JP3487677B2 - Crystalline polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin resin composition, and more particularly, to a composition comprising a crystalline polyolefin resin and an ethylene copolymer rubber, which has excellent rigidity and heat resistance and impact resistance, especially at low temperatures. The present invention relates to a crystalline polyolefin resin composition capable of providing a molded article having excellent impact resistance in the above.

[0002]

BACKGROUND OF THE INVENTION Molded articles made of polyolefin resins such as polyethylene and polypropylene have been used for a wide range of applications because of their excellent rigidity and heat resistance.

[0003] However, among polyolefin resins, polypropylene has crystallinity and a high glass transition temperature, so that a polypropylene molded article is inferior in impact resistance, especially in low temperature, and its use is limited. .

[0004] Therefore, in order to improve the impact resistance of a molded polypropylene article, polyethylene has been conventionally compounded with polypropylene or a rubber-like substance such as polyisobutylene, polybutadiene or an amorphous ethylene-propylene copolymer has been used. A method of improving the impact resistance of a polypropylene molded article by blending is adopted. Among these compounding agents, an amorphous or low-crystalline ethylene / propylene random copolymer is often used.

However, in such a composition comprising an amorphous or low crystalline ethylene / propylene random copolymer and polypropylene, the amorphous or low crystalline ethylene / propylene random copolymer is
Since the effect of improving the impact resistance is small, it is necessary to include a large amount of an ethylene / propylene random copolymer in the polypropylene composition in order to improve the impact resistance of the polypropylene molded article.

Therefore, when a large amount of the ethylene / propylene random copolymer is used, the impact resistance of the molded article made of the polypropylene composition is improved, but the rigidity and heat resistance inherent to the polypropylene are greatly increased. The problem of lowering occurs. On the other hand, when the amount of the ethylene-propylene random copolymer in the polypropylene composition is reduced to maintain the rigidity, heat resistance, and the like inherent to polypropylene, the impact resistance at low temperatures is not sufficiently improved. Occurs.

The inventors of the present application have conducted intensive studies to obtain a polypropylene resin composition which can provide a molded polypropylene article having excellent rigidity and heat resistance and excellent impact resistance, particularly excellent impact resistance at low temperatures. Crystalline polypropylene resin and specific ethylene / α-olefin /
By using a polypropylene resin composition comprising a non-conjugated polyene copolymer rubber, it is found that a molded article having excellent rigidity, heat resistance and impact resistance, particularly excellent in impact resistance at low temperatures, can be obtained. It was completed.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to provide a polyolefin molding which is excellent in rigidity, heat resistance and impact resistance, especially at low temperatures. It is an object of the present invention to provide a crystalline polyolefin resin composition, particularly a crystalline polypropylene resin composition, from which a product can be obtained.

[0009]

SUMMARY OF THE INVENTION The crystalline polyolefin resin composition according to the present invention comprises a crystalline polyolefin resin (A) 95-60.
Parts by weight and 5 to 40 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprising ethylene, an α-olefin having 4 to 10 carbon atoms and a non-conjugated polyene [(A) and (B) ) Is 100 parts by weight].
-Olefin and non-conjugated polyene copolymer rubber (B)
In the presence of a metallocene catalyst, ethylene and carbon atoms
It is obtained by random copolymerization of an α-olefin of 4 to 10 and a non-conjugated polyene, and (1) a unit derived from (a) ethylene and (b) an α-olefin having 4 to 10 carbon atoms. (2) the iodine value is from 1 to 50, and (3) it is measured in 135 ° C decalin. Intrinsic viscosity [η]
Is 0.1 to 10 dl / g.

The metallocene catalyst used for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) may contain a metallocene compound represented by the following formula [III] or [IV]. preferable.

[0011]

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[Wherein, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a carbon atom having 1 to 2 carbon atoms which may be substituted with halogen.
0 hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having a carbon number of 1 to 20, X ¹ And X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a carbon atom A divalent hydrocarbon group of the formulas 1 to 20,
A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, -O
-, - CO -, - S -, - SO -, - SO 2 -, - NR
^{7 -, - P (R 7} ) -, - P (O) (R 7) -, - BR
⁷ - or -AlR ⁷ - it is. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)]

[0013]

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[Wherein, M is a transition metal of Group IVB of the periodic table, R ²¹ may be the same or different, and may be a hydrogen atom, a halogen atom, a carbon atom which may be halogenated. An alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms
Aryl group, or -NR ₂ of 10, -SR, -OSi
R ₃ , —SiR ₃ or —PR ₂ (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are as defined above. It is the same as R ²¹ , or adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, and X ³ and X ⁴ may be the same or different from each other. Hydrogen atom, halogen atom, O
H group, alkyl group having 1 to 10 carbon atoms, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, carbon atom An alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,

[0015]

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-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . (However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. 10 to 10 aryl groups,
C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C8-C40 aryl An alkenyl group or an alkylaryl group having 7 to 40 carbon atoms, or R
²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )] The above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has, in addition to the properties (1) to (3), further (4) a T with respect to Tαα in the ¹³ C-NMR spectrum.
αβ intensity ratio D (Tαβ / Tαα) is 0.5 or less; (5) B value obtained from ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the content mole fraction of the unit derived from (a) ethylene in the random copolymer rubber. ,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
(6) The glass transition temperature (Tg) determined by DSC is -5.
The temperature is preferably 0 ° C. or lower.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The crystalline polyolefin resin composition according to the present invention will be specifically described. The crystalline polyolefin resin composition according to the present invention contains a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).

Crystalline polyolefin resin (A) Crystalline polyolefin resin (A) used in the present invention
Consists of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high-pressure method or the low-pressure method. Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

The suitable starting olefin for the crystalline polyolefin resin (A) is, for example, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 2-methyl-1-
Examples thereof include propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 3-methyl-1-hexene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornene. These olefins are
They are used alone or as a mixture of two or more.

In the present invention, propylene or a mixed olefin comprising propylene and another olefin is preferably used. That is, as the crystalline polyolefin resin (A) used in the present invention, polypropylene is preferable.

Examples of the polypropylene include a propylene homopolymer and a propylene / α-olefin copolymer containing a structural unit derived from an α-olefin other than propylene in an amount of 10 mol% or less. Examples of the α-olefin constituting the propylene / α-olefin copolymer include the above-mentioned α-olefin.

Regarding the polymerization mode for obtaining the above-mentioned crystalline polyolefin resin, any type of polymerization mode may be employed as long as a resinous material can be obtained, whether it is a random type or a block type.
Crystalline polyolefin resin (A) used in the present invention
Is 230 ° C., 2.1 according to ASTM-D1288.
Melt flow rate (MFR) measured under 6 kg load
But usually 0.01 to 200 g / 10 min, preferably 0.1 to 200 g / 10 min.
05 to 100 g / 10 min, more preferably 0.1 to 1
It is preferably in the range of 00 g / 10 minutes.

These crystalline polyolefin resins may be used alone or in combination of two or more. In the present invention, the crystalline polyolefin resin (A) is used in an amount of 95 to 95 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). It is used in a proportion of 60 parts by weight, preferably 85 to 65 parts by weight.

Ethylene / α - olefin / non-
Role Polyene Copolymer Rubber (B) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention is prepared by reacting ethylene with carbon in the presence of a specific metallocene catalyst as described later. Number of atoms
It can be obtained by random copolymerizing 4 to 10 α-olefins and a non-conjugated polyene.

Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 3-
Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, and combinations thereof.

Of these, 1-butene, 1-hexene, 1-octene, 1-decene and the like are particularly preferably used.
Further, as the non-conjugated polyene, aliphatic polyene,
Alicyclic polyenes and the like can be mentioned.

As the aliphatic polyene, specifically, 1,
4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1, Five,
9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4
-Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl
-1,5-hexadiene, 5-methyl-1,4-heptadiene, 5-
Ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 3-methyl-1,6-heptadiene, 4- Methyl-1,6
-Heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-
Ethyl-1,6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5- Methyl-1,5
-Octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene,
6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-
Octadiene, 6-butyl-1,6-octadiene, 4-methyl
-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl -1,5-nonadiene, 5-
Ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene,
6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-
Decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5
-Decadiene, 6-ethyl-1,5-decadiene, 6-methyl-
1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl- 1,7-decadiene, 7-
Ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene,
8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, etc. Aliphatic polyene, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, dicyclopentadiene,
Cyclooctadiene, 2,5-norbornadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,
3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,
Examples include 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and the like.

Specific examples of the aromatic polyene include divinylbenzene and vinylisopropenylbenzene. In the present invention, among these, non-conjugated polyenes having 7 or more carbon atoms are preferable. Ethylidene norbornene (ENB), dicyclopentadiene (DCPD) and the like are preferably used.

These non-conjugated polyenes can be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention has the following properties. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention comprises (a) a unit derived from ethylene, and (b) 4 carbon atoms. A unit derived from an α-olefin of from 10 to 10 (hereinafter sometimes simply referred to as α-olefin) from 40/60 to 95/5, preferably 4
0/60 to 90/10, particularly preferably 50/50 to 8
It is contained at a molar ratio of 5/15 [(a) / (b)].

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio has excellent low-temperature flexibility, impact resistance at low temperatures, and heat resistance. I have. In addition, ethylene
When the ethylene / α-olefin component ratio exceeds 95/5, the olefin / non-conjugated polyene copolymer rubber exhibits resin properties and lowers low-temperature flexibility.
If it is less than 40/60, the heat resistance tends to decrease. (2) Iodine Value The iodine value, which is an index of the amount of the non-conjugated polyene component of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), is 1 to 50, preferably 5 to 40. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured at 135 ° C in decalin is 0.1 to 10 dl / g, preferably 0.5 ~
It is 7 dl / g, more preferably 0.9 to 5 dl / g.

Further, the ethylene / α used in the present invention
-Olefin and non-conjugated polyene copolymer rubber (B)
It is preferable that the following characteristics (4) to (6) are satisfied. (4) D value Intensity (area) ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) D (Tαβ / Tαα)
Is desirably 0.5 or less, particularly preferably 0.3 or less.

The strength ratio D of the random copolymer rubber differs depending on the type of α-olefin constituting the random copolymer rubber. Here, Tαβ and Tαα in the ¹³ C-NMR spectrum are the peak intensities of CH _{2 in} the unit derived from α-olefin, respectively, and two types of CH ₂ having different positions with respect to the tertiary carbon as shown below. Means

[0033]

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The strength ratio D of the random copolymer rubber can be determined as follows. The ¹³ C-NMR spectrum of the random copolymer rubber was measured using, for example, a JEOL-GX270 NMR measuring apparatus manufactured by JEOL Ltd. to obtain a hexachlorobutadiene / d having a sample concentration of 5% by weight.
A mixed solution of ₆ -benzene = 2/1 (volume ratio) was added to 67.8.
It is measured on the basis of d ₆ -benzene (128 ppm) at 25 ° C. and MHz.

The analysis of the ¹³ C-NMR spectrum is basically based on the proposal of Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

Here, the above-mentioned strength ratio D will be described more specifically by taking ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer rubber as an example. This ethylene 1-
Butene-7-methyl-1,6-octadiene copolymer rubber ¹³
In the C-NMR spectrum, the peak appearing at 39 to 40 ppm is assigned to Tαα, and the peak appearing at 31 to 32 ppm is assigned to Tαβ.

The intensity ratio D is calculated from the integrated value (area) ratio of each peak portion. The intensity ratio D thus determined is generally the ratio of the occurrence of the 1,1 addition reaction of 1-butene followed by the 2,1 addition reaction, or the ratio of 1-butene of 2,1 addition.
It is considered to be a scale indicating the rate at which 1,2 addition reactions occur after addition reactions. Therefore, it is shown that the larger the value of the strength ratio D, the more irregular the bonding direction of α-olefin (1-butene). Conversely, the smaller the D value, the more α
-It indicates that the bonding direction of the olefin is regular. If the regularity is high, the molecular chains are easy to assemble, and the random copolymer rubber is preferable because it tends to have excellent strength and the like.

In the present invention, as described later, ethylene, α-olefin and non-conjugated polyene are copolymerized using a specific Group IVB metallocene catalyst.
A random copolymer rubber having the above strength ratio D of 0.5 or less is obtained. For example, ethylene, 1-butene and 7-methyl-1,6 are used in the presence of a VB group metallocene catalyst such as vanadium. -Even if copolymerized with octadiene, the above-mentioned intensity ratio D is 0.5 or less, ethylene / 1-butene / 7-methyl-
No 1,6-octadiene copolymer rubber can be obtained. The same applies to α-olefins other than 1-butene. (5) B value In the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the B value determined from the ¹³ C-NMR spectrum and the following formula is desirably 1.00 to 1.50. .

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the unit derived from (a) ethylene in the random copolymer rubber) Content mole fraction,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
It is the ratio of the number of α-olefin / ethylene chains to the number of chains. The B value is an index indicating the distribution of ethylene and α-olefin in the copolymer rubber.
l (Macromolecules, 15, 353 (1982)), J. Ray (Macromolecules
olecules, 10,773 (1977)).

The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. I have. Note that the composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber is, for example, vulcanized as compared with a copolymer rubber having a narrow composition distribution. Physical properties such as strength may not be sufficiently exhibited.

In the present invention, as will be described later,
By copolymerizing ethylene, an α-olefin and a non-conjugated polyene using a Group IVB metallocene catalyst, a random copolymer rubber having the above B value of 1.00 to 1.50 has been obtained. Even if ethylene, α-olefin and non-conjugated polyene are copolymerized in the presence of a titanium-based non-metallocene catalyst, an ethylene / α-olefin / non-conjugated polyene copolymer rubber having a B value in the above range can be obtained. It is not possible. (6) Glass transition temperature The glass transition temperature (Tg) of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured by DSC (differential scanning calorimeter) may be -50 ° C or less. desirable.

From a random copolymer rubber having a glass transition temperature (Tg) of -50 ° C. or lower, a crystalline polyolefin resin composition having excellent low-temperature flexibility can be obtained.
The ethylene / α-olefin used in the present invention
Non-conjugated polyene copolymer rubbers, for example, a random copolymer rubber of ethylene, 1-butene and ethylidene norbornene (ENB), have the same composition ratio of this random copolymer rubber, ethylene, α-olefin, and non-conjugated polyene. Has a glass transition temperature (Tg) of about 5 as compared with a copolymer rubber of ethylene, propylene and ENB (EPDM).
It has a low temperature of 10 ° C. and excellent low-temperature properties, for example, excellent impact resistance at low temperatures.

The ethylene / α-olefin /
The gη ^* value determined from the intrinsic viscosity [η] of the non-conjugated polyene copolymer rubber (B) desirably exceeds 0.95.

This gη ^* value is defined by the following equation. gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in the above (3), and [η] _blank is the ethylene • α- (Intrinsic viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by the light scattering method) as the olefin / non-conjugated polyene copolymer rubber and having an ethylene content of 70 mol%.) Ethylene-α-olefin
From a non-conjugated polyene copolymer rubber, a crystalline polyolefin resin composition having excellent mechanical strength, weather resistance and ozone resistance, and also excellent in both cold resistance (low-temperature flexibility) and heat resistance, and a molded article thereof are provided. Obtainable.

The above specific ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is prepared by adding ethylene and carbon atoms in the presence of a specific metallocene catalyst.
It is produced by randomly copolymerizing 4 to 10 α-olefins and a non-conjugated polyene.

The metallocene catalyst used in the present invention is:
It is not particularly limited except that it contains the metallocene compound [A]. For example, a compound that forms an ion pair by reacting with the metallocene compound [A] and the organoaluminum oxy compound [B] and / or the metallocene compound [A] [ C]. Further, it may be formed from a metallocene compound [A], an organic aluminum compound [D] together with an organic aluminum oxy compound [B] and / or a compound [C] forming an ion pair.

Hereinafter, each component used in forming the metallocene catalyst in the present invention will be described. Metallocene compound [A] The metallocene compound [A] used in the present invention includes:
Examples include compounds represented by the following general formula [I].

MLx ... [I] In the formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and x is an atom of the transition metal. Value.

L is a ligand which coordinates to the transition metal,
At least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having a cyclopentadienyl skeleton may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl Group, fluore And a nyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

When the compound represented by the formula [I] has two or more groups having a cyclopentadienyl skeleton as the ligand L, two of the groups having the cyclopentadienyl skeleton are It may be bonded via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene and methylphenylsilylene.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms,
An alkoxy group, an aryloxy group, a halogen atom, a hydrogen atom or a sulfonic acid-containing group (—SO ₃ R ^a )
^Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group. And the like.

The hydrocarbon group having 1 to 12 carbon atoms includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. More specifically, methyl, ethyl, n-propyl, isopropyl, n Alkyl groups such as -butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl and tolyl, and aralkyl such as benzyl and neophyl Groups.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,
Examples include an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group.

Examples of the aryloxy group include a phenoxy group. Examples of the sulfonic acid-containing group (—SO ₃ R ^a ) include a methanesulfonato group, a p-toluenesulfonate group,
Examples include a trifluoromethanesulfonato group and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the valence of the transition metal is 4, for example, the metallocene compound represented by the above formula is more specifically represented by the following formula [II].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M [II] In the formula [II], M is the above-mentioned transition metal, and R ² is a group having a cyclopentadienyl skeleton (coordination) Child) and R ³ ,
R ⁴ and R ⁵ are independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula [I]. k is an integer of 1 or more, and k + 1 + m + n = 4.

In the following, M is zirconium, and
A metallocene compound containing at least two ligands having a cyclopentadienyl skeleton is exemplified. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentane Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, Bis (sec-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride, bis (indenyl) Zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium Dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentane Dienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (butylcyclopentadi Enil)
Zirconium bis (trifluoromethanesulfonato),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadi) (Enyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (Trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-
Methyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-octylcyclopentadienyl) zirconium dichloride, bis (1-ethyl
-3-butylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methyl Examples thereof include benzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, and bis (methylcyclohexylcyclopentadienyl) zirconium dichloride.

A compound in which the above-mentioned 1,3-position-substituted cyclopentadienyl group is substituted by a 1,2-position-substituted cyclopentadienyl group can also be used in the present invention. In the above formula [II], at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups having a cyclopentadienyl skeleton (ligand).
Each group can also be exemplified by a bridge-type metallocene compound bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. At this time, R ⁴ and R ⁵ are each independently the same as L except for the ligand having a cyclopentadienyl skeleton described in the formula [I].

Examples of such bridge type metallocene compounds include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), and ethylene bis (indenyl) zirconium. Bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (p-chlorobenzenesulfonato), ethylenebis (4,5,6,7-tetrahydro Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium Dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis ( Cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, Methylphenylsilylenebis (indenyl) zirconium dichloride and the like can be mentioned.

Further, Japanese Patent Application Laid-Open No.
Metallocene compounds described in JP-A-268307. The metallocene has the formula [A]:

[0063]

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[In the formula [A], M ¹ is a metal belonging to Group IVB of the periodic table, and specific examples thereof include titanium, zirconium and hafnium. R ¹ and R ² may be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms; 7 to 40 carbon atoms, preferably 7-1
0 arylalkyl group, 7 to 40 carbon atoms, preferably 7 to 12 alkylaryl group, 8 to 4 carbon atoms
It is 0, preferably 8 to 12 arylalkenyl groups, or halogen atoms, preferably chlorine atoms.

R ³ and R ⁴ may be the same or different and are each a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, an optionally halogenated carbon atom having 1 to 10 carbon atoms, preferably 1 to 4 alkyl group, having 6 to 10 carbon atoms, preferably 6-8 aryl _{^{group, -NR 10 2, -SR 10,}} -OSiR 10 3, -Si
R ¹⁰ ₃ or —PR ¹⁰ ₂ groups, wherein R ¹⁰ is a halogen atom, preferably a chlorine atom, or a group having 1 to 1 carbon atoms.
It is an alkyl group having 0, preferably 1 to 3 or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ^6, which may be the same or different from each other, preferably the same, R ⁵ and R
⁶ represents R ³ and R ³ provided that they are not hydrogen atoms.
^It has the meaning described for ⁴ . R ⁵ and R ⁶ are
Preferably 1 to 1 carbon atoms which may be halogenated
And an alkyl group of 4, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a trifluoromethyl group, and a methyl group is preferable.

R ⁷ is as follows:

[0068]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO _Two, = NR¹¹, =
CO, = PR¹¹ Or = P (O) R¹¹At that time
R¹¹, R ¹²And R¹³Are the same but different
And a hydrogen atom, a halogen atom, and a carbon atom having 1 to 1
0, preferably 1-4 alkyl groups, more preferably
A methyl group, a fluoroalkyl group having 1 to 10 carbon atoms,
Preferably CF_Three Group, having 6 to 10 carbon atoms, preferably
An aryl group having 6 to 8 carbon atoms, a fluorocarbon having 6 to 10 carbon atoms
Reel group, preferably pentafluorophenyl group, carbon
An alkoxy group having 1 to 10 atoms, preferably 1 to 4 atoms,
Preferably a methoxy group, having 2 to 10 carbon atoms, preferably
Or 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferably
Or 7 to 10 arylalkyl groups, 8 to 8 carbon atoms
40, preferably 8 to 12 arylalkenyl groups, or
Or an alkyl having 7 to 40, preferably 7 to 12 carbon atoms
A aryl group or R¹¹And R¹²Or R¹¹When
R¹³Together with the atoms to which they are attached
To form a ring.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different and have the same meaning as described for R ¹¹ . m and n may be the same or different from each other and are 0, 1 or 2, preferably 0 or 1
And m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocene compounds satisfying the above conditions are shown in the following (i) to (iii).

[0073]

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[In the above formulas (i), (ii) and (iii),
M ¹ is Zr or Hf, R ¹ and R ² are a methyl group or a chlorine atom, R ⁵ and R ⁶ are a methyl group,
An ethyl group or a trifluoromethyl group, R ⁸ , R
^9, R ¹⁰ and R ¹² have the meaning given above. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium-
Dichloride, rac-dimethylsilylene (2-methyl-1
-Indenyl) ₂ -zirconium-dimethyl, rac-ethylene- (2-methyl-1-indenyl) ₂ -zirconium-
Dimethyl, rac-phenyl (methyl) silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-methylethylene- ( 2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene- (2-ethyl-1-indenyl) ₂ -zirconium-dichloride.

The method for producing such a metallocene compound can be produced by a conventionally known method (for example, see JP-A-4-268307). In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] can also be used.

[0077]

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In the formula [B], M represents a transition metal atom belonging to Group IVB of the periodic table, and is specifically titanium, zirconium or hafnium. R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, A containing group, a nitrogen-containing group or a phosphorus-containing group, and specifically, halogen atoms such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, Norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl,
Phenylethyl, an arylalkyl group such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, an aryl group such as phenanthryl; A hydrocarbon group; a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group; a monohydrocarbon-substituted silyl group such as methylsilyl and phenylsilyl, a dihydrocarbon-substituted silyl group such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethyl Trihydrocarbon-substituted silyls such as silyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl , Hydrocarbon-substituted silyl ether groups of the silyl, silicon-substituted alkyl groups, such as trimethylsilylmethyl, silicon-containing substituents such as silicon-substituted aryl groups, such as trimethylsilyl phenyl such as trimethylsilyl ether; hydroxycarbonate groups, methoxy, ethoxy,
Oxygen-containing groups such as alkoxy groups such as propoxy and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and arylalkoxy groups such as phenylmethoxy and phenylethoxy;
A sulfur-containing group such as a substituent in which oxygen of the oxygen-containing group is substituted with sulfur; an amino group, an amino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, or dicyclohexylamino;
Phenylamino, diphenylamino, ditolylamino,
A nitrogen-containing group such as an arylamino group or an alkylarylamino group such as dinaphthylamino and methylphenylamino; and a phosphorus-containing group such as a phosphino group such as dimethylphosphino and diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, particularly preferably a methyl, ethyl or propyl hydrocarbon group having 1 to 3 carbon atoms. Also R ²
Is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a C 1-20
And a halogenated hydrocarbon group having 1 to 20 carbon atoms, and among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴
And R ^5, at least one pair of R ⁵ and R ⁶ may form an aromatic ring of a single together with the carbon atoms to which they are attached rings.

In the case where there are two or more hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above for R ¹ and R ² .

A ligand coordinated to M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ with each other. Are as follows.

[0084]

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Of these, those represented by the above formula (1) are preferred. The aromatic ring may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms which are substituted on the aromatic ring include the same groups as those described above for R ¹ and R ^2. Can be illustrated.

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. A group represented by the formula:
The same halogen atom as that of ¹ and R ² , having 1 to 2 carbon atoms
Examples include a hydrocarbon group of 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing group.

Examples of the sulfur-containing group include the same groups as those described above for R ¹ and R ² , and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate and trimethylbenzenesulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 7 -, - P (R 7) -, - P
^{(O) (R 7) -} , - BR 7 - or -AlR ⁷ - [however, R ⁷ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
C 1-20 carbon atoms such as alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene A divalent hydrocarbon group of the above;
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of 0; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl Alkylsilylene groups such as phenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, tetramethyl-1,2-disilylene, tetraphenyl-1, A divalent silicon-containing group such as an alkyldisilylene group such as 2-disilylene, an alkylaryldisilylene group, or an aryldisilylene group; a divalent germanium-containing group in which silicon of the divalent silicon-containing group is replaced with germanium; Divalent tin-containing base in which silicon of the divalent silicon-containing group is replaced with tin Group and the like, R ⁷ is,
The same halogen atom and carbon number 1 to R ¹ and R ²
And a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Among these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable.
Among them, an alkylsilylene group, an alkylarylsilylene group, and an arylsilylene group are particularly preferable.

Specific examples of the transition metal compound represented by the formula [B] are shown below.

[0092]

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[0093]

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[0094]

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In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be of the R or S type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the following reaction route using a conventional organic synthesis technique.

[0097]

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The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used.

[0100]

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In the formula [C], M, R ¹ , R ² , R ³ ,
As R ⁴ , R ⁵ and R ⁶ , those similar to the case of the formula [B] can be mentioned. R ³ , R ⁴ , R ⁵ and R ⁶
Among them, two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group.
^And the substituents exemplified for R ² .

Of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl groups are preferably hydrogen atoms. As a hydrocarbon group having 1 to 20 carbon atoms,
Methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl,
Chain and cyclic alkyl groups such as dodecyl, eicosyl, norbornyl, and adamantyl; benzyl,
Examples include an arylalkyl group such as phenylethyl, phenylpropyl, and tolylmethyl, and may include a double bond or a triple bond.

Further, two groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

As X ¹ , X ² , Y and R ⁷ , those similar to the above formula [B] can be mentioned. Hereinafter, specific examples of the metallocene compound (transition metal compound) represented by the above formula [C] will be shown.

Rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,5,6-trimethyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,5,6,7-pentamethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-n-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-methyl-6-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-5-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4,6-di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6
-Di (i-propyl) -7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-methyl
-4-sec-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-t
ert-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
Cyclohexyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-benzyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-Phenylethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyldichloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-chloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl) zirconium dichloride , Rac-diethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2-
Methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl
-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4,6-di (i-propyl)-
1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di
(p-chlorophenyl) silylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2 -Methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium-
Bis (methanesulfonato), rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i
-Propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i
-Propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4
-i-Propyl-6-methyl-1-indenyl) zirconium dichloride.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a racemic compound, but it is also possible to use an R type or an S type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the same reaction route as described above using a conventional organic synthesis technique. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, among the above-mentioned metallocene compounds, in particular, the following general formula [III] or [I
V] is preferably used. General formula [I
The metallocene compound represented by the formula [II] is a part of the compound represented by the above formula [C], and the metallocene compound represented by the general formula [IV] is a part of the compound represented by the above formula [B] It is.

[0109]

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In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ¹¹ and R ¹² R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, -Containing group or phosphorus-containing group, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, Alkyl groups such as cyclohexyl, octyl, nonyl, dodecyl, iconosyl, norbornyl and adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl,
Phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, And aryl groups such as phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

These hydrocarbon groups include halogen atoms such as fluorine, chlorine, bromine and iodine, trimethylsilyl groups,
It may be substituted with an organic silyl group such as a triethylsilyl group and a triphenylsilyl group.

Specific examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and phenylmethoxy and phenylethoxy. And arylalkoxy groups.

Examples of the sulfur-containing group include substituents in which the oxygen of the oxygen-containing group is replaced with sulfur, methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluene Sulfonate groups such as sulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, and benzylsulfinate , P-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Examples of the nitrogen-containing group include an amino group, methylamino, dimethylamino, diethylamino,
Examples thereof include an alkylamino group such as dipropylamino, dibutylamino, and dicyclohexylamino; an arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; or an alkylarylamino group.

Specific examples of the phosphorus-containing group include a dimethylphosphino group and a diphenylphosphino group. R ¹¹ is preferably a hydrocarbon group among them, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹² is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹³ and R ¹⁴ R ¹³ and R ^{14 each} have 1 carbon atom as exemplified above.
-20 alkyl groups.

R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond. X ¹ and X ² X ¹ and X ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group as exemplified above. Group or a sulfur-containing group, a halogen atom,
It is preferably 20 hydrocarbon groups.

[0119] Y Y is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 15 -, -
^{P (R 15) -, -} P (O) (R 15) -, - BR 15 - or -AlR ¹⁵ - [however, R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups], and specifically,
Methylene, dimethylmethylene, 1,2-ethylene, dimethyl
Alkylene groups such as -1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2-
1 carbon atom such as an arylalkylene group such as ethylene
To 20 divalent hydrocarbon groups; halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon groups having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n -Propyl) silylene,
Di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene,
Alkyl silylene groups such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, and alkyl such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl A divalent silicon-containing group such as a disilyl group, an alkylaryldisilyl group, and an aryldisilyl group; and a divalent germanium-containing group in which silicon of the above-described divalent silicon-containing group is substituted with germanium.

R ¹⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among these, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene. Particularly preferred is a group.

Specific examples of the metallocene compound represented by the above general formula [III] are shown below. rac-Dimethylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2, 7-dimethyl-4-sec
-Butyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2,7-dimethyl-4-t-butyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n -Hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,7-dimethyl-4-phenyldichloromethyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsilylmethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-
Diethylsilylene-bis (2,7-dimethyl-4-i-propyl
-1-indenyl) zirconium dichloride, rac-di (i-
Propyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,7-dimethyl-4-i-propyl-1 -Indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,7-dimethyl-4-i
-Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac
-Diphenylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-i-propyl-1)
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2,7-dimethyl-4- i-propyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2,7-dimethyl-4-i-propyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-ethyl-1
-Indenyl) zirconium dibromide rac-dimethylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n -Propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-i-propyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-butyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-sec-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4- t-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,3,7-trimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-n-hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,3,7-trimethyl-4-methylcyclohexyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsilylmethyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenylethyl-1- Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4 -Chloromethyl-1-indenyl)
Zirconium dichloride, rac-diethylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene
-Bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,3,7-trimethyl-4-i-propyl- 1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3, 7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-
Methylphenylsilylene-bis (2,3,7-trimethyl-4-t
-Butyl-1-indenyl) zirconium dichloride, ra
c-diphenylsilylene-bis (2,3,7-trimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac-
Diphenylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-
Diphenylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2,3,7-trimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, ra
c-Di (p-chlorophenyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4
-i-Propyl-7-methyl-1-indenyl) zirconium
-Bis (methanesulfonato), rac-dimethylsilylene-
Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4
-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-i-propyl-7-methyl-1-indenyl) titanium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i
-Propyl-7-methyl-1-indenyl) hafnium dichloride.

Among these, an i-propyl group at the 4-position, sec-
Compounds having a branched alkyl group such as a butyl group and a tert-butyl group are particularly preferred. In the present invention, usually, a racemic form of the transition metal compound is used as a catalyst component for olefin polymerization, but R-type or S-type can also be used.

The transition metal compound as described above can be prepared from an indene derivative by a known method, for example, as described in JP-A-4-268307.
Can be synthesized by the method described in Japanese Patent Application Laid-open No. The compound represented by the following formula [IV] preferably used in the present invention is described in EP-549900 and Canada-20
No. 84017.

[0124]

Embedded image

In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, and an optionally halogenated carbon atom number of 1 to 1.
0, preferably 1-4 alkyl groups, 6-1 carbon atoms
0, preferably 6-8 aryl group, -NR _2, -S
R, —OSiR ₃ , —SiR ₃ or —PR ₂ groups (where R is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms or 6 to 10 carbon atoms; Preferably 6 to 8 aryl groups).

[0126] R ²² to R ²⁸ may be the same or different, have the same atom or group as R ^21, these R ²² to R
^At least two adjacent groups out of ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded.

X ³ and X ⁴ may be the same or different, and each represents a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 1 to 10 carbon atoms. Preferably 1 to 3 alkoxy groups, 6 to 10 carbon atoms, preferably 6 to 8 aryl groups, 6 to 10 carbon atoms, preferably 6 to 8 aryloxy groups, 2 to 10 carbon atoms, Preferably, it has 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferably 7 to 10 arylalkyl groups, and 7 to 40 carbon atoms, preferably 7 to
It is a 12 alkylaryl group, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms.

[0128]

Embedded image

-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methyl group and 1 carbon atom. 10 to 10 fluoroalkyl group, preferably CF ₃ group, 6 to 10 carbon atom, preferably 6 to 8 aryl group, 6 to 10 carbon atom fluoroaryl group, preferably pentafluorophenyl group, 1-10, preferably 1-4 alkoxy groups, particularly preferably methoxy group, 2-1 carbon atom
0, preferably 2 to 4 alkenyl groups, 7 to 7 carbon atoms
It is an arylalkyl group having 40, preferably 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may form a ring together with the atoms to which they are bonded. M ² is silicon, germanium or tin.

The above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine, chlorine, bromine or iodine atom, particularly preferably a fluorine or chlorine atom. is there.

Among the compounds represented by the formula [IV], M is zirconium or hafnium,
R ²¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, and R ^{22 to} R ²⁸ may be the same or different from each other and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ³ and X ⁴ may be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom;

[0133]

Embedded image

(M ² is silicon, R ²⁹ and R
³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. ) Is preferably a compound which is, substituents R ²² and R ²⁸ are hydrogen atoms, R ²³ to R ²⁷ is more preferably a compound is an alkyl group or a hydrogen atom from 1 to 4 carbon atoms.

Further, M is zirconium, and R
²¹ is the same alkyl group having 1 to 4 carbon atoms from each other, R ²² and R ²⁸ are hydrogen atoms, R ²³ to R
²⁷ may be the same or different, and has 1 to 4 carbon atoms.
X ³ and X ^3
4 is a chlorine atom,

[0136]

Embedded image

(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different, and have 1 carbon atom
Or an alkyl group having 4 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Is preferred, and in particular, M is zirconium, R ²¹ is a methyl group, and R ^{22 to} R ^22
28 is a hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0138]

Embedded image

(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different and each is a methyl group or a phenyl group). Several examples of such a metallocene compound represented by the formula [IV] are shown below.

Rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,5-
Acenaphthocyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis -(2-methyl-4,5-benzoindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl
-4,5-acenaphthocyclopentadienyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1-
(4,5-benzoindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,6-dimethyl)
-4,5-benzoindenyl)｝ zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, the compound represented by the formula [III] or [I
A racemic metallocene compound represented by the formula [V] is preferably used as a catalyst component, but R-type or S-type may also be used.

The above metallocene compounds may be used in combination of two or more. Organoaluminum oxy compound [B] The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble compound as exemplified in JP-A-2-78687. May be the organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution. (2) A method in which water, ice or steam is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover a hydrocarbon solution. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

As the organoaluminum compound used in the production of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec Trialkylaluminum such as -butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride; Diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; dialkylaluminum aryloxy such as diethylaluminum phenoxide And the like.

Among these, aluminum trialkyl and aluminum tricycloalkyl are particularly preferred.
As the organoaluminum compound used for preparing the aluminoxane formulas _{(i-C 4 H 9)} x Al y (C
₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧
2x. ) Can also be used.

The above-mentioned organoaluminum compounds can be used in combination of two or more. Solvents used in the production of aluminoxane include, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and fats such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane Petroleum fractions such as cyclic hydrocarbons, gasoline, kerosene, and gas oil; and hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, especially chlorinated compounds and bromide compounds. Can be

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred. Reacts with metallocene compound [A] to form an ion pair
Compound [C] The compound [C] which forms an ion pair by reacting with the metallocene compound [A] used in the present invention is described in
JP-A-501950, JP-T1-5020236,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in US Pat. No. 207704 and US Pat.

As the Lewis acid, a Mg-containing Lewis acid, A
Examples thereof include l-containing Lewis acids and B-containing Lewis acids, and among them, B-containing Lewis acids are preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ¹ R ² R ³ (wherein R ¹ R ² and R ³ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group, a trifluoromethyl group, etc. Or a fluorine atom.) As the compound represented by the above general formula, specifically,
Trifluoroboron, triphenylboron, tris (4-
Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl)
Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron,
Tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound used in the present invention is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A], thereby stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and an anion that is relatively bulky and stabilizes a transition metal cation species is preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.
Specifically, triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation and the like can be exemplified.

In the present invention, an ionic compound having an organic boron compound anion is preferred. In particular,
Triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o,
p-dimethylphenyl) boron, tributylammoniumtetra (m, m-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (o-tolyl) boron, tri ( n-butyl) ammonium tetra (4-
Trialkyl-substituted ammonium salts such as fluorophenyl) boron, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6-pentamethyl N, N-dialkylanilinium salts such as anilinium tetra (phenyl) boron; dialkylammonium salts such as di (n-propyl) ammonium tetra (pentafluorophenyl) boron; dicyclohexylammonium tetra (phenyl) boron; triphenylphospho And triarylphosphonium salts such as ammonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

In the present invention, as the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentane) Fluorophenyl) borate can also be mentioned.

Further, the following ionic compounds containing a boron atom can also be exemplified. (Note that the counter ion in the ionic compounds listed below is, but is not limited to, tri (n-butyl) ammonium.) Salts of anions, for example, bis [tri (n-butyl) ammonium] nonaborate, bis (tri-n-butyl) ammonium [Tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc. Include the following borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Examples of the borane compound, the carborane complex compound and the salt of the carborane anion include decaborane (14), 7,8-dicarboundecaborane (13),
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium
7-carboundecaborate (13), tri (n-butyl)
Ammonium 7,8-dicarboundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride 8-ethyl-7,9-dicarboundecaborate, tri (n-
Butyl) ammonium undecahydride-8-butyl
-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-Dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-9-trimethylsilyl-7 , 8-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-4,6-dibromo-7-carboundecaborate, and the like.

Examples of the carborane compound and the salt of carborane include 4-carbanonaborane (14), 1,3-
Dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-
Dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane and the like.

Further, the following compounds can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl) ammonium,
It is not limited to this. Metal salt of carborane and metal borane anion such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II)
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Decahydride-7,8-dicarboundecaborate) cubate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal Bounce decarborate) nickelate (IV) and the like.

The above compound [C] can be used in combination of two or more kinds. Organoaluminum compound [D] The organoaluminum compound [D] used in the present invention is:
For example, it can be represented by the following general formula (a).

R ⁵ _n AlX _3-n (a) (wherein, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to
3. In the above formula (a), R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, etc. Ethyl aluminum Alkylaluminum sesquihalide such as Kiburomido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

As the organoaluminum compound [D], a compound represented by the following formula (b) can also be used. During ^{_{R 5 n AlY 3-n ···}} (b) ( wherein, R ⁵ is the same as R ⁵ in the formula (a), Y is -OR ⁶ group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂
Group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ group or -N (R ¹¹⁾
A AlR ¹² ₂ group, n is 1~2, R ^6, R ^7,
R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc. And R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. Specific examples of such an organoaluminum compound include the following compounds.

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , for example, dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.

[0163] _{^{(ii) R 5 n Al (}} OSiR 7 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C 2 H 5) 3)
Such.

[0164] _{^{(iii) R 5 n Al (}} OAlR 8 2) 3-n compound represented by, for example, _{(C 2 H 5) 2 Al} (OAl (C 2
_{H 5) 2), (iso} -C 4 H 9) 2 Al (OAl (iso-C
₄ H _{9) 2),} etc..

[0165] _{^{(iv) R 5 n Al (}} NR 9 2) a compound represented by _3-n, e.g., _{(CH 3) 2 Al (N} (C 2 H 5) 2),
(C ₂ H ₅ ) ₂ Al (NH (CH ₃ )), (CH ₃ ) ₂ Al
_{(NH (C 2 H 5)} ), (C 2 H 5) 2 Al [N (Si (CH
₃ ) ₃ ) ₂ ], (iso-C ₄ H ₉ ) ₂ Al [N (Si (C
Such as H _{3) 3) 2].}

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (C
H _{3) 3),} such as. In the present invention, also R ⁵ ₃ Al Among these, R ⁵ _n Al (O
R ⁶⁾ _3-n, can be mentioned organoaluminum compounds represented by _{^{R 5 n Al (OAlR 8 2}} ) 3-n Suitable examples, R ⁵ is an isoalkyl group, compounds which are n = 2 is Particularly preferred. These organoaluminum compounds can be used in combination of two or more.

The specific metallocene catalyst used in the present invention contains the above metallocene compound [A]. For example, as described above, the metallocene compound [A]
And an organic aluminum oxy compound [B]. It may be formed from a metallocene compound [A] and a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] may be used. And a compound [C] that reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organoaluminum compound [D].

In the present invention, the metallocene compound [A]
Is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms per liter of polymerization volume.

Also, the organic aluminum oxy compound [B]
Is usually about 1 to 10,000 moles, preferably 10 to 10 moles of aluminum atoms per mole of transition metal atom.
It can be used in an amount of 5,000 mol.

The compound [C] which forms an ion pair by reacting with the metallocene compound [A] has a boron atom of usually about 0.5 to 20 mol, preferably 1 to 1 mol, per mol of the transition metal atom. It is used in an amount to give 10 moles.

Further, the organoaluminum compound [D] is
It is usually about 0-1,000 mol, preferably about 0-500 mol, per 1 mol of boron atom in the compound [C] forming an aluminum atom or an ion pair in the organic aluminum oxy compound [B]. Such amounts are used as needed.

When ethylene, an α-olefin having 4 to 10 carbon atoms, and a non-conjugated polyene are copolymerized using the metallocene catalyst as described above, ethylene / α-olefin / A non-conjugated polyene copolymer rubber (B) can be obtained.

Even if ethylene, an α-olefin having 4 to 10 carbon atoms, and a non-conjugated polyene are copolymerized using a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, sufficient polymerization can be performed. Activity makes it impossible to obtain a copolymer rubber.

When an ethylene / 1-butene / non-conjugated polyene copolymer rubber or the like is produced using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene is not limited to norbornene ring such as ENB. It is often limited to contained polyenes.

On the other hand, when a metallocene-based catalyst is used as in the present invention, the non-conjugated polyene is not limited to the norbornene ring-containing polyenes, but various polyenes as described above, for example, 7-methyl-1,6- -Chain non-conjugated polyenes such as methyl octadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and C 4
When copolymerizing an α-olefin of 10 to 10 with a non-conjugated polyene, the metallocene compound [A], the organoaluminumoxy compound [B], and the compound [C] forming an ion pair, which constitute a metallocene catalyst, Furthermore, the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the copolymerization reaction.

In preparing a metallocene catalyst,
A hydrocarbon solvent which is inactive with the catalyst component can be used. Specific examples of the inert hydrocarbon solvent include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrocarbon, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, aromatic hydrocarbons such as xylene, ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane can be used. These hydrocarbon solvents can be used alone or in combination.

The metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair and the organoaluminum compound [D] are usually
Mixing contact can be performed at 100 to 200 ° C, preferably at -70 to 100 ° C.

In the present invention, ethylene and C 4
Copolymerization of α-olefin of 10 to 10 with a non-conjugated polyene is usually 40 to 200 ° C, preferably 50 to 150 ° C,
Particularly preferably, at 60 to 120 ° C. and at atmospheric pressure to 100 kg /
cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

The copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. At this time, as the polymerization solvent, the above-mentioned hydrocarbon solvent can be used.

The copolymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system, but is preferably carried out by a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The ethylene / α- used in the present invention
The olefin / non-conjugated polyene copolymer rubber (B) is obtained by the method described above, and the molecular weight of the copolymer rubber (B) is adjusted by changing polymerization conditions such as a polymerization temperature. It can also be controlled by controlling the amount of hydrogen (molecular weight regulator) used.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) Total amount of 100
5 to 40 parts by weight, preferably 15 to 3 parts by weight based on parts by weight
Used in a proportion of 5 parts by weight.

Crystalline Polyolefin Resin Composition The crystalline polyolefin resin composition according to the present invention contains a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). .

The crystalline polyolefin resin composition according to the present invention comprises, in addition to the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), an amorphous propylene / ethylene random Copolymer (C) is used in combination with components (A) and (B) in a total amount of 10
5 to 15 parts by weight, preferably 5-1 to 0 parts by weight
0 parts by weight may be contained.

This amorphous propylene / ethylene random copolymer (C) contains a constituent unit derived from ethylene in an amount of 30 to 60 mol%, preferably 35 to 45 mol%.

The crystalline polyolefin resin composition according to the present invention may contain an inorganic filler in an amount of 5 to 20% by weight, if necessary. As such an inorganic filler, specifically, calcium carbonate, calcium silicate, clay, carion, talc, silica, diatomaceous earth,
Mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker And the like.

Further, the crystalline polyolefin resin composition according to the present invention may be a heat-resistant stabilizer, such as an aluminum salt of an aromatic carboxylate, an aromatic phosphate ester salt or dibenzylidene sorbitol, within a range not to impair the object of the present invention. Nucleating agent; ultraviolet absorber; lubricant; antistatic agent; flame retardant; pigment;
Dye; may contain other polymers.

The crystalline polyolefin resin composition according to the present invention was kneaded by supplying the above-mentioned components simultaneously or sequentially to a kneading apparatus such as a Henschel mixer, a V-type blender, a tumbler blender, and a ribbon blender. Thereafter, it can be obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.

Among these melt kneaders, when a device having excellent kneading properties such as a multi-screw extruder, a kneader, and a Banbury mixer is used, a high-quality crystalline polyolefin resin composition in which each component is uniformly dispersed is used. Obtainable.

[0191]

The crystalline polyolefin resin composition according to the present invention comprises: [I] a crystalline polyolefin resin (A), [II] ethylene prepared using a metallocene-based catalyst, ethylene, having 4 to 4 carbon atoms . A random copolymer comprising an α-olefin of 10 and a non-conjugated polyene, and a molar ratio of a unit derived from ethylene to a unit derived from an α-olefin having 4 to 10 carbon atoms, an iodine value and It contains a specific ratio of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having intrinsic viscosity [η] in a specific range, so that it has excellent rigidity, heat resistance and impact resistance, especially A polyolefin molded article having excellent low-temperature impact resistance can be provided.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. In addition, the evaluation test method of the composition in an Example and a comparative example is as follows. (1) MFR MFR was measured according to ASTM D1238.

Conditions: 230 ° C., 2.16 kg (2) Flexural modulus (FM) A flexural test was performed in accordance with ASTM D790, and the flexural modulus (FM) was measured.

Specimen width: 12.7 mm, thickness: 6.
4 mm, length: 127 mm, span: 100 mm, bending speed: 2 mm / min (3) Izod impact strength (IZ) An impact test was performed in accordance with ASTM D256 to measure Izod impact strength (IZ).

Temperature -30 ° C. Specimen Width: 12.7 mm, thickness: 6.4 mm, length:
64mm ・ Notch is machined

[0196]

[Reference Example 1]Preliminary contact between zirconium compounds and methylalumoxane
Preparation of catalyst solution

[0197]

Embedded image

A predetermined amount of a zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) are stirred in a dark place at room temperature for 30 minutes. To prepare a toluene solution in which the zirconium compound and methylalumoxane were dissolved. The Zr concentration of this toluene solution was 0.004 mmol / ml, and the methylalumoxane concentration was 1.
2 milligram atoms / ml.

Next, to this toluene solution, hexane, a 5-fold solution of toluene, was added with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, and this was polymerized. Used as a reaction catalyst.

Zr concentration: 0.00067 mmol / ml
(= 0.67 mmol / l) Methylalumoxane concentration (converted to Al atom): 0.1.
20 mmol / ml (= 200 mmol / l) using a stainless steel polymerization vessel 15 liters of capacity, equipped with Polymerization stirring blade, and continuously ethylene, 1-butene, 5-ethylidene-2-norbornene (hereinafter (Also referred to as ENB) in the presence of the above-mentioned polymerization reaction catalyst.

That is, first, 3.185 liters / hour of dehydrated and purified hexane was poured into the polymerization vessel from the top of the polymerization vessel.
0.67 l / h of the above catalyst solution, 0.3 l / h of a hexane solution of triisobutylaluminum (concentration: 17 mmol / l), 1.5 l / h of a hexane solution of ENB (concentration: 0.02 l / l) Each was fed continuously.

Further, 200 liters / hour of ethylene and 155 liters / hour of 1-butene were continuously supplied from the upper part of the polymerization vessel into the polymerization vessel. This copolymerization reaction is 8
The reaction was performed at 0 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

Next, a small amount of methanol was added to the polymerization solution withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction.
After separating the copolymer from the solvent by steam stripping, under conditions of 100 ° C. and reduced pressure (100 mmHg)
Dry for 24 hours.

As described above, ethylene / 1-butene
ENB copolymer rubber [Copolymer rubber (B-1)] was obtained in an amount of 250 g per hour. The resulting copolymer rubber has a molar ratio of units derived from ethylene to units derived from 1-butene (ethylene / 1-butene) of 79/21,
The iodine value based on ENB was 10.

[0205] Further, this copolymer rubber has an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 2.7 dl / g, T for Tαα in ¹³ C-NMR spectrum
αβ intensity ratio D is less than 0.01, B value is 1.1, glass transition temperature (Tg) is −56 ° C., gη
^{* The} value was 0.98.

The results are shown in Table 1.

[0207]

REFERENCE EXAMPLES 2 AND 3 An ethylene / α-olefin / non-conjugated polyene copolymer rubber [copolymer] was prepared in the same manner as in Reference Example 1, except that the copolymerization reaction was carried out under different polymerization conditions. Rubbers (B-2) and (B-3)] were produced.

In these copolymer rubbers, the molar ratio of units derived from ethylene to units derived from α-olefin, iodine value, intrinsic viscosity [η], D value, B value, Tg, and gη ^* value Are shown in Table 1.

[0209]

[Table 1]

[0210]

Example 1 75 parts by weight of a crystalline propylene homopolymer (A-1) having an MFR of 25 g / 10 min and a melting point (Tm) measured by DSC of 162 ° C. Using 25 parts by weight of 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-1), an injection molding machine (resin temperature 200 ° C, mold temperature 40 ° C) was used to prepare a crystalline polypropylene resin composition. ASTM test pieces for measuring flexural modulus and Izod impact strength were prepared and subjected to the bending test and the impact test.

Table 2 shows the results.

[0212]

Example 2 In Example 1, the ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-2) obtained in Reference Example 2 was used instead of (B-1). A polypropylene resin composition was prepared and the physical properties were measured in the same manner as in Example 1 except for the difference.

Table 2 shows the results.

[0214]

Example 3 In Example 1, the ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer rubber (B-3) obtained in Reference Example 3 was used in place of (B-1). A polypropylene resin composition was prepared and the physical properties were measured in the same manner as in Example 1 except for the difference.

Table 2 shows the results.

[0216]

Comparative Example 1 In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
Instead of having an ethylene content of 80 mol% and an iodine value of 1
2, ethylene / propylene / 5-ethylidene having an intrinsic viscosity [η] of 2.7 dl / g measured in decalin at 135 ° C.
A polypropylene resin composition was prepared and its physical properties were measured in the same manner as in Example 1 except that 2-norbornene copolymer rubber (EPDM-1) was used.

Table 2 shows the results. Note that the above E
PDM-1 was prepared using a vanadium-based catalyst.

[0218]

[Table 2]

[0219]

Example 4 In Example 1, the compounding amounts of the crystalline propylene homopolymer (A-1) and the ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-1) were each adjusted to 60. Parts by weight, and 20 parts by weight of talc having an average particle size of 2.5 μm,
In the same manner as in Example 1, a polypropylene resin composition was prepared, and its physical properties were measured.

Table 3 shows the results.

[0221]

Comparative Example 2 In Example 4, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
In place of EPDM-1 used in Comparative Example 1, a polypropylene resin composition was prepared in the same manner as in Example 4, and the physical properties were measured.

The results are shown in Table 3.

[0223]

[Table 3]

[0224]

Example 5 In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
Is an amorphous propylene / ethylene random copolymer (C-1) having an ethylene content of 41 mol% and an intrinsic viscosity [η] of 3.0 dl / g measured in decalin at 135 ° C. Was added in the same manner as in Example 1 except that 10 parts by weight of [11.1 parts by weight based on 100 parts by weight of the total amount of the components (A-1) and (B-1)] were blended. It was prepared and its physical properties were measured.

Table 4 shows the results.

[0226]

Comparative Example 3 In Example 5, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
In place of EPDM-1 used in Comparative Example 1, a polypropylene resin composition was prepared in the same manner as in Example 5, and the physical properties were measured.

Table 4 shows the results.

[0228]

[Table 4]

[0229]

Example 6 The same procedure as in Example 1 was carried out except that the crystalline propylene homopolymer (A-1) had an MFR of 15 g / 10 min.
A polypropylene resin composition was prepared in the same manner as in Example 1 except that the high crystalline propylene homopolymer (A-2) having a melting point (Tm) of 167 ° C. measured by DSC was used.
Its physical properties were measured.

Table 5 shows the results.

[0231]

Example 7 In Example 6, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
Of the ethylene homopolymer (A-
3) [MFR (ASTM D1238): 13 g / 10
Min, density (ASTM D 1505): 0.965 g / c
m ³ ] was blended in the same manner as in Example 6 except that 5 parts by weight of the polypropylene resin composition was prepared, and the physical properties thereof were measured.

The results are shown in Table 5.

[0233]

Example 8 The procedure of Example 1 was repeated, except that the crystalline propylene homopolymer (A-1) was replaced by an MFR of 22 g / 10
The content of constituent units derived from ethylene is 8% by weight, the amount of n-decane-soluble component at normal temperature is 11% by weight,
Except for using a propylene / ethylene block copolymer (A-4) having an intrinsic viscosity [η] of 2.9 dl / g measured in decalin at 135 ° C. in a decane-soluble portion, in the same manner as in Example 1, A polypropylene resin composition was prepared and its physical properties were measured.

The results are shown in Table 5.

[0235]

[Table 5]

Continued on the front page. (72) Inventor Toshiyuki Tsutsui 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industries Co., Ltd. (72) Inventor Toshihiro Aine Wakamachi, Kuga-gun, Yamaguchi Prefecture 6-1-2 Ki, Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-4-218547 (JP, A) JP-A-2-281915 (JP, A) (58) Fields investigated (Int. Cl ^7, DB name) C08L 23/00 -. 23/36 C08F 4/64 - 4/69 C08F 210/00 - 210/18

Claims (6)

(57) [Claims] 1. A crystalline polyolefin resin (A) 95-6.
0 parts by weight and 5 to 40 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprising ethylene, an α-olefin having 4 to 10 carbon atoms and a non-conjugated polyene [(A) and ( The total amount of B) is 100 parts by weight]
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises: ethylene, an α-olefin having 4 to 10 carbon atoms,
(1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 4 to 10 carbon atoms, obtained by random copolymerization with a non-conjugated polyene; 95/5 [(a) / (b)], (2) iodine value is 1 to 50, (3) intrinsic viscosity [η] measured in 135 ° C decalin
Is from 0.1 to 10 dl / g. 2. The crystalline polyolefin resin composition according to claim 1, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is obtained in the presence of a metallocene catalyst. . 3. The metallocene catalyst according to the following formula [III]
Or a crystalline polyolefin resin composition according to claim 1 or 2, comprising a metallocene compound represented by [IV]; [Wherein, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² are A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group; Divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - a. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [In the formula, M is a transition metal of Group IVB of the periodic table, R ²¹ may be the same or different, and may be a hydrogen atom, a halogen atom, or an optionally halogenated carbon atom having 1 to 1 carbon atoms. 10 alkyl group, aryl group, or -NR ₂ carbon atoms 6 to 10, -SR, -OSiR _3, -SiR
₃ or —PR ₂ group (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are the same as defined above for R ²¹ . And R ^{22 to} R ^{28 which} are present or adjacent to each other may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, X ³ and X ⁴ may be the same or different from each other; Hydrogen atom, halogen atom, OH group, 1-carbon atom
10 alkyl groups, 1-10 carbon atom alkoxy groups, 6-10 carbon atom aryl groups, 6-6 carbon atoms
An aryloxy group having 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, and 8 carbon atoms
~ 40 arylalkenyl groups; -Sn -, - O -, - S -, = SO, = SO 2, = NR
^29, = CO, a = PR ²⁹ or = P (O) R ^29.
(However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, and
10 alkyl groups, C1-10 fluoroalkyl groups, C6-10 aryl groups, C6-10 fluoroaryl groups, C1-10 alkoxy groups, carbon atoms An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms
-40 arylalkenyl groups or 7-4 carbon atoms
0 may be an alkylaryl group, or R ²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )]. 4. The method of claim 1, wherein said that the crystalline polyolefin resin (A) is a polypropylene resin
The crystalline polyolefin resin composition according to any one of the above. Wherein said ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B) is, T for Tαα in (4) ¹³ C-NMR spectrum
αβ intensity ratio D (Tαβ / Tαα) is 0.5 or less; (5) B value obtained from ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the content mole fraction of the unit derived from (a) ethylene in the random copolymer rubber. , [P _O ] is the mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is the total dyad chain in the random copolymer rubber. (6) The glass transition temperature (Tg) determined by DSC is -5.
The crystalline polyolefin resin composition according to claim 1, wherein the temperature is 0 ° C. or lower. To wherein said other crystalline polyolefin resin (A) and the ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B), amorphous propylene-ethylene random copolymer component (C) ( The crystalline polyolefin resin composition according to any one of claims 1 to 5, wherein the crystalline polyolefin resin composition is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the total amount of A) and (B).