JPH08277307A - Catalyst for olefin polymerization and polymerization using the same - Google Patents

Abstract

PURPOSE: To obtain a highly active catalyst capable of producing olefin polymers excellent in granular properties at low cost by suspension polymerization, solution polymerization, etc., comprising a specific solid catalytic component, an organoaluminum compound and a transition metal compound. CONSTITUTION: This catalyst for olefin polymerization comprises (A) a compound of formula I [M is a group 1-13 metal; R<1> is a 1-8C alkyl; R2 -R<4> are each a 2-20C hydrocarbon group; α is 0-0.3 or 0.9-1.1; β is 0-0.5; (p) and (t) are each a positive number; (q), (r) and (s) are each >=0; satisfying the relationships II ((k) is the valence of M) and III], (B) a compound of formula, AlR<5> n Z<1> 3-n (R<5> is a 1-20C hydrocarbon group; Z<1> is H, a halogen, etc.; 0<(n)<=3), and (C) a compound of formula IV [M is Zr, Ti, etc.; R<7> is a ligand for cyclopentadienyl skeleton, etc.; R<8> -R<10> are each a ligand for cyclopentadienyl skeleton, etc.; R<6> is a 1-20C (substituted) alkylene connecting one of R<8> -R<10> and R<7> to each other, etc.; R<7> -R<10> are each connected to M; (a) >=1; (b), (c) and (d) are each 0-3; (a)-(d) sum to 4; (z) is 0 or 1].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst, and more specifically to various olefin polymerization methods such as suspension polymerization method, gas phase polymerization method and solution polymerization method. The present invention relates to an olefin polymerization catalyst that can be applied and has a high polymerization activity and can inexpensively produce an olefin polymer having excellent particle properties without using an aluminoxane, and an olefin polymerization method using this catalyst.

[0002]

2. Description of the Related Art A so-called Ziegler-Natta type catalyst composed of a titanium compound and an organoaluminum compound has been known as a catalyst for producing an olefin polymer or copolymer. On the other hand, in recent years, by homopolymerization of ethylene or copolymerization of ethylene with other α-olefins, by using a catalyst composed of a soluble halogen-containing transition metal compound such as bis (cyclopentadienyl) zirconium dichloride and an aluminoxane, Techniques have been found to perform polymerization with high activity. For details of the technology, see Japanese Patent Publication No. 4-12
283 (corresponding to DE31271333.2).

Further, as an application technique of a catalyst comprising the above transition metal compound and aluminoxane, two or more kinds of metallocenes are mixed and used as a transition metal compound component, or a metallocene having a substituent is used. A technique for changing the molecular weight, the molecular weight distribution, the copolymerizability, etc. is disclosed in Japanese Patent Laid-Open No.
Nos. 0-35006, 60-35007, and 60-35008 are proposed.

However, the catalyst formed from the transition metal compound and aluminoxane proposed in these prior arts requires a large amount of expensive aluminoxane, so that the catalyst cost is much higher than that of the Ziegler-Natta type catalyst. There was a big drawback that it became very expensive. Further, in the above-mentioned conventional technique, since the transition metal compound and the aluminoxane are soluble in the solvent, when applied to the suspension polymerization method or the gas phase polymerization method, the particle properties of the obtained polymer are poor and it is difficult to handle as it is. Therefore, there is also a problem that at least one component of the transition metal compound and the aluminoxane must be used by supporting it on a porous inorganic oxide carrier such as silica, alumina, silica-alumina, which also increases the catalyst cost. It was a factor.

To solve the above problems, various methods have been proposed which do not use expensive aluminoxane. For example, Japanese Patent Publication No. 1-501950 and Japanese Patent Publication No. 1-502036.
The publication proposes a catalyst comprising a transition metal compound and a compound containing a bulky anion capable of stabilizing a metal cation (hereinafter referred to as a stabilized anion-containing compound). However, although these stabilizing anion-containing compounds do not need to be used in a large amount like aluminoxane, they are more expensive than aluminoxane, so that the total cost of the catalyst is equal to or higher than that when aluminoxane is used. There was a problem of becoming. Further, since the stabilized anion-containing compound is also soluble in the solvent, the problem of loading still remains. Furthermore, the stabilized anion-containing compound is often unconfirmed in terms of safety to living bodies, and this is also a problem.

As another method which does not use aluminoxane, Soga et al. Proposed that a transition metal compound is supported on a carrier such as alumina or MgCl ₂ having a Lewis acidic active site, and by using this together with an organoaluminum compound, Was polymerized [Proceedings of the Polymer Society of Japan, 41 (2), 283 (1992)]. However, in such a method, there is a problem that the activity per carrier is low because a sufficient amount of the transition metal compound cannot be supported on the carrier, and the activity per transition metal is not sufficient, so that it cannot be industrially used. there were.

As still another method, Japanese Patent Laid-Open No. 3-290408 proposes an olefin polymerization catalyst comprising a transition metal compound and a catalyst activator comprising a mixture of an organoaluminum compound and a dialkylmagnesium compound. . However, even with this method, sufficient polymerization activity could not be obtained. Further, although a floating component insoluble in a solvent can be obtained from a mixture of an organoaluminum compound and a dialkylmagnesium compound, it cannot be a solid enough to be used as a carrier, and therefore a polymer having good particle properties can be obtained. Can not
There is a problem that it cannot be applied to the suspension polymerization method or the gas phase polymerization method as it is. Therefore, this method is also difficult to use industrially.

[0008]

Accordingly, the suspension polymerization method,
A novel olefin that can be applied to various olefin polymerization methods such as a gas phase polymerization method and a solution polymerization method, and that has high polymerization activity and can be produced at low cost without using an aluminoxane, an olefin polymer having excellent particle properties. The development of a polymerization catalyst has been desired.

That is, if such a catalyst is found, it will overcome the drawbacks of the conventional methods and its industrial value will be extremely great.

[0010]

Under these circumstances, the present inventors have solved the problems in the prior art, and have proposed a suspension polymerization method, a gas phase polymerization method, a solution polymerization method, etc. It can be applied to various olefin polymerization methods and has high polymerization activity.
In order to develop a novel olefin polymerization catalyst that can produce an olefin polymer having excellent particle properties at low cost without using an aluminoxane, intensive research was conducted.

As a result, the present inventors have found that the Group 4 metal (zirconium, titanium, or hafnium) of the periodic table containing a specific solid catalyst component, an organoaluminum compound, and a polydentate or monodentate ligand. Surprisingly, when olefin polymerization is carried out using a catalyst containing the transition metal compound of 1), a polymer having high polymerization activity and excellent particle properties can be effectively and efficiently produced without using aluminoxane. The inventors have found that they can be achieved and have completed the present invention.

Accordingly, one object of the present invention is to provide a novel olefin polymerization catalyst capable of inexpensively producing an olefin polymer having high polymerization activity and excellent particle properties without using aluminoxane. It is in. Another object of the present invention is to polymerize olefins using a novel olefin polymerization catalyst capable of effectively and efficiently producing an olefin polymer having a high polymerization activity and excellent particle properties. To provide a method.

The above and other objects, features, and benefits of the present invention will be apparent from the following detailed description. According to a basic aspect of the present invention, the following component (A),
An olefin polymerization catalyst comprising (B) and (C) is provided. (A) The solid catalyst component represented by the general formula (1) (hereinafter,
It may be referred to as "solid catalyst component (A)" or simply "component (A)". ) MgMαSiβR ¹ _p R ² _q R ³ _r OR ⁴ _s Cl _t (1) (In the formula: M is a metal atom belonging to Group 1 to Group 13 of the periodic table, and R ¹ has 1 to 8 carbon atoms. It is an alkyl group, R ² , R ³ and R ⁴ are hydrocarbon groups having 2 to 20 carbon atoms, and α, β, p, q, r, s and t are numbers satisfying the following relationships.

0 ≦ α ≦ 0.3 or 0.9 ≦ α ≦ 1.
1, 0 ≦ β ≦ 0.5, 0 <p, 0 ≦ q, 0 ≦ r, 0 ≦
s, 0 <t, (kα + 2 + 4β) × 0.7 ≦ t <kα +
2 + 4β, kα + 2 + 4β = p + q + r + s + t, where k is the valence of M) (B) Organoaluminum compound represented by the general formula (2) (hereinafter referred to as “organoaluminum compound (B)” or simply “component (B)”) AlR ⁵ _n Z ¹ _3-n (2) (In the formula, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, Z ¹ is a hydrogen atom, a halogen atom, a hydrocarbyloxy group or a siloxy group. , N is a number that satisfies the relationship of 0 <n ≦ 3. (C) At least one transition metal compound selected from transition metal compounds of Group 4 of the periodic table represented by the general formula (3) (hereinafter, . may be referred to as "transition metal compound (C)" or simply "component _{^{(C)") R 6 z R 7 a R}} 8 b R 9 c R 10 d M (3) ( wherein: M is zirconium, Selected from the group consisting of titanium and hafnium A transition metal; R ⁷ is a ligand having cyclopentadienyl skeleton or nitrogen, phosphorus, arsenic, heterocyclic 5-membered ring ligand having 1 to 4 carbon atoms containing antimony or bismuth as a hetero atom, or, nitrogen,
A hetero tridentate ligand in which phosphorus or oxygen occupies a coordination site, and each of these ligands is not substituted, or is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An aralkyl group in which an alkyl group having 1 to 20 carbon atoms is substituted with at least one aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms is at least one alkyl group having 1 to 20 carbon atoms. It is substituted with at least one substituent selected from the group consisting of substituted alkylaryl groups, in which case one substituent may substitute at least two parts of the ligand, and the alkyl group is It may be linear, branched or cyclic, and at least one of the above-mentioned substituents may be bound to a ligand via oxygen, nitrogen, sulfur or phosphorus, and further constitutes a substituent. At least one element may be a silicon; R ^8, R ⁹ and R ¹⁰ are each independently a cyclopentadienyl ligand having the skeleton, nitrogen, phosphorus, arsenic, antimony or bismuth heteroatoms 5-membered heterocyclic ring ligand having 1 to 4 carbon atoms, a hetero tridentate ligand having nitrogen, phosphorus or oxygen as a coordination site, and 1 to 20 carbon atoms
Alkyl group, C6-20 aryl group, C1
-20 alkyl groups having at least one carbon number of 6-20
Aralkyl groups substituted with aryl groups of 6 carbon atoms
To 20 aryl groups have at least one carbon number of 1 to 20
An alkylaryl group substituted with an alkyl group of
SO ₃ R (R is a hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or substituted with at least one halogen), a halogen atom or a hydrogen atom, and in this case, the alkyl group is a straight chain. , Branched, or cyclic, and the alkyl group, aryl group, alkylaryl group, and aralkyl group may form a heteroatom ligand that is bonded to a transition metal through oxygen, nitrogen, sulfur, or phosphorus. Further, at least one of the carbons constituting the alkyl group, aryl group, alkylaryl group and aralkyl group may be silicon, and a ligand having a cyclopentadienyl skeleton, and nitrogen, phosphorus, arsenic, antimony Alternatively, each of a 5-membered heterocyclic 5-membered ring ligand containing bismuth as a hetero atom and a hetero tridentate ligand in which nitrogen, phosphorus or oxygen occupies a coordination site. Is not substituted, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms is substituted with at least one aryl group having 6 to 20 carbon atoms. And an aralkyl group consisting of the above, and an aryl group having 6 to 20 carbon atoms are substituted with at least one substituent selected from the group consisting of alkylaryl groups substituted with at least one alkyl group having 1 to 20 carbon atoms. In this case, one substituent may substitute at least two parts of the ligand, the alkyl group is linear, branched or cyclic, and at least one of the substituents is oxygen or nitrogen. , May be bound to the ligand via sulfur or phosphorus, and at least one of the carbons constituting the substituent may be silicon; a is an integer of 1 or more. , B, c, d
Is an integer from 0 to 3 with the proviso that a + b + c + d = 4; each of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is bound to the transition metal M; R ⁶ is R ⁸ , R ⁹ and An alkylene group having 1 to 20 carbon atoms, a alkylene group having 1 to 20 carbon atoms, a substituted alkylene group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms, which bonds one selected from R ¹⁰ and R ^7.
0 alkylidene group, silylene group, or silylene group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having at least one alkyl group having 1 to 20 carbon atoms and having 6 to 20 carbon atoms. An aralkyl group substituted with, and an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of alkylaryl groups substituted with at least one alkyl group having 1 to 20 carbon atoms. A substituted silylene group; and
z is 0 or 1. The olefin polymerization catalyst of the present invention contains the solid catalyst component (A), the organoaluminum compound (B) and the transition metal compound (C) as described above.

The mechanism by which the catalyst of the present invention develops the polymerization performance is probably due to the alkylation reaction of the transition metal compound (C) between the solid catalyst component (A) and the transition metal compound (C), and further the cation. It is considered that the cationization progresses and the cationized transition metal compound (C) exhibits olefin polymerization activity, but details are unknown. Further, the organoaluminum compound (B) of the present invention is considered to play an auxiliary role in the reaction.

The novel olefin polymerization catalyst according to the present invention and the olefin polymerization method using this catalyst will be described in more detail below. In the present invention, "polymerization" is often used to mean not only homopolymerization but also copolymerization, and "polymer" means not only homopolymer but also copolymer. Often used.

As mentioned above, the solid catalyst component (A) is
It is represented by the following general formula (1). MgMαSiβR ¹ _p R ² _q R ³ _r OR ⁴ _s Cl _t (1) (In the formula: M is a metal atom belonging to Group 1 to Group 13 of the periodic table, and R ¹ is an alkyl group having 1 to 8 carbon atoms. a group, R ^2, R ³ and R ⁴ is a hydrocarbon group having 2 to 20 carbon atoms, α, β, p, q , r, s and t are numbers that satisfy the following relationship.

0 ≦ α ≦ 0.3 or 0.9 ≦ α ≦ 1.
1, 0 ≦ β ≦ 0.5, 0 <p, 0 ≦ q, 0 ≦ r, 0 ≦
s, 0 <t, (kα + 2 + 4β) × 0.7 ≦ t <kα +
2 + 4β, kα + 2 + 4β = p + q + r + s + t, where k is the valence of M) As shown in the general formula (1), magnesium, alkyl group and chlorine are essential in the solid catalyst component (A) of the present invention.

The solid catalyst component (A) of the present invention may contain a metal atom M as shown in the general formula (1). Examples of the metal atom M of the present invention include groups 1 to 1 of the periodic table.
Metal elements belonging to Group 3 can be used. Examples of the metal element include lithium, sodium, potassium, beryllium, zinc, boron, aluminum and the like. Of the above-exemplified metal elements, aluminum and zinc are particularly preferable.

In the solid catalyst component (A) of the present invention, the metal atom M is not always essential, but by incorporating the metal atom M, the ability of the solid catalyst component (A) such as alkylation can be adjusted. It will be possible. Therefore, the value of α indicating the molar ratio (M / Mg) of the metal atom M to the magnesium atom in the general formula (1) may be 0, but in practice, α is preferably larger than 0. .
However, when α exceeds 0.3, the stability of the solid catalyst component (A) as a solid is impaired, and it becomes difficult to obtain a polymer having excellent particle properties. Therefore, α needs to be 0.3 or less, and α is preferably 0.1 or less in order to further secure the stability of the solid catalyst component (A). However, when α becomes much larger than 0.3 and close to 1, the solid catalyst component (A) can regain stability as a solid. This is because when α is 1, the metal atom M
This is because a complex chloride having a molar ratio of 1 to magnesium atom can be generated. At this time, even if the molar ratio of the metal atom M and the magnesium atom is not necessarily exactly 1, the solid catalyst component (A) can be stabilized if α is in a specific range near 1. The range of such α is 0.9 or more and 1.1 or less. If α is out of this range, the stability of the solid catalyst component (A) is rapidly impaired. A more preferable range of α for improving the stability of the solid catalyst component (A) is 0.95 or more and 1.
It is less than or equal to 05.

The solid catalyst component (A) of the present invention may contain silicon. In the solid catalyst component (A), silicon is not always essential, but by including silicon,
R ¹ , R ² , R ³ and O contained in the solid catalyst component (A)
The amount of R ⁴ can be increased more stably. Therefore, it is preferable that the solid catalyst component (A) contains silicon. However, when the amount of silicon increases, it becomes difficult to stably maintain the solid catalyst component (A) as a solid, and therefore the amount is limited. Such a limit is
Molar ratio of silicon to magnesium atom (Si / Mg)
The value of β is 0.5. Therefore, in the present invention, β is 0.5 or less, preferably 0.3 or less, and more preferably 0.1 or less.

In the general formula (1) of the present invention, R ¹ is an alkyl group having 1 to 8 carbon atoms. R ¹ is specifically
Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and the like, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable.
The alkyl groups such as the propyl group and the butyl group exemplified above include isomers such as n-, sec-, tert-, and iso-.

In the present invention, since the solid catalyst component (A) contains an alkyl group, the transition metal compound (C) can be alkylated. Therefore, the alkyl group is essential in the solid catalyst component (A), and therefore the value of p indicating the molar ratio of R ¹ to magnesium atom (R ¹ / Mg) must be greater than 0. 2 to 20 carbon atoms represented by R ² and R ³ in the general formula (1)
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and the like.

Specifically, for example, ethyl group, propyl group, butyl group, amyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, phenyl group,
Examples thereof include a tolyl group and the like, with an ethyl group, a propyl group and a butyl group being particularly preferable. The alkyl groups such as the propyl group and the butyl group exemplified above include isomers such as n-, sec-, tert-, and iso-.

In the general formula (1), q and r are R respectively.²And R
³Molar ratio of magnesium to magnesium atom (R²/ Mg and
R³/ Mg), and q and r are 0 or more.
It In the present invention, R²And R³Is not always required
Absent. But R²And R ³Is R¹Transition with
Plays a role of alkylating the metal compound (C),
R is R¹Alkylation of the transition metal compound (C) with
Contributes to the alkylation ability of the solid catalyst component (A) by promoting it
be able to.

The hydrocarbon group having 2 to 20 carbon atoms represented by R ⁴ in the general formula (1) is preferably an alkyl group or an aryl group. Specifically, for example, an ethyl group,
Propyl group, butyl group, amyl group, 2-methylpentyl group, 2-ethylhexyl group, octyl group, decyl group, phenyl group, tolyl group and the like. Incidentally, alkyl groups such as propyl group and butyl group exemplified as R ⁴ are n-, sec-,
Includes isomers such as tert- and iso-.

R ⁴ combines with an oxygen atom to form an OR group, which constitutes the solid catalyst component (A). The presence of such an OR group in the solid catalyst component (A) tends to suppress the generation of fine particles in the solid catalyst component (A). Therefore, agglomeration due to fine particles is unlikely to occur, and uniform solid catalyst components (A) with no aggregation as a whole are easily obtained. That is, if an OR group is present in the solid catalyst component (A), it is possible to improve the particle properties of the resulting polymer. Therefore, it is not a problem that the OR group does not exist in the solid catalyst component (A), but when a polymer having more excellent particle properties is required, the solid catalyst component (A)
Can include an OR group. That is, in the general formula (1), the molar ratio of the OR group to the magnesium atom (OR ⁴
The value of s indicating (/ Mg) may be 0, but 0
It may be larger. However, if the amount of the OR group is too large, the catalytic activity will decrease, so that the amount is limited. Usually, when s exceeds 0.1, the catalytic activity is remarkably deteriorated and is not practical. That is, in the present invention, s
Is 0.1 or less, and in order to stably obtain a higher catalytic activity, s is preferably 0.05 or less, more preferably 0.01 or less.

The solid catalyst component (A) of the present invention contains chlorine as an essential component. The effect of the applied chlorine is to combine with the metal atom M, the magnesium atom and the silicon atom, which are cations, as an anion to form the main skeleton portion of the crystal structure in the solid catalyst component (A). Therefore, the closer the amount of chlorine atoms contained in the solid catalyst component (A) is to the total amount of positive charges due to the metal atom M, magnesium atom and silicon atom, the closer the crystal structure of the solid catalyst component (A) becomes. Stability is improved. In the present invention, in order to secure the stability of the crystal structure, the amount of chlorine atoms contained in the solid catalyst component (A) needs to be at least 70% or more of the total amount of positive charges. On the other hand, the closer the amount of chlorine atoms contained in the solid catalyst component (A) to the total amount of positive charges due to the metal atoms M, magnesium atoms and silicon atoms, the closer
R ¹ , R ² , R ³ and O contained in the solid catalyst component (A)
The amount of groups having a negative charge other than chlorine atoms such as R ⁴ decreases, and the functions of the solid catalyst component (A) such as alkylation decrease. For the above reason, the value of t indicating the molar ratio of chlorine atom to magnesium atom (Cl / Mg) is in the following range in the present invention.

(Kα + 2 + 4β) × 0.7 ≦ t <kα + 2 + 4β) where k is the valence of M. As described above, since the crystal stability increases as the amount of chlorine atoms approaches the equivalent amount to the total amount of positive charges, a more preferable range of t is (kα + 2 + 4β) × 0.8 ≦ t <kα + 2 + 4β And a more preferable range is (kα + 2 + 4β) × 0.9 ≦ t <kα + 2 + 4β.

In order for the solid catalyst component (A) of the present invention to satisfy electrical neutrality, the total amount of positive charge and the total amount of negative charge in the solid catalyst component (A) must match. . That is, as shown in the following equation, kα + 2 + 4β = p + q + r + s + t [where k is M
The valence of

The olefin polymerization catalyst of the present invention is
Two or more solid catalyst components (A) can be used simultaneously. The solid catalyst component (A) of the present invention can be obtained by bringing the following components (D), (E) and (F) into contact with each other. (D) Organomagnesium component soluble in a hydrocarbon solvent represented by the following general formula (4), (hereinafter referred to as "organomagnesium component (D)" or simply "component (D)"
Sometimes called. ) MgMγR ¹¹ _u R ¹² _v OR ¹³ _w (4) (In the formula: M is a metal atom belonging to Groups 1 to 13 of the periodic table, and R ¹¹ , R ¹² and R ¹³ have 1 to 20 carbon atoms. Is a hydrocarbon group of, and γ, u, v, and w are numbers that satisfy the following relationships.

0 ≦ γ ≦ 2, 0 <u, 0 ≦ v, 0 ≦ w kγ + 2 = u + v + w where k is the valence of the metal atom M) (E) Si-H bond represented by the following general formula (5) A chlorosilane compound having: (hereinafter sometimes referred to as "chlorosilane compound (E)" or simply "component (E)") H _x SiCl _y R ¹⁵ _{4- (x + y)} (5) (wherein R is ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, x
And y are numbers that satisfy the following relationship.

0 <x, 0 <y, x + y ≦ 4) (F) An organoaluminum compound represented by the following general formula (6) (hereinafter referred to as “organoaluminum compound (F)” or simply “component (F)”) AlR ¹⁶ _m Z ² _3-m (6) (In the formula: R ¹⁶ is a hydrocarbon group having 1 to 12 carbon atoms, Z ² is a hydrogen atom, a halogen atom, a —OR ¹⁷ group, a —OSiR.
¹⁸ ₃ group, —OAlR ¹⁹ ₂ group or —SiR ²⁰ ₃ group, wherein R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are methyl group, ethyl group,
An isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like, and m is a number satisfying the relationship of 0 <m ≦ 3) The organomagnesium component (D) of the present invention has the following general formula (4) ).

MgMγR ¹¹ u R ¹² v OR ¹³ w (4) In the general formula (4), M is the first to the first groups of the periodic table.
It is a metal atom belonging to Group 3, R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups having 1 to 20 carbon atoms, and γ, u, v and w are numbers satisfying the following relationships. 0 ≦ γ ≦ 2, 0 <u, 0 ≦ v, 0 ≦ w kγ + 2 = u + v + w where k is the valence of M.

The organomagnesium component (D) of the present invention is
For example, an organic magnesium compound is first represented by the general formula R ¹¹ ₂ Mg, general formula MR ¹² _k (where, k is the valence of M) or MR ¹² _k-1 H (Here, k is the valence of M With an organometallic compound represented by R) in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene, and toluene at room temperature to 150 ° C., and further represented by R ¹³ if necessary. It can be obtained by reacting with an alcohol having a hydrocarbon group or by reacting with a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ¹³ which is soluble in a hydrocarbon solvent.

The organomagnesium component (D) of the present invention is
As shown in the general formula (4), the metal atom M can be included. As the metal atom M contained in the organomagnesium component (D), a metal element belonging to Groups 1 to 13 of the periodic table can be used, as in the case of the general formula (1). Examples of the metal element include lithium, sodium, potassium, beryllium, zinc, boron, aluminum and the like. Of the above-exemplified metal elements, aluminum and zinc are particularly preferable.

In the present invention, the organomagnesium component (D)
The particle size of the solid catalyst component (A) obtained by contacting the organomagnesium component (D) with the chlorosilane compound (E) and the organoaluminum compound (F) becomes gradually smaller as the amount of the metal atom M therein increases. Tends to become. In the general formula (4), when the value of γ indicating the molar ratio (M / Mg) of magnesium atom to metal atom M becomes larger than 2, the organomagnesium component (D), the chlorosilane compound (E), the organoaluminum compound ( The particle size of the solid catalyst component (A) obtained by contact with F) becomes too small, which is not practical. Therefore, γ needs to be 2 or less, preferably 1 or less, and more preferably 0.5 or less.

In the present invention, the organomagnesium component (D)
Therefore, the amount of the metal atom M contained in is reduced, and thus the solubility of the organomagnesium component (D) in the hydrocarbon solvent is gradually reduced. Especially, when γ is smaller than 0.01, this tendency becomes remarkable. Therefore, γ can be solubilized even if it is 0, but it is preferably 0.01 or more if possible. Even if γ is smaller than 0.01, by increasing the carbon number of R ¹¹ and R ¹² , the organomagnesium component (D)
Can be solubilized in a hydrocarbon solvent. However, in this case, the viscosity of the solution tends to increase as the carbon number of R ¹¹ and R ¹² increases, and increasing the carbon number more than necessary is not preferable in handling the solution.

In the present invention, R ¹¹ in the general formula (4),
R ¹² is a hydrocarbon group having 1 to 20 carbon atoms. R ¹¹ , R
^When the carbon number of ¹² is more than 20, the viscosity of the solution becomes high and the handling of the solution becomes difficult. C1-C1 of the present invention
R ¹¹ and R ¹² which are hydrocarbon groups of 20 are an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, Examples thereof include a decyl group, a cyclohexyl group, a phenyl group and a tolyl group. Incidentally, the alkyl groups such as the propyl group and the butyl group exemplified above are n-, sec-, tert.
Includes isomers such as-and iso-.

In the present invention, the charcoal represented by the general formula (4) is
R which is a hydrocarbon group having a prime number of 1 to 20 ¹³Specifically,
It is an alkyl group, a cycloalkyl group or an aryl group.
For example, methyl group, ethyl group, propyl group, butyl group,
Amyl group, hexyl group, decyl group, cyclohexyl group,
Examples thereof include a phenyl group and a tolyl group. In the present invention,
Alkyl groups are preferred. Incidentally, the propyl group exemplified above,
Alkyl groups such as butyl are n-, sec-, tert-, iso-, etc.
Includes isomers of.

The chlorosilane compound (E) of the present invention is represented by the following general formula (5) as described above. ^{_{H x SiCl y R 15 4- (}} x + y) (5) wherein, R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, x
And y are numbers that satisfy the following relationship.

0 <x, 0 <y, x + y ≦ 4] In the general formula (5), R ¹⁵ which is a hydrocarbon group having 1 to 20 carbon atoms is specifically, for example, an alkyl group, a cycloalkyl group or aryl. More specifically, examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a decyl group, a cyclohexyl group, a phenyl group and a tolyl group. In the present invention, the hydrocarbon group is preferably an alkyl group having 1 to 10 carbon atoms, and a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group is most preferable.

Further, x and y are numbers larger than 0 satisfying the relation of x + y ≦ 4, and particularly y is preferably 2 or 3. Examples of these compounds include H
SiCl ₃ , HSiCl ₂ CH ₃ , HSiCl ₂ Et,
HSiCl ₂ (n-Bu), HSiCl ₂ (iso-Bu), HSi
Cl ₂ (n-C ₄ H ₉ ), HSiCl ₂ C ₆ H ₅ , HSiCl ₂ (4-
Cl-Bu), HSiCl ₂ CH = CH ₂ , HSiCl ₂ CH
₂ C ₆ H ₅ , HSiCl ₂ (1-C ₁₀ H ₇ ), HSiCl ₂ CH _{2
CH = CH 2, H 2 SiClCH} 3, H 2 SiClEt, H
_{SiCl (CH 3) 2, HSiClEt} 2, HSiClCH 3
(iso-Bu), HSiClCH ₃ (C ₆ H ₅ ), HSiCl (C
₆ H ₅ ) _{2 and the} like. In the present invention, a chlorosilane compound composed of these compounds and a mixture with a compound selected from these compounds is used. In the present invention, among the above-illustrated chlorosilane compounds, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane and the like are preferable, and trichlorosilane and monomethyldichlorosilane are particularly preferable.

In the chemical formulas of the above examples, the symbols Et and Bu represent an ethyl group and a butyl group, respectively. The organoaluminum compound (F) of the present invention is represented by the following general formula (6) as described above. AlR ¹⁶ _m Z ² _3-m (6) (In the formula, R ¹⁶ is a hydrocarbon group having 1 to 12 carbon atoms, Z ² is a hydrogen atom, a halogen atom, a —OR ¹⁷ group, —OSiR.
¹⁸ ₃ group, —OAlR ¹⁹ ₂ group or —SiR ²⁰ ₃ group, wherein R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are methyl group, ethyl group,
It is an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like, and m is a number satisfying the relationship of 0 <m ≦ 3.) R ¹⁶ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an aliphatic hydrocarbon. It is a base. Specific examples of such an aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, and a propenyl group. A group, an ethyl group, a propyl group and a butyl group are preferred.

In the present invention, propyl group, butyl group
Alkyl groups such as groups are isomers such as n-, iso-, sec-, tert-, etc.
Including the body. Z²Is a hydrogen atom, a halogen atom, -OR
¹⁷Group, -OSiR¹⁸ ₃Group, -OAlR ¹⁹ ₂Group or -S
iR²⁰ ₃Group. Organoaluminum compound of the present invention
Specific examples of (F) include trialkylaluminization
Compound, aluminum hydride alkyl compound, halogenated
Aluminum alkyl compound, hydrocarbyloxy
Aluminum alkyl compound, siloxy group-containing aluminum
Aluminum compounds, aluminoxy group-containing aluminum
Alkyl compound, aluminum alkylation containing silyl group
Examples include compound.

Examples of the trialkylaluminum compound represented by AlR ¹⁶ ₃ in the general formula (6) include:
Trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-hexyl aluminum, tri-2-ethylhexyl aluminum, tri-n -Octyl aluminum, tri-n-decyl aluminum, tri-n-dodecyl aluminum, tri-n-hexadecyl aluminum and the like.

Examples of the aluminum hydride alkyl compound represented by AlR ¹⁶ _m H _3-m in the general formula (6) include diethylaluminum hydride, diisobutylaluminum hydride and the like. Examples of the halogenated aluminum alkyl compound in the general formula (6) include dimethylaluminum chloride, diethylaluminium chloride, di-n-propylaluminium chloride, di-iso-propylaluminum chloride, di-n-butylaluminum chloride and di-iso-. Butyl aluminum chloride, di-n-hexyl aluminum chloride, di
-iso-hexyl aluminum chloride, di (2-ethylhexyl) aluminum chloride, di-n-decyl aluminum chloride, methyl-iso-butyl aluminum chloride, ethyl-iso-butyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, diethyl aluminum Dialkyl aluminum halides such as iodide; alkenyl aluminum such as isoprenyl aluminum; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, iso-
Alkyl aluminum sesquihalides such as propyl aluminum sesquichloride, iso-butyl aluminum sesqui chloride, n-butyl aluminum sesqui chloride, ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum dibromide, iso-propyl aluminum dichloride, iso -Alkyl aluminum dihalides such as butyl aluminum dichloride.

In the general formula (6), R ⁷ _n Al (O
Examples of the hydrocarbyloxyaluminum alkyl compound represented by R ¹⁷ ) _3-n include dimethylaluminum methoxide, diethylaluminum ethoxide,
Examples thereof include di-iso-propylaluminum methoxide and di-iso-butylaluminum methoxide. Such a hydrocarbyloxyaluminum alkyl compound can be usually obtained by reacting a trialkylaluminum compound with carbinol. Carbinol includes methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n- or iso- or sec- or tert-butyl alcohol, n- or iso-
Alternatively, sec- or tert-amyl alcohol, phenol, cresol and the like can be mentioned. In this case, the ratio of carbinol to be reacted with the trialkylaluminum is 0.1 to 1 mol, preferably 0.2 to 0.9 mol per 1 mol of the trialkylaluminum.

In the general formula (6), R ⁷ _n Al (OSi
Examples of the siloxy group-containing aluminum alkyl compound represented by R ¹⁸ ₃ ) _3-n include Et ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-
Bu) ₂ Al (OSiEt ₃ ) and the like. Such siloxy group-containing aluminum alkyl compound,
Usually, it can be used by reacting a trialkylaluminum compound with silanol or siloxane.

In this case, as the silanol, in addition to trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, a hydrolyzate of chlorosilane can be used, and polysilanols can also be used. Examples of the siloxane include methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, propyl hydrogen polysiloxane, butyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, dimethyl polysiloxane, methyl ethyl polysiloxane, and methylphenyl polysiloxane. To be

Reacted with trialkylaluminum compounds
The ratio of silanol or siloxane to be added is
0.1 to 2 based on Si for 1 mol of kill aluminum
Mol, preferably 0.2 to 1.5 mol,
More preferably, the range of 0.2 to 1.2 mol is recommended.
R in the general formula (6)⁷ _nAl (OAlR¹⁹ ₂)_3-n
Alkylation of aluminoxy group-containing aluminum represented by
As a compound, for example, Et₂AlOAlEt ₂, (Iso
-Bu)₂AlOAl (iso-Bu)₂And the like.

In the general formula (6), R ⁷ _n Al (SiR ²⁰
₃ ) As the silyl group-containing aluminum alkyl compound represented by _3-n , for example, (iso-Bu) ₂ AlSiMe ₃ ,
(Iso-Bu) ₂ AlSiEt _{3 and the} like. still,
In the chemical formula of the present invention, the symbols Me, Et and Bu are
They represent a methyl group, an ethyl group and a butyl group, respectively.

The above compounds exemplified as the component (F) of the present invention may be used alone or in combination of two or more kinds. In the present invention, the contact between the organomagnesium component (D), the chlorosilane compound (E) and the organoaluminum compound (F) is not particularly limited, but it is preferably carried out in an inert hydrocarbon solvent. Examples of such a contact method include first diluting the organomagnesium component (D), the chlorosilane compound (E), and the organoaluminum compound (F) with an inert hydrocarbon solvent, and further preparing an inert hydrocarbon separately prepared. Contact can be performed by injecting each of the diluted solutions into a solvent.

Examples of the inert hydrocarbon solvent used in the contact include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and methylcyclohexane. And the like, chlorinated hydrocarbons such as 1,2-dichloroethane, o-dichlorobenzene, and dichloromethane, and mixed media thereof.

The contact temperature is not particularly limited, but a temperature range of 40 ° C. or higher or lower than the boiling point of the inert hydrocarbon solvent used for contact is preferable. That is,
Within this temperature range, the solid catalyst component (A) can be rapidly and efficiently obtained by contacting the organomagnesium component (D) with the chlorosilane compound (E) and the organoaluminum compound (F).

The order of contacting the component (D), the component (E) and the component (F) is not particularly limited, and for example, the component (D), the component (E) and the component (F) are simultaneously contacted. Alternatively, one of the two components may be contacted in advance and the other one component may be contacted. The ratio of the organomagnesium component (D), the chlorosilane compound (E), and the organoaluminum compound (F) at the time of the contact is such that the chlorosilane compound (E) is 1 mole of the magnesium atom of the organomagnesium component (D). 0.01 ~
100 mol, 0.001 of organoaluminum compound (F)
It is sufficient that it is 10 to 10 moles, and more preferably 0.1 to 10 moles of the chlorosilane compound (D) and 0.01 to 2 moles of the organoaluminum compound (F) per 1 mole of magnesium atom of the organomagnesium component (D). Is the range.

The solid catalyst component (A) obtained by the above contact is separated by a known method such as filtration or decantation, and then sufficiently washed with an inert hydrocarbon solvent to obtain an unreacted product or It is preferable to remove by-products and the like. At this time, a chlorinated hydrocarbon solvent may be used for cleaning before the cleaning with an inert hydrocarbon solvent. In the present invention, the following component (G) can be used together when the components (D), (E) and (F) are contacted. (G) Polysiloxane component represented by the general formula (8) (hereinafter, may be referred to as "polysiloxane component (G)" or simply "component (G)".)

[0058]

Embedded image

(In the formula, X and Y are hydrogen, halogen, a hydrocarbon group having 1 to 12 carbon atoms, and n is 5 to 100.) The hydrocarbon group having 1 to 12 carbon atoms in the general formula (8). The group is, for example, an alkyl group, a cycloalkyl group or an aryl group, and more specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a decyl group or a cyclohexyl group. , Phenyl group,
A tolyl group and the like are exemplified. In the present invention, the hydrocarbon group is preferably an alkyl group having 1 to 8 carbon atoms, and a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group is most preferable.

In the present invention, the method of using the component (G) together when the components (D), (E) and (F) are brought into contact with each other is not particularly limited. D), component (E), component (F) and component (G) may be contacted at the same time, or two or three components may be contacted in advance and then the remaining components may be contacted, or four components may be contacted. It is also possible to divide the above-mentioned components into two groups of two types of components and contact them separately, and then contact the contacting substances.

In the present invention, in particular, the component (D) and the component (G) are contacted with each other in advance, and the component (E) is further contacted therewith to obtain a solid component, and then the component (F) is added to the solid component. The method of contact is recommended. The solid component obtained by contacting the component (D), the component (E) and the component (F) can be easily separated by a known method such as filtration or decantation. Conditions for contacting the components (D), the components (E), the components (F) and the components (G), such as the solvent and the temperature, are as follows. The contact conditions may be the same.

By using the component (G) in this way, it becomes possible to increase the content of aluminum atoms contained in the obtained solid catalyst component (A). It is considered that this is because the amount of the component (F) taken into the solid catalyst component (A) increases. Therefore, the content of the hydrocarbon group R ¹⁶ contained in the component (F) in the solid catalyst component (A) also increases as the content of aluminum atoms increases. Therefore, the use of the component (G) is effective in increasing the content of hydrocarbon groups, particularly alkyl groups, in the solid catalyst component (A).

Organoaluminum compound (B) of the present invention
Is expressed by the following general formula (2) as described above. AlR ⁵ _n Z ¹ _3-n (2) (In the formula: R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, Z ¹ is a hydrogen atom, a halogen atom, or a hydrocarbyloxy group, and n is 0 <n ≦ R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of such a hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, allyl group,
Propenyl group and the like, especially, methyl group, ethyl group,
A propyl group and a butyl group are preferred. The hydrocarbon group in the present invention includes isomers such as n-, iso-, sec- and tert-.

Z ¹ is a hydrogen atom, a halogen atom, or a hydrocarbyloxy group. Specific examples of the organoaluminum compound (B) of the present invention include trialkylaluminum compounds, aluminum hydride alkyl compounds, halogenated aluminum alkyl compounds, hydrocarbyloxyaluminum alkyl compounds and the like.

Examples of the trialkylaluminum compound in the general formula (2) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-iso-propylaluminum, tri-n-butylaluminum and tri-iso-. Butyl aluminum, tri-
Examples thereof include n-hexylaluminum, tri2-ethylhexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum and tri-n-hexadecylaluminum.

Examples of the aluminum hydride alkyl compound in the general formula (2) include diethylaluminum hydride, diisobutylaluminum hydride and the like. Examples of the aluminum halide alkyl compound in the general formula (2) include dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-iso-propyl aluminum chloride, di-n-butyl aluminum chloride, di-
iso-butyl aluminum chloride, di-n-hexyl aluminum chloride, di-iso-hexyl aluminum chloride, di (2-ethylhexyl) aluminum chloride,
Di-alkyl aluminum halides such as di-n-decyl aluminum chloride, methyl-iso-butyl aluminum chloride, ethyl-iso-butyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, diethyl aluminum iodide; alkenyl aluminum such as isoprenyl aluminum; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, iso-propyl aluminum sesquichloride, iso-butyl aluminum sesquichloride, n-butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum dichloride, Ethyl aluminum dibromide, iso-propyl aluminum dichloride Alkylaluminum dihalides such as iso- butyl aluminum dichloride.

Examples of the hydrocarbyloxy aluminum alkyl compound in the general formula (2) include dimethyl aluminum methoxide, diethyl aluminum ethoxide, di-iso-propyl aluminum methoxide, di-iso-butyl aluminum methoxide and the like. Can be mentioned. Such a hydrocarbyloxyaluminum alkyl compound can be usually obtained by reacting a trialkylaluminum compound with carbinol. As carbinol, methyl alcohol,
Ethyl alcohol, n- or iso-propyl alcohol,
Examples thereof include n- or iso- or sec- or tert-butyl alcohol, n- or iso- or sec- or tert-amyl alcohol, phenol, cresol and the like. In this case, the ratio of carbinol to be reacted with the trialkylaluminum is 0.1 to 1 mol, preferably 0.2 to 0.9 mol per 1 mol of the trialkylaluminum.

In the compounds exemplified above, the compounds containing an alkyl group such as propyl and butyl are not limited to the above-exemplified alkyl groups, and other alkyl groups such as n-, iso-, sec-, tert-, etc. It may be an isomer. The olefin polymerization catalyst of the present invention can also use two or more kinds of the organoaluminum compound (B) at the same time.

In the present invention, the catalytic activity can be exhibited only by the solid catalyst component (A) and the transition metal compound (C).
However, in the catalyst of the present invention, the presence of the organoaluminum component (B) further improves the polymerization activity. The reason why such an effect is obtained is not clear in detail, but for example, as one hypothesis, the organoaluminum component (B) plays some role in the alkylation of the transition metal compound (C). Can be considered. Also, the role of the organoaluminum component (B) as an impurity killer in the polymerization system cannot be overlooked. In any case, in the catalyst of the present invention, if the organoaluminum component (B) is present,
The catalytic action can be obtained more effectively and efficiently.

At least one transition metal compound (C) selected from the group 4 transition metal compounds of the present invention.
Can be represented by the following general formula (3) as described above. R ⁶ _z R ⁷ _a R ⁸ _b R ⁹ _c R ¹⁰ _d M (3) [wherein M is a transition metal selected from the group consisting of zirconium, titanium and hafnium; R ⁷ is a cyclopentadienyl skeleton; Having a ligand, or nitrogen, phosphorus,
A hetero 5-membered ring ligand having 1 to 4 carbon atoms containing arsenic, antimony or bismuth as a hetero atom, or a hetero tridentate ligand in which nitrogen, phosphorus or oxygen occupies a coordination site,
Each of these ligands is not substituted, or has at least one alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms and having 6 to 20 carbon atoms. And an at least one substituent selected from the group consisting of an aralkyl group substituted with an aryl group and an aryl group having 6 to 20 carbon atoms substituted with at least one alkyl group having 1 to 20 carbon atoms. Substituted, in which case one substituent may replace at least two parts of the ligand, the alkyl group is straight-chain, branched or cyclic, and said substituent is at least 1 one oxygen, nitrogen, may be associated with the ligand via a sulfur or phosphorus, furthermore at least one carbon atoms constituting a substituent may be a silicon; R ^8, R ⁹ Contact Fine R ¹⁰ are each independently a ligand having a cyclopentadienyl skeleton, nitrogen, phosphorus, arsenic,
Hetero 5-membered ring ligand having 1 to 4 carbon atoms containing antimony or bismuth as a hetero atom, hetero tridentate ligand having nitrogen, phosphorus or oxygen as a coordination site, alkyl group having 1 to 20 carbon atoms, carbon Aryl group having 6 to 20 carbon atoms and 1 to 2 carbon atoms
An aralkyl group in which an alkyl group of 0 is substituted with at least one aryl group having 6 to 20 carbon atoms, and 6 to 2 carbon atoms
An alkylaryl group in which an aryl group of 0 is substituted with at least one alkyl group having 1 to 20 carbon atoms, -SO
₃ R (R is unsubstituted or at least 1
Hydrocarbon group having 1 to 8 carbon atoms substituted by halogen), a halogen atom, or a hydrogen atom, in which the alkyl group is linear, branched or cyclic, and an alkyl group, an aryl group, The alkylaryl group and aralkyl group may form a heteroatom ligand which is bonded to a transition metal through oxygen, nitrogen, sulfur or phosphorus, and also constitutes an alkyl group, an aryl group, an alkylaryl group or an aralkyl group. At least one of the carbon atoms may be silicon, a ligand having a cyclopentadienyl skeleton, and a 5-membered complex having 1 to 4 carbon atoms containing nitrogen, phosphorus, arsenic, antimony or bismuth as a hetero atom. Each of the ring ligand and the hetero tridentate ligand in which nitrogen, phosphorus or oxygen occupies a coordination site is not substituted or has 1 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, an aralkyl group obtained by substituting an alkyl group having 1 to 20 carbon atoms with at least one aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It is substituted with at least one substituent selected from the group consisting of alkylaryl groups substituted with at least one alkyl group having 1 to 20 carbon atoms, in which one substituent is at least two of the ligands. The alkyl group may be linear, branched or cyclic, and at least one of the above substituents may be bonded to the ligand via oxygen, nitrogen, sulfur or phosphorus. In addition, at least one of the carbon atoms constituting the substituent may be silicon; a is an integer of 1 or more, and b, c, d
Is an integer from 0 to 3 with the proviso that a + b + c + d = 4; each of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is bound to the transition metal M; R ⁶ is R ⁸ , R ⁹ and An alkylene group having 1 to 20 carbon atoms, a alkylene group having 1 to 20 carbon atoms, a substituted alkylene group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms, which bonds one selected from R ¹⁰ and R ^7.
0 alkylidene group, silylene group, or silylene group is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having at least one alkyl group having 1 to 20 carbon atoms and having 6 to 20 carbon atoms. An aralkyl group substituted with, and an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of alkylaryl groups substituted with at least one alkyl group having 1 to 20 carbon atoms. A substituted silylene group; and
z is 0 or 1. In the present invention, R ⁷ in the general formula (3) is a ligand having a cyclopentadienyl skeleton, and one of R ⁸ , R ⁹ and R ¹⁰ is a coordination having a cyclopentadienyl skeleton. Child, hetero tridentate ligand or heteroatom ligand R
A transition metal compound of ⁷ is preferably used. That is,
For example, R ⁷ and R ⁸ are transition metal compounds having a cyclopentadienyl skeleton, R ⁷ is a ligand having a cyclopentadienyl skeleton, and R ⁸ is hetero 3
A transition metal compound that is a bidentate ligand, R ⁷ is a ligand having a cyclopentadienyl skeleton, and R ⁸ is a heteroatom ligand. These ligands include alkylene groups such as methylene, ethylene and propylene, substituted alkylene groups such as diphenylmethylene, alkylidene groups such as isopropylidene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene. May be connected via. R ⁹ and R ¹⁰ are ligands having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups, SO
3R or hydrogen atom. In the present invention, R ⁹ and R
Particularly preferably, ¹⁰ is an alkyl group, an aryl group, a halogen atom or the like.

In the present invention, examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and tetra Methylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group Group, an alkyl-substituted cyclopentadienyl group such as a methylbutylcyclopentadienyl group, a hexylcyclopentadienyl group or an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. .
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.

In the present invention, the number of carbon atoms containing nitrogen, phosphorus, arsenic, antimony or bismuth as a hetero atom is 1
As an example of the hetero 5-membered ring ligand of 4 to 4, a pyrrolyl group,
Examples thereof include a phosphoryl group, an assoryl group, a styboryl group and a bismolyl group. Further, in the present invention, the hetero tridentate ligand in which nitrogen, phosphorus or oxygen has a coordination site is specifically a ligand having a trispyrazolyl borate skeleton or a trisphosphoranylmethanide skeleton. Say the order. Examples of such a hetero tridentate ligand include a hydrotrispyrazolyl borate group and a trisbisphenyloxophosphoranylmethanide group.

Further, when the alkyl group, the aryl group, the alkylaryl group or the aralkyl group forms a heteroatom ligand which is bonded to a transition metal through oxygen, nitrogen, sulfur or phosphorus, the heteroatom coordination An example of a child is t
ert-butylamide group, methylamide group, ethylamide group, benzylamide group, methoxyphenylamide group,
A phenyl phosphide group etc. can be mentioned.

Examples of the halogen atom of the present invention include fluorine, chlorine, bromine and iodine. Further, the ligand represented by -SO3R of the present invention is a hydrocarbon group having 1 to 8 carbon atoms in which R is not substituted or is substituted with halogen, preferably a direct group having 1 to 8 carbon atoms. A chain, branched or cyclic alkyl group or an aryl group having 6 to 8 carbon atoms, and specific examples thereof include p-toluenesulfonato group, methanesulfonato group, trifluoromethanesulfonato group and the like. be able to.

Specific examples of the transition metal compound when M in the formula (1) 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 (trimethylcyclopentadienyl) zirconium dichloride, ethylenebis (tetramethylcyclopentadienyl) zirconium dichloride, ethyl Bis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis ( Methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium Dichloride, diphenylmethylene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorene) Le)
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 (trifluoromethanesulfonato), methylenebis (4,4)
5,6,7-tetrahydroindenyl) zirconium dichloride, methylene (cyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, Dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silylene bis (4,5,6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-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 (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (Methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride , Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bi (Trimethylsilyl cyclopentadienyl) zirconium dichloride, bis (tetramethyl phosphonium Holy Le) zirconium dichloride, bis (3,
4-dimethylphosphoryl) zirconium dichloride,
Hydrotrispyrazolyl borate cyclopentadienyl zirconium dichloride, tris (diphenyloxophosphoranyl) methanide cyclopentadienyl zirconium dichloride, hydrotrispyrazolyl borate zirconium trichloride, tris (diphenyloxophosphoranyl) methanide zirconium trichloride,
Hydrotris (3,5-dimethylpyrazolyl) borate zirconium trichloride, tris (diphenyloxophosphoranyl) methanide pentamethylcyclopentadienyl zirconium dichloride and the like.

In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is 1,2,3- and 1,2,4-. Including substitutes. Alkyl groups such as propyl and butyl are
It includes isomers such as n-, iso-, sec-, and tert-. Further, in the present invention, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

As a further example of the transition metal compound represented by the formula (1) of the present invention, (tert-butylamido) (tetramethyl-η 5 -cyclopentadienyl)-
1,2-ethanediyl zirconium dichloride, (te
rt-Butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (tert-butylamide) (tetramethyl-η5
-Cyclopentadienyl) methylene zirconium dichloride, (tert-butylamide) (tetramethyl-η
5-Cyclopentadienyl) methylene titanium dichloride, (tert-butylamide) (tetramethyl-η 5
-Cyclopentadienyl) methylene zirconium dimethyl, (tert-butylamide) (tetramethyl-η5
-Cyclopentadienyl) methylene titanium dimethyl,
(Tert-Butylamide) (tetramethyl-η5-cyclopentadienyl) isopropylidene zirconium dichloride, (tert-butylamide) (tetramethyl-η5-cyclopentadienyl) isopropylidene titanium dichloride, (tert-butylamide) (tetramethyl -Η5-Cyclopentadienyl) isopropylidene zirconium dimethyl, (tert-butylamide)
(Tetramethyl-η5-cyclopentadienyl) isopropylidene titanium dimethyl, (tert-butylamide) (tetramethyl-η5-cyclopentadienyl)-
1,2-ethanediylzirconium dimethyl, (ter
t-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl titanium dimethyl,
(Methylamido) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamido) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide ) (Tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dibenzyl, (methylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyltitanium dimethyl, (methylamide) Dimethyl (tetramethyl-η
5-cyclopentadienyl) silane titanium dichloride,
(Methylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride,
(Ethylamido) (tetramethyl-η5-cyclopentadienyl) -methylenetitanium dichloride, (ethylamido) (tetramethyl-η5-cyclopentadienyl)-
Methylene titanium dimethyl, (tert-butylamide)
Dimethyl (tetramethyl-η5-cyclopentadienyl) silane titanium dichloride, (tert-butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, (tert-butylamido) dibenzyl (tetramethyl-η5-cyclo) Pentadienyl) silane zirconium dibenzyl, (t
ert-butylamido) dimethyl (tetramethyl-η5
-Cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η5
-Cyclopentadienyl) silane titanium dichloride,
(Benzylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane titanium diphenyl, (phenylphosphido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dibenzyl,
(Phenylphosphide) dimethyl (tetramethyl-η5
-Cyclopentadienyl) silane titanium dichloride,
(Phenylphosphide) dimethyl (tetramethyl-η5-
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-η5
-Cyclopentadienyl) amido titanium dichloride,
(4-Methoxyphenylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane titanium dichloride, (tetramethyl-η5-cyclopentadienyl)
Dimethyl (1-methylethoxy) silane titanium trichloride, 1- (tert-butylamido) -2- (tetramethyl-η5-cyclopentadienyl) -1,1,2,
2-tetramethyldisilane titanium dichloride, 1- (t
ert-Butylamide) -2- (tetramethyl-η5-
Cyclopentadienyl) -1,1,2,2-tetramethyldisilane zirconium dichloride, (tert-butylamido) dimethyl (tetramethyl-η 5 -cyclopentadienyl) silane zirconium dimethyl, (tert
-Butylamido) dimethyl (η5-cyclopentadienyl) silane titanium dichloride, (tert-butylamido) dimethyl (η5-cyclopentadienyl) silane zirconium dichloride, (anilide) dimethyl (tetramethyl-η5-cyclopentadienyl) silane Titanium dichloride, (anilide) dimethyl (tetramethyl-η5
-Cyclopentadienyl) silane zirconium dichloride and the like.

As described above, the transition metal compound which is the component (A) of the catalyst of the present invention is a transition metal compound containing a polydentate ligand or a monodentate ligand. For details of the transition metal compounds containing a polydentate ligand, EP0617052A (European publication number) can be referred to, for example. In the present invention, by appropriately selecting the component (C), it becomes possible to arbitrarily control the molecular weight of the polymer, the copolymer composition and the like.

Further, in the present invention, by appropriately selecting at least two kinds of components (C), the molecular weight,
It becomes possible to control the molecular structure of the polymer in a wide range such as copolymer composition, molecular weight distribution, copolymer composition distribution, long chain branching, etc., which is more effective. By controlling the molecular structure of the polymer in this way, the physical properties of the polymer, such as melt tension, melt strength, rigidity, strength, impact strength, environmental stress crack resistance, extrusion moldability, bubble stability, swell property It becomes possible to control physical properties such as solvent resistance and transparency.

Olefin can be advantageously polymerized by using the catalyst of the present invention containing the components (A), (B) and (C) detailed above. A specific mode of carrying out the olefin polymerization in the presence of the catalyst of the present invention will be described.
When the component (A), the component (B) and the component (C) are used in the present invention, they can be dispersed or dissolved in an inert hydrocarbon solvent in advance. Specific examples of such an inert hydrocarbon solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane. And the like; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The method of combining the component (A), the component (B) and the component (C) in the present invention includes, for example, the component (A), the component (B) and the component (C) separately in a polymerization system. Or a method of introducing a contact mixture of component (A), component (B) and component (C) into the polymerization system.
A method in which the contact mixture of the component (A) and the component (C) and the component (B) are separately introduced into the polymerization system, or the contact mixture of the component (A) and the component (B) and the component (C) are separately polymerized. A method of introducing into the system can be adopted, and such a method can achieve high activity, and at the same time, maintain such high activity stably.

When the component (A), the component (B) and the component (C) are contacted with each other prior to the polymerization, the temperature at the time of contact is 0 ° C. or higher, and the temperature at the time of contact is not particularly limited. Temperatures below the boiling point of the inert hydrocarbon solvent used are recommended. The ratio of the component (A), the component (B) and the component (C) contained in the olefin polymerization catalyst of the present invention is such that the component (B) is in the range of 0.1 to 500 mmol with respect to 1 g of the component (A). Of the component (C) is in the range of 0.01 to 1000 mmol, preferably in the range of 0.05 to 500 mmol, and more preferably in the range of 0.1 to 100. It is in the millimolar range.

Using such an olefin polymerization catalyst, an α-olefin having 3 to 20 carbon atoms and 3 to 20 carbon atoms are used.
At least one olefin selected from the group consisting of 20 cyclic olefins, or by polymerizing at least one olefin with the formula H ₂ C═CHR ²¹ (wherein R ²¹
Is an aryl group having 6 to 20 carbon atoms. ) Or a linear, branched or cyclic diene having 4 to 20 carbon atoms can be copolymerized.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-.
A cyclic olefin having 3 to 20 carbon atoms, selected from the group consisting of decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene,
For example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-.
1,2,3,4,4a, selected from the group consisting 5,8,8a- octahydronaphthalene, general formula H ₂ C = CHR
²¹ (In the formula, R ²¹ is an aryl group having 6 to 20 carbon atoms.)
The compound represented by is, for example, styrene, and the linear, branched or cyclic diene having 4 to 20 carbon atoms is, for example, 1,3-butadiene, 1,4-pentadiene, 1,
It is selected from the group consisting of 5-hexadiene, 1,4-hexadiene, and cyclohexadiene.

The catalyst of the present invention may also be obtained by homopolymerizing ethylene, or by using ethylene and the formula H ₂ C = CHR ²² (wherein R ²²
Is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group is linear, branched or cyclic. ), A compound represented by), having 3 to 20 carbon atoms
Can be advantageously used for copolymerization with the above cyclic olefin and at least one selected from the group consisting of linear, branched or cyclic dienes having 4 to 20 carbon atoms.

In this case, the formula H ₂ C = CHR ²² (wherein R
²² is an alkyl group having 1 to 18 carbon atoms or 6 to 20 carbon atoms
And an alkyl group is linear, branched or cyclic. ) Is a compound represented by, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
It is selected from the group consisting of 1-octadecene, 1-eicosene, vinylcyclohexane, and styrene and has 3 to 3 carbon atoms.
20 cyclic olefins include, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1.
4,5.8-Dimethano-1,2,3,4,4a, 5
The linear, branched or cyclic diene having 4 to 20 carbon atoms selected from the group consisting of 8,8a-octahydronaphthalene is, for example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene. , 1,4-hexadiene, and cyclohexadiene.

By copolymerizing ethylene with the above-mentioned comonomer, the density and physical properties of the ethylene polymer can be controlled. The olefin polymerization according to the present invention can be carried out by any of suspension polymerization method, gas phase polymerization method, solution polymerization method and high pressure polymerization method, and is particularly effective in suspension polymerization method and gas phase polymerization method.

In the suspension polymerization method, an inert hydrocarbon solvent can be used, and the olefin itself can also be used as a solvent. Specific examples of the inert hydrocarbon solvent used in the suspension polymerization method include propane and
Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene; Examples thereof include halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The catalyst feed amount in the olefin polymerization using the olefin polymerization catalyst of the present invention is, for example, 1 wt% to 0.0001 wt% of the component (A) based on the weight of the polymer obtained per hour. It is desirable to adjust the catalyst concentration in the polymerization system so that it becomes%.
The polymerization temperature is usually 0 ° C or higher, preferably 50 ° C or higher, more preferably 60 ° C or higher, and 300 ° C or lower, preferably 200 ° C or lower, more preferably 100 ° C.
The range is as follows. The polymerization pressure is usually from atmospheric pressure to 3000.
kg / cm ^2, preferably 2~200kg / cm ^2, more preferably under conditions of 5 to 50 kg / cm ^2, the polymerization reaction is a batch, semi-continuous, also be carried out in any of the methods of continuous You can

When the olefin polymerization catalyst of the present invention is used, it is particularly effective in controlling the molecular weight distribution, comonomer distribution, etc. if the polymerization is carried out in two or more stages under different reaction conditions. Further, the molecular weight of the obtained olefin polymer can be adjusted by, for example, allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above-mentioned components. The catalyst for olefin polymerization of the present invention can be applied to various olefin polymerization methods such as suspension polymerization method, gas phase polymerization method and solution polymerization method, and has high polymerization activity, and an olefin polymer excellent in particle properties is used without using aluminoxane. It can be manufactured at low cost and its industrial value is extremely high.

[0093]

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, it is 2.16 at 190 ° C.
The MFR measured under a load of kg is defined as MI, and the MFR measured under a load of 21.6 kg at 190 ° C. is defined as HMI.

In the present invention, the physical properties of the ethylene polymer are measured as follows. [Amount of n-decane-soluble component] The amount of the n-decane-soluble component, which is a low molecular weight wax component in the ethylene polymer obtained by the present invention, is about 3 g of the polymer added to 450 ml of n-decane, After dissolution at 145 ° C., the mixture was cooled to 23 ° C., the n-decane-insoluble part was removed by filtration, and the n-decane-soluble part was recovered from the filtrate for measurement. [Density] 2.16 at 190 ℃
12 strands obtained when measuring MFR under kg load
It heat-processed at 0 degreeC for 1 hour, and after gradually cooling to room temperature over 1 hour, it measured with the density gradient tube. [Average particle size and amount of fine powder] The average particle size of the polymer and the amount of fine powder of 100 µm or less were measured with a sieve.

[0095]

[Example 1] [Preparation of solid catalyst component (A)];
200 ml of hexane was placed in a 00 ml flask, and 50 mmol of butylethylmagnesium and 7 mmol of triethylaluminum were added and mixed to obtain 50 mmol of an organomagnesium component (D) soluble in an organic solvent.

Further, 200 ml of hexane was placed in a 500 ml flask that had been sufficiently replaced with nitrogen, and 30 mmol of the organomagnesium component (D) obtained by the above procedure, 30 mmol of dichlorosilane and 3 parts of trimethylaluminum were added.
When 0 mmol was added and the mixture was stirred, a white precipitate was deposited. The precipitate was filtered and washed under a nitrogen atmosphere to obtain about 3 g of solid catalyst component (A).

The obtained solid catalyst component (A) was analyzed and the composition was examined. As a result, 0.01 mol or less of aluminum, 0.02 mol of silicon, and 1 mol of magnesium in the solid catalyst component (A) were used. Methyl group 0.02 mol, ethyl group 0.
It was found to contain 06 mol, 0.06 mol of butyl groups and 1.91 mol of chlorine. [Polymerization]; Solid catalyst component (A) 1 prepared as described above
g and 25 micromoles of bis (n-butylcyclopentadienyl) zirconium dichloride were mixed in hexane. At this time, the white solid catalyst component (A) was colored yellow.

On the other hand, 0.8 g of hexane was placed in a stainless steel autoclave having an internal volume of 1.6 liter which had been sufficiently replaced with nitrogen.
Lithium and 0.3 mmol of triisobutylaluminum were added, and 60 ml of 1-hexene was further added. After that, ethylene was introduced to bring the total pressure to 7 kg / cm.
^2- G, and the temperature in the system was set to 65 ° C. Into this autoclave, the solid catalyst component (A) and bis (n
-Butylcyclopentadienyl) zirconium dichloride (20 mg) was added, and the temperature in the system was immediately increased to 7
The temperature was raised to 0 ° C. to initiate polymerization.

After that, ethylene was replenished to bring the total pressure to 7 kg.
Polymerization was carried out at 70 ° C. for 1 hour while maintaining / cm ² -G. 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. As a result of such polymerization, MI at 190 ° C. was 0.81 g / 10 minutes,
HMI is 14.1 g / 10 min and density is 0.926
g / cm ³ , decane-soluble content at 23 ° C. is 0.1% by weight or less, and bulk density is 0.30 g / cm ³ .
38 g of an ethylene-hexene copolymer having a polymer average particle diameter of 440 μm and a fine polymer amount of 100 μm or less and less than 0.1% by weight was obtained.

[0100]

Examples 2 to 4 Using the solid catalyst component (A) obtained in Example 1, the type and amount of transition metal compound used, 1-
Polymerization was carried out by the same procedure as in Example 1 except that the amount of hexene used, the amount of hydrogen added as a molecular weight modifier, the polymerization temperature and the like were changed. Tables 1 and 2 show the working conditions and polymerization results of each of the above examples.

[0101]

Example 5 [Preparation of solid catalyst component (A)]; In the same manner as in Example 1, an organic magnesium component (D) soluble in an organic solvent was obtained. 30 mmol of the organomagnesium component (D) thus obtained and 30 mmol of hydromethylsiloxane were mixed in 200 ml of a hexane solution, to which 30 mmol of trichlorosilane was added to obtain about 3 g of a solid component as a white precipitate. It was This solid component was further contacted with 10 mmol of triisobutylaluminum, and only the solid component was separated by filtration and washed to obtain a solid catalyst component (A).

The solid catalyst component (A) thus obtained was analyzed and the composition was investigated. As a result, 0.05 mol of aluminum and 0. 02 mol, ethyl group 0.04
It was found to contain moles, 0.21 moles of butyl groups and 1.93 moles of chlorine. [Polymerization] 1 g of the solid catalyst component (A) prepared as described above
And 100 micromoles of bis (n-butylcyclopentadienyl) zirconium dichloride were mixed in hexane. At this time, the white solid catalyst component (A) was colored yellow.

On the other hand, 0.8 g of hexane was placed in a stainless steel autoclave having an internal volume of 1.6 liter which had been sufficiently replaced with nitrogen.
1 liter and 0.3 mmol of triisobutylaluminum were added, and 160 ml of 1-hexene was further added. Then, ethylene was introduced to bring the total pressure to 7 kg / c.
m ² -G, and the temperature in the system was 65 ° C. To this autoclave, 10 mg of the previously prepared solid catalyst component (A) and a mixture of bis (n-butylcyclopentadienyl) zirconium dichloride was added, and the temperature in the system was immediately raised to 70 ° C. to initiate polymerization. .

After that, ethylene was replenished to bring the total pressure to 7 kg.
Polymerization was carried out at 70 ° C. for 1 hour while maintaining / cm ² -G. 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. As a result of such polymerization, MI was 0.84 g / 10 minutes and HMI was 1
4.6 g / 10 min with a density of 0.928 g / cm ^3.
The decane-soluble content at 23 ° C. is 0.1% by weight or less, the bulk density is 0.32 g / cm ³ , the polymer average particle size is 480 μm, and the amount of finely divided polymer of 100 μm or less is 0. 36 g of an ethylene-hexene copolymer less than 0.1% by weight was obtained.

[0105]

Examples 6 to 11 Same as Example 1 except that the solid catalyst component (A) obtained in Example 1 was used and the amount of 1-hexene used, the type of transition metal compound and the amount used were changed. Polymerization was performed according to the procedure of. Table 1 shows the implementation conditions of each of the above examples.
Table 2 shows the polymerization results.

The abbreviations in the table represent the contents shown below. Me; Methyl group Et; Ethyl group Bu; Butyl group (including isomers such as n- and iso-) (nBuCp) 2ZrCl2; Bis (n-butylcyclopentadienyl) zirconium dichloride (nBuMeCp) 2ZrCl2; Bis (n -Butylmethylcyclopentadienyl) zirconium dichloride (Me2Cp) 2ZrCl2; bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Ind) 2ZrCl2; bis (indenyl) zirconium dichloride CGC; (tertiary butylamido) dimethyl (Tetramethyl- [eta] ⁵ -cyclopentadienyl) silane titanium dichloride TEA; triethylaluminum TIBA; triisobutylaluminum

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

INDUSTRIAL APPLICABILITY The olefin polymerization catalyst of the present invention can be applied to various olefin polymerization methods such as suspension polymerization method, gas phase polymerization method and solution polymerization method, and has high polymerization activity and excellent particle properties. The olefin polymer can be produced inexpensively without using aluminoxane, and its industrial value is extremely large.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a step of adjusting an olefin polymerization catalyst according to the present invention.

Claims (18)

[Claims] 1. An olefin polymerization catalyst comprising the following components (A), (B) and (C). (A) Solid catalyst component represented by the general formula (1), MgMαSiβR ¹ _p R ² _q R ³ _r OR ⁴ _s Cl _t (1) (in the formula: M belongs to Groups 1 to 13 of the periodic table) R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² , R ³ and R ⁴ are hydrocarbon groups having 2 to 20 carbon atoms, α, β, p, q, r, s and t are numbers that satisfy the following relationship: 0 ≦ α ≦ 0.3 or 0.9 ≦ α ≦ 1.1, 0 ≦ β ≦
0.5 0 <p, 0 ≦ q, 0 ≦ r, 0 ≦ s, 0 <t (kα + 2 + 4β) × 0.7 ≦ t <kα + 2 + 4β kα + 2 + 4β = p + q + r + s + t, where k is M
(B) organoaluminum compound represented by the general formula (2), AlR ⁵ _n Z ¹ _3-n (2) (in the formula: R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Z ¹ is A hydrogen atom, a halogen atom, a hydrocarbyloxy group or a siloxy group, and n is a number satisfying the relationship of 0 <n ≦ 3) (C) Transition metal of Group 4 of the periodic table represented by the general formula (3) At least one transition metal compound selected from compounds, R ⁶ _z R ⁷ _a R ⁸ _b R ⁹ _c R ¹⁰ _d M (3) [wherein M is a transition metal selected from the group consisting of zirconium, titanium and hafnium] R ⁷ is a ligand having a cyclopentadienyl skeleton, or nitrogen, phosphorus,
A hetero 5-membered ring ligand having 1 to 4 carbon atoms containing arsenic, antimony or bismuth as a hetero atom, or a hetero tridentate ligand in which nitrogen, phosphorus or oxygen occupies a coordination site,
Each of these ligands is not substituted, or has at least one alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms and having 6 to 20 carbon atoms. And an at least one substituent selected from the group consisting of an aralkyl group substituted with an aryl group and an aryl group having 6 to 20 carbon atoms substituted with at least one alkyl group having 1 to 20 carbon atoms. Substituted, in which case one substituent may replace at least two parts of the ligand, the alkyl group is straight-chain, branched or cyclic, and said substituent is at least 1 one oxygen, nitrogen, may be associated with the ligand via a sulfur or phosphorus, furthermore at least one carbon atoms constituting a substituent may be a silicon; R ^8, R ⁹ Contact Fine R ¹⁰ are each independently a ligand having a cyclopentadienyl skeleton, nitrogen, phosphorus, arsenic, antimony or bismuth heterocyclic 5-membered ring ligand having 1 to 4 carbon atoms containing a hetero atom, a nitrogen, Hetero tridentate ligand having phosphorus or oxygen as coordination site, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and 1 to 20 carbon atoms
An aralkyl group obtained by substituting at least one aryl group having 6 to 20 carbon atoms with an alkyl group of 6 to 20 carbon atoms
An arylaryl group represented by -SO ₃ which is substituted with at least one alkyl group having 1 to 20 carbon atoms.
R (R is a hydrocarbon group having 1 to 8 carbon atoms, which is unsubstituted or substituted with at least one halogen),
Halogen atom or hydrogen atom, in which case the alkyl group is linear, branched or cyclic, and the alkyl group, aryl group, alkylaryl group or aralkyl group transitions via oxygen, nitrogen, sulfur or phosphorus. It may form a heteroatom ligand that binds to a metal, and at least one carbon atom that constitutes an alkyl group, an aryl group, an alkylaryl group or an aralkyl group may be silicon, and cyclopentadiene A ligand having an enyl skeleton, and a 5-membered heterocyclic ring ligand having 1 to 4 carbon atoms containing nitrogen, phosphorus, arsenic, antimony or bismuth as a hetero atom,
And Hetero 3 in which nitrogen, phosphorus or oxygen occupies the coordination site
Each of the bidentate ligands is not substituted, or is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms and having 6 to 20 carbon atoms. At least one substituent selected from the group consisting of an aralkyl group substituted with an aryl group and a C6-20 aryl group substituted with at least one C1-20 alkyl group. Is substituted with a group, in which case one substituent may replace at least two parts of the ligand, the alkyl group is straight-chain, branched or cyclic, and said substituent is At least one may be bound to the ligand via oxygen, nitrogen, sulfur or phosphorus, and at least one carbon constituting the substituent may be silicon; a is 1 or more. Is a number, b, c, d is an integer of 0 to 3, provided that be a + b + c + d = 4; R 7,
Each of R ⁸ , R ⁹ and R ¹⁰ is bound to a transition metal M; R ⁶ is one selected from R ⁸ , R ⁹ and R ¹⁰ and R
An alkylene group having 1 to 20 carbon atoms, a substituted alkylene group having 1 to 20 carbon atoms, an alkylidene group having 1 to 20 carbon atoms, a silylene group, or a silylene group, which binds to ⁷
20 alkyl groups, 6-20 carbon aryl groups, and 1-20 carbon alkyl groups having at least one carbon atom of 6-
An aralkyl group substituted with an aryl group having 20 carbon atoms and an aryl group having 6 to 20 carbon atoms having at least one carbon atom 1
A substituted silylene group substituted with at least one substituent selected from the group consisting of alkylaryl groups substituted with 20 to 20 alkyl groups; and z is 0 or 1. ] 2. A general formula (1) showing the solid catalyst component (A).
2. The catalyst for olefin polymerization according to claim 1, wherein M, which is a metal atom belonging to Groups 1 to 13 of the periodic table, is aluminum or zinc. 3. A general formula (1) showing the solid catalyst component (A).
The catalyst for olefin polymerization according to claim 2, wherein R ¹ which is an alkyl group having 1 to 8 carbon atoms is a methyl group. 4. The solid catalyst component (A) is a solid catalyst component obtained by bringing the following components (D), (E) and (F) into contact with each other, wherein: The catalyst for olefin polymerization according to any one of 1. (D) Organomagnesium component soluble in a hydrocarbon solvent represented by the following general formula (4): MgMγR ¹¹ _u R ¹² _v OR ¹³ _w (4) [In the formula, M is Group 1 to Group 13 of the periodic table. R ¹¹ , R ¹² and R ¹³ are hydrocarbon groups having 1 to 20 carbon atoms, and γ, u, v and w are numbers satisfying the following relationships. 0 ≦ γ ≦ 2, 0 <u, 0 ≦ v, 0 ≦ w kγ + 2 = u + v + w, where k is the valence of the metal atom M]; (E) having a Si—H bond represented by the following general formula (5) chlorosilane compounds, in _{^{H x SiCl y R 15 4- (}} x + y) (5) ( wherein, R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, x
And y are numbers that satisfy the following relationship. 0 <x, 0
<Y, x + y ≦ 4]; and (F) an organoaluminum compound represented by the following general formula (6): AlR ¹⁶ _m Z ² _3-m (6) (In the formula, R ¹⁶ is carbonized with 1 to 12 carbon atoms. Hydrogen group, Z ² is hydrogen atom, halogen atom, —OR ¹⁷ group, —OSiR
¹⁸ ₃ group, —OAlR ¹⁹ ₂ group or —SiR ²⁰ ₃ group, wherein R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are methyl group, ethyl group,
It is an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like, and m is a number satisfying the relationship of 0 <m ≦ 3). 5. The catalyst for olefin polymerization according to claim 4, wherein the metal atom M belonging to Groups 1 to 13 of the periodic table in the general formula (4) is aluminum or zinc. 6. The catalyst for olefin polymerization according to claim 5, wherein the organoaluminum compound represented by the general formula (6) is trimethylaluminum. 7. A group consisting of an α-olefin having 3 to 20 carbon atoms and a cyclic olefin having 3 to 20 carbon atoms, using an olefin polymerization catalyst containing the component (A), the component (B) and the component (C). At least one olefin selected from the group consisting of at least one olefin is polymerized or represented by the formula H ₂ C═CHR ²¹ (wherein R ²¹ is an aryl group having 6 to 20 carbon atoms). Compound or carbon number 4
To 20 linear, branched or cyclic dienes are copolymerized. 8. An α-olefin having 3 to 20 carbon atoms is propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and a cyclic group having 3 to 20 carbon atoms The olefin includes cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2
-Methyl-1.4,5.8-dimethano-1,2,3,3
Selected from the group consisting of 4,4a, 5,8,8a-octahydronaphthalene and having the general formula H ₂ C═CHR ²¹ (wherein R ²¹
Is an aryl group having 6 to 20 carbon atoms. ) Is styrene, and the linear, branched or cyclic diene having 4 to 20 carbon atoms is 1,3-butadiene, 1,4-
The method for polymerizing an olefin according to claim 7, wherein the method is selected from the group consisting of pentadiene, 1,5-hexadiene, 1,4-hexadiene, and cyclohexadiene. 9. The olefin according to claim 7 or 8, wherein the component (A), the component (B) and the component (C) are separately introduced into the polymerization system to carry out the polymerization. Polymerization method. 10. The olefin according to claim 7 or 8, wherein the component (A), the component (B) and the component (C) are brought into contact with each other in advance and introduced into the polymerization system to carry out the polymerization. Polymerization method. 11. The method according to claim 7 or 8, wherein the contact mixture of the component (A) and the component (C) and the component (B) are separately introduced into the polymerization system to carry out the polymerization. Method for polymerizing olefins. 12. The olefin according to claim 7, wherein the catalytic mixture of the component (A) and the component (B) and the component (C) are separately introduced into the polymerization system to carry out the polymerization. Polymerization method. 13. Component (A), component (B), component (C)
Ethylene using a catalyst for olefin polymerization containing, or ethylene and the formula H ₂ C = CHR ²² (wherein R
²² is an alkyl group having 1 to 18 carbon atoms or 6 to 20 carbon atoms
And an alkyl group is linear, branched, or cyclic. ) Compounds represented by), having 3 to 2 carbon atoms
0 cyclic olefin, and a straight chain having 4 to 20 carbon atoms,
A method for polymerizing ethylene, which comprises copolymerizing at least one selected from the group consisting of branched or cyclic dienes. 14. A compound of formula H ₂ C═CHR ²² (wherein R ²² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group is linear, branched, or The compound represented by cyclic) is 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, vinylcyclohexane, and a styrene ring having 3 to 20 carbon atoms. The olefins are cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-1,2,3,4,4a, 5,8, Selected from the group consisting of 8a-octahydronaphthalene, wherein the linear, branched or cyclic diene having 4 to 20 carbon atoms is 1,3-butadiene,
1,4-pentadiene, 1,5-hexadiene, 1,4
-The method for polymerizing ethylene according to claim 13, characterized in that it is selected from the group consisting of hexadiene and cyclohexadiene. 15. The polymerization of ethylene according to claim 13, wherein the component (A), the component (B) and the component (C) are separately introduced into the polymerization system to carry out the polymerization. Method. 16. Polymerization of ethylene according to claim 13 or 14, wherein the component (A), the component (B) and the component (C) are brought into contact with each other in advance and introduced into the polymerization system to carry out the polymerization. Method. 17. The ethylene according to claim 13, wherein the contact mixture of the component (A) and the component (C) and the component (B) are separately introduced into the polymerization system to carry out the polymerization. Polymerization method. 18. The ethylene according to claim 13, wherein the contact mixture of the component (A) and the component (B) and the component (C) are separately introduced into the polymerization system to carry out the polymerization. Polymerization method.