JPH08165310A - Catalyst component for polyolefin production, polyolefin production catalyst containing this component, and production of polyolefin - Google Patents

Abstract

PURPOSE: To produce a polyolefin having a high melt tension and even a high molecular weight by polymerizing an olefin in the presence of a catalyst comprising a metallocene compound having specified substituents. CONSTITUTION: A polyolefin production catalyst comprises a catalyst component comprising a metallocene compound represented by the formula, a Lewis acid compound and an organoaluminum compounds. In the formula, M<1> is Ti, Zr or Hf; X<1> and X<2> are each a 1-20C hydroarbon group, OR, SR, OCOR or the like (wherein R is H or a 1-7 Chydrocarbon group); R<1> and R<2> are each H, a 1-20C hydrocarbon group, OR or SR; R<3> is a 1-5C hydrocarbon group; R is a 1-20C hydrocarbon group; R<5> to R<15> are each H or a 1-20C hydrocarbon group; Y<1> is C, Si or Ge; and n is 1-3. An olefin is polymerized in the presence of this catalyst. When an α-olefin, particularly propylene, is polymerized in the presence of this catalyst, an amorphous polypropylene having elastic properties can be obtained in high catalytic activity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst component for polyolefin polymerization and a method for producing polyolefin using the same. Specifically, (1) an ethylene polymer having a high melt tension, (2) an ethylene-based copolymer having a uniform comonomer distribution, and (3) a poly (α-olefin) elastomer, particularly a polypropylene elastomer The present invention also relates to a catalyst component capable of polymerizing a polymer containing the same, and a method for polymerizing these polyolefins using the catalyst component. The polymer is
It can be used in a wide range of fields including automobiles, home appliances, construction, and civil engineering.

[0002]

[Prior art]

(1) Ethylene Polymer It is known that it is necessary to increase the melt tension (melt tension, MT) in order to improve the moldability of the ethylene polymer. Therefore, studies have been conducted to improve the melt tension of an ethylene-based copolymer obtained by using a Ziegler type titanium-based catalyst or a chromium-based catalyst. For example, JP-A-56-90810 and JP-A-60-106806 disclose a method of improving the moldability by improving the melt tension of an ethylene polymer obtained by using a Ziegler type titanium catalyst. There is. However, although the melt tension of ethylene-based polymers generally obtained by using titanium-based catalysts and chromium-based catalysts is improved, the molecular weight distribution is wide and there are many low-molecular-weight components such as those extracted with hexane, which causes smoke emission during molding. There was a problem that was generated. Further, the ethylene-based copolymer has a problem in that the composition distribution is wide and the molded product becomes sticky. On the other hand, an ethylene polymer obtained by using a metallocene catalyst composed of a metallocene compound and methylaluminoxane has a narrow molecular weight distribution and a small amount of low molecular weight components, so that smoking during molding is improved. On the other hand, the polymer obtained by the metallocene catalyst has a low melt tension and has a problem in its moldability. To solve this problem, methods of improving melt tension in metallocene catalyst systems have been investigated. For example, JP-A-4-213306, JP-A-5-140224, and JP-A-5140225 disclose a method for polymerizing an olefin polymer using a solid catalyst containing a metallocene compound having a specific crosslinked structure and an organic aluminoxy compound. ing. Using this method, the melt tension of the polymer is improved (in the disclosed examples, a remarkable effect is observed when a metallocene compound which is an ethylenebisindenylzirconium compound is used in practice). However, in the system disclosed herein, the molecular weight of the polymer obtained is insufficient, so that it is difficult to control the molecular weight of the polymer by the polymerization conditions such as hydrogen. In particular, it is difficult to polymerize a polymer having a molecular weight of 0.1 or less by MFR (melt flow rate, JIS K-6301 standard), and thus it is difficult to apply it to multistage polymerization. Further, even as a modifier for other polyolefins, the molecular weight of the polymer was insufficient. On the other hand, JP-A-5-34
5793 discloses the polymerization of ethylene with limited cross-linked indene-fluorene metallocene compounds. However, the polyethylene polymerized by this method has a low melt tension and is inferior in moldability like the conventional metallocene compound. Therefore, there is a need for a method of polymerizing a high molecular weight ethylene polymer having a high melt tension with a metallocene catalyst system.

(2) Ethylene Copolymer In the case of an ethylene copolymer, it is known that the molecular weight of the polymer and the composition distribution of the comonomer in the polymer chain are important factors that determine the performance of the polymer. There is. In particular, a high molecular weight component with a uniform comonomer distribution is used for final product performance (ES
It greatly contributes to the improvement of CR, rigidity, impact resistance, etc. (Japanese Patent Publication No. 61-43378, Macromol. Chem., Macromol. Symp., 41 , 55
(1991), J. Polym. Sci .: Part B, 29 , 129 (1991)). Generally, the ethylene-based copolymer polymerized by using the Ziegler-Natta catalyst maintains its performance due to this high molecular weight component. However, since the composition distribution of the comonomer in the polymer chain is blocky, the crystallinity of the polymer is increased, which adversely affects the final product. On the other hand, when a metallocene catalyst is used, the homogeneity of the comonomer distribution in the polymer chain is considerably improved. However, in the system of zirconocene / methylaluminoxane found in the early stage, the molecular weight of the polymer was not sufficient. An attempt to raise the molecular weight of an ethylene-based copolymer by improving a metallocene compound in a metallocene catalyst system is disclosed in, for example, USP 5,001,205 or JP-A-5-148317. However, in the system disclosed herein, the molecular weight is still insufficient, especially when considering the use as a high molecular weight component for improving the final performance of the above products. Therefore, if a metallocene catalyst system capable of increasing the molecular weight of the polymer while maintaining the homogeneity of the composition distribution of the comonomer in the polymer chain, its industrial value is extremely large.

(3) Polypropylene Elastomer Among polypropylenes, one having a performance as an elastic body (polypropylene elastomer) exists in Na
It has been known since tta et al. reported for the first time. USP 4,335,2
25, Macromolecules 22, 3851 (1989), ibid 22, 3858 (198
9), J.Polym.Sci.A: 27, 3063 (1989), JP-B-63-26122,
JP-A-2-206608, JP-A-2-206633 and recent JP-A-7-90
The polypropylene elastomer disclosed in 010 is
It is reported that a high-molecular-weight atactic component is present in the diethyl ether extraction component, and the performance as an elastomer is exhibited. However, the catalyst system disclosed here is a catalyst system in which an alkyl complex of Ti and Zr is supported on alumina, and its activity is remarkably low. Recently, a method of directly polymerizing a polypropylene elastomer by propylene polymerization using a metallocene catalyst system has been reported. The elastic body obtained by this catalyst system does not require a separation operation by fractionation. Chien et al. Obtained a thermoplastic elastomer by polymerizing propylene using a crosslinked indene-cyclopentadiene metallocene compound (GB2241244, J. Am. C.
hem.Soc. 1990, 112 , 2030, Macromolecules 1991, 24 , 85
0, J. Am. Chem. Soc. 1991, 113 , 8569, Macromolecules 19
92, 25 , 7400, ibid 1992, 25 , 1242, J.Polym.Sci.A: 30 ,
2601 (1992)). Waymouth et al. Obtained a thermoplastic elastomer polypropylene using a non-crosslinked bisindene metallocene compound (Science 267, 217 (1995)). However, in all of the above cases, it is difficult to obtain a sufficient polymer molecular weight at a polymerization temperature that is practically effective. The properties as an elastomer are known to correlate with the primary structure of the polymer and the molecular weight. The above metallocene catalyst systems, which do not provide sufficient molecular weight, impose severe restrictions on the performance of the polymer. On the other hand, a crosslinked bisfluorene-based metallocene compound (JP-A-6-234813, JP-A-6-256369) or a monocyclopentadienyl-based complex (WO95 / 00562) is used to produce a substantially amorphous high molecular weight atactic compound. A method of polymerizing polypropylene is disclosed,
It has been reported to have performance as an elastic body. However, the tensile strength of the polymer is low and the performance as an elastic body is poor. Therefore, it is difficult to control the polymer performance depending on the polymerization conditions. On the other hand, as the bridged indene-fluorene metallocene compound, a metallocene compound having no substituents on the indene ring and the fluorene ring is actually disclosed (Japanese Patent Laid-Open No. 5-345793, Organometallics 1994 , 13 , 64).
7). However, since the polymerized PP has an extremely low molecular weight, most of them are oily or waxy and are unrelated to the thermoplastic elastomer.

[0005]

The problems of the present invention are: (1) a high molecular weight ethylene polymer having a high melt tension and (2) a high comonomer composition distribution due to the difference in the olefin used for the polymerization. Molecular weight ethylene copolymer (3) It is to provide a metallocene catalyst system capable of producing a poly (α-olefin) elastomer, particularly a polypropylene elastomer and a polymer containing the same. Each of the above-mentioned three kinds of polymers is extremely desired in industrial production, and further, if these polymers are produced by the same catalyst system, it is extremely advantageous in production cost. Further, by using the multi-stage polymerization method to produce a plurality of polymers in a single polymerization vessel, it becomes possible to produce a high-performance resin.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a metallocene having a specific substituent in a group of bridged metallocene compounds having an indene ring and a fluorene ring. The present invention has been accomplished by discovering that a compound can be an extremely excellent catalyst component for solving the above problems. That is, the present invention provides a metallocene compound represented by the general formula (1).

[Chemical 4] [In the formula (1), M ¹ represents a transition metal atom of Ti, Zr, or Hf. X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ¹ ,
R ^{2 s} may be the same as or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a group having 1 to 7 carbon atoms). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ³ means a hydrocarbon group having 1 to 5 carbon atoms and may contain a silicon atom. R ⁴ has 1 carbon atom
To 20 hydrocarbon groups, which may include silicon atoms.
R ^{5 to} R ¹⁵ may be the same as or different from each other, are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may contain a silicon atom, and may bond to each other to form a ring. Y ¹ means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] As a catalyst component is used as the core of the invention, and (A) a metallocene compound represented by the general formula (1) (B) a Lewis acid compound (C) an organoaluminum compound and, if necessary, (D) a fine particle carrier. The above problem is solved by producing a polyolefin using a metallocene catalyst system consisting of

The method for producing a polyolefin using the olefin polymerization catalyst according to the present invention will be specifically described below. The novel metallocene compound which is the first catalyst component in the polymerization method of the present invention is represented by the general formula (1). The general formula (1) will be specifically described below. R
³ means a hydrocarbon group having 1 to 5 carbon atoms which may contain a silicon atom. Specifically, methyl, ethyl,
Examples thereof include alkyl groups such as n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl and cyclopentyl, and alkylsilyl groups such as trimethylsilyl. Of these, R ³ is preferably selected from a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a silicon atom. Specifically, alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, cyclopentyl, cyclohexyl, octyl, nonyl and adamanryl, vinyl, propenyl. , Alkenyl groups such as, phenyl, tolyl, 2,6-dimethylphenyl, 2,4
Aryl groups such as 6-trimethylphenyl, naphthyl and anthracenyl, arylalkyl groups such as benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl and phenylethyl, methylsilyl, dimethylsilyl,
Examples thereof include an alkylsilyl group such as trimethylsilyl and a silylalkyl group such as tris (trimethylsilyl) methyl group. Of these, R ⁴ is a primary or secondary carbon atom at the α-position, such as an alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or phenyl or tolyl. Aryl groups such as 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl and anthracenyl are preferable. Particularly, it is preferably selected from aryl groups such as methyl group, ethyl group, i-propyl group, phenyl group and 1-naphthyl group. In the metallocene compound represented by the general formula (1) according to the present invention, it is important that both R ³ and R ⁴ are not hydrogen atoms and that the 3-position of the indene ring is a hydrogen atom. In the general formula (1), when both R ³ and R ⁴ are hydrogen atoms, or when the 3-position of the indene ring is not a hydrogen atom, the effect of the present invention is not exhibited at all.

R ^{5 to} R ¹⁵ may be the same or different from each other and mean a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a silicon atom. Specifically, it means a hydrogen atom or a group similar to R ⁴ . Also,
R ^{5 to} R ¹⁵ may combine with each other to form a ring. In particular, it is desirable that adjacent groups be bonded to each other to form an aromatic 6-membered ring. Specifically, in the general formula (1), the indene ring has 4,5-benzoindene, 5,6-benzoindene, 6,7-benzoindene, and the fluorene ring has 1,2-benzofluorene and 2,3-. Benzofluorene, 3,4-benzofluorene, 5,6-benzofluorene, 6,7-benzofluorene, 7,8-benzofluorene, 3,4,5,6-dibenzofluorene, 4,5
-Means to be methylenephenanthrene and the like.
In this case, it is preferable that the indene ring is 4,5-benzoindene.

X ¹ and X ² may be the same as or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group. , SO ₂ R group, OSO ₂
R group and NRR 'group (here, R and R'mean a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and may include a halogen atom). Specifically, the halogen atom means fluorine, chlorine, bromine, iodine and the like. 1 to 20 carbon atoms that may contain halogen atoms
The hydrocarbon group of is, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl,
Alkyl groups such as cyclopentyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, tolyl, aryl groups such as 2,6-dimethylphenyl and 2,4,6-trimethylphenyl, benzyl, phenylmethyl, diphenylmethyl, triphenyl It means an arylalkyl group such as methyl and phenylethyl, a halogenated alkyl group such as trifluoromethyl and a halogenated aryl group such as pentafluorophenyl. Also, O
The R group is a hydroxy group or an alkoxy group such as methoxy, ethoxy, propoxy, butoxy or an aryloxy group such as phenoxy, the SR group is a mercapto group or an alkylthio group such as methylthio or an arylthio group such as phenylthio, and the OCOR group is a carboxy group or Alkoxycarbonyl groups such as methoxycarbonyl, SO ₂ R groups include sulfino groups, alkylsulfino groups such as methylsulfino, and arylsulfino groups such as phenylsulfino, and OSO ₂ R groups.
The group is a sulfo group or an alkylsulfo group such as methylsulfo, or an arylsulfo group such as phenylsulfo, p-toluenesulfo, and the NRR 'group is an amino group or an alkyl such as methylamino, dimethylamino, diethylamino or dibutylamino. It means an amino group or an arylamino group such as phenylamino.
Of these, X ¹ and X ² are preferably selected from a halogen atom or an alkyl group such as a methyl group.

R ¹ and R ² may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a carbon atom). Means a hydrocarbon group having 1 to 7 atoms,
(Which may include a halogen atom), and may combine with each other to form a ring. Specifically, the hydrocarbon group having 1 to 20 carbon atoms means methyl, ethyl, n-propyl,
Alkyl groups such as i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, cyclopentyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, tolyl, 2,6-dimethylphenyl, 2,4 , 6-
Aryl groups such as trimethylphenyl, benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl,
Means an arylalkyl group such as phenylethyl.
The OR group means a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, butoxy or an aryloxy group such as phenoxy, and the SR group means a mercapto group, an alkylthio group such as methylthio or an arylthio group such as phenylthio. Preferably, it is desirable to be selected from methyl group, ethyl group and phenyl group. Y ¹ means a carbon atom, a silicon atom or a germanium atom. The crosslinked portion represented by (R ¹ -Y ¹ -R ² ) n is particularly preferably n = 1. In addition, R ¹ and R ² may include Y ¹ and combine with each other to form a ring. For example, a 1,1-cyclohexylidene ring is preferable.

As the metallocene compound of the present invention, Me ₂ Si [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ Me ₂ Si [2-Et-4- (1-Naph) Ind is used. ] (Flu) ZrCl ₂ iPr [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ Me ₂ Si [2-Me-4-PhInd] (Flu) ZrCl ₂ Me ₂ Si [2-Et -4-PhInd] (Flu) ZrCl ₂ iPr [2-Me-4-PhInd] (Flu) ZrCl ₂ Me ₂ Si [2-Me-4-iPrInd] (Flu) ZrCl ₂ Me ₂ Si [2-Et- 4-iPrInd] (Flu) ZrCl ₂ iPr [2-Me-4-iPrInd] (Flu) ZrCl ₂ Me ₂ Si [2-Me-4-EtInd] (Flu) ZrCl ₂ iPr [2-Me-4-EtInd ] (Flu) ZrCl ₂ Me ₂ Si [2,4-Me ₂ Ind] (Flu) ZrCl ₂ iPr [2,4-Me ₂ Ind] (Flu) ZrCl ₂ Me ₂ Si [2,4,7-Me ₃ Ind] (Flu) ZrCl ₂ iPr [2,4,7-Me ₃ Ind] (Flu) ZrCl ₂ Me ₂ Si [2-Me-4,6-iPr ₂ Ind] (Flu) ZrCl ₂ iPr [2-Me -4,6-iPr ₂ Ind] (Flu) ZrCl ₂ Me ₂ Si [2-MeBenzind] (Flu) ZrCl ₂ iPr [2-MeBenzind] (Flu) ZrCl ₂ Me ₂ Si [2-Me-4- (1 -Naph) Ind] (2,7-tBu ₂ Flu) ZrCl ₂ iPr [2-Me-4- (1-Naph) Ind] (2,7-tBu ₂ Flu) ZrCl ₂ MePhSi [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ Ph ₂ Si [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ Me ₂ Ge [2-Me-4- (1-Naph) Ind ] (Flu) titanium ZrCl ₂ and the corresponding, be mentioned hafnium compounds That. In particular, Me ₂ Si [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ iPr [2-Me-4- (1-Naph) Ind] (Flu) ZrCl ₂ Me ₂ Si [2- Me-4-PhInd] (Flu) ZrCl ₂ iPr [2-Me-4-PhInd] (Flu) ZrCl ₂ is preferred. However, the above terms correspond to the following. Me = methyl group, Et = ethyl group, iPr = isopropyl group,
tBu = t-butyl group, Ph = phenyl group, Naph = naphthyl group, Ind = indenyl group, Benzind = 4,5-benzoindenyl group, Flu = fluorenyl group, Si [] = silylene group,
iPr [] = isopropylidene group, Ge [] = germylene group,
Zr = Zirconium, Cl = Chloride The number indicating the position of the substituent on the indene ring and the fluorene ring in the general formula (1) is shown in the formula (5).

Embedded image Further, the metallocene compound of the present invention can be used alone or in combination of two or more kinds.

A representative synthetic route for the metallocene compound is abbreviated below. However, this does not limit the synthetic route. The substituted indene as a raw material may be a commercially available one, or may be synthesized by a known method. The following is an example. Substitution indene is, for example, Organometallics, 1
3 , 954 (1994)

[Chemical 6] Is synthesized like. Substituted fluorene (11) as the other raw material

[0013]

[Chemical 7] As for the compound, a commercially available product can be used or, if necessary, can be synthesized by a known technique. next,
The indenyl anion (12) is obtained by deprotonating the substituted indene (10) with a strong base such as n-butyllithium, sodium hydride, potassium hydride or metallic sodium or metallic potassium in a solvent.

Embedded image "In the formula, M ⁴ means an alkali metal atom such as lithium, sodium or potassium." Indenyl anion (12) and compound (13) deprotonated by the above strong base

[Chemical 9] [In the formula, X ⁷ and X ⁸ may be the same or different from each other, and are a halogen atom, OR group, SR group, OCO
R group, OSO ₂ R group and NRR ′ group. Where R,
R'means a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. With the compound (14)

[Chemical 10] Get. The reaction is carried out in a molar ratio of (12) :( 13) of 1: 0.5 to 1:50, in particular 1: 1 to 1:20,
The concentration of the substrate is in the range of 0.1 mol / l to 10 mol / l, and the reaction temperature is in the range of -78 ° C to 120 ° C. At this time, as the reaction solvent, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran (THF) are preferable.

Further, the compound (14) and the substituted fluorene (11) are deprotonated with the above strong base to produce a fluorenyl anion (15).

[Chemical 11] Reacting "wherein M ⁵ represents an alkali metal atom such as lithium, sodium, potassium, etc." in a molar ratio of 1: 0.5 to 1:50, particularly 1: 1 to 1:20, Compound (16)

[Chemical 12] Get. In the above reaction, the substrate concentration was 0.1 mol /
In the range of 1 to 10 mol / l, the reaction temperature is -78 ° C.
To 120 ° C, especially in the range of -20 ° C to 20 ° C. As a reaction solvent, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran (T
Ethers such as HF) are preferred.

The compound represented by the general formula (16) has n =
When 1 and Y ¹ are carbon atoms, the following synthetic method is also effective. That is, substituted indene (10) and ketone (1
7)

[Chemical 13] Substituted benzofulvene by reacting with (18)

Embedded image Get. In the reaction, sodium indolerate in ethanol or n-butyllithium, sodium hydride, potassium hydride, or a strong base such as metallic sodium or metallic potassium is allowed to act on the substituted indene (10), and then the ketone (20) is added. , (10) :( 17), but 1:
The reaction is carried out in a molar ratio of 0.5 to 1:50, in particular 1: 1 to 1:20. The substituted benzofulvene (1
8) and the substituted fluorene (12) are reacted in a molar ratio of 1: 0.5 to 1:50, particularly 1: 1 to 1:20 to give the compound (19)

[Chemical 15] Get.

Compound (19) thus synthesized
Is a metallocene compound by a known method conventionally known from literature (J. Am. Chem. Soc., 1995, 95 , 6263, Orga
nometallics 1995, 14, 5, etc.). That is, the compound (1
9) is deprotonated with the above strong base to give the dianion (20)

Embedded image "In the formula, M ⁶ means an alkali metal atom such as lithium, sodium and potassium." Then, the compound (21) M ¹ (X ¹ _n X ² _4-n ) (21) “In the formula, X ¹ and X ² may be the same or different from each other, and are a halogen atom, an OR group, or an SR group. , OCO
R group, OSO ₂ R group and NRR ′ group. Where R,
R'means a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. In addition, n is an integer of 1 to 3. "
With the compound (16) or the dianion (20) to obtain the metallocene compound (1) (provided that X
¹ , except when X ² is an alkyl group). The above reaction is
Substrate concentration is 0.01 mol / l to 10 mol / l
In the range of, the reaction temperature is -78 ° C to 120 ° C, in particular,
It is performed in the range of -78 ° C to 30 ° C. As the reaction solvent, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, diethyl ether, ethers such as tetrahydrofuran (THF) and the like are preferable. In the general formula (1), when X ¹ and X ² are hydrocarbon groups, the general formula (22) R ³² -M ⁷ (22) "wherein R ³² is a hydrocarbon group having 1 to 20 carbon atoms, M
⁷ means an alkali metal atom such as lithium, sodium or potassium. The metallocene compound represented by the general formula (1) is synthesized by acting an alkylating agent represented by

The second catalyst component used in the polymerization in the present invention is a Lewis acid compound and is roughly classified into the following two types. One is an organic aluminoxy compound represented by the general formula (23) or (24).

[Chemical 17] [In the formulas (23) and (24), R ³³ , R ³⁴ , and R ³⁵ are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and preferably a methyl group, an ethyl group, or a propyl group. , A butyl group and an isobutyl group, and particularly preferably a methyl group and an isobutyl group. R ^{36, which} may be the same or different, are hydrocarbon groups having 1 to 10 carbon atoms,
Preferably, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, particularly preferably a methyl group,
It is an isobutyl group. n is an integer of 1 to 100, preferably an organic aluminoxy compound composed of a mixture of 3 to 100. Further, it may be a mixture of (23) and (24). ]

As a method for producing this type of compound, a known method can be used. For example, a method of adding a trialkylaluminum to a hydrocarbon solvent suspension of salts having water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate), or a solid,
A method of using liquid or gaseous water can be exemplified. When n is 2 or more and R ³⁶ is the same, 1
When three kinds of trialkylaluminum are used and each R ³⁶ is different, two or more kinds of trialkylaluminum may be used, or one or more kinds of trialkylaluminum and one or more kinds of dialkylaluminum monohalide may be used. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri n-butyl aluminum,
Triisobutylaluminum, tris-butylaluminum, tri-t-butylaluminum, tripentylbutylaluminum, trihexylbutylaluminum, trialkylaluminum such as tricyclohexylbutylaluminum, dialkylaluminum halide such as dimethylaluminum chloride and diisobutylaluminum chloride, dimethyl. It is selected from among dialkylaluminum aryloxides such as aluminum methoxide. Among them, trialkylaluminum, particularly trimethylaluminum and triisobutylaluminum are preferably selected. Further, the organoaluminoxy compound used in the present invention is further reacted with a compound having active hydrogen such as water to give a compound represented by the general formula (23) or (24)
The organic aluminoxy compound may be crosslinked. Alternatively, it may be an addition reaction product with an organic polar compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in the molecule and having no active hydrogen. The organic aluminoxy compound may be added with an additive such as an alcohol in order to suppress the change over time. Examples of the organic polar compound include trimethyl phosphate and triethyl phosphate. In this case, it is possible to polymerize a polyolefin having excellent powder properties without adhesion of the polymer to the wall of the polymerization vessel.

Another group as the second catalyst component is another Lewis acid compound which reacts with the metallocene compound to form an ionic complex. Among them, a boron compound is preferable, and a boron compound having a pentafluorophenyl group, a p-methyltetrafluorophenyl group, a pt-butyltetrafluorophenyl group, and a p-trimethylsilyltetrafluorophenyl group is particularly preferable. Specifically, tri (pentafluorophenyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Dimethylanilinium borate, pyridinium tetra (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) (4-methyl- 2, 3,
Triphenylcarbenium 5,6-tetrafluorophenyl) borate, tri (pentafluorophenyl) (4-
Triphenylcarbenium t-butyl-2,3,5,6-tetrafluorophenyl) borate or tri (pentafluorophenyl) (4-trimethylsilyl-2,3
Examples thereof include triphenylcarbenium 5,6-tetrafluorophenyl) borate.

The third catalyst component used for polymerization in the present invention is an organoaluminum compound. For example, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri te.
Trialkylaluminums such as rt-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trisichexylaluminum, etc., dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum methoxide, diethyl. It is selected from dialkyl aluminum alkoxides such as aluminum ethoxide, dialkyl aluminum aryloxides such as diethyl aluminum phenoxide, and aluminoxane. Among them, trialkylaluminum, particularly trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum are preferably selected. Further, an organic aluminoxy compound represented by the general formula (23) or (24) may be substituted.

The fourth catalyst component used for polymerization in the present invention is a fine particle carrier. The first to third catalyst components of the present invention can be carried on each or all of them on a fine particle carrier (hereinafter, carrier). The fine particle carrier used in the present invention has an average particle size of 10 to 300 μm, preferably 20 to 200 μm. In the form of fine particles,
There is no particular limitation as long as it is solid in the polymerization medium, and it is selected from organic substances and inorganic substances. The inorganic substance is preferably selected from inorganic oxides, inorganic chlorides, inorganic carbonates, inorganic sulfates, inorganic hydroxides, and organic polymers. For example, as an inorganic carrier, oxides such as silica and alumina, chlorides such as magnesium chloride, carbonates such as magnesium carbonate and calcium carbonate, sulfates such as magnesium sulfate and calcium sulfate, magnesium hydroxide and calcium hydroxide. And the like. Examples of the organic substance include organic polymer carriers, and examples thereof include fine particles of polyethylene, polypropylene, polystyrene and the like. Preferably, it is an inorganic oxide, especially silica,
It is desirable to be selected from alumina and its composite oxide. Among these, the porous fine particle carrier is preferable, and in this case, the adhesion of the polymer to the inner wall of the reaction vessel is small and the bulk density of the obtained polymer is high, which is particularly preferable. The porous fine particles according to the present invention have a specific surface area of 10 to 100.
It is preferably in the range of 0 m ² / g, further 100 to 8
It is preferably in the range of 00m ² / g, particularly preferably from 200~600m ² / g. Further, the pore volume is preferably in the range of 0.3 to 3 cc / g, more preferably 0.5 to 2.5 cc / g, and particularly preferably 1.0 to 2 0.0 cc /
It is in the range of g. Also, the amount of water adsorbed and the amount of surface hydroxyl groups differ depending on the treatment conditions. As a preferable range of these, the water content is 5% by weight or less, and the surface hydroxyl group content is 1 / nm ² or more based on the surface area. The water content and the amount of surface hydroxyl groups can be controlled by the firing temperature and treatment with an organic aluminum compound or an organic boron compound. Furthermore, it is also possible to use a prepolymerized olefin. The polymerization catalyst of the present invention may contain other components useful for olefin polymerization, in addition to the above components.

In the present invention, olefins used for polyolefin polymerization include ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 3-methyl-1-butene, 4-methyl-
1-Pentene, cyclopentene, cyclohexene, styrene and the like can be mentioned. Further, as the olefin represented by the general formula (2) used for polymerization in the present invention, propylene, 1-butene, 1-pentene, 1-hexene, 1
-Heptene, 1-octene, 3-methyl-1-butene,
4-methyl-1-pentene, cyclopentene, cyclohexene, styrene and the like can be mentioned. Ethylene and formula (2)
As the olefin of the formula (2) used in the copolymerization with the olefin represented by: propylene, 1-butene,
1-Hexene and 1-octene are preferable, and propylene is particularly preferable. In the method of (co) polymerizing one or more olefins represented by formula (2), homopolymerization of propylene, copolymers of propylene and 1-butene, propylene and 1-hexene, and the like can be mentioned. Among them, propylene homopolymer is preferable. Further, polyvalent ene can be subjected to polymerization. In this case, the polyvalent ene used in the polymerization has a plurality of non-conjugated vinyl groups and has at least two vinyl type double bonds and has 5 carbon atoms.
A polyvalent ene having a molecular weight of 1100 or less at -80 is effective. A particularly effective polyvalent ene has 8 to 20 carbon atoms. Specifically, 1
, 4-pentadiene, 1,5-hexadiene, 1,6
-Heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,4-pentadiene, 4-methyl-1,5-hexadiene, 3 -Methyl-1,5-hexadiene, 1,5,9-decatriene and the like can be mentioned. In particular, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene is preferred. The polyvalent ene used in the polymerization is based on the olefin represented by the general formula (2):
The range of 0.05% to 2% is preferable.

The timing of contact between the first catalyst component and the other catalyst component during the polymerization reaction can be arbitrarily selected. For example, the first catalyst component and the second catalyst component are brought into contact with each other in advance (pre-contact), while the reaction vessel is charged with the third catalyst component and the olefin to be used for polymerization, and the olefin to be used for polymerization is added to start the polymerization reaction. There is a method. Alternatively, the reaction vessel may have a third
The polymerization reaction may be initiated by charging the catalyst component and the olefin to be used for the polymerization and separately adding the first catalyst component and the second catalyst component. In particular, the second catalyst component is represented by the general formula (23),
In the case of the organic aluminoxy compound of (24), if the first catalyst component and the second catalyst component are contacted in advance and then supplied to the reaction system, the polymerization activity is significantly improved. Also, the first to the third
The catalyst component can be supported on the fourth catalyst component at a necessary time, if necessary. The order of the supporting method at this time can be selected arbitrarily, but preferably, the second catalyst component is mixed and contacted with the fourth catalyst component and then the first catalyst component is contacted, or the first catalyst component and the second catalyst component are contacted. After pre-contacting the catalyst components,
A method of mixing and contacting the fourth catalyst component is selected. The above components are mixed in a solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane. Can be prepared in the presence or absence of olefins. The temperature at the time of mixing is −70 ° C. to 200 ° C., preferably −20 ° C. to 120 ° C., and the mixing time is 1 minute to 600 minutes. Moreover, the concentration at the time of mixing is 10 ⁻⁶ to 10 ⁻³ mo of the first catalyst component per 1 g of the fourth catalyst component.
Use at a concentration of l. The polymerization method used in the present invention may be any method known in the art, such as solution polymerization, slurry polymerization method, gas phase polymerization method or high temperature melt polymerization method, and it may be continuous or discontinuous. Alternatively, it can be carried out in one step or in multiple steps. There are no particular restrictions on the polymerization conditions other than the conditions for the use process, but the polymerization temperature ranges from 0 ° C to 300 ° C.
℃, especially 20 ℃ ~ 150 ℃, more preferably 40 ℃ ~
Commonly used at 90 ° C.

The concentration of the polyolefin polymerization catalyst component of the present invention is not particularly limited, but the concentration of the metallocene compound of the first catalyst component is 10 ^-3 to 10 ^-10 mol / l with respect to the volume of the solvent or the reaction vessel. preferable. Further, in the case of the second catalyst component, the concentration of the organic aluminoxy compound of the general formulas (24) and (25) is 10 to 10,000, particularly, the molar ratio of (aluminum atom in the organic aluminoxy compound) / (metallocene compound). , 100 to 5,000 is preferable, and in the case of other Lewis acid compounds, the molar ratio of (Lewis acid compound) / (metallocene compound) is 0.1.
The range of -100 to 100, especially 0.2 to 10, is preferable. Third
In the case of the catalyst component, the molar ratio of the metallocene compound of the first catalyst component to the organoaluminum compound (aluminum atom in the organoaluminum compound) / (metallocene compound)
And 10 to 100,000, preferably 100 to 10,
The range is 000. Further, the organoaluminum compound used in the polymerization may be used in advance in contact with the first catalyst component or the second catalyst component, or may be used without prior contact. The molecular weight during the polymerization can be adjusted by known means, for example, selecting the temperature or introducing hydrogen.

The olefin polymerization catalyst of the present invention can be used in combination with other olefin polymerization catalysts. When ethylene is polymerized, or when ethylene and one or more olefins represented by the general formula (2) are copolymerized, the metallocene compound of the present invention is used in combination with another generally known metallocene compound to obtain a molecular weight distribution. It becomes possible to polymerize ethylene-based polymers having different values. on the other hand,
When (co) polymerizing one kind or two or more kinds of olefins represented by the general formula (2), the metallocene compound of the present invention is used in combination with a crystalline polyolefin, particularly a crystalline metallocene compound for polymerizing polypropylene. The elastic properties of the obtained polymer can be further improved.

The metallocene compound for polymerizing the crystalline polypropylene used in the present invention is represented by the general formula (3)

Embedded image [In the formula (3), M ² means a transition metal atom of Ti, Zr, or Hf. X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ¹⁸ ,
R ^{19 s} may be the same or different from each other, and each is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a group having 1 to 7 carbon atoms). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ²⁴ means a hydrocarbon group having 1 to 20 carbon atoms and may contain a silicon atom. R ^{20 to} R ²³ , R ²⁵ ,
R ^{26 s} may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain silicon. R ²³ and R ²⁵ and R ²⁴ and R ²⁶ may form a ring with each other via a hydrocarbon group. Y ² is
It means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] Or general formula (4)

[Chemical 19] [In the formula (4), M ³ represents a transition metal atom of Ti, Zr, or Hf. X ⁵ and X ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ²⁷ ,
R ^{28 s} may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a C 1 to 7 carbon atom). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ²⁹ means a hydrocarbon group having 1 to 20 carbon atoms and may contain a silicon atom. R ³⁰ and R ³¹ may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may contain silicon. R ²⁹ and R ³¹ may form a ring with each other via a hydrocarbon group. Y ³ means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] It is a metallocene compound represented by.

Specific description of each substituent follows the description in the general formula (1). However, general formulas (3) and (4)
The metallocene compound represented by, among known metallocene compounds, when an α-olefin such as propylene is polymerized, the polymer does not become an amorphous atactic polyolefin, but may become a crystalline polyolefin. It shall represent a known metallocene compound.
Specifically, as shown in general formula (3), iPr [(Cp) (Flu)] ZrCl ₂ iPr [(3-tBuCp) (3-tBuInd)] ZrCl ₂ Me ₂ Si [(3-tBuCp) ( Flu)] ZrCl _{2 As} general formula (4), Et [Ind] ₂ ZrCl ₂ Et [THInd] ₂ ZrCl ₂ Me ₂ Si [Ind] ₂ ZrCl ₂ Me ₂ Si [2-MeInd] ₂ ZrCl ₂ Me ₂ Si [ 2,4-Me ₂ Ind] ₂ ZrCl ₂ Me ₂ Si [2,4,7-Me ₃ Ind] ₂ ZrCl ₂ Me ₂ Si [2-Me-4,6-iPr ₂ Ind] ₂ ZrCl ₂ Me ₂ Si [2-Me-4-iPrInd] ₂ ZrCl ₂ Me ₂ Si [2-Me-4-PhInd] ₂ ZrCl ₂ Me ₂ Si [2-Me-4- (1-Naph) Ind] ₂ ZrCl ₂ Me ₂ Si [2-MeBenzind] ₂ ZrCl ₂ Me ₂ Si [3-tBuCp] ₂ ZrCl ₂ Me ₂ Si [2-Me-4-tBuCp] ₂ ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] ₂ ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] ₂ HfCl _{2 and the} like can be exemplified. However, the above terms correspond to the following. Me = methyl group, iPr = isopropyl group, tBu = t-butyl group, Ph = phenyl group, Naph = naphthyl group, Cp = cyclopentadienyl group, Ind = indenyl group, THInd = 4,5,6,
7- tetrahydroindenyl group, Benzind = 4,5-benzoindenyl group, Flu = fluorenyl group, Si [] = silylene group, iPr [] = isopropylidene group, Et [] = ethylidene group, Zr = zirconium, Hf = Hafnium, Cl = chloride The metallocene compounds exemplified above are all known compounds (JP-A-3-314978, JP-A-61-2718, USP 5,13).
2,262, Angew.Chem.Int.Ed.Engl., 24, 507 (1985), J.Am.
Chem.Soc., 1998, 110, 6255, Chem.Lett., 1853 (1989), O
rganometallics 1994, 13, 954, ibid 1994, 13 , 964).

In addition, in the synthesis stage of the metallocene compound represented by the general formula (1) of the present invention, a crystalline polyolefin,
In particular, it is also possible to simultaneously synthesize the crystalline polypropylene metallocene compound (3) or (4) for polymerization and use them for the polymerization without isolating both. Further, the metallocene catalyst containing the metallocene compound represented by the general formula (1) is not limited to the above-mentioned metallocene catalyst for polymerizing a crystalline polyolefin, and a conventionally known catalyst for polymerizing a crystalline polyolefin, such as magnesium chloride-supporting Ziegler.
It can be used in combination with a Natta catalyst or the like.

The polyolefin of the present invention can also be used as a modifier and compounding agent for various resins. A polyolefin obtained by polymerizing ethylene or copolymerizing ethylene with one or more olefins represented by the general formula (2) is blended with other polyolefin to obtain its moldability or final product. The performance can be improved. Olefin 1 represented by the general formula (2)
The polyolefin of the present invention obtained by (co) polymerizing two or more types exhibits excellent performance as a composition with another poly (α-olefin). For example, when a crystalline poly (α-olefin) is mixed at 50 wt% or less as a composition with crystalline poly (α-olefin) having stereoregularity of mm% ≧ 80% or rr% ≧ 80%, The elastic properties of the polyolefin of the present invention can be improved. In addition, crystalline poly (α-olefin) has 5
By incorporating 0 wt% or less of the polyolefin of the present invention, the impact resistance can be significantly improved. In particular, the composition of the polyolefin of the present invention, particularly a polypropylene polymer, is very effective for an isotactic polypropylene resin which is required to have high impact resistance such as a bumper material for automobiles. On the other hand, the polyolefin of the present invention obtained by (co) polymerizing one or more olefins represented by the general formula (2) is
Since it is essentially non-crystalline, it is a compounding agent having extremely excellent radiation resistance. The polyolefin obtained in the present invention can be used for various products by utilizing its properties such as transparency, flexibility, strength, moldability and heat sealability. Further, in addition to the above crystalline polyolefin, the polyolefin of the present invention includes other resins such as an ethylene-vinyl acetate copolymer and a saponified product thereof, an ethylene-vinyl alcohol copolymer, and a halogen-containing copolymer (exemplification). Then, polyvinylidene chloride, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, polychloroprene, chlorinated rubber, etc.), polymers of unsaturated carboxylic acids and their derivatives (for example,
It can also be used as a modifier and compounding agent for resins such as polymethylmethacrylate and polyalkylacrylate. Further, the polyolefin of the present invention can be used as a raw material for various graft copolymers, block copolymers and the like. The invention is further described in the following examples, which do not limit the scope of the invention.

[0030]

EXAMPLES In the following examples, the metallocene compound of the present invention was identified by the following method. ¹ H-NMR : measured in deuterated chloroform at 30 ° C. Mass spectrometry : A sample was introduced by the direct introduction method, ionized by the electron impact method (70 eV), and measured. The physical properties of the polymer were measured as follows. ¹³ C-NMR : performed in a mixed solvent of heavy benzene and 1,3,5-trichlorobenzene (1: 3 wt ratio) at 120 ° C. (measurement mode: proton decoupling method, pulse width: 8.0 μs, pulse repetition). Time: 3.0 s, integration number: 20000 times, internal standard: hexamethyldisiloxane). The reactivity ratio r ₁ r ₂ showing the comonomer composition distribution of the ethylene-based copolymer and the proportion of the comonomer in the polymer chain are described in J. Polm. Sci., Polym. Chem. 29, 1585 (1991), Po.
Calculated according to Lym. Bull. 26, 325 (1991). The stereoregularity of polypropylene is Macrolecules 6 , 925 (1973), ibid.
8 and 687 (1975), derived from methyl group, mm, m
It was evaluated as the intensity ratio of r and rr signals. Gel Permeation Chromatography (GPC) :
It was carried out in 1,2,4-trichlorobenzene at a column temperature of 135 ° C and a solvent flow rate of 1 ml / mim. Differential scanning calorimetry (DSC) : 23 after heating to 230 ° C.
The mixture was kept at 0 ° C. for 5 minutes, the heat of crystallization was measured by a cooling scan at 20 ° C./min, and the heat of fusion was measured again by keeping at 25 ° C. for 5 minutes and a heating scan at 20 ° C./min.

Further, the following measurement was performed on the ethylene polymer. Melt flow rate (MFR) : JIS K-6760
The temperature was 190 ° C. and the load was 2.16 kg. High load melt flow rate (HLMFR) : JIS
According to K-6760, temperature 190 ℃, load 21.6k
It was measured under the condition of g. Density : 190 at 23 ° C. according to JIS K-6760
The sample pressed at ℃ was cut, degassed in ethanol, and then measured with a density gradient tube. Melt tension (MT) : Polymer powder as a measurement sample,
The measurement was performed under the conditions of an orifice inner diameter of 2.095 ± 0.005 mm, an orifice length of 8.000 ± 0.025, a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, and a winding speed of 6.5 m / min.

The following measurements were carried out on the propylene polymer. Tensile test : According to JIS K-6301, kneading with a 3-inch roll for 5 minutes at 230 ° C gives a thickness of 1 mm.
The press plate molded into No. 2 was used as a No. 2 1/2 dumbbell test piece, and the measurement was performed at a tensile speed of 200 mm / min. Permanent elongation : A test piece with a marked line length of 20 mm was elongated by 100% and kept as it was for 1 minute. Ten minutes after the release, the length between the marked lines was measured (this is designated as D), and the permanent elongation was calculated from the following formula. Permanent elongation (%) = (D-20) x 100/20 Internal haze : Using a 0.5 mm thick press-formed plate, JIS
It was measured according to K7105. The analytical instruments used for measuring physical properties are as follows. NMR JEOL EX-400 mass spectrometry JEOL AX-500 GPC Waters 150C (Shodex; GPC AT-806MS column) DSC Perkin Elmer DSC7 MT Toyo Seiki Seisakusho melt tension tester type II

Of the known metallocene compounds, the following compounds were synthesized according to known references. That is, JP-A-5-345793: dimethylsilylene (1-indenyl)
(9-Fluorenyl) zirconium dichloride JP-A-63-235309: Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride J. Organomet. Chem., 288, 63 (1985): ethylidenebis (indenyl) zirconium Dichloride USP 5,001,205: Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride Organometallics 1994, 13, 954: rac-Dimethylsilylenebis (2-methyl-4- (1-naphthyl) indenyl)
Zirconium dichloride. Furthermore, the isopropylidene (3-t-butyl-1-indenyl) (9-fluorenyl) zirconium dichloride used in Comparative Example 16 was the same as in Example 1 and Example 2.
Was synthesized in the same manner as.

(Synthesis of Metallocene Compound) Example 1 Dimethylsilylene (2-methyl-4- (1-naphthyl))
Indenyl) (9-fluorenyl) zirconium dichloride
Synthesis of Ride (IMNFZ) (1) Synthesis of Dimethyl (2-methyl-7- (1-naphthyl) indenyl) (9-fluorenyl) silane All reactions were performed under a nitrogen gas atmosphere. The glass reaction vessels used were all dried in advance. Dry tetrahydrofuran (THF) 1
2-methyl-7- (1-naphthyl) indene (synthesized according to Organometallics, 1994, 13,954) 5.0 ml in 00 ml
g (19.5 mmol) was dissolved and 1.6 mo
13.0 ml of 1 / l n-butyllithium hexane solution
(20.8 mmol) was added under an ice bath. The reaction was carried out at room temperature for 3 hours to obtain a light brown solution. On the other hand, a solution prepared by dissolving 2.7 g (21 mmol) of dimethyldichlorosilane in 200 ml of THF was cooled to 0 ° C., and the orange solution was added dropwise over 2 hours. After the dropping, the temperature was raised to room temperature and the mixture was stirred for 12 hours. Then, a fluorenyllithium solution prepared in the same manner from 3.32 g (20 mmol) of fluorene and 13.0 ml of an n-butyllithium solution was added dropwise under ice cooling in 15 minutes.
It was raised to room temperature and stirred for 12 hours. The reaction solution was stirred with an aqueous solution of ammonium chloride and then 500 ml of diethyl ether.
And extracted with anhydrous sodium sulfate. Separated from the raw material by column chromatography (silica gel, developing solvent n-hexane) to obtain 5.6 g (11.7 mmo) of the desired product.
1, yield 59%) was obtained. The elemental analysis value of this compound is shown below. Elemental analysis: (C ₃₅ H ₃₀ Si) Calculated (%): C; 87.82, H; 6.32 Found (%): C; 87.95, H; 6.55 (2) the following All the synthetic reactions to the zirconium complex were performed under an argon gas atmosphere. 100 ml of dry THF
To dimethyl (2-methyl-7- (1-naphthyl) indenyl) (9-fluorenyl) silane 6.5 g (13.6).
mmol), and 1.65 mol / l of n
-Butyl lithium hexane solution 18.7 ml (28.7
(mmol) was added under ice cooling. After reacting for 2 hours at room temperature, THF was distilled off under reduced pressure. Further, while cooling to -78 ° C, 50 ml of dry toluene was added to obtain a greenish brown suspension solution. In a separately prepared flask, 3.2 g (13.6 mmol) of zirconium tetrachloride and 10 parts of dry toluene were added.
It was suspended in 0 ml. This was cooled to −78 ° C., and the greenish brown toluene solution was added with a cannula while cooling. After stirring at −78 ° C. for 1 hour, the temperature was raised to room temperature and the reaction was performed for 10 hours to obtain a red suspension solution. The suspension solution was centrifuged to remove the toluene solution portion and separate a red solid.
This was extracted with 600 ml of dry methylene chloride by a Soxhlet extractor, and the obtained red transparent solution was concentrated to precipitate red crystals. Mass spectrometry "EI (70 eV), direct introduction method" 638 (M
⁺ ) ¹ H-NMR (400 NHz, CDCl ₃ ) δ1.43 (3H, Si-C
_{H 3), 1.60 (3H,} Si-CH 3), 2.17 (3H, Ind-CH 3)
, 6.25 (1H, Ind-H), 6.9-8.4 (18H, Ar
yl-H) Elemental _{analysis: (C 35 H 28 SiZrCl 2} ) Calculated (%): C; 65.81, H; 4.42 Found (%): C; 64.20, H; 3.91

Example 2 Dimethylsilylene (2-methyl-4-phenylindeni
(9-fluorenyl) zirconium dichloride
Synthesis of (IMPFZ) (1) Synthesis of dimethyl (2-methyl-7- phenylindenyl) (9-fluorenyl) silane A procedure similar to that in Example 1 was followed. That is, 2-methyl-7- in 100 ml of dry tetrahydrofuran (THF).
Phenylindene (synthesized according to Organometallics, 1994, 13 , 954) 6.3 g (30.5 mmol) was dissolved,
To this, 21.0 ml (33.6 mmol) of a 1.6 mol / l n-butyllithium hexane solution was added in an ice bath.
After reacting for 3 hours at room temperature, 4.4 g of dimethyldichlorosilane
(34 mmol) was dissolved in 200 ml of THF, and the solution was added dropwise under ice cooling for 2 hours. After the dropping, the temperature was raised to room temperature and the mixture was stirred for 12 hours. Next, 5.1 g of fluorene (3
0.5 mmol) and n-butyllithium solution 21.0 ml
A fluorenyllithium solution prepared in the same manner as above was added dropwise under ice cooling in 15 minutes, and the temperature was raised to room temperature and stirred for 12 hours. The reaction solution was stirred with an aqueous solution of ammonium chloride,
It was extracted with diethyl ether and dried over anhydrous sodium sulfate. Column chromatography (silica gel, developing solvent)
Separated from the raw material with n-hexane) to obtain 8.5 g (1
9.8 mmol, yield 65%) was obtained. The elemental analysis value of this compound is shown below. Elemental analysis value: (C ₃₁ H ₂₈ Si) Calculated value (%): C; 86.92, H; 6.54 Actual value (%): C; 86.95, H; 6.75 (2) Next The synthetic reaction to the zirconium complex also followed the same procedure as in Example 1. 6.8 g (15.9 mmol) of dimethyl (2-methyl-7-phenylindenyl) (9-fluorenyl) silane was dissolved in 100 ml of dry THF, and 21.8 ml of a 1.65 mol / l n-butyllithium hexane solution was dissolved therein. (35.0 mmol) was added under ice cooling. After reacting for 2 hours at room temperature, THF was distilled off under reduced pressure. Further, while cooling to −78 ° C., 50 ml of dry toluene was added. In a separately prepared flask, 3.7 g (15.9 mmol) of zirconium tetrachloride was suspended in 100 ml of dry toluene. This was cooled to −78 ° C., and the greenish brown toluene solution was added with a cannula while cooling. After stirring at −78 ° C. for 1 hour, the temperature was raised to room temperature and the reaction was performed for 10 hours to obtain a red suspension solution. The suspension solution is
The toluene solution part was removed by centrifugation to separate a red solid. This was extracted into dry methylene chloride with a Soxhlet extractor, and red crystals were obtained from the obtained red transparent solution. Mass spectrometry "EI (70 eV), direct introduction method" 588 (M
^{+) 1 H-NMR (400MH} Z, CDCl 3) δ1.43 (3H, Si-C
_{H 3), 1.60 (3H,} Si-CH 3), 2.21 (3H, Ind-CH 3)
, 6.40 (1H, Ind-H), 6.9-8.4 (18H, Aryl-
H) Elemental _{analysis: (C 31 H 26 SiZrCl 2} ) Calculated (%): C; 63.27, H; 4.42 Found (%): C; 63.20, H; 4.20

(Production of Ethylene Polymer) Example 3 Support of Methylaluminoxane on a Carrier Toluene 25 was added to a 100 ml flask which had been sufficiently replaced with nitrogen.
ml and silica (1.5 g of Davison 952 calcined at 300 ° C. for 4 hours) were added, and 37 ml of methylaluminoxane (manufactured by Tosoh Akzo, 1.35 mol / l (Al atom conversion) toluene solution) was added to this suspension. The mixture was stirred at room temperature for 30 minutes. Then, the solvent was distilled off under reduced pressure. 50 ml of heptane was added, and the mixture was stirred at 80 ° C. for 4 hours. Then, the solid component was obtained by washing twice with heptane at 80 ° C. 33% by weight of the obtained solid component was methylaluminoxane. Polymerization 3.2 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen, and methylaluminoxane supported on silica prepared above was used. 105 mg,
Dimethylsilylene synthesized in Example 1 (2-methyl-
4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) 2.02
a solution of mg in 6 ml of toluene and isobutane 8
After introducing 00 ml, the temperature was raised to 70 ° C. Polymerization was started by introducing ethylene, and ethylene pressure was 10 kg / c.
Polymerization was carried out for 30 minutes at 70 ° C. and m ² to obtain 69.3 g of polymer. The activity per complex was 6.9 kg-polymer / g-complex · hr · atm. The physical properties of this polymer were as follows. Mw = 990,000, Mw / Mn = 4.25 The density was 0.948 g / cm ³ , the melting point was 132 ° C., and the melt tension could not be measured.

Example 4 3.2 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was prepared in Example 3 in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen. 105m of methylaluminoxane supported on silica
g, dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) 2.0 synthesized in Example 1
After introducing a solution of 2 mg dissolved in 6 ml of toluene and 800 ml of isobutane, the temperature was raised to 70 ° C. Mixed gas of ethylene and hydrogen (H ₂ / C ₂ (wt ratio) = 4 × 1
0 ^-5 ) was introduced to initiate polymerization, and the mixed gas pressure was adjusted to 10
Polymerization was carried out at 70 ° C. for 30 minutes at 70 kg / cm ² , 37.
6 g of polymer was obtained. Activity per complex is 3.7 kg
-Polymer / g-complex / hr / atm. HLMFR = 0.11, Mw = 407,000, Mw /
Mn = 3.94 Density was 0.957 g / cm ³ , melting point was 132 ° C., and melt tension could not be measured.

Examples 5 to 7 Polymerization was carried out in the same manner as in Example 4 except that the mixed gas ratio was changed.
Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

Examples 8 to 10 Dimethylsilylene (2-methyl-4-phenylindenyl) (9- synthesized in Example 2 as a metallocene compound
Fluorenyl) zirconium dichloride (IMPF
Polymerization was performed in the same manner as in Examples 3 to 7 using Z). Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

Comparative Example 1 Metallocene compound was added to isopropylidene (indenyl)
Polymerization was carried out in the same manner as in Example 3 using (fluorenyl) zirconium dichloride (a). Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

Comparative Examples 2 to 3 Polymerization was carried out in the same manner as in Examples 3 to 4, using bis (n-butylcyclopentadienyl) zirconium dichloride (b) as the metallocene compound. Table 1 shows the polymerization conditions and results.
Table 2 shows the physical property values of the obtained polymer.

Comparative Examples 4 to 5 Bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride (c) was used as the metallocene compound, and polymerization was carried out in the same manner as in Examples 3 to 4.
Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

Comparative Example 6 Polymerization was carried out in the same manner as in Example 4 using bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride (d) as the metallocene compound. Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

Comparative Examples 7 to 8 Ethylidene bis (indenyl) zirconium dichloride (e) was used as the metallocene compound, and polymerization was carried out in the same manner as in Examples 3 to 5. Polymerization conditions and results are shown in Table 1, and physical properties of the obtained polymer are shown in Table 2.

From the above results, the relationship between MT and MFR is summarized in FIG. From the comparison between the above examples and Comparative Examples 1 to 6, it can be seen that the metallocene compound of the present invention can serve as a catalyst for polymerizing polyethylene having a high melt tension. From the comparison with Comparative Example 1, in particular, among the group of bridged metallocene compounds having an indene ring and a fluorene ring, one group having a substituent of the present invention can be a catalyst for specifically polymerizing polyethylene having a high melt tension. I understand. Further, from the comparison with Comparative Examples 7 to 8, the metallocene compound of the present invention is more excellent even when hydrogen is introduced in the polymerization, as compared with the metallocene compound which is conventionally known as a catalyst for polymerizing high melt tension polyethylene. It can be seen that high molecular weight polyethylene can be polymerized.

(Production of Ethylene Copolymer) Example 11 A hexane solution of triisobutylaluminum (0.5 mol / l) was added to an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen. 0.1 ml, 36 mg of the silica-supported methylaluminoxane prepared above, and the dimethylsilylene (2-methyl-4) synthesized in Example 1.
-(1-Naphthyl) indenyl) (9-fluorenyl)
Zirconium dichloride (IMNFZ) 0.69m
g solution in 6 ml of toluene, 1-hexene 90
After introducing g and 800 ml of isobutane, the temperature was raised to 70 ° C. Polymerization was started by introducing ethylene, and the polymerization was carried out at 70 ° C. for 30 minutes at an ethylene pressure of 10 kg / cm 2, to obtain 173 g of a polymer. The activity per complex is
It was 49.4 kg-polymer / g-complex.hr.atm. The physical properties of this polymer were as follows. Mw = 705,000, Mw / Mn = 4.16 Density was 0.88 g / cm ³ or less, and enthalpy peaks due to melting and crystallization were not detected by DSC.
^{From the 13} C-NMR measurement, the hexene content in the polymer chain was 35.2 wt% and r ₁ r ₂ = 0.49.

Example 12 3.2 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was prepared in Example 3 in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen. 105m of methylaluminoxane supported on silica
g of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) synthesized in Example 1.
After introducing a solution of 69 mg dissolved in 6 ml of toluene, 90 g of 1-hexene and 800 ml of isobutane, 70
The temperature was raised to ° C. Mixed gas of ethylene and hydrogen (H ₂ / C ₂
(Wt ratio) = 5.2 × 10 ⁻⁵ ) was introduced to initiate the polymerization, and the mixed gas pressure was 10 kg / cm ² and the temperature was 30 at 70 ° C.
Partial polymerization was carried out to obtain 191 g of a polymer. The activity per complex is 18.2 kg-polymer / g-complex · hr
・ It was atm. The physical properties of this polymer were as follows. HLMFR = 1.85, Mw = 251,000, Mw /
Mn = 4.20 Density was 0.88 g / cm ³ or less, and enthalpy peaks due to melting and crystallization were not detected by DSC.
^{From the 13} C-NMR measurement, the hexene content in the polymer chain was 35.7 wt% and r ₁ r ₂ = 0.51.

Example 13 Polymerization was carried out in the same manner as in Example 12 except that the mixed gas ratio was changed. Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

Examples 14 to 15 Polymerization was carried out in the same manner as in Example 13 except that the amount of 1-hexene was changed. Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

Examples 16 to 17 Using IMPFZ as the metallocene compound,
Polymerization was performed in the same manner as 15. The polymerization conditions and results are shown in Table 3,
The physical properties of the obtained polymer are summarized in Table 4.

Comparative Example 9 Metallocene compound as isopropylidene (indenyl)
Polymerization was performed in the same manner as in Example 11 using (fluorenyl) zirconium dichloride (a). Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

Comparative Examples 10 to 11 Polymerization was carried out in the same manner as in Examples 11 to 12 using bis (n-butylcyclopentadienyl) zirconium dichloride (b) as the metallocene compound. Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

Comparative Examples 12 to 13 Examples 11 to 1 were prepared by using ethylidene bis (indenyl) zirconium dichloride (e) as a metallocene compound.
Polymerization was carried out in the same manner as in 2. Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

Comparative Example 14 Polymerization was carried out in the same manner as in Example 11 except that dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride (f) was used as the metallocene compound. Polymerization conditions and results are shown in Table 3, and physical properties of the obtained polymer are shown in Table 4.

From the above examples, it is understood that in the polymerization of ethylene copolymer, the metallocene compound of the present invention can attain high molecular weight while maintaining the uniformity of comonomer distribution. Furthermore, it can be seen that the catalyst system of the present invention has a higher comonomer conversion rate (ratio of the comonomer to be charged into the polymer chain due to the polymerization reaction) than the conventional metallocene catalyst.

(Production of Polypropylene Elastomer) Example 18 Triisobutylaluminum (TIB) was placed in an autoclave made of SUS having an internal volume of 1.5 liters, which was sufficiently replaced with nitrogen.
A) A toluene solution (0.5 M, 11.7 ml) was added, and subsequently 8 mol of liquid propylene was charged and kept at 30 ° C. On the other hand, 2.5 m of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) synthesized in Example 1
g (0.0039 mmol) in a toluene solution, TIB
Add a toluene solution of A (0.5 M, 3.9 ml) and add 3
The reaction was carried out at 0 ° C for 5 minutes (Catalyst A). In addition, [Ph ₃
A toluene solution of C] [B (C ₆ F ₅ ) ₄ ] (TPFPB) (2.9 mM, 2.0 ml) was prepared (catalyst B). Immediately after mixing catalysts A and B, add them to the reactor at 50 ° C.
Polymerization was carried out for 1 hour. After the reaction, the obtained polypropylene was dried under vacuum. As a result, 240 g of a transparent amorphous polypropylene elastic body was obtained. The activity per metallocene is 96 kg-PP / g-Zr · h. The stereoregularity of the obtained polymer was as follows: mm = 17%, mr = 47%,
It was rr = 36% (the ¹³ C-NMR spectrum in the methyl region is shown in FIG. 2). The molecular weight is Mw = 593,000, and the molecular weight distribution is Mw.
In /Mn=2.8 DSC, enthalpy peaks due to melting and crystallization were not detected.

Example 19 The polymerization temperature was changed to 20 ° C., and 1.1 mg of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) synthesized in Example 1 was used. (0.0017 mmol)
Was used to carry out propylene polymerization in the same manner as in Example 18. As a result, 54 g of a transparent amorphous polypropylene elastic body was obtained. The activity per metallocene is 32 kg-P
P / g-Zr · h. mm = 17%, mr = 45%, rr = 38% Mw = 853,000, Mw / Mn = 2.8

Example 20 The metallocene compound was added to the dimethylsilylene (2-methyl-4-phenylindenyl) (9-fluorenyl) zirconium dichloride (IMPFZ) synthesized in Example 2.
Propylene polymerization was carried out in the same manner as in Example 18 using 1.2 mg (0.0020 mmol). As a result, 125 g of a transparent amorphous polypropylene elastic body was obtained.
The activity per metallocene is 61 kg-PP / g-Zr · h
Is. mm = 16%, mr = 46%, rr = 38% Mw = 493,000, Mw / Mn = 2.5

Example 21 The polymerization temperature was changed to 20 ° C., and dimethylsilylene (2-methyl-4-phenylindenyl) (9 synthesized in Example 2 was used.
-Fluorenyl) zirconium dichloride (IMPF
Z) using 0.8 mg (0.0014 mmol),
Propylene was polymerized in the same manner as in Example 18. As a result, 38 g of a transparent amorphous polypropylene elastic material was obtained. The activity per metallocene is 28 kg-PP / g-Z
r · h. mm = 16%, mr = 44%, rr = 40% Mw = 793,000, Mw / Mn = 2.5 All the polymers obtained in Examples 17 to 19 have enthalpies of melting and crystallization. No peak was detected.

Comparative Example 15 0.77 mg of isopropylidene (1-indenyl) (9-fluorenyl) zirconium dichloride (a)
Using (0.0016 mmol), propylene was polymerized in the same manner as in Example 18. As a result, 17 g of oily atactic polypropylene was obtained. The activity per metallocene compound is 22 kg-PP / g-Zr · h
Is. mm = 27%, mr = 33%, rr = 40% Mw = 5,200, Mw / Mn = 2.8

Comparative Example 16 Isopropylidene (3-t-butyl-1-indenyl)
(9-Fluorenyl) zirconium dichloride (g)
Propylene polymerization was carried out in the same manner as in Example 18 using 0.92 mg (0.0017 mmol). As a result, 1
9 g of powdered isotactic polypropylene were obtained. The activity per metallocene compound is 21 kg-PP
/ G-Zr · h. mm = 78%, mr = 12%, rr = 10% Mw = 214,000, Mw / Mn = 2.6

From the above examples, it is understood that among the group of bridged metallocene compounds having an indene ring and a fluorene ring, one group having a substituent of the present invention can be a catalyst for specifically polymerizing a polypropylene elastic body.

Example 22 1.8 g (2.8 mmo) of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (9-fluorenyl) zirconium dichloride (IMNFZ) was previously prepared.
l) and rac-dimethylsilylene bis (2-methyl-4-)
10 mg (0.014 mmol) of (1-naphthyl) indenyl) zirconium dichloride (h) was dissolved in 100 m of toluene (distilled and dried from Na—K alloy). Using 0.10 ml of this toluene solution (0.0028 mmol per metallocene compound), a polymerization temperature of 60
Propylene polymerization was carried out at the same temperature as in Example 18. As a result, 72 g of a transparent polypropylene elastic body was obtained. The activity per metallocene compound is 40 kg-PP / g
-Zr · h. mm = 25%, mr = 42%, rr = 33% ( ¹³ C-NMR spectrum of methyl region is shown in FIG. 3) Mw = 428,000, Mw / Mn = 5.2 From DSC, melting point at 146.4 ° C. Was observed.

Example 23 In Example 22, 0.13 ml of a toluene solution of a metallocene compound (0.0035 m per metallocene compound) was used.
propylene) was similarly carried out at a polymerization temperature of 70 ° C. As a result, 78 g of a transparent polypropylene elastic body was obtained. The activity per metallocene compound is 35
It is kg-PP / g-Zr · h. mm = 28%, mr = 41%, rr = 31% Mw = 320,000, Mw / Mn = 8.9 From DSC, a melting point was observed at 146.2 ° C. The above results are summarized in Tables 5 and 6.

The polypropylenes obtained in Examples 18 to 23 were tested for elasticity. The results are summarized in Table 7. The stress-strain curves of polypropylene obtained in Examples 18 and 22 are shown in FIGS. 4 and 5, respectively.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

[Table 7]

[0073]

When an olefin is polymerized by using the metallocene compound of the present invention as an essential catalyst component, the following plural effects are exhibited depending on the olefin used for the polymerization.
That is, in the case of producing an ethylene polymer, it is possible to polymerize a polymer having a high melt tension up to a high molecular weight.
In the case of producing an ethylene-based copolymer, a polymer having excellent uniformity of comonomer distribution can be polymerized up to a high molecular weight range. Further, the incorporation rate of the comonomer into the polymer chain is high, and the cost is also excellent. In the case of polymerization of α-olefin, especially propylene, amorphous polypropylene having elastic performance can be polymerized with high activity. In addition, when used in combination with another metallocene compound, the elastic performance can be controlled under industrially effective polymerization conditions.

[Brief description of drawings]

FIG. 1 MT and MFR of an ethylene polymer according to the present invention
connection of.

2 is a ¹³ C-NMR spectrum in the methyl region of PP polymerized under the conditions of Example 18. FIG.

FIG. 3 ¹³ C-NMR spectrum of the methyl region of PP polymerized under the conditions of Example 22.

4 is a stress-strain curve of PP polymerized under the conditions of Example 18. FIG.

5 is a stress-strain curve of PP polymerized under the conditions of Example 22. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Hori No. 2 Nakasu, Oita City, Oita Prefecture Showa Denko Oita Laboratory (72) Inventor Kiyotaka Ishida No. 2 Nakasu, Oita City, Oita Prefecture Showa Denko Oita Laboratory Co., Ltd. (72) Inventor Shigenobu Miyake, Oita City, Oita Prefecture, No. 2 in Naka, Showa Denko Co., Ltd. Oita Laboratory, Inc. Oita Institute

Claims (9)

[Claims] 1. A metallocene compound represented by the general formula (1): [In the formula (1), M ¹ represents a transition metal atom of Ti, Zr, or Hf. X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ¹ ,
R ^{2 s} may be the same as or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a group having 1 to 7 carbon atoms). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ³ means a hydrocarbon group having 1 to 5 carbon atoms and may contain a silicon atom. R ⁴ has 1 carbon atom
To 20 hydrocarbon groups, which may include silicon atoms.
R ^{5 to} R ¹⁵ may be the same as or different from each other, are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may contain a silicon atom, and may bond to each other to form a ring. Y ¹ means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] The catalyst component for polyolefin production which consists of these. 2. A metallocene compound represented by the general formula (1), wherein R ³ is a methyl group or an ethyl group, and R ⁴ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group or A catalyst component for polyolefin production, comprising a metallocene compound which is an aryl group having 6 to 20 carbon atoms. 3. A metallocene compound represented by the general formula (1), wherein R ³ is a methyl group or an ethyl group, R ⁴ is a phenyl group or a 1-naphthyl group, and R
^A catalyst component for polyolefin production, comprising a metallocene compound in which ⁵ to R ¹⁵ are hydrogen atoms and n = 1. 4. A catalyst for polyolefin production comprising (A) the catalyst component according to any one of claims 1 to 3 (B) a Lewis acid compound (C) an organoaluminum compound 5. A catalyst for producing a polyolefin comprising (A) the catalyst component according to any one of claims 1 to 3 (B) a Lewis acid compound (C) an organoaluminum compound (D) a fine particle carrier. 6. A homopolymerization of ethylene, or an olefin represented by the general formula (2), R ¹⁶ —CH═CH—R, wherein the catalyst according to claim 4 or 5 is used. ¹⁷ (2) “In the formula (2), R ¹⁶ and R ^{17, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, which form a ring with each other. However, excluding ethylene. "A method for producing a polyolefin by copolymerizing one or more kinds of 7. A method for producing a polyolefin which (co) polymerizes one or more olefins represented by the general formula (2), characterized in that the catalyst according to claim 4 or 5 is used. . 8. (A-1) The catalyst component according to any one of claims 1 to 3. (A-2) General formula (3) [In the formula (3), M ² means a transition metal atom of Ti, Zr, or Hf. X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ¹⁸ ,
R ^{19 s} may be the same or different from each other, and each is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a group having 1 to 7 carbon atoms). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ²⁴ means a hydrocarbon group having 1 to 20 carbon atoms and may contain a silicon atom. R ^{20 to} R ²³ , R ²⁵ ,
R ^{26 s} may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain silicon. R ²³ and R ²⁵ and R ²⁴ and R ²⁶ may form a ring with each other via a hydrocarbon group. Y ² is
It means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] Or, in the general formula (4): [In the formula (4), M ³ represents a transition metal atom of Ti, Zr, or Hf. X ⁵ and X ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, or an OR group, an SR group, an OCOR group, SO ₂ R
Group, OSO ₂ R group, NRR ′ group (wherein R and R ′ are
Hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, which may include a halogen atom). R ²⁷ ,
R ^{28 s} may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (wherein R is a hydrogen atom or a C 1 to 7 carbon atom). Means a hydrocarbon group, which may include a halogen atom), and may combine with each other to form a ring. R ²⁹ means a hydrocarbon group having 1 to 20 carbon atoms and may contain a silicon atom. R ³⁰ and R ³¹ may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may contain silicon. R ²⁹ and R ³¹ may form a ring with each other via a hydrocarbon group. Y ³ means a carbon atom, a silicon atom or a germanium atom. In the formula, n is an integer of 1 to 3. ] A metallocene compound represented by the following formula (B) Lewis acid compound (C) Organoaluminum compound Production method. 9. A method of (co) polymerizing one or more olefins represented by the general formula (2), wherein (A-1) the catalyst component according to any one of claims 1 to 3 -2) Metallocene compound represented by the general formula (3) or (4) (B) Lewis acid compound (C) Organoaluminum compound (D) Fine particle carrier represented by the general formula (2) A method for producing a polyolefin by (co) polymerizing one or more olefins.