JPH0853509A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain an olefinic polymer capable of controlling each structural level of molecular structure, micro structure, a macro structure, etc., of a polymer and having an excellent physical properties. CONSTITUTION:This method for producing a polyolefin comprises carrying out the first stage polymerization in multistage polymerization using a catalyst for an olefine polymerization comprising [A] a transition metal compound of a group IVB containing a ligand having a cyclopendadienyl skeleton and [B] an inorganic solid component obtained by supporting an organoaluminum compound on a fine-particle inorganic solid having hydroxyl group on the surface and as necessary, [C] an organoaluminum compound and further adding a similar compound different from a compound of the group IVB containing the ligand having cyclopentadienyl skeleton added in the first stage polymerization to the polymerization stage in at least one polymerization stage among the second or more stages thereto and carrying out polymerization of olefin.

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 the polymer thereof, and more specifically, it comprises a transition metal compound and an inorganic solid component carrying an organoaluminumoxy compound. By combining the method using a catalyst, the multi-step polymerization method and the polymerization method using at least two kinds of transition metal compounds, and controlling the structure at each structural level such as molecular structure, microstructure and macrostructure of the polymer, It relates to a method for producing an olefin polymer having dramatically superior physical properties,
It 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 organic aluminum 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 having a high polymerization activity have been formed from a soluble halogen-containing transition metal compound such as bis (cyclopentadienyl) zirconium dichloride and alumoxane which is one of organoaluminum oxy compounds. A technique for polymerizing with high activity by using a catalyst has been found, and is disclosed in JP-A-58-193.
It became publicly known in Japanese Patent Publication No. 09.

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. Sho 60-35007 does not rely on the conventional method of relying on the control of hydrogen concentration or polymerization temperature, but instead of a variety of transition metal compounds including the above transition metal compounds, a transition metal suitable for the purpose. A method of adjusting the molecular weight and the comonomer content of the olefin polymer by the method of selecting the compound has also been proposed.

The catalyst system composed of 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 a comonomer. Since it is possible to obtain a large amount of a polymer or a polymer having a uniform comonomer distribution, it is possible to obtain a polymer having excellent physical properties such as impact resistance and solvent resistance. .

However, recent industrial progress has been remarkable, and together with rising expectations for polyolefins from the standpoint of environmental problems, the performance requirements for polyolefins have dramatically increased to a wide range and at a high level. The mere use of a catalyst system composed of a metal compound and an organoaluminum oxy compound has not been sufficient to satisfy such required performance, and further improvement in performance is strongly demanded.

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, and the wall surface of a reactor or a stirring blade is There is a problem in that it adheres and cannot be used industrially as it is. Further, although the narrow molecular weight distribution of the polymer is advantageous for obtaining excellent physical properties as described above, there is a practical problem that it causes deterioration of molding processability. Due to these problems, a catalyst system composed of a transition metal compound and an organoaluminum oxy compound is
The current situation is that full-scale industrialization by the suspension polymerization method and the gas phase polymerization method has not yet been reached.

Therefore, the development of a polymerization method using a catalyst system containing a transition metal compound and an organoaluminum oxy compound, which has been carried out up to now, is to improve the polymer properties rather than to further improve the polymer physical properties. The emphasis was on solving the above problems, such as improving molding processability. 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 silica, alumina, or a porous inorganic oxide such as silica-alumina for olefin polymerization. Attempts have been made to use it.

Further, as a method for improving the molding workability,
A method using a known multistage polymerization method has been proposed. For example, in JP-A-3-234717, a multi-stage polymerization method using an olefin polymerization catalyst composed of the above transition metal compound and an organoaluminum oxy compound,
A method of improving the melting properties of polymers is disclosed. Further, as another means for improving the moldability, at least 2
Japanese Patent Application Laid-Open No. 60-35008 proposes a method of broadening the molecular weight distribution by using a mixture of two 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 or silica-alumina.

Further, JP-A-5-155923 and JP-A-5-155933 use at least two or more kinds of transition metal compounds and a fine particle carrier having an adsorbed water amount and a surface hydroxyl group amount within a specific range. Then, a preliminary polymerization is carried out to improve physical properties such as melt tension and particle properties of the olefin polymer to improve molding processability.

All of these conventional methods are aimed at improving the molding processability, which is far from the viewpoint of further improving the physical properties of the polymer. Further, regarding the improvement of the moldability, the conventional method showed some improvement effect, but it was not always sufficient. For example, in a multi-stage polymerization method, there is a restriction in obtaining a desired molecular weight distribution only by controlling the polymerization conditions, and in a method using at least two kinds of transition metal compounds, a transition metal suitable for obtaining a desired molecular weight distribution is obtained. It is practically difficult to find a combination of compounds, and even if such a combination of transition metal compounds can be found, it is generally expensive and labor-intensive. The transition metal compound found was a special compound, and it was not practical because there were many problems that it was very expensive.

On the other hand, a method for producing a reactive blend using at least two kinds of transition metal compounds is disclosed in JP-A-5-31083.
It is proposed in Japanese Patent No. JP-A-5-3108
Japanese Patent No. 31 discloses a method of using a plurality of reactors as a mixing means.

[0012]

However, in the conventional methods, when applied to the suspension polymerization method and the gas phase polymerization method, it is premised that a catalyst carrying a transition metal compound is used, and such a method is used. In the case of carrying out multi-stage polymerization based on the above, even if a transition metal compound supported in the latter-stage polymerization is newly added, it is polymerized by the transition metal compound added in the latter stage and the transition metal compound coming from the former stage. The polymer to be formed is a so-called different type of polymer having different molecular weight and composition distribution depending on each catalyst, so that the different type of polymer is independently produced for each carrier loaded with each catalyst. Therefore, since the particles of the different type of polymer are respectively grown, it is virtually the same as mixing the particles of the different type of polymer with each other. 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.

Therefore, when carrying out 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 mixture as a simple polymer powder can be obtained. No physical merits were observed in the physical properties of the polymer, or, in the worst case, unfavorable adverse effects such as reduced mechanical strength and gel formation due to the non-uniform composition distribution of the obtained polymer. However, it could not be put to practical use.

Further, by applying the multi-stage polymerization method and the method using at least two kinds of transition metal compounds, for example, structure control at a molecular level such as molecular weight distribution, comonomer distribution in a molecular chain, or intermonomeric comonomer distribution, Control of microstructure such as crystal size, crystallinity, and dispersion state at the crystal level,
Furthermore, it becomes possible to optimally control each structure at each structural level of the polymer, such as control of macrostructure such as sea-island structure for each composition unit, and olefins with dramatically superior physical properties compared to conventional ones. There was no specific example in which the production of the system polymer was possible. Furthermore, as a more specific example of applying the above-mentioned multi-stage polymerization method and the method using at least two kinds of transition metal compounds, for example, when a second-stage polymerization is performed, a transition metal compound different from the transition-metal compound used in the first-stage polymerization is added. It is possible to control the molecular weight distribution easily and in a wide range by adding a different transition metal compound and adopting a polymerization condition which is different from the polymerization condition of the preceding stage. Disclosure is
It has never been seen before.

The present invention provides a method for producing an olefin polymer which is substantially uniformly mixed, and a polymer obtained by the method. Furthermore, the present invention provides a molecular weight distribution, a comonomer distribution in a molecular chain and an intermolecular structure. Comonomer distribution, structure control at the molecular level such as mixed state of molecules, crystal size and distribution of the crystal size, control of microstructure such as crystallinity, dispersed state at the crystal level, and further for each composition unit A method for producing an olefin-based polymer having dramatically superior physical properties as compared with the conventional method by optimally controlling each structure at each structural level of the polymer, such as control of macrostructure such as sea-island structure, and the method thereof It is intended to provide a polymer obtained by

[0016]

Means for Solving the Problems In the catalyst system comprising a transition metal compound and an organoaluminum oxy compound, the present inventors have earnestly studied to improve the physical properties of the obtained polymer, and as a result, By combining a method using a catalyst comprising an inorganic solid component supporting a metal compound and an organoaluminum oxy compound and optionally an organoaluminum component, a multistage polymerization method and a polymerization method using at least two transition metal compounds, It is possible to control the molecular structure, microstructure, macrostructure, etc. of the polymer at each structural level, and by optimizing the structure at each structural level, a synergistic effect is expressed, which can be generally achieved by conventional techniques. It was found that an olefin-based polymer having a surprising performance which was not obtained was obtained, and the present invention was completed.

The present invention relates to a group IVB transition metal compound containing at least two [A] cyclopentadienyl skeleton-containing ligands, and [B] (b-1) a fine-particle inorganic solid having a hydroxyl group on the surface. In (b-2) an inorganic solid component carrying an organoaluminum oxy compound and, if necessary, a [C] organoaluminum compound, a catalyst for olefin polymerization is used, and further multistage polymerization is used. At least one cyclopentadiene different from the Group IVB transition metal compound containing a ligand having a cyclopentadienyl skeleton added to the first stage in at least one of the second and subsequent polymerization stages By adding a transition metal compound of Group IVB containing a ligand having an enyl skeleton and conducting polymerization, each structure such as molecular structure, microstructure and macrostructure of the polymer can be obtained. Performs control bell, excellent physical properties are those which provide a method for producing an olefin polymer having, also it is to provide a polymer obtained by the production method.

The olefin multistage polymerization method according to the present invention and the olefin polymer polymerized by this method will be specifically described below. 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 sense.

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

In the present invention, when a mixture of polymers is polymerized by coexisting two kinds of transition metal compounds in one polymerization stage, for example, the mixing ratio of the two kinds of polymers to be produced is such that the organoaluminum of the transition metal compound is used. Coordination power for oxy compounds,
Depends on polymerization activity etc. Therefore, for example, in the example of mixing the high molecular weight ethylene polymer and the low molecular weight ethylene polymer, the amount ratio of the high molecular weight portion and the low molecular weight portion of the ethylene polymer can be controlled by selecting an appropriate transition metal compound. It is therefore possible to polymerize ethylene polymers with the desired molecular weight distribution using such techniques. Thus, in the present invention, it is possible to control the polymer at the molecular level.

Surprisingly, polymerization of a polymer in which two kinds of polymers are substantially mixed at the molecular level can be realized by gradually adding two kinds of [A] transition metal compounds.
For example, when the polymerization is first performed using one kind of transition metal compound, and then the polymerization is performed by adding another kind of transition metal compound, in the first polymerization, a polymer corresponding to the transition metal compound used first is produced, After the addition of another type of transition metal compound, a polymer in which the transition metal compound used first and two types of polymers corresponding to the other type of transition metal compound are uniformly mixed is formed. As a result of such polymerization, the polymer obtained becomes a polymer having a sea-island structure in which the polymer initially obtained and the polymer in which two kinds of polymers are uniformly mixed are mixed. The sea-island structure of the finally obtained polymer can be controlled by controlling the amount ratio of the polymer obtained first and the polymer in which two kinds of polymers are uniformly mixed.

It is unexpected from the common sense of the prior art that polymerization based on another kind of transition metal compound occurs by newly adding another kind of transition metal compound after the first polymerization as in the above example. It was amazing. That is, what is usually expected in the above examples is that the polymerization active sites formed on the carrier will be covered with the polymer formed in the first polymerization, and then a new transition metal of another kind is added. Even if a compound is added, the other transition metal compound cannot contact with the organoaluminum oxy compound on the carrier, and therefore, a polymerization active point cannot be formed. The activity is unlikely to be expected.

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

In the present invention, in order to further expand the effect of such polymerization, the polymerization is carried out by multistage polymerization. That is, when another kind of transition metal compound is newly added, a polymerization condition different from the initial polymerization condition is adopted by multi-stage polymerization, which enables further optimization of the polymer structure. The multi-stage polymerization method referred to in the present invention means that polymerization units are arranged in series and catalyst components or /
And a polymerization method in which stepwise polymerization is carried out by sequentially passing the polymerization products during the polymerization through the polymerization vessels arranged in series.

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

For example, a homopolymerization of ethylene is carried out by using a transition metal compound capable of increasing the molecular weight of ethylene during the first-stage polymerization to polymerize an ultra-high molecular weight ethylene polymer, and 2
If a low density ethylene polymer is polymerized by adding α-olefin as a comonomer component and a transition metal compound that is newly excellent in copolymerization in the second stage polymerization, it becomes an unprecedented ultra high molecular weight ethylene polymer. It is possible to produce a polymer in which a low-density ethylene polymer is finely dispersed or a polymer in which an ultrahigh molecular weight ethylene polymer is finely dispersed in a low-density ethylene polymer, and to appropriately control such a sea-island structure. As a result, it becomes possible to perform extrusion molding and injection molding of an ultrahigh molecular weight ethylene polymer, which has hitherto been impossible.

In the present invention, between the polymerization vessels arranged in series,
There may be steps such as a mixing step, a degassing step, a cooling or temperature raising step in which polymerization is not substantially performed. The catalyst system of the present invention and the polymerization method using the same enable the structure control of the polymer. Therefore, according to the method of the present invention,
It enables the production of synergistic polyolefins.

The synergistic polyolefin referred to in the present invention means molecular structure control such as molecular weight distribution, comonomer distribution in the molecular chain or intermolecular comonomer distribution, control of microstructure such as crystal size, crystallinity and crystal arrangement, Furthermore, by optimally controlling each structure at each structural level of the polymer, such as controlling macrostructure such as sea-island structure for each composition unit, the olefin-based polymer whose physical properties are dramatically improved as compared with the conventional polyolefins. Says a polymer. In such an olefin polymer, it is possible to improve both physical properties in a combination of physical properties which are considered to be incompatible with each other in the prior art because of the contradictory physical properties.

The reason why such excellent physical properties can be realized is thought to be due to the synergistic effect of optimization at each structural level such as the above-mentioned molecular structure, microstructure or macrostructure. Optimization at each structural level can only be realized by the method of the invention. The dramatic improvement of the physical properties in the present invention means, for example, the case where the physical properties of interest are improved by 30% or more.

Specific examples of the above synergistic polyolefin include ultrahigh molecular weight polyethylene which can be extruded or injection molded, but as another example, high molecular weight polyethylene has a narrow molecular weight distribution (Mw /
(Mn = 2-5) By finely dispersing low-density polyethylene having a uniform comonomer distribution, polyethylene that has been realized to have both high rigidity, high impact resistance, and high ESCR, which have not been considered to be parallel, can be obtained. Can be mentioned.

As another example, the extrusion rate and die swell are improved by optimally controlling the molecular weight distribution, and the ESCR and impact resistance are optimized by optimally controlling the comonomer content in each molecular weight. And polyethylene, which can improve moldability, high ESCR and high impact resistance as a result.

According to the method of the present invention, it is possible to produce a polyolefin having excellent properties which could not be obtained by the prior art. Especially in the case of an ethylene polymer, the effect is great. The present invention will be described in more detail below. Examples of the group IVB transition metal compound containing a ligand having an [A] cyclopentadienyl skeleton used in the present invention include compounds represented by the following general formula. MLx ...

In the above general formula, M is I of the periodic table.
It is a transition metal of Group VB, specifically zirconium, titanium or hafnium, L is a ligand that coordinates to the transition metal, and at least one L has a cyclopentadienyl skeleton. L, which is a ligand and has a cyclopentadienyl skeleton, has 1 to 1 carbon atoms.
2 hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, trialkylsilyl group, -SO ₃ R (where,
R has 1 carbon atom which may have a substituent such as halogen.
~ 8 hydrocarbon groups. ) Or a hydrogen atom, or may be a hetero tridentate ligand, where x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, 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 with a halogen atom, a trialkylsilyl group or the like, and further may be substituted with a hetero atom which can serve as a bonding site. Further, 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 preferable. 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
Alkylene groups such as methylene, ethylene, propylene; substituted alkylene groups such as isopropylidene, diphenylmethylene; silylene groups or dimethylsilylene groups, diphenylsilylene groups, methylphenylsilylene groups, and the like Good.

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

Examples of the alkoxy group include methoxy group, ethoxy group, butoxy group and the like. A phenoxy group etc. are illustrated as an aryloxy group. Further, examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Further, examples of the ligand represented by —SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. Further, examples of the hetero tridentate ligand include a hydrotrispyrazolyl borate group and a trisbisphenyloxophosphoranyl group.

The compound represented by the above general formula is more specifically represented by the following general formula when the valence of the transition metal is 4, for example. 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 is 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, in the above general formula, R ² , R ^2
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. To be Ligands having these cyclopentadienyl skeletons 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 via a substituted silylene group or the like, and R ³ and R ⁴ are ligands having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups. A group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be 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, ethylenebis (tetramethylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) Diphenylzirconium, ethylenebis (indenyl) methylzirconium 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) zirconium bis (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) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,4) 5,6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclo N-diphenylenyl-fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl)
Zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl)
Zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylsi-η ⁵ -cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (tertiary butylamide) (tetramethyl-η ^5- Cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (tertiary butyl amide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene zirconium dichloride, (tertiary butyl amide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene Titanium dichloride, (tertiary butyl amide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene zirconium dimethyl (tertiary butyl amide)
(Tetramethyl- [eta] ⁵ -cyclopentadienyl) methylene titanium dimethyl, (tertiary butylamide) (tetramethyl- [eta] ⁵ -cyclopentadienyl) isopropylidene zirconium dichloride, (tertiary butylamide) (tetramethyl- [eta] ⁵ -Cyclopentadienyl) isopropylidene titanium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) isopropylidene zirconium dimethyl, (tertiary butylamide)
(Tetramethyl- [eta] ⁵ -cyclopentadienyl) isopropylidene titanium dimethyl, (tertiary butylamide)
(Tetramethyl- [eta] ⁵ -cyclopentadienyl) -1,
2-ethanediylzirconium dimethyl, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dimethyl, (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride,
(Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl titanium dichloride,
(Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dibenzyl, (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl titanium dimethyl , (Methylamido) dimethyl (tetramethyl-η ^5-
Cyclopentadienyl) silane titanium dichloride, (methylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (ethylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -methylene titanium dichloride, ( Ethylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -methylene titanium dimethyl, (tertiary butyl amide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (tertiary butyl amide) dimethyl (tetramethyl -[Eta] ⁵ -Cyclopentadienyl) silane zirconium dichloride, (tertiary butylamido) dibenzyl (tetramethyl- [eta] ⁵ -cyclopentadienyl)
Silane zirconium dibenzyl, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (Benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium diphenyl, (phenylphosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (phenylphosphide)
Dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (phenylphosphide)
Dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (2-methoxyphenylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (4-fluorophenylamido) 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-tetramethyldisilane titanium dichloride, 1- (tertiary butyramide) -2-
(Tetramethyl- [eta] ⁵ -cyclopentadienyl) -1,
1,2,2-Tetramethyldisilane zirconium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dimethyl, (tertiary butylamido) dimethyl (η ⁵ -cyclopentadienyl) ) Silane titanium dichloride, (tertiary butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane zirconium dichloride, (anilide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (anilide) dimethyl ( Tetramethyl- [eta] ⁵ -cyclopentadienyl) silane zirconium dichloride and the like are also exemplified.

In the present invention, a Group IVB transition metal compound containing at least two [A] cyclopentadienyl skeleton-containing ligands is selected in order to produce a polymer having desired physical properties. By appropriate selection, it becomes possible to arbitrarily control the molecular weight of the polymer, the copolymer composition and the like.

The (b-1) particulate inorganic solid of the present invention is preferably a porous inorganic solid such as SiO ₂ or 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, such as 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 and the like. Among these, SiO ₂ , Al ₂ O
It is preferable that the main component is at least one component selected from the group consisting of ₃ , MgO and MgCl ₂ .

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 fine particle inorganic solid usually means an OH group which is firmly held on the surface of the fine particle inorganic solid under polymerization conditions to generate H ₂ O by heating at a high temperature.

The method for obtaining a finely divided 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 during polymerization or at a temperature higher than that. Under the method, the fine particulate inorganic solid is allowed to stand, for example, for 3 hours or more. In the present invention, the amount of the hydroxyl groups on the surface of the fine particulate inorganic solid is the ratio of the weight reduction amount of the fine particulate inorganic solid to the weight of the fine particulate inorganic solid before heating at 1000 ° C. under normal pressure (weight. %).

The amount of the hydroxyl group on the surface of the fine particle inorganic solid of the present invention is preferably an amount that works effectively when the fine particle inorganic solid (b-2) is supported on the fine particle inorganic solid. In this case, if the amount of the hydroxyl group is too large with respect to the amount of the organoaluminum oxy compound used, the alkyl group in the organoaluminum oxy compound is crushed by the hydroxyl group, and the development of catalytic performance is hindered. Further, if the amount of hydroxyl groups on the surface of the particulate inorganic solid is too small with respect to the organoaluminum oxy compound used, the loading of the organoaluminum oxy compound will be hindered. That is, the hydroxyl group on the surface of the finely divided inorganic solid reacts with the alkyl group of the organoaluminum oxy compound to form O.
-Al bond is considered to be formed, but if the amount of hydroxyl groups on the surface of the fine particulate inorganic solid is too small with respect to the organoaluminum oxy compound, a desired amount of the organoaluminum oxy compound is firmly supported on the fine particulate inorganic solid surface. I can't do it.

In the present invention, the molar ratio (OH / Al _b-2 ) of the hydroxyl group (OH) on the surface of the finely divided inorganic solid to the aluminum (Al _b-2 ) in the (b-2) organoaluminum oxy compound is 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, preferably 0.05 or more.

Further, in order to support an amount of the organoaluminum oxy compound necessary and effective for polymerization, the amount of hydroxyl groups on the surface of the fine particle inorganic solid is at least 0.5% by weight or more of the fine particle inorganic solid. It is desirable that the content be 1% by weight or more. However, if the amount of the hydroxyl group on the surface of the particulate inorganic solid is too large,
The activity tends to decrease. This is probably because there are too many reaction sites with the organoaluminum oxy compound, and as a result, the effect of the organoaluminum oxy compound as a cocatalyst is limited, but the details are unknown. Since the activity tends to decrease when the amount of the hydroxyl group on the surface of the particulate inorganic solid is too low, the upper limit amount of the hydroxyl group is preferably 12% by weight, more preferably 10% by weight. , More preferably 8% by weight, and 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 by heating under appropriate conditions, if necessary. In the present invention, the hydroxyl group on the surface of the particulate inorganic solid can be modified by chemically treating it with an organic aluminum compound or the like. Thus, by modifying the hydroxyl group on the surface of the finely divided inorganic solid with the organoaluminum compound, the amount of the hydroxyl group can be substantially adjusted, and (b-2) use of the organoaluminum oxy compound The effect of reducing the amount is also found.

As such an organic aluminum compound, for example, an organic aluminum 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, and X is
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 such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n- group.
Examples thereof include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organoaluminum compound, the following compounds are specifically used. For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride,
Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; methyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum 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 the hydroxyl group (b-1) on the surface of the finely divided inorganic solid, the amount of the organoaluminum used is the amount of aluminum (Al _R )
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-particle inorganic solid, the (b-1) fine-particle inorganic solid is usually (b-2). ) Before loading the organoaluminum oxy compound, the hydroxyl group is modified by bringing the organoaluminum compound into contact with the (b-1) fine-particle inorganic solid.
2) The organoaluminum oxy compound may be mixed, and thereafter, the mixture may be brought into contact with (b-1) the fine particle inorganic solid to simultaneously modify the hydroxyl group and carry the organoaluminum oxy compound.

In the present invention, when the above-mentioned organoaluminum compound is used to modify the hydroxyl group (b-1) on the surface of the finely divided inorganic solid, the hydroxyl group (b) of the hydroxyl group (OH) on the surface of the finely divided inorganic solid is -2) Aluminum in a molar ratio (OH / Al _b-2 ) to aluminum (Al _b-2 ) in the organoaluminum oxy compound is considered to be a value obtained by adding aluminum (Al _R ) in the organoaluminum compound. . Therefore, the molar ratio (OH / Al _b-2 ) of the hydroxyl group (OH) on the surface of the particulate inorganic solid to the 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.
The above, preferably in the range of 0.05 or more, in the case of modifying the hydroxyl group on the surface of the fine-particle inorganic solid using the organoaluminum compound, the hydroxyl group (OH) on the surface of the fine-particle inorganic solid. (B-2) Aluminum in an organoaluminum oxy compound (Al _b-2 ).
And the molar ratio (OH) to the sum of aluminum (Al _R ) in the organic aluminum used for modifying the hydroxyl group.
/ Al _b-2 + Al _R ) has a desirable range of 1 or less as an upper limit, preferably 0.7 or less as a lower limit, and 0.01 as a lower limit.
The above is considered, and preferably 0.05 or more.

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

[0055]

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(In the formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms.) In the above formula, R ⁶ is specifically methyl group, ethyl group, n-propyl group, isopropyl group, 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, an organoaluminumoxy compound composed of one type of alkylaluminum unit is:
Methyl alumoxane, ethyl alumoxane, n-propyl alumoxane, isopropyl alumoxane, n-butyl alumoxane, isobutyl alumoxane, pentyl alumoxane, hexyl alumoxane, octyl alumoxane, decyl alumoxane, cyclohexyl alumoxane, cyclooctyl. There are alumoxane etc. Of these, methylalumoxane and ethylalumoxane are preferable, and methylalumoxane is particularly preferable. As described above, the organoaluminum oxy compound of the present invention is composed of the alkyloxy aluminum unit represented by the above formula, but is not necessarily limited to the compound composed of one kind of constitutional unit, and a plurality of kinds May be a constituent unit of For example, methyl ethyl alumoxane,
Methyl propyl alumoxane, methyl butyl alumoxane, etc., and the ratio of various structural units can be arbitrarily set in the range of 0 to 100%. Further, it may be a mixture of a plurality of kinds of organoaluminum oxy compounds composed of one kind of constitutional unit. For example, a mixture of methyl alumoxane and ethyl alumoxane, a mixture of methyl alumoxane and n-propyl alumoxane, a mixture of methyl alumoxane and isobutyl alumoxane, and the like.

Further, the organoaluminum oxy compound of the present invention may contain unreacted chemical substances derived from the production method thereof. That is, the organoaluminum oxy compound is generally obtained by the reaction of trialkylaluminum and H ₂ O, but some of these raw materials may remain as unreacted chemical substances. For example, when 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 above-described method for producing an organoaluminum oxy compound, trialkylaluminum is usually used in a larger amount than H ₂ O, so that a trialkylaluminum is often contained in the organoaluminum oxy compound as a residual chemical substance.

Organoaluminum compound [C] used in the present invention (hereinafter sometimes referred to as "component [C]").
For example, an organoaluminum compound represented by the following general formula can be exemplified. R ⁷ _n AlX _3-n (wherein R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, and X is
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, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-
Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum;
Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquipro 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 nitrites such as diethyl aluminum hydride and diisobutyl aluminum hydride Such as beam hydride.

Further, as the [C] organoaluminum compound, 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 a —OR ⁸ group, —
OSiR ⁹ ₃ group, -OAlR ¹⁰ ₂ group, -NR ¹¹ ₂ group,-
SiR ¹² ₃ group or —N (R ¹³ ) 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 and the like, and R ¹¹ is hydrogen, a methyl group, ethyl. Group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ¹² and R ¹³ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used.

(I) a compound represented by R ⁷ _n Al (OR ⁸ ) _3-n , for example, dimethyl aluminum methoxide,
Diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (Ii) a compound represented by R ⁷ _n Al (OSiR ⁹ ₃ ) _3-n , for example, Et ₂ Al (OSiMe ₃ ) (iso-
Bu) ₂ Al (OsiMe ₃ ), (iso-Bu) ₂ A
1 (OSiEt ₃ ), etc. (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.

(Iv) Compounds represented by R ⁷ _n Al (NR ¹¹ ₂ ) _3-n , such as Me ₂ AlNEt ₂ and Et ₂ Al
NHMe, Me ₂ AlNHEt, Et ₂ AlN (SiM
_{e 3) 2, (iso-} Bu) 2 AlN (SiMe 3) 2
Such. (V) A compound represented by R ⁷ _n Al (SiR ¹² ₃ ) _3-n , for example, (iso-Bu) ₂ AlSiMe ₃ .

[0063]

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Among the organoaluminum compounds represented by the above general formula, R ⁷ ₃ Al, R ⁷ _n Al (OR ⁸ )
Suitable examples include organoaluminum compounds represented by _3-n and R ⁷ _n (OAlR ¹⁰ ₂ ) _3-n ,
It is particularly preferable that R ⁷ is an isoalkyl group and n = 2. Two or more kinds of these organoaluminum compounds may be mixed and used.

The olefin polymerization catalyst according to the present invention is
Group IVB transition metal compound containing at least two kinds of [A] cyclopentadienyl skeleton ligands (hereinafter sometimes referred to as “component [A]”), and (b-1) fine particles (B-2) Organoaluminum oxy compound (hereinafter sometimes referred to as "component (b-2)") in the inorganic solid (hereinafter sometimes referred to as "component (b-1)").
[B] an inorganic solid component (hereinafter sometimes referred to as “component [B]”) supporting C and, if necessary, an [C] organoaluminum compound (hereinafter referred to as “component [C]”). Sometimes it is).

FIG. 1 shows the structure of the olefin polymerization catalyst according to the present invention. In the present invention, two or more components [A]
And the component [B] and, if necessary, the component [C] may be combined by, for example, polymerizing two or more kinds of the component [A] and the component [B] and, if necessary, the component [C] under polymerization conditions. Each of them may be directly introduced into the system independently, or two or more kinds 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 used under polymerization conditions. By direct introduction into the polymerization system.

In the present invention, the component [B] can be prepared 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 thereof include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

When the component (b-1) and the component (b-2) are mixed, the component (b-2) is usually 5 × 10 ⁻⁴ to 2 × 10 ⁻² mol per 1 g of the component (b-1). , Preferably 10
It is preferably in the range of ^-3 to 10 ^-2 mol, and the component (b
The concentration of -2) is usually 5 × 10 ^{-2 to} 5 mol / liter,
It is preferably in the range of 0.1 to 3 mol / liter.

The mixing temperature for mixing the components (b-1) and (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 mixing, but rather the component (b-
Since the reaction between 1) and the component (b-2) is exothermic, for example, the temperature in the initial stage of mixing should be kept as low as possible, and the reaction temperature should be increased in the latter stage of mixing to complete the reaction. It is desirable to control In the case of the above example, the preferable temperature at the initial stage 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 stage of the reaction is usually 50 to 150 ° C., preferably 60 to 120 ° C. Further, 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 the aluminum (Al _b-2 ) in the component ( _b-2 ) and the transition metal (M) in all the components [A] is large. The higher the activity of the catalyst, the better the cost. On the other hand, since the cost of (b-2) is generally high, the cost rises if the atomic ratio is too high. Therefore, the component (b-
The upper limit of the atomic ratio (Al _b-2 / M) of aluminum in 2) to the transition metal in all components [A] is preferably 2000, more preferably 1000, and further preferably Is 500, more preferably 300, and its lower limit is preferably 10 or more, more preferably 20 or more, and further 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), which are used as necessary.
lb _-2 ) is usually 0.01 to 3, preferably 0.03 to
A range of 1.5 is desirable. 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 atom, preferably 5 × 10 ^{−4 to} 5 × 10 ⁻² gram atom of aluminum atom is supported per 1 g.

As olefins which can be polymerized by such an olefin polymerization catalyst, ethylene and α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4
-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
Examples thereof include a-octahydronaphthalene.
Further, styrene, vinylcyclohexane, dienes and the like can be used.

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

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

[0075]

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

[MI and HMI] MI and HMI in the present invention are the conditions E in ASTM D1238, respectively.
And the condition F. [Melt Tension] The melt tension (MT) in the present invention can be determined by measuring the stress when the molten polymer is stretched at a constant rate. In the present invention, a resin temperature of 19 is used with a melt tension measuring machine manufactured by Toyo Seiki Seisakusho.
0 ° C, extrusion speed 10 mm / min, winding speed 10-20 m /
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,
To the polymer, 0.1 wt% of 2,6-di-t-butylparacresol as a heat stabilizer is added in advance.

[Izod Impact Value] The Izod impact value in the present invention means a value that can be obtained according to the method described in JIS K7110. [ESCR] Environmental stress crack value (ESC) in the present invention
R) is determined as a 50% crack initiation time in the method of constant strain environmental stress crack test according to JIS K 6760. [Dirt Impact Value] The dirt impact value of the present invention was measured using a film having a thickness of 30 μm 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
Using a film with a thickness of 30 μm formed under the same film forming conditions, the film distortion is 2 according to JIS K 7127.
It was determined by measuring the modulus value when it reached%.

(Example 1) [Preparation of silica supporting methylalumoxane] In a 200 ml glass flask sufficiently replaced 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 added to form a suspension-
Cooled to 5 ° C. In this suspension, a toluene solution of methylalumoxane (MMAO-3A manufactured by Toso Akzo Co., Ltd.,
30 ml of Al; 1.15 mol / 1) was added dropwise over 1 hour while maintaining the temperature of the suspension at -5 ° C. Then 0 ℃
For 1 hour, at room temperature for 1 hour, and further under reflux conditions for 3 hours, and after the reaction was completed, the reaction mixture was cooled to 20 ° C. to obtain a suspension of silica carrying methylalumoxane.

[Polymerization] Fully nitrogen-substituted internal volume 1.6
Hexane in a liter stainless steel autoclave.
80 liters were put and 0.35 mol of 1-hexene was added. After adding 0.5 mmol of the silica suspension adjusted as described above in terms of aluminum, hydrogen was added to 1
5Nml was added and ethylene was introduced to bring the total pressure to 7k.
and g / cm ² -G, and the temperature in the system and 60 ° C.. Thereafter, a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride was converted into zirconium in an amount of 0.
5 micromol was added, the temperature in the system was raised to 70 ° C., and the first stage polymerization was started. Then, ethylene was replenished, and while maintaining the total pressure at 7 kg / cm ² -G, the first-stage polymerization was continued at 70 ° C.

Forty minutes after the initiation of the first-stage polymerization, the second-stage polymerization is carried out. Therefore, hydrogen in the polymerization system is once purged, and bis (1,2,3,4,5-pentamethylcyclohexene) is newly added. After adding a toluene solution of pentadienyl) zirconium dichloride into the polymerization system of 0.5 micromol in terms of zirconium, ethylene is replenished to bring the total pressure to 7 kg / cm ^2.
-G, the second stage polymerization was started. In this example, bis (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride was newly added to the polymerization system, and the subsequent steps were the second-stage polymerization. After that, polymerization was carried out for 20 minutes, and then the second-stage polymerization was completed. After the completion of the second-stage polymerization, the polymer was filtered, washed with methanol, and then dried at 50 ° C. overnight. No polymer adhesion was observed on the wall surface of the polymerization reactor. The working conditions and polymerization results of this Example 1 are shown in Table 1 and Table 2, respectively.

(Examples 2 to 6) Polymerization of each stage was carried out in the same manner as in Example 7 except that the type of metallocene and the number of types thereof used in each polymerization stage, the comonomer and the hydrogenation amount, the polymerization time and the like were changed. Carried out. The working conditions and the polymerization results of each example are shown in Tables 1 and 2.

Example 7 [Preparation of methylalumoxane-supporting silica] The same procedure as in Example 1 was carried out to obtain a suspension of silica supporting methylalumoxane. [Polymerization] 0.80 liters of hexane was put into a stainless steel autoclave having an internal volume of 1.6 liters, which had been sufficiently replaced with nitrogen, and 0.5 mmol of the silica suspension prepared as above was added in terms of aluminum. Add 15 ml of hydrogen to this, and further introduce ethylene to bring the total pressure to 7 k.
and g / cm ² -G, and the temperature in the system and 60 ° C.. Thereafter, a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride was converted into zirconium in an amount of 0.
5 μmol was added, the temperature in the system was immediately raised to 70 ° C., and the first-stage polymerization was started.

Thereafter, ethylene was replenished to bring the total pressure to 7 kg / c.
while keeping the m ² -G, and the polymerization was continued for the first stage. Twenty minutes after the initiation of the polymerization, the second-stage polymerization is carried out. Therefore, hydrogen in the polymerization system is once purged, and new bis (1, 2, 3, 4,
A toluene solution of 5-pentamethylcyclopentadienyl) zirconium dichloride is converted to 0.5 in terms of zirconium.
Micromol was added, and 1-hexene was added to 0.10.
After adding mol, add ethylene again to bring the total pressure to 7k.
The second stage of polymerization was started at g / cm ² -G. Then, ethylene was supplied to carry out polymerization for 40 minutes while maintaining the total pressure at 7 kg / cm ² -G, and then the second-stage polymerization was terminated.

After completion of the polymerization, the polymer was filtered, washed with methanol, and then dried at 50 ° C. overnight. No polymer adhesion was observed on the wall surface of the polymerization reactor. The working conditions and polymerization results of this Example 2 are shown in Table 1 and Table 3, respectively.

(Examples 8 to 10) Polymerization of each stage was carried out in the same manner as in Example 7 except that the type of metallocene and the number of types thereof used in each polymerization stage, the comonomer and the hydrogenation amount, and the polymerization time were changed. Carried out. The working conditions and the polymerization results of each example are shown in Tables 1 and 2.

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, the addition amount of hydrogen was 15 ml, the first-stage polymerization was carried out for 60 minutes, and the second-stage polymerization was not carried out. Polymerization and post-treatment were carried out to obtain a polymer. The execution conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

Comparative Example 2 In the polymerization of Example 7, 1
-Adding 0.05 mol of hexene to the first stage polymerization of 6
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, to obtain a polymer. The execution conditions and the polymerization results are shown in Table 1 and Table 3, respectively.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

EFFECTS OF THE INVENTION A multi-stage polymerization method and a polymerization method using at least two kinds of transition metal compounds using a catalyst composed of an inorganic solid component carrying a transition metal compound and an organoaluminum oxy compound and, if necessary, an organoaluminum component. By combining with, it becomes possible to control the molecular structure, microstructure, macrostructure, etc. of the polymer at each structural level, and by optimizing the structure at each structural level, a synergistic effect can be expressed. It is possible to obtain an olefin-based polymer having a surprising performance that could not be obtained in the past.

[Brief description of drawings]

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

Claims (4)

[Claims] 1. A transition metal compound of Group IVB containing at least two [A] ligands having a cyclopentadienyl skeleton and [B] (b-1) a fine particle inorganic solid having a hydroxyl group on the surface ( b-2) When carrying out multi-stage polymerization using an olefin polymerization catalyst comprising an inorganic solid component carrying an organoaluminum oxy compound, at least one polymerization stage among the second and subsequent polymerization stages has one stage. IVB containing a ligand having a cyclopentadienyl skeleton added to the eye
Group IVB transition metal compound containing at least one ligand having a cyclopentadienyl skeleton different from group III transition metal compound is newly added to carry out polymerization. . 2. A group IVB transition metal compound containing at least two kinds of [A] ligands having a cyclopentadienyl skeleton and [B] (b-1) a fine particle inorganic solid having a hydroxyl group on the surface ( b-2) When carrying out multi-stage polymerization using an olefin polymerization catalyst comprising an inorganic solid component carrying an organoaluminum oxy compound and [C] an organoaluminum compound, at least one of the second and subsequent polymerization stages Group IVB containing a ligand having at least one cyclopentadienyl skeleton different from the Group IVB transition metal compound containing a ligand having a cyclopentadienyl skeleton added to the first stage in one polymerization stage The method for producing an olefin-based polymer, characterized in that the transition metal compound is added to carry out polymerization. 3. The transition metal compound [A] in the polymerization catalyst is a group IVB transition metal compound containing a ligand having a hydrocarbon-substituted cyclopentadienyl group. The method for producing an olefin-based polymer according to 1. 4. The production method according to claim 1, 2 or 3, wherein the olefin polymer is an ethylene homopolymer or a copolymer of ethylene and another α-olefin.