the suspension polymerization method and the gas phase polymerization method.

Therefore, the development of a polymerization method using a catalyst system containing a transition metal compound and an organoaluminum oxy compound, which has been performed so far, is intended to improve the properties of the polymer rather than to further improve the physical properties of the polymer. The emphasis was placed on solving the above problems, such as improvement of the moldability and moldability. For example, in order to solve the problem that the properties of the polymer are extremely poor, at least one component of a transition metal compound and an organoaluminum oxy compound is supported on a porous inorganic oxide such as silica, alumina, and silica-alumina for olefin polymerization. Attempts have been made to use it.

Further, as a method for improving the moldability,
A method using a multi-stage polymerization method, which is a known technique, has been proposed. For example, JP-A-3-234717 discloses a multistage polymerization method using an olefin polymerization catalyst comprising the above transition metal compound and an organic aluminum oxy compound.
Methods for improving the melting properties of polymers are disclosed. As another means for improving the formability, at least 2
Japanese Patent Application Laid-open No. Sho 60-35008 proposes a method of broadening the molecular weight distribution by mixing and using various kinds of transition metal compounds. JP-A-60-35008 also describes that a transition metal compound can be supported on a porous inorganic carrier such as silica, alumina and silica-alumina.

Further, JP-A-5-155933 and JP-A-5-155933 use at least two transition metal compounds and a particulate carrier having a specific range of the amount of adsorbed water and the amount of surface hydroxyl groups. In addition, there is described a method in which prepolymerization is performed to improve physical properties such as melt tension and particle properties of the olefin polymer, thereby improving moldability.

[0010] All of these conventional methods aim at improving the moldability, and are far from the viewpoint of further improving the physical properties of the polymer. In addition, although the conventional method showed a certain improvement effect on the moldability itself, it was not always sufficient. For example, in a multi-stage polymerization method, there is a limitation in obtaining a desired molecular weight distribution only by controlling polymerization conditions. In a method using at least two types of transition metal compounds, a transition metal suitable for obtaining a desired molecular weight distribution is used. It is practically difficult to find a combination of compounds, and even if such a combination of transition metal compounds can be found, it generally requires a great deal of cost and labor until then. The transition metal compound found is a special compound, and is often not very practical, and is not practical.

On the other hand, a method for producing a reaction blend using at least two kinds of transition metal compounds is disclosed in JP-A-5-31083.
No. 1 proposes this. JP-A-5-3108
Japanese Patent Publication No. 31 also exemplifies a method using a plurality of reactors as a mixing means.

[0012]

However, in the conventional method, when applied to a suspension polymerization method or a gas phase polymerization method, it is premised that a catalyst supporting a transition metal compound is used. When multi-stage polymerization is carried out based on, even if a transition metal compound supported in the latter stage is newly added, polymerization is performed by the polymer that is polymerized by the transition metal compound added in the latter stage and the transition metal compound that comes from the former stage. Is a different kind of polymer having different molecular weights and composition distributions according to each catalyst, so that the different kinds of polymers are generated independently for each carrier on which each catalyst is supported. Therefore, each of them grows into a particle of the different type of polymer, which is effectively the same as mixing particles of the different type of polymer. Uniform sea-island structure in each position, that more uniformly mixed back to microstructure in the crystal level, there is a problem that it is practically difficult.

For this reason, when performing the multi-stage polymerization, even if a new transition metal compound is added in the subsequent polymerization step based on the prior art to carry out the polymerization, the same as a simple polymer powder mixture can be obtained. There is no practical advantage in the physical properties of the polymer, or in cases where it is severe, unfavorable adverse effects such as a decrease in mechanical strength and gel formation due to the uneven composition distribution of the obtained polymer However, it could not be put to practical use.

Furthermore, by applying the multi-stage polymerization method and the method using at least two types of transition metal compounds, for example, structural control at the molecular level such as molecular weight distribution, comonomer distribution in molecular chains, and comonomer distribution between molecules, Control of microstructure such as crystal size, crystallinity, dispersion state at crystal level,
Furthermore, it is possible to optimally control each structure at each structural level of the polymer, such as controlling the macro structure such as the sea-island structure for each composition unit, and olefins with dramatically superior physical properties compared to conventional There was no specific example to the effect that a polymer could be produced. Further, as a more specific example of applying the above-mentioned multi-stage polymerization method and a method using at least two kinds of transition metal compounds, for example, when performing the latter-stage polymerization, a new transition metal compound different from the transition-metal compound used for the former-stage polymerization is used. By adding a suitable transition metal compound and adopting polymerization conditions that are different from the polymerization conditions in the preceding stage, it is possible to easily control the molecular weight distribution in a wide range. Disclosure is
It has never been seen before.

The present invention provides a process for producing an olefin polymer which is substantially uniformly mixed, and a polymer obtained by the process, and further provides a molecular weight distribution, a comonomer distribution in a molecular chain and an intermolecular distribution. Control of molecular structure such as comonomer distribution, mixed state of molecules, molecular size and distribution of crystal size, degree of crystallinity, control of microstructure such as dispersion state at crystal level, and further, for each composition unit A method for producing an olefin polymer having dramatically superior physical properties as compared with conventional ones by optimally controlling each structure at each structural level of the polymer, such as controlling a macro structure such as a sea-island structure, and the like. The object of the present invention is to provide a polymer obtained by the method.

[0016]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a catalyst system comprising a transition metal compound and an organoaluminum oxy compound in order to improve the physical properties of the obtained polymer. If a method using a catalyst comprising an inorganic solid component carrying a metal compound and an organoaluminum oxy compound and an organoaluminum component as needed, a multi-stage polymerization method and a polymerization method using at least two transition metal compounds are combined, Control at each structural level such as the molecular structure, microstructure, and macrostructure of the polymer is possible, and by optimizing the structure at each structural level, a synergistic effect can be achieved, which can be achieved with conventional technology. The present inventors have found that an olefin polymer having surprising performance which has not been obtained can be obtained, and the present invention has been accomplished.

The present invention includes at least two kinds of ligands having [A] cyclopentadienyl skeleton.
Group 4 transition metal compound with (B) (b-1) to the particulate inorganic solid having hydroxyl groups on the surface (b-2) If the organoaluminum oxy-compound is necessary and supported inorganic solid component (C) an organic aluminum A catalyst for olefin polymerization comprising a compound, and further using multi-stage polymerization, wherein in the multi-stage polymerization, cyclopentadienyl added to the first stage in at least one of the second and subsequent polymerization stages. by performing the polymerization newly added 4 group transition metal compound containing a ligand having a different at least one cyclopentadienyl skeleton and group 4 transition metal compound containing a ligand having a skeleton, It is intended to provide a method for producing an olefin-based polymer having excellent physical properties by controlling the molecular structure of the polymer, microstructure, macrostructure, and other structural levels, and There is provided a polymer obtainable by the production method.

Hereinafter, the multistage polymerization method for olefins according to the present invention and the olefin polymer polymerized by this method will be described in detail. In the present invention, "polymerization" may be used to mean not only homopolymerization but also copolymerization, and "polymer" includes not only homopolymer but also copolymer. Sometimes used in a meaning.

In the present invention, [A] a transition metal compound and (b-
1) Olefin polymerization is carried out using an olefin polymerization catalyst comprising [B] an inorganic solid component in which (b-2) an organoaluminum oxy compound is supported on a particulate inorganic solid and, if necessary, [C] an organoaluminum compound. If
Since (A) the transition metal compound and (B) the organoaluminum oxy compound supported on the inorganic solid component form a polymerization active site, the polymer is (b-2) the organoaluminum oxy compound. It is formed on the supported [B] inorganic solid component, and as a result, the [B] inorganic solid component grows into polymer particles. If two or more [A] transition metal compounds are present in the polymerization system during polymerization, two types of polymers are produced according to each [A] transition metal compound. In this case, since the two types of polymers are simultaneously formed on the same [B] inorganic solid component, polymer particles in which the two types of polymers are substantially uniformly mixed at the molecular level are obtained. . As described above, as a result of the two types of polymers being substantially uniformly mixed at the molecular level, it has become possible to produce a polymer which has been considered to be impossible at all. For example, mixing of a high molecular weight ethylene polymer and a low molecular weight ethylene polymer does not mix uniformly unless an ethylene polymer having a molecular weight between the high molecular weight portion and the low molecular weight portion is present, and mechanical mixing does not occur. It has been considered that the use of a mixture cannot be achieved at all, because of lowering of the mechanical strength and generation of a gel. However, by using the method of the present invention, it becomes possible to directly mix a high-molecular-weight ethylene polymer and a low-molecular-weight ethylene polymer at a molecular level without the presence of an ethylene polymer having a molecular weight of the intermediate portion. Was.

In the present invention, for example, when a mixture of polymers is polymerized in the presence of two transition metal compounds in one polymerization stage, the mixing ratio of the two kinds of produced polymers is determined by the ratio of the organoaluminum of the transition metal compound. Coordination force for oxy compounds,
It depends on the polymerization activity and the like. Therefore, for example, in the above-mentioned example of mixing the high-molecular-weight ethylene polymer and the low-molecular-weight ethylene polymer, the ratio of the high-molecular-weight portion to the low-molecular-weight portion of the ethylene polymer is controlled by selecting an appropriate transition metal compound. Therefore, using such a technique, an ethylene polymer having a desired molecular weight distribution can be polymerized. Thus, in the present invention, it is possible to control the polymer at the molecular level.

Surprisingly, the polymerization of a polymer in which two polymers are substantially mixed at a molecular level can be realized by gradually adding two [A] transition metal compounds.
For example, when first performing polymerization using one type of transition metal compound and then performing polymerization by adding another type of transition metal compound, in the first polymerization, a polymer corresponding to the transition metal compound used first is generated, Thereafter, from the time when another type of transition metal compound is added, a polymer in which the first type of transition metal compound and two types of polymers corresponding to the other type of transition metal compound are uniformly mixed is produced. As a result of such polymerization, the obtained polymer is a polymer having a sea-island structure in which the initially obtained polymer and the polymer in which two kinds of polymers are uniformly mixed are mixed. By controlling the quantitative ratio of the polymer obtained first and the polymer in which two kinds of polymers are uniformly mixed, it becomes possible to control the sea-island structure of the polymer finally obtained.

As in this example, it is unexpected from the common knowledge of the prior art that the addition of another transition metal compound after the initial polymerization causes the polymerization based on another transition metal compound to occur. It was surprising. That is, what is usually expected in the above example is that the polymerization active sites formed on the carrier will be covered by the polymer generated in the first polymerization, and thereafter, a new transition metal of another kind is newly added. Even when the compound is added, the other transition metal compound cannot come into contact with the organoaluminum oxy compound on the carrier, and therefore cannot form a polymerization active site, and is polymerized by the newly added transition metal compound. No activity would be expected.

However, surprisingly, in the catalyst system of the present invention, even if another transition metal compound is newly added after the initial polymerization as in the above example, the polymerization activity based on the other transition metal compound is not increased. Express. This is considered to suggest that the different transition metal compound diffuses in the polymer formed first and reaches the organoaluminum oxy compound supported on the inorganic solid component to form a polymerization active site. However, details are unknown.

In the present invention, in order to further expand the effect of the polymerization, the polymerization is carried out by multi-stage polymerization. That is, when another kind of transition metal compound is newly added, polymerization conditions different from the initial polymerization conditions are adopted by multi-stage polymerization, thereby enabling further optimization of the polymer structure. The multi-stage polymerization method referred to in the present invention means that polymerization reactors are arranged in series and a catalyst component or /
And a polymerization method in which polymerization products in the course of polymerization are sequentially passed through the polymerization reactors arranged in series to carry out polymerization stepwise.

In the multistage polymerization of the present invention, (A) a transition metal compound and (b-1) an inorganic solid component in which (b-2) an organoaluminum oxy compound is supported on a particulate inorganic solid, and (B) an inorganic solid component if necessary. [C] at least one transition metal different from the transition metal compound added in the first stage in at least one of the second and subsequent polymerization stages using an olefin polymerization catalyst comprising an organoaluminum compound The polymerization is carried out by newly adding the compound. Therefore, in the present invention, at least two types of the transition metal compound [A] are used. In the multistage polymerization of the present invention, in addition to the catalyst components, a polymerization monomer, a comonomer, a solvent and the like may be added in the second and subsequent polymerization stages. By controlling the type and amount of the additive other than the catalyst component, the range of controlling the structure of the polymer can be further expanded.

For example, during the first stage polymerization, homopolymerization of ethylene is performed using a transition metal compound capable of increasing the molecular weight of ethylene to polymerize an ultrahigh molecular weight ethylene polymer,
If a low-density ethylene polymer is polymerized by adding a transition metal compound having excellent copolymerizability and an α-olefin as a comonomer component in the second-stage polymerization, a new, ultra-high-molecular-weight ethylene polymer can be obtained. It is possible to produce a polymer in which low-density ethylene polymer is finely dispersed or a polymer in which ultra-high-molecular-weight ethylene polymer is finely dispersed in low-density ethylene polymer, and such sea-island structure is appropriately controlled. Thereby, extrusion molding and injection molding of an ultrahigh molecular weight ethylene polymer, which has been impossible at all, becomes possible.

In the present invention, between the polymerization units arranged in series,
There may be a step in which polymerization is not substantially performed, such as a mixing step, a degassing step, a cooling or heating step, and the like. The structure of the polymer can be controlled only by the catalyst system of the present invention and the polymerization method using the same. Thus, according to the method of the present invention,
Production of synergy polyolefin becomes possible.

The synergistic polyolefin referred to in the present invention refers to the control of molecular structure such as molecular weight distribution, comonomer distribution in a molecular chain and intermolecular comonomer distribution, control of microstructure such as crystal size, crystallinity and crystal arrangement, Furthermore, by controlling each structure optimally at each structural level of the polymer, such as controlling the macro-structure such as the sea-island structure for each composition unit, the olefin-based material has dramatically improved physical properties compared to the conventional polyolefin. Refers to polymer. In such an olefin-based polymer, it is possible to improve both physical properties in a combination of physical properties which have been contradictory in the prior art and cannot be compatible.

It is considered that the reasonably excellent physical properties can be realized as described above is due to the synergistic effect of optimization at each structural level such as the above molecular structure, micro structure and macro structure. Optimization at each structural level can only be realized with the method according to the invention. The dramatic improvement in the physical properties according to the present invention refers to, for example, a case where the physical properties of interest have been improved by 30% or more.

Specific examples of the above-mentioned synergistic polyolefin include, for example, ultra-high molecular weight polyethylene which can be extruded and injection-molded, and as another example, the molecular weight distribution is narrow in high-density polyethylene (Mw /
Mn = 2-5) By finely dispersing a low-density polyethylene having a uniform comonomer distribution, a polyethylene which can realize high rigidity, high impact resistance and high ESCR, which have been considered to be inconsistent, has been realized. No.

As still another example, extrusion control and die swell are improved by optimally controlling the molecular weight distribution, and ESCR and impact resistance are improved by optimally controlling the comonomer content at each molecular weight. , And as a result, a polyethylene that can realize moldability, high ESCR, and high impact resistance.

According to the method of the present invention, it is possible to produce a polyolefin having excellent performance which could not be obtained by the prior art. In particular, the effect is enormous in ethylene-based polymers. The present invention will be described more specifically below. Examples of the [A] IVB group transition metal compound containing a ligand having a cyclopentadienyl skeleton used in the present invention include compounds represented by the following general formula. MLx ......

In the above general formula, M is the fourth in the periodic table.
Group, specifically, zirconium, titanium or hafnium, L is a ligand coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton. L other than a ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, -SO ₃ R (provided that , R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen.) Or a hydrogen atom, or may be a hetero tridentate ligand; The valence of the metal.

Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted by a halogen atom, a trialkylsilyl group, or the like, and may be further substituted by a hetero atom which can be a bonding site. The cyclopentadienyl skeleton of the present invention may contain a hetero atom in the skeleton.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the above general formula contains two or more ligands having a cyclopentadienyl skeleton, the ligand having two cyclopentadienyl skeletons is
An alkylene group such as methylene, ethylene and propylene; a substituted alkylene group such as isopropylidene and diphenylmethylene; even if they are bonded via a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group. Good.

In the present invention, more specific examples of ligands other than the ligand having a cyclopentadienyl skeleton include the following. For example, specific examples of the hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and n.
-Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group and decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group; phenyl group and tolyl Examples include an aryl group such as a group, and an aralkyl group such as a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Still ligand represented by -SO ₃ R, p-toluenesulfonate group, methanesulfonate sulfonato group, trifluoromethanesulfonate group and the like. Further, examples of the hetero tridentate ligand include a hydrotrispirazolyl borate group and a trisbisphenyloxophosphoranyl group.

The compound represented by the above general formula, for example, when the valence of the transition metal is 4, is more specifically represented by the following general formula. R ¹ _a R ² _b R ³ _c R ⁴ _d M (wherein M is zirconium, titanium or hafnium, R ¹ is a ligand having a cyclopentadienyl skeleton, and R ² , R ³ And R ⁴ are a ligand having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, -S
O ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. )

In the present invention, R ² , R
^A transition metal compound in which one of ³ and R ⁴ is a ligand having a cyclopentadienyl skeleton, for example, a transition metal compound in which R ¹ and R ² are ligands having a cyclopentadienyl skeleton is preferably used. Can be These ligands having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene; substituted alkylene groups such as diphenylmethylene; alkylidene groups such as isopropylidene; silylene groups or dimethylsilylene, diphenylsilylene, methylphenylsilylene and the like. R ³ and R ⁴ may be bonded through a substituted silylene group or the like, and R ³ and R ⁴ may be a ligand having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group. Group, halogen atom, trialkylsilyl group, SO ₃ R or hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. That is, for example, bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride,
Bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (trimethylcyclo) (Pentadienyl) zirconium dichloride, ethylene bis (tetramethylcyclopentadienyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) Diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethyl Bis (indenyl) zirconium bis (methane sulfonato), ethylenebis (indenyl) zirconium bis (p- toluenesulfonate), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylenebis (4,5,6,
7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadiphenyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis ( Methylcyclopentadienyl) zirconium dichloride, methylenebis (dimethylcyclopentadienyl) zirconium dichloride, methylenebis (trimethylcyclopentadienyl) zirconium dichloride, methylenebis (tetramethylcyclopentadienyl) zirconium dichloride, methylenebis (indenyl) zirconium dichloride, Methylenebis (indenyl) zirconiumbis (trifluoro Tansuruhonato), methylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, methylene (cyclopentadienyl -
Fluorenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopenta Dienyl) zirconium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (4 5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclo Antadiphenyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl)
Zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl)
Zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcy-η ⁵ -cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ − Cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (tertiary butylamide) (tetramethyl- eta ⁵ - cyclopentadienyl) methylene zirconium dichloride, (tertiary butylamide) (tetramethyl- eta ⁵ - cyclopentadienyl) methylene Titanium dichloride, (tertiary butyl amide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene zirconium dimethyl (tertiary butyl amide)
(Tetramethyl-η ⁵ -cyclopentadienyl) methylene titanium dimethyl, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) isopropylidene zirconium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ - cyclopentadienyl) isopropylidene titanium dichloride, (tertiary butylamide) (tetramethyl- eta ⁵ - cyclopentadienyl) isopropylidene zirconium dimethyl, (tertiary butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) isopropylidene titanium dimethyl, (tertiary butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,
2-ethane-diyl zirconium dimethyl, (tertiary butylamide) (tetramethyl- eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dimethyl, (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride,
(Methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dibenzyl, (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dimethyl , (methylamide) dimethyl (tetramethyl-eta ⁵ -
Cyclopentadienyl) silane titanium dichloride, (methylamide) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dichloride, (ethylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) - methylene titanium dichloride, ( Ethylamide)
(Tetramethyl- eta ⁵ - cyclopentadienyl) - methylene titanium dimethyl, (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride, (tertiary butylamide) dimethyl (tetramethyl -[Eta] ⁵ -cyclopentadienyl) silane zirconium dichloride, (tert-butylamido) dibenzyl (tetramethyl- [eta] ⁵ -cyclopentadienyl)
Silane zirconium dibenzyl, (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dibenzyl, (benzylamide) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride, (Benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium diphenyl, (phenyl phosphine id) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dibenzyl, (phenyl phosphine id)
Dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (phenylphosphide)
Dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dichloride, (2-methoxyphenyl amide) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride, (4-fluorophenyl amide) dimethyl ( Tetramethyl-η ⁵ −
Cyclopentadienyl) silane titanium dichloride,
((2,6-di (1-methylethyl) phenyl) amido) dimethyl (tetramethyl- [eta] ⁵ -cyclopentadienyl) amido titanium dichloride, (4-methoxyphenylamido) dimethyl (tetramethyl- [eta] ⁵ -cyclo) (Pentadienyl) silane titanium dichloride, (tetramethyl-η ⁵ -cyclopentadienyl) dimethyl (1-methylethoxy) silane titanium trichloride, 1- (tertiary butylamide) -2- (tetramethyl-η ⁵ − Cyclopentadienyl) -1,1,2,2-tetramethyldisilanetitanium dichloride, 1- (tert-butylamide) -2-
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,
1,2,2-tetramethyldisilanezirconium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dimethyl, (tertiary butylamido) dimethyl (η ⁵ -cyclopentadienyl) ) silane titanium dichloride, (tertiary butylamide) dimethyl (eta ⁵ - cyclopentadienyl) silane zirconium dichloride, (anilide) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride, (anilide) dimethyl ( tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dichloride and the like are also exemplified.

In the present invention, in order to produce a polymer having desired physical properties, at least two kinds of [A] ligands having a cyclopentadienyl skeleton are contained.
A group 4 transition metal compound is selected, and by appropriate selection, the molecular weight of the polymer, the copolymer composition, and the like can be arbitrarily controlled.

The (b-1) particulate inorganic solid of the present invention is preferably a porous inorganic solid, for example, SiO ₂ , A
l ₂ O ₃ , MgO, MgCl ₂ , ZrO ₂ , TiO ₂ ,
B ₂ O ₃ , CaO, ZnO, BaO, V ₂ O ₅ , Cr ₂
O ₃ , ThO, etc., or a mixture containing them, or a composite oxide thereof, for example, SiO ₂ —MgO,
SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2
-V 2 O 5, SiO 2 -Cr} 2 O 3, SiO 2 -TiO
_2- MgO or the like. Among them, SiO ₂ , Al ₂ O
_3, which MgO and at least one component selected from the group consisting of MgCl ₂ as a main component is preferable.

The particulate inorganic solid of the present invention has a hydroxyl group on the surface. In the present invention, the hydroxyl group on the surface of the particulate inorganic solid generally refers to an OH group which is firmly held on the surface of the particulate inorganic solid under polymerization conditions and generates H ₂ O by heating at a high temperature.

A method for obtaining a particulate inorganic solid in which hydroxyl groups are firmly retained on the surface under polymerization conditions is, for example, in dry nitrogen under the same temperature conditions as in the polymerization or at a higher temperature. In this case, for example, the fine inorganic solid particles are allowed to stand for 3 hours or more. In the present invention, the amount of hydroxyl groups on the surface of the particulate inorganic solid is determined by the ratio (weight) of the weight reduction amount of the inorganic solid when the particulate inorganic solid is heated at 1000 ° C. under normal pressure to the weight of the particulate inorganic solid before heating. %).

The amount of hydroxyl groups on the surface of the finely divided inorganic solid of the present invention is preferably an amount that works effectively when (b-2) the organoaluminum oxy compound is supported on the finely divided inorganic solid. In this case, if the amount of the hydroxyl group is too large with respect to the amount of the organic aluminum oxy compound to be used, the alkyl group in the organic aluminum oxy compound is crushed by the hydroxyl group, and the development of catalytic performance is inhibited. On the other hand, if the amount of hydroxyl groups on the surface of the particulate inorganic solid is too small relative to the organoaluminum oxy compound used, the loading of the organoaluminum oxy compound is hindered. That is, the hydroxyl group on the surface of the particulate inorganic solid reacts with the alkyl group of the organic aluminum oxy compound to form O
-It is thought that an Al bond is formed, but when the amount of hydroxyl groups on the surface of the particulate inorganic solid is too small relative to the organic aluminum oxy compound, a desired amount of the organic aluminum oxy compound is firmly supported on the surface of the particulate inorganic solid. You will not be able to do it.

In the present invention, the molar ratio (OH / Al _b-2 ) of the hydroxyl group (OH) on the surface of the particulate inorganic solid to aluminum (Al _b-2 ) in the (b-2) organoaluminum oxy compound is determined. It is desirable that the range has an upper limit of 1 or less, preferably 0.7 or less, and a lower limit of 0.01 or more, and more preferably 0.05 or more.

In order to carry an organoaluminum oxy compound in an amount necessary and effective for polymerization, the amount of hydroxyl groups on the surface of the particulate inorganic solid is at least 0.5% by weight or more of the particulate inorganic solid. And more preferably 1% by weight or more. However, if the amount of hydroxyl groups that the particulate inorganic solid has on the surface is too large,
The activity tends to decrease. This is probably because the number of reaction sites with the organoaluminum oxy compound is too large, and as a result, the effect of the organoaluminum oxy compound as a cocatalyst is limited, but the details are unknown. If the amount of the hydroxyl group on the surface of the particulate inorganic solid is too large, the activity tends to decrease. Therefore, the upper limit amount of the hydroxyl group is preferably 12% by weight, more preferably 10% by weight. , More preferably 8% by weight, even more preferably 6% by weight.

In the present invention, the amount of hydroxyl groups on the surface of the particulate inorganic solid can be adjusted, if necessary, by heating under appropriate conditions. In the present invention, the hydroxyl group on the surface of the particulate inorganic solid can be modified by chemical treatment with an organoaluminum compound or the like. By modifying the hydroxyl groups on the surface of the finely divided inorganic solid with the organoaluminum compound, the amount of the hydroxyl groups can be substantially adjusted, and (b-2) the use of the organoaluminum oxy compound The effect of reducing the amount is also found.

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following general formula can be exemplified. R ⁵ _n AlX _3-n (wherein, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. In the above general formula, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-
Propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

As such organoaluminum compounds, the following compounds are specifically used. For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminumchloride, diethylaluminumchloride, diisopropylaluminumchloride,
Dialkylaluminum halides such as diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; methylaluminum dichloride and ethylaluminum Alkyl aluminum dihalides such as dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

In the present invention, when the above-mentioned organoaluminum compound is used to modify (b-1) the hydroxyl group on the surface of the particulate inorganic solid, the amount of the organoaluminum used is limited to the aluminum (Al) in the organoaluminum. _R )
Is such that the molar ratio (Al _R / OH) to the hydroxyl group (OH) is 1 or less.

In the present invention, when the above-mentioned organoaluminum compound is used to modify the hydroxyl group on the surface of the (b-1) fine-grain inorganic solid, the (b-1) fine-grain inorganic solid is usually modified into (b-2) ) Before the organoaluminum oxy compound is supported, the hydroxyl group is modified by bringing the organoaluminum compound into contact with the (b-1) particulate inorganic solid.
2) The modification of the hydroxyl group and the supporting of the organic aluminum oxy compound may be carried out simultaneously by mixing the organic aluminum oxy compound and then bringing the mixture into contact with the finely divided inorganic solid (b-1).

In the present invention, when the above-mentioned organoaluminum compound is used to modify (b-1) the hydroxyl group on the surface of the particulate inorganic solid, the (b-1) of the hydroxyl group (OH) on the surface of the particulate inorganic solid is modified. -2) Aluminum in a molar ratio (OH / Al _b-2 ) to aluminum (Al _b- 2) in the organic aluminum oxy compound is regarded as a value to which aluminum (Al _R ) in the organic aluminum compound is added. . Therefore, the molar ratio (OH / Al _b-2 ) of the hydroxyl group (OH) on the surface of the particulate inorganic solid to aluminum (Al _b-2 ) in the (b-2) organoaluminum oxy compound is within a desirable range. The upper limit is 1 or less, preferably 0.7 or less, and the lower limit is 0.01.
When the organoaluminum compound is used to modify the hydroxyl groups on the surface of the particulate inorganic solid, the hydroxyl group (OH) on the surface of the particulate inorganic solid is preferably in the range of 0.05 or more. (B-2) Aluminum (Al _b-2 ) in organoaluminum oxy compound
And the molar ratio (OH) to the sum of aluminum (Al _R ) in the organoaluminum used to modify the hydroxyl group.
/ Al _b-2 + Al _R ) has an upper limit of 1 or less, preferably 0.7 or less, and a lower limit of 0.01.
Or less, preferably 0.05 or more.

In the present invention, when the above-mentioned organoaluminum compound is used to modify the hydroxyl group on the surface of the (b-1) particulate inorganic solid, (b-2) of aluminum (Al _R ) in the organoaluminum compound The molar ratio (Al _R / Al _b-2 ) to aluminum (Al _b-2 ) in the organic aluminum oxy compound is preferably 1 or less. The organoaluminum oxy compound (b-2) used in the present invention has an alkyloxyaluminum unit represented by the following formula.

[0055]

Embedded image

(In the formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms.) In the above formula, R ⁶ is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group, and a cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable. In the above formula, for example, as an example of an organoaluminum oxy compound composed of one type of alkylaluminum unit,
Methylalumoxane, ethylalumoxane, n-propylalumoxane, isopropylalumoxane, n-butylalumoxane, isobutylalumoxane, pentylalumoxane, hexylalumoxane, octylalumoxane, decylalumoxane, cyclohexylalumoxane, cyclooctyl Alumoxane and the like. Of these, methylalumoxane and ethylalumoxane are preferred, and methylalumoxane is particularly preferred. As described above, the organoaluminum oxy compound of the present invention is constituted by the alkyloxyaluminum unit represented by the above formula, but is not necessarily limited to a compound having one kind of constitutional unit. May be composed of the following structural units. For example, methylethylalumoxane,
Examples thereof include methylpropylalumoxane and methylbutylalumoxane, and the ratio of various constituent units can be arbitrarily set within a range of 0 to 100%. In addition, a mixture of a plurality of types of organic aluminum oxy compounds composed of one type of structural unit may be used. For example, a mixture of methylalumoxane and ethylalumoxane, a mixture of methylalumoxane and n-propylalumoxane, a mixture of methylalumoxane and isobutylalumoxane, and the like.

The organoaluminum oxy compound of the present invention may contain an unreacted chemical substance derived from the production method. That is, the organoaluminum oxy compound is generally obtained by a reaction between a trialkylaluminum and H ₂ O, but a part of these raw materials may remain as unreacted chemical substances. For example, in the case of synthesizing methylalumoxane, trimethylaluminum and H ₂ O are used as raw materials, and one or both of these raw materials are contained in methylalumoxane as an unreacted chemical substance. In the method for producing an organoaluminum oxy compound described above, a trialkylaluminum is usually used in a larger amount than H ₂ O, so that trialkylaluminum is often contained in the organoaluminum oxy compound as a residual chemical substance.

The [C] organoaluminum compound used in the present invention (hereinafter sometimes referred to as “component [C]”).
Examples thereof include an organic aluminum compound represented by the following general formula. R ⁷ _n AlX _3-n (wherein, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. In the above general formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-
Propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminumpromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichlor Alkyl aluminum sesquihalides such as amides; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum sesquihalides such as diethyl aluminum hydride and diisobutyl aluminum hydride Such as beam hydride.

As the organoaluminum compound (C), a compound represented by the following formula can also be used. R ⁷ _n AlY _3-n (wherein, R ⁷ is the same as above, Y is —OR ⁸ group,
OSiR ⁹ ₃ groups, -OAlR ¹⁰ ₂ groups, -NR ¹¹ ₂ groups,-
SiR ¹² ₃ group or -N (R ¹³⁾ is AlR ¹⁴ ₂ group,
n is 1 to 2, R ⁸ , R ⁹ , R ¹⁰ and R ¹⁴ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹¹ is a hydrogen, a methyl group, an ethyl group. Group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ¹² and R ¹³ are methyl group, ethyl group and the like. The following compounds are specifically used as such organoaluminum compounds.

(I) a compound represented by R ⁷ _n Al (OR ⁸ ) _3-n , for example, dimethyl aluminum methoxide
Diethylaluminum ethoxide, diisobutylaluminum methoxide and the like. _{^{(Ii) R 7 n Al (}} OSiR 9 3) compounds represented by _{3-n, e.g., Et 2 Al (OSiMe 3)} (iso-
(Bu) ₂ Al (OsiMe ₃ ), (iso-Bu) ₂ A
1 (OSiEt ₃ ) and the like. (Iii) a compound represented by R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-
Bu) ₂ AlOAl (iso-Bu) _{2 and the} like.

[0062] _{^{(iv) R 7 n Al (}} NR 11 2) a compound represented by _3-n, e.g., Me ₂ AlNEt _2, Et ₂ Al
NHMe, Me ₂ AlNHEt, Et ₂ AlN (SiM
e ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂
Such. _{^{(V) R 7 n Al (}} SiR 12 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} .

[0063]

Embedded image

[0064] R ⁷ ₃ Al is in the above general formula, in an organic aluminum compound _{^{represented, R 7 n Al (OR 8}} )
Preferred examples include organoaluminum compounds represented by _3-n and R ⁷ _n (OAlR ¹⁰ ₂ ) _3-n .
R ⁷ is preferably an isoalkyl group, and n = 2 is particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

The olefin polymerization catalyst according to the present invention comprises:
A transition metal compound of Group 4 containing at least two kinds of [A] ligands having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component [A]”), and (b-1) fine particles An inorganic solid (hereinafter sometimes referred to as “component (b-1)”) carries (b-2) an organoaluminum oxy compound (hereinafter sometimes referred to as “component (b-2)”). [B] inorganic solid component (hereinafter referred to as “component [B]”
May be described. ) And, if necessary, [C] an organoaluminum compound (hereinafter sometimes referred to as “component [C]”).

FIG. 1 shows the structure of the olefin polymerization catalyst according to the present invention. In the present invention, two or more components [A]
As a method for combining the component [B] and the component [C] as needed, for example, two or more types of the component [A] and the component [B] and optionally the component [C] are polymerized under polymerization conditions. The components may be directly introduced into the system independently, or two or more types of the components [A] may be mixed in advance, and then the mixture of the components [A] and the components [B] and, if necessary, the components [C] may be added under polymerization conditions. And directly introducing them into the polymerization system.

In the present invention, the component (B) can be adjusted by mixing the component (b-1) and the component (b-2) in an inert hydrocarbon catalyst. Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic rings such as cyclopentane, cyclohexane, and methylcyclopentane. Group hydrocarbons;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof.

In mixing the component (b-1) and the component (b-2), the component (b-2) is usually used in an amount of 5 × 10 ^-4 to 2 × 10 ^-2 mol per 1 g of the component (b-1). , Preferably 10
^-3 to 10 ^-2 mol is desirable, and the component (b)
The concentration of -2) is usually 5 × 10 ^{-2 to} 5 mol / l,
Preferably, it is in the range of 0.1 to 3 mol / liter.

The mixing temperature for mixing the component (b-1) and the component (b-2) is usually -50 to 150 ° C, preferably -20 to 120 ° C. The temperature of such mixing does not necessarily have to be kept constant during the mixing, but rather the components (b-
Since the reaction between 1) and the component (b-2) is exothermic, for example, the temperature at the beginning of mixing is kept as low as possible, and the reaction temperature is increased at the latter stage of mixing to complete the reaction. It is desirable to control In the case of the above example, the preferred temperature at the beginning of the reaction is usually -50 to 5
The temperature is 0 ° C, preferably -20 to 30 ° C, and the preferable temperature in the latter half of the reaction is usually 50 to 150 ° C, preferably 60 to 120 ° C. The component (b-1) and the component (b
The contact time of -2) is 0.5 to 100 hours, preferably 1
~ 50 hours.

In the present invention, the atomic ratio (Al _b-2 / M) between aluminum (Al _b-2 ) in component ( _b-2 ) and the transition metal (M) in all components [A] is large. The higher the activity of the catalyst, the more advantageous in terms of cost. On the other hand, in general, the price of (b-2) is high, so that if the atomic ratio is too high, the cost will rather rise. Therefore, the component (b-
The upper limit of the range of the atomic ratio (Al _b-2 / M) of the aluminum in 2) to the transition metal in all the components [A] is preferably 2,000, more preferably 1,000, and still more preferably. Is 500, more preferably 300, and the lower limit is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more.

The atomic ratio (Alc / A) of the aluminum atom (Alc) in the component [C] and the aluminum atom (Al _b-2 ) in the component (b-2) used as required.
lb _-2 ) is usually 0.01 to 3, preferably 0.03 to
It is desirable to be in the range of 1.5. The olefin polymerization catalyst of the present invention obtained as described above comprises the component (b-
1) It is desirable that about 10 ^-4 to 10 ^-1 gram atoms, preferably 5 × 10 ^{-4 to} 5 × 10 ^-2 gram atoms of aluminum atoms are supported per gram.

Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene and the like can be mentioned.
Further, styrene, vinylcyclohexane, dienes and the like can be used.

In the present invention, the polymerization can be carried out by either a suspension polymerization method or a gas phase polymerization method. In the suspension polymerization method, the same inert hydrocarbon solvent as used in the preparation of the component [B] can be used, and the olefin itself can be used as the solvent. The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50.
To 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction may be carried out in any of batch, semi-continuous and continuous methods. Can be.

The polymerization of the present invention is carried out using a multi-stage polymerization method. That is, the polymerization is carried out by arranging the polymerization reactors in series, and by sequentially passing the catalyst component and / or the polymerization product in the course of polymerization through the polymerization reactors arranged in series. In the present invention, the molecular weight of the olefin polymer is
Selection of an appropriate component [A] or at least two components [A]
Can be adjusted by the combination of the type and the amount of the above, and can also be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. In the present invention, the catalyst for olefin polymerization can contain other components useful for olefin polymerization in addition to the above components.

[0075]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the present invention, the physical properties of the ethylene-based polymer are measured as follows. [Density] The density in the present invention is ASTM-D-150.
5 was measured.

[MI and HMI] In the present invention, MI and HMI are each defined by the condition E in ASTM D1238.
And condition F. [Melting tension] The melting tension (MT) in the present invention can be determined by measuring a stress when a molten polymer is stretched at a constant speed. In the present invention, using a melt tension measuring device manufactured by Toyo Seiki Seisaku-sho,
0 ° C., extrusion speed 10 mm / min, winding speed 10-20 m / min
The melt tension was measured under the conditions of a nozzle diameter of 2.09 mmφ and a nozzle length of 8 mm. When measuring the melt tension,
0.1 wt% of 2,6-di-tert-butylparacresol is added to the polymer in advance as a heat stabilizer.

[Izod Impact Value] The Izod impact value in the present invention refers to a value that can be determined according to the method described in JIS K 7110. [ESCR] Environmental stress crack resistance (ESC) in the present invention
R) is determined as the 50% crack initiation time in the method of constant strain environmental stress crack test according to JIS K 6760. [Dart Impact Value] The dart impact value of the present invention is determined by using a 30 μm thick film formed under the same film forming conditions according to JIS.
It was determined according to the method described in K 7124. [2% modulus] The 2% modulus in the present invention is:
According to JIS K 7127, a film having a thickness of 30 μm was formed under the same film forming conditions, and the film distortion was 2 μm.
It was determined by measuring the modulus value when it reached%.

(Example 1) [Preparation of silica supported on methylalumoxane] In a 200 ml glass flask sufficiently purged with nitrogen, silica (pore volume: 1.10 cm ³ / g, specific surface area: 318 cm ² / g,
Bulk density 0.38 g / cm ³ , surface hydroxyl group amount 4.1 wt
%) 4.0 g and 40 ml of toluene were put into a suspension,
Cooled to 5 ° C. In this suspension, a toluene solution of methylalumoxane (MMAO-3A manufactured by Tosoh Akzo Corporation,
Al; 1.15 mol / 1) 30 ml was added dropwise over 1 hour while maintaining the temperature of the suspension at -5 ° C. Then 0 ° C
For 1 hour, at room temperature for 1 hour, and further under reflux conditions for 3 hours. After the completion of the reaction, the reaction was cooled to 20 ° C. to obtain a suspension of silica supporting methylalumoxane.

[Polymerization] Internal volume 1.6 sufficiently purged with nitrogen.
Hexane in a 1 liter stainless steel autoclave.
80 liters were charged, and 0.35 mol of 1-hexene was added. To this was added 0.5 mmol of the above-prepared silica suspension in terms of aluminum, and hydrogen was added to the suspension.
5N ml was added and ethylene was further introduced to increase the total pressure to 7k.
g / cm ² -G, and the temperature in the system was 60 ° C. Thereafter, a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride was added to a solution of 0.1 in terms of zirconium.
5 μmol was added, the temperature in the system was set to 70 ° C., and the first-stage polymerization was started. Thereafter, ethylene was supplied, and the first-stage polymerization was continued at 70 ° C. while maintaining the total pressure at 7 kg / cm ² -G.

Forty minutes after the start of the first-stage polymerization, hydrogen in the polymerization system was purged once, and bis (1,2,3,4,5-pentamethylcyclo) was newly purged in order to perform the second-stage polymerization. After a toluene solution of (pentadienyl) zirconium dichloride was added to the polymerization system of 0.5 μmol in terms of zirconium, ethylene was supplied again to reduce the total pressure to 7 kg / cm ^2.
As -G, the second-stage polymerization was started. In the present example, bis (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride was newly added to the polymerization system, and the subsequent polymerization was performed in the second stage. Then, after performing polymerization for 20 minutes, the second-stage polymerization was completed. After the completion of the second-stage polymerization, the polymer was filtered, washed with methanol, and dried at 50 ° C. overnight. No adhesion of polymer was observed on the walls of the polymerization reactor. Table 1 and Table 2 show the conditions and the polymerization results of Example 1, respectively.

(Examples 2 to 6) The polymerization of each stage was carried out in the same manner as in Example 7 except that the kind of metallocene and the number of kinds used, the comonomer and the amount of hydrogen added, and the polymerization time in each polymerization stage were changed. Carried out. Tables 1 and 2 show the conditions and polymerization results of each example.

(Example 7) [Preparation of silica carrying methylalumoxane] A suspension of silica carrying methylalumoxane was obtained in the same manner as in Example 1. [Polymerization] 0.80 liter of hexane was placed in a 1.6 liter stainless steel autoclave sufficiently purged with nitrogen, and then 0.5 mmol of a silica suspension adjusted as described above was added in terms of aluminum. 15 ml of hydrogen was added thereto, and ethylene was further introduced to increase the total pressure to 7 k.
g / cm ² -G, and the temperature in the system was 60 ° C. Thereafter, a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride was added to a solution of 0.1 in terms of zirconium.
5 μmol was added, the temperature in the system was immediately set to 70 ° C., and the first-stage polymerization was started.

Thereafter, ethylene was supplied and the total pressure was reduced to 7 kg / c.
While maintaining the m ² -G, the first-stage polymerization was continued. Twenty minutes after the start of the polymerization, hydrogen in the polymerization system was purged once and a new bis (1,2,3,4,
A solution of 5-pentamethylcyclopentadienyl) zirconium dichloride in toluene was converted to 0.5 in terms of zirconium.
Micromolar addition and 1-hexene in 0.10
mol, and then replenish ethylene again to increase the total pressure to 7k.
g / cm ² -G, the second stage polymerization was started. Thereafter, the polymerization was carried out for 40 minutes while supplying ethylene to keep the total pressure at 7 kg / cm ² -G, and then the second-stage polymerization was completed.

After completion of the polymerization, the polymer was filtered, washed with methanol, and dried at 50 ° C. overnight. No adhesion of polymer was observed on the walls of the polymerization reactor. Tables 1 and 3 show the conditions and polymerization results of Example 2, respectively.

(Examples 8 to 10) The polymerization of each stage was carried out in the same manner as in Example 7 except that the kind of metallocene and the number of kinds used, the comonomer and the amount of hydrogen added, and the polymerization time in each polymerization stage were changed. Carried out. Tables 1 and 2 show the conditions and polymerization results of each example.

Comparative Example 1 In the polymerization of Example 1, 1
A procedure similar to that of Example 1 except that the addition amount of hexene was 0.35 mol and the addition amount of hydrogen was 15 ml, the first-stage polymerization was performed for 60 minutes, and the second-stage polymerization was not performed. , Polymerization and post-treatment were carried out to obtain a polymer. The running conditions and the polymerization results are shown in Tables 1 and 2, respectively.

Comparative Example 2 In the polymerization of Example 7, 1
-Addition of 0.05 mol of hexene and
Polymerization and post-treatment were carried out in the same procedure as in Example 7, except that the polymerization was carried out for 0 minutes and the second-stage polymerization was not carried out, thereby obtaining a polymer. The running conditions and the polymerization results are shown in Tables 1 and 3, respectively.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

EFFECTS OF THE INVENTION A multistage polymerization method and a polymerization method using at least two transition metal compounds using a catalyst comprising an inorganic solid component carrying a transition metal compound and an organic aluminum oxy compound and, if necessary, an organic aluminum component. By combining with the above, it becomes possible to control the polymer at each structural level such as molecular structure, micro structure, macro structure, etc. Thus, an olefin polymer having surprising performance that could not be obtained at all is obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of an olefin polymerization catalyst according to the present invention.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-155930 (JP, A) JP-A-3-234710 (JP, A) JP-A-5-155932 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (4)

(57) [Claims] 1. A method comprising at least two kinds of ligands having [A] cyclopentadienyl skeleton
Using an olefin polymerization catalyst comprising a Group 4 transition metal compound and [B] (b-1) an inorganic solid component in which (b-2) an organoaluminum oxy compound is supported on a particulate inorganic solid having a hydroxyl group on its surface When performing the multi-stage polymerization by using at least one of the second and subsequent polymerization stages, the group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton added to the first stage is A method for producing an olefin polymer, which comprises newly adding a group 4 transition metal compound containing a ligand having at least one different cyclopentadienyl skeleton to carry out polymerization. 2. It comprises at least two kinds of ligands having [A] cyclopentadienyl skeleton
A transition metal compound of group 4 and [B] (b-1) an inorganic solid component in which an organoaluminum oxy compound is supported on a particulate inorganic solid having a hydroxyl group on its surface, and [C] an organoaluminum compound. When performing multi-stage polymerization using the olefin polymerization catalyst, at least one of the second and subsequent polymerization stages includes a ligand having a cyclopentadienyl skeleton added to the first stage
Production of olefin polymer and performing a new addition polymerization of Group 4 transition metal compound containing a ligand having a different at least one cyclopentadienyl skeleton and Group 4 transition metal compounds Method. 3. The transition metal compound [A] in the polymerization catalyst is a Group 4 transition metal compound containing a ligand having a hydrocarbon-substituted cyclopentadienyl group. 3. The method for producing an olefin polymer according to item 1. 4. The method according to claim 1, wherein the olefin polymer is an ethylene homopolymer or a copolymer of ethylene and another α-olefin.