JPH1087713A - Method for producing propylene polymer composition - Google Patents

Abstract

(57) Abstract: A method for producing a composition comprising a metallocene-catalyzed elastomer and a Ziegler-Natta catalyzed propylene polymer in a particulate form without mechanical mixing. The present invention comprises, after a step (A) for producing a propylene polymer with a nonmetallocene catalyst (a), a step (B) for producing an elastomer with a catalyst comprising at least a metallocene compound (b) and a cocatalyst component (c). In the production method, the metallocene compound (b) and the co-catalyst component (c)
The method for producing a propylene polymer composition, wherein the step (A) is performed in the presence of any one of the above, and then the other is added to perform the step (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a propylene polymer composition. More specifically, the present invention relates to a method for producing a propylene polymer composition comprising a propylene polymer using a Ziegler-Natta catalyst and an elastomer using a metallocene catalyst.

[0002]

2. Description of the Related Art Compositions comprising a propylene polymer and an ethylene-α-olefin copolymer elastomer are widely used for automobile exteriors, interiors, home appliances and the like. Such a composition is generally produced by a multi-stage polymerization in which propylene is polymerized by a so-called Ziegler-Natta catalyst, and then ethylene and an α-olefin are continuously copolymerized.
However, in this method, it is difficult at present to satisfy the demand for a composition having better performance because the elastomers that can be produced are limited.

On the other hand, a copolymer elastomer of ethylene and α-olefin obtained by a metallocene catalyst in recent years is:
It has attracted attention because it exhibits properties not found in conventional elastomers. Propylene polymer compositions containing such elastomers have also been proposed, and are reported to have better performance than compositions obtained by conventional multistage polymerization using a Ziegler-Natta catalyst.

For example, JP-A-6-192500 and JP-A-8-192500
No. 12826, JP-A-8-12827, etc., it is reported that a composition comprising a metallocene-catalyzed elastomer and a propylene polymer obtained by a Ziegler-Natta catalyst is superior to conventional compositions in impact resistance. ing.

Further, Japanese Patent Application Laid-Open No. Hei 7-102126 discloses flexibility,
A propylene polymer composition having excellent transparency is disclosed. Furthermore, JP-A-7-81551 reports that a composition comprising a metallocene-catalyzed elastomer and a propylene block copolymer obtained with a Ziegler-Natta catalyst has excellent rigidity and impact resistance.

In each of these methods, a composition is produced by separately producing an elastomer and a propylene polymer using a metallocene catalyst and then mechanically mixing them. However, in this method, mechanical mixing is costly, and since the elastomer used is generally in a bale (thin cloth) form, it is not easy to continuously produce it by an extruder or the like.

As a method for more easily obtaining a composition comprising an elastomer and a propylene polymer using a metallocene catalyst, a method has been proposed in which propylene is polymerized using a metallocene catalyst, followed by multistage polymerization in which an elastomer is produced (for example, Japanese Patent Application Laid-Open No. H11-157572). JP-A-5-202152, JP-A-6-202152
172414, JP-A-6-206921, JP-A-6-287257
JP-A-8-27237, etc.).

In this method, it is possible to produce an elastomer composition in the form of particles using a metallocene catalyst without mechanical mixing. However, the performance, especially rigidity and heat resistance, of a propylene polymer obtained by using a metallocene catalyst are low. The performance of the composition is also reduced because it is significantly inferior to that of the Ziegler-Natta catalyst.

[0009]

An object of the present invention is to provide a method for efficiently producing a composition comprising a metallocene-catalyzed elastomer and a Ziegler-Natta-catalyzed propylene polymer in a particulate form without mechanical mixing. Is to provide.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above situation, and as a result, by adding the metallocene compound (b) and the co-catalyst component (c) in different steps of the multistage polymerization, the metallocene compound was added. The present inventors have found that a composition comprising a catalyst-based elastomer and a Ziegler-Natta catalyst-based propylene polymer can be produced in the form of particles without mechanical mixing, and have completed the present invention.

That is, in the present invention, after the step (A) of producing a propylene polymer using a nonmetallocene catalyst (a), a step of producing an elastomer with a catalyst comprising at least a metallocene compound (b) and a cocatalyst component (c). In the production method having (B), after performing the step (A) in the presence of one of the metallocene compound (b) and the cocatalyst component (c), the other is added to perform the step (B). This is a method for producing a propylene polymer composition.

Hereinafter, the present invention will be described in detail. The present invention is characterized in that the step (A) is performed in the presence of one of the metallocene compound (b) and the co-catalyst component (c), and then the other is added to produce the elastomer in the step (B). There is. If both the metallocene compound (b) and the co-catalyst component (c) are added in the step (A) or the step (B), it becomes difficult to produce the propylene polymer composition in the form of particles.

Next, the step (A) of the present invention will be described. In the step (A) of the present invention, a propylene polymer is produced by using the nonmetallocene catalyst (a). As the non-metallocene catalyst (a) used herein, there is a so-called Ziegler-Natta catalyst. More specifically, a solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components
1), an organoaluminum compound (a2) and an electron donor catalyst component (a3).

Such a solid titanium catalyst component (a1) is prepared by bringing a magnesium compound, a titanium compound and an electron donor as described below into contact with each other. For example, JP-A-50-108385, JP-A-50-108385 No. -20297, JP-A-55-152710, JP-A-58-138715, JP-A-62
It can be prepared according to the methods disclosed in JP-A-104810, JP-A-63-54405 and the like.

In the present invention, the solid titanium catalyst component (a
Examples of the titanium compound used in the preparation of 1) include a tetravalent titanium compound represented by Ti (OR) _n X _4-n (R is a hydrocarbon group, X is a halogen atom, and 0 <n <4). be able to. Specifically, TiCl ₄ , TiBr
_4, titanium tetrahalides of TiI ₄ such, Ti (OC
_{H 3) Cl 3, Ti (} OC 2 H 5) Cl 3, Ti (n-
OC ₄ H ₉ ) Cl ₃ , Ti (i-OC ₄ H ₉ ) Cl ₃ ,
Ti (OCH ₃ ) Br ₃ , Ti (OC ₂ H ₅ ) Br ₃ ,
_{Ti (n-OC 4 H 9} ) trihalide alkoxy titanium Br _{3 etc., Ti (OCH 3) 2 Cl} 2, Ti (OC
_{2 H 5) 2 Cl 2,} Ti (n-OC 4 H 9) 2 Cl 2,
Ti (OCH ₃ ) ₂ Br ₂ , Ti (OC ₂ H ₅ ) ₂ Br
_{2, Ti (n-OC 4} H 9) such as ₂ Br ₂ dihalogenated dialkoxy _{titanium, Ti (OCH 3) 3 Cl} , Ti
_{(OC 2 H 5) 3 Cl} , Ti (n-OC 4 H 9) 3 C
1, Ti (OCH ₃ ) ₃ Br, Ti (OC ₂ H ₅ ) ₃ B
_{r, Ti (n-OC 4} H 9) 3 monohalogenated trialkoxy titanium and _{Br, Ti (OCH 3) 4,} Ti (O
_{C 2 H 5) 4, Ti} (-O-n-C 4 H 9) 4, Ti
Tetraalkoxy titanium such as (-OiC ₄ H ₉ ) _{4 and the} like can be mentioned. Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferred. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, the solid titanium catalyst component (a
Examples of the type of magnesium compound used in the preparation of 1) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.
Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond.
Specific examples of such compounds include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dibutyl magnesium, dipentyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, pentyl magnesium chloride, hexyl magnesium chloride, ethyl magnesium ethoxide, butyl magnesium ethoxide, ethyl butyl magnesium, etc. Can be. These compounds can be used alone or in combination of two or more, and may form a complex compound with an organic aluminum compound described later.

The non-reducing magnesium compounds include:
Examples thereof include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide, and alkoxy salts such as ethoxy magnesium, isopropoxy magnesium and butoxy magnesium, and magnesium salts such as magnesium stearate and magnesium laurate.

The electron donor used for preparing the solid titanium catalyst component (a1) includes organic carboxylic acid esters,
Polycarboxylic acid esters are exemplified. Examples thereof include aliphatic polyhydric acids such as malonic acid, methyl malonic acid, succinic acid, methyl succinic acid, glutaric acid, itaconic acid, maleic acid, citraconic acid, 1,2-cyclohexanecarboxylic acid, tetrahydrophthalic acid, and nadic acid. Examples include alkyl and aryl esters of polyvalent carboxylic acids, and alkyl and aryl esters of aromatic polycarboxylic acids such as phthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and furandicarboxylic acid.

Specific examples thereof include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, diethyl malonate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl allylmalonate,
Diethyl diethylmalonate, diethyl diisobutylmalonate, diethyl di-n-butylmalonate, diisobutyl maleate, diisooctyl maleate, diethyl butyl maleate, diisobutyl butyl maleate, diisopropyl butyl-methylglutarate, dimethyl phthalate, phthalic acid Diethyl, methyl ethyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-2-ethylhexyl phthalate, di-n-phthalate
Examples include heptyl, didecyl phthalate, n-butyl benzyl phthalate, diphenyl phthalate, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, dibutyl trimellitate, and the like.

Of these, phthalic acid, maleic acid,
An ester composed of substituted malonic acid and an alkyl group having 2 or more carbon atoms is preferred, and an ester composed of phthalic acid and an alkyl group having 2 or more carbon atoms is particularly preferred.

Examples of the electron donor other than the polyvalent carboxylic acid that can be used in preparing the solid catalyst component (a1) include alcohols, amines, amides, ethers, carboxylic acids, and acid anhydrides described below. , Acid halides,
Examples include esters, ketones, aldehydes, nitriles, phosphines, stibines, arsines, organosilane compounds such as alkoxysilanes, and metal amides and salts of Groups I to IV in the periodic table.

The organoaluminum compound (a2) used as the nonmetallocene catalyst component has at least one A
It is a compound having an l-carbon bond. Specifically, triethylaluminum, trialkylaluminums such as triisobutylaluminum, diethylaluminum chloride, dibutylaluminum chloride, dialkylaluminum halide such as diethylaluminum bromide,
Aluminum sesquihalides such as ethyl aluminum sesquichloride, dibutyl aluminum sesquichloride,
Partially halogenated alkyl aluminum such as ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum bromide, etc. Partially alkylated alkylaluminums such as partially hydrogenated alkylaluminum, diethylaluminum ethoxide, dibutylaluminum ethoxide, etc., LiAl (C ₂ H ₅ ) ₄ , LiAl
Complex compounds with Group I metals such as (C ₇ H ₁₅ ) ₄ . Of these, trialkylaluminum is particularly preferred.

As the electron donor catalyst component (a3), alcohols, phenols, carboxylic acids, acid anhydrides, acid halides, esters, amides, aldehydes, ketones, ethers, amines , Nitriles, organosilicon compounds and the like. Among these, esters such as methyl formate, ethyl acetate, methyl benzoate, ethyl benzoate and the above-mentioned polycarboxylic acid esters, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, methyl-t-butyldimethoxysilane, diisopropyldimethoxy Organosilicon compounds such as silane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane and phenyltrimethoxysilane are particularly preferred.

The non-metallocene catalyst usable in the present invention can be obtained by bringing the above components (a1) to (a3) into contact with each other by any method. The non-metallocene catalyst that can be used in the present invention is not limited to these,
Other catalysts having propylene polymerization activity may be used.

The propylene polymer produced in the step (A) by the nonmetallocene catalyst (a) is a propylene homopolymer or a copolymer obtained by copolymerizing a small amount of ethylene and / or α-olefin. Or a mixture of both. When the propylene polymer is a copolymer, the content of ethylene and / or α-olefin is 10% by weight or less, preferably 8% by weight or less, particularly preferably 6% by weight or less.

The amount of the propylene polymer produced in the step (A) is from 25 parts by weight to 95 parts by weight in 100 parts by weight of the propylene polymer composition produced by the present invention.
Parts by weight. When the propylene polymer is a homopolymer, its production amount is preferably 45 to 90 parts by weight, and more preferably 65 to 85 parts by weight. When the propylene polymer contains a copolymer, its production amount is preferably 30 to 85 parts by weight, more preferably 3 to 85 parts by weight.
5 to 80 parts by weight.

The method for producing the propylene polymer in the step (A) is not particularly limited, and any polymerization method can be applied. Specific examples include bulk polymerization performed in liquid propylene, solution polymerization and slurry polymerization performed in a liquid phase in the presence of an inert solvent, and gas phase polymerization performed in a gas phase monomer. Of these, bulk polymerization and gas phase polymerization are preferred.

The polymerization temperature is generally in the range of -78 ° C to 200 ° C, preferably in the range of 0 ° C to 120 ° C,
Particularly preferably, it is in the range of 40 ° C to 90 ° C. Pressure atmospheric pressure ~70kg / cm ² in the polymerization in the liquid phase, in gas phase range from normal pressure to 50 kg / cm ² are typical. These conditions can be appropriately selected in consideration of the properties of the propylene polymer composition to be obtained, productivity, and the like.
At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen and selection of temperature and pressure.

The number of stages in the step (A) is not particularly limited. For example, it is possible to produce a copolymer after producing a propylene homopolymer, or to carry out gas-phase polymerization after carrying out bulk polymerization. .

Further, prior to the step (A), it is possible to carry out prepolymerization in which a small amount of a monomer is brought into contact with a catalyst. Preliminary polymerization is preferred in that it improves the catalytic activity and the resulting propylene polymer composition tends to be easily handled into powder having properties. Prepolymerization involves contacting the catalyst with a small amount of monomer in a hydrocarbon solvent or in the liquid or gaseous phase of the monomer for a time sufficient to obtain a polymer in an amount of about 0.5 to 5 times the weight of the catalyst. Do with. Here, as the hydrocarbon solvent, for example, hexane or heptane can be used. Further, the monomer may be the same as or different from the monomer used for the polymerization.

In the step (B) of the present invention, an elastomer is produced by a catalyst comprising the metallocene compound (b) and the co-catalyst component (c). More specifically, after a propylene is polymerized in a batch polymerization reactor in the presence of either the metallocene compound (b) or the co-catalyst component (c), the other is added, and the necessary monomer is introduced. This starts the production of the elastomer. Alternatively, after a propylene is polymerized in a batch polymerization reactor in the presence of either the metallocene compound (b) or the co-catalyst component (c), the monomer required for the step (B) is introduced, and the other is introduced. The addition starts the production of the elastomer.
Here, after polymerizing propylene for a predetermined time, the polymerization of propylene may be stopped by adding an active hydrogen compound such as methanol or removing propylene, or the operation may be continuously performed without stopping the polymerization of propylene. Is also good.

When the polymerization is carried out in a flow polymerization reactor, one of the metallocene compound (b) and the cocatalyst component (c) is added to the polymerization reactor for carrying out the step (A), and the other is added to the step (A). ) And the polymerization reactor for performing the step (B) or the polymerization reactor for performing the step (B). To be more specific, the intermediate point between the polymerization reactors for performing the steps (A) and (B) is a pipe connecting the polymerization reactor for performing the step (A) and the polymerization reactor for performing the step (B). The polymerization reactor and the step (B) for performing the step (A) include a solid-liquid separator for separating the polymer and the liquid propylene, and a separator such as a degassing tank for vaporizing and separating the liquid propylene from the propylene polymer. It means equipment attached to the middle of the polymerization reactor to be performed. Further, a vessel having no separation function is provided between the polymerization reactor for performing the step (A) and the polymerization reactor for performing the step (B), and the propylene polymer produced in the step (A) is provided in the vessel. It is also possible to add a solution or slurry containing one of the metallocene compound (b) and the co-catalyst component (c) to the container in the state where it is present.

In these methods, after performing step (A) using either the metallocene compound (b) or the cocatalyst component (c), the other is added in the absence of liquid propylene. Is preferred. In the present invention, the absence of liquid propylene means that the concentration of propylene in the liquid phase around the propylene polymer particles is 5 mol.
% Or less.

More specifically, when a batch polymerization reactor is used, it is preferable to add propylene after the step (A) has been carried out, after removing propylene. When a flow-type polymerization reactor is used, for example, after the propylene polymer produced in the step (A) and liquid propylene are separated by a solid-liquid separator or the like, It is preferable to add propylene during the stage of vaporization and separation or after separation.

When step (B) is carried out in the gas phase in this embodiment, one of the metallocene compound (b) and the co-catalyst component (c) is subjected to step (B) in the form of a solution or slurry in the polymerization. It can be added by spraying into the reactor. The solution or slurry is prepared using a suitable solvent such as an aliphatic or aromatic hydrocarbon such as hexane, heptane or toluene.

The production method in the step (B) is not particularly limited, and an elastomer can be produced by polymerizing a monomer such as ethylene or propylene by an arbitrary polymerization method. Specific examples include bulk polymerization performed in a liquid monomer, solution polymerization and slurry polymerization performed in a liquid phase in the presence of an inert solvent, and gas phase polymerization performed in a gas phase monomer. Among these, bulk polymerization and gas phase polymerization are preferable, and gas phase polymerization is particularly preferable.

[0037] The polymerization temperature is generally in the range of -78 ° C to 200 ° C, preferably in the range of 0 ° C to 120 ° C, and particularly preferably in the range of 40 ° C to 90 ° C. Pressure atmospheric pressure ~70kg / cm ² in the polymerization in the liquid phase, in gas phase range from normal pressure to 50 kg / cm ² are typical.
These conditions can be appropriately selected in consideration of the properties of the propylene polymer composition to be obtained, productivity, and the like. At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen and selection of temperature and pressure.

In the step (B), an elastomer is produced by at least the metallocene compound (b) and the cocatalyst component (c). At the same time, the elastomer is produced by the non-metallocene catalyst (a) used in the step (A). It is possible to manufacture. The total amount of the elastomer produced in the step (B) is 5 parts by weight to 75 parts by weight based on 100 parts by weight of the propylene polymer composition produced according to the present invention. Among them, the elastomer produced by the metallocene compound (b) and the co-catalyst component (c) is obtained in the step (B).
20% by weight or more, preferably 35% by weight or more, more preferably 5% by weight of the total elastomer produced in
0% by weight or more.

The number of stages in the step (B) is not particularly limited. For example, after an ethylene-propylene copolymer elastomer is produced, an ethylene-butene copolymer elastomer is produced, or after an elastomer is produced by bulk polymerization, It is also possible to produce elastomers by gas phase polymerization.

The monomers constituting the elastomer produced in the step (B) of the present invention include those having 2 to 2 carbon atoms.
0 α-olefin, specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene,
-Decene, 1-dodecene, 4-methyl-1-pentene,
Examples are 3-methyl-1-butene, vinylcyclohexane and the like. Preferred among these are ethylene, propylene, 1-butene, 1-hexene and mixtures thereof. In addition to the above olefins, butadiene, isoprene, 1,5-hexadiene, 2,5-norbornadiene, vinylnorbornene, ethylidene norbornene,
It is also possible to copolymerize a small amount of a conjugated or non-conjugated diene compound such as dicyclopentadiene or a vinyl aromatic compound such as styrene. Incidentally, the content of the monomer contained in the largest amount in the elastomer produced by copolymerizing them is less than 90% by weight.

Examples of the metallocene compound (b) usable in the present invention include monocyclopentadienyl compounds such as cyclopentadienyl titanium trichloride, cyclopentadienyl zirconium trichloride, cyclopentadienyl hafnium trichloride, and the like. , Biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (Pentamethylcyclopentadienyl) hafnium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadi Nil) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (i-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (i-butylcyclo Biscyclopentadienyl compounds such as (pentadienyl) zirconium dichloride and bis (t-butylcyclopentadienyl) zirconium dichloride; and bisindenyl compounds such as bis (indenyl) zirconium dichloride.

Other examples of the metallocene compound (b) include ethylene-1,2-bis (1-indenyl) zirconium dichloride and dimethylsilylenebis (1-
Compounds having a crosslinked indene group, such as indenyl) zirconium dichloride, isopropylidenecyclopentadienyl (9-fluorenyl) zirconium dichloride, dimethylsilylenecyclopentadienyl (9-
Fluorenyl) zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (t-butylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilylenebis (9-fluorenyl) ) Compounds having a fluorenyl group, such as zirconium dichloride and ethylene-1,2-bis (9-fluorenyl) zirconium dichloride.

Of these, those containing hafnium metal are preferred. Specific examples thereof include cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, biscyclopentadienyl hafnium dichloride, (Pentamethylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride, bis (t-butylcyclopentadienyl) hafnium dichloride, ethylene-1,2-bis (1-indenyl) hafnium Dichloride, dimethylsilylenebis (1-indenyl) hafnium dichloride, ethylene-1,2-bis [2-methyl- (1-indenyl)] hafnium dichloride, dimethylsilylenebis [2-methyl- 1-indenyl)] hafnium dichloride, dimethylsilylene-bis [2-methyl-4-
Phenyl- (1-indenyl)] hafnium dichloride, dimethylsilylenebis [2-methyl-4- (1-naphthyl)-(1-indenyl)] hafnium dichloride, dimethylsilylenebis [2-methyl-4,5-benzo ( 1-indenyl)] hafnium dichloride and the like. Other preferred metallocene compounds (b) include those represented by the following general formula (I).

[0044]

Embedded image

In the formula, Cp and Cp ^* are hydrocarbon groups having a cyclopentadienyl skeleton bridged by Q,
Further, at least one of Cp and Cp ^* is an indenyl group or a substituted indenyl group, preferably a substituted indenyl group having any of alkyl, aryl, aralkyl and silyl groups at the 2-position. Q is carbon number 1-2
0 hydrocarbon group or silylene group. Q is 1 carbon
In the case of a hydrocarbon group of 20 to 20, it is preferably an ethylene group, a substituted ethylene group, a methylene group, or a substituted methylene group. Q
Is a silylene group, preferably a dimethylsilylene group,
Methylethylsilylene group, diethylsilylene group, di-n
-A dialkylsilylene group such as a butylsilylene group, a diarylsilylene group such as a diphenylsilylene group, or an alkylarylsilylene group such as a methylphenylsilylene group. M is Ti or Zr, X ¹ and X ²
Is any of hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy and amide, which may be different from each other or may be the same.

More specifically, the metallocene compounds represented by the formula (I) are ethylene-1,2-bis (1-indenyl) zirconium dichloride, dimethylsilylenebis (1-indenyl) zirconium dichloride,
Ethylene-1,2-bis [2-methyl- (1-indenyl)] zirconium dichloride, ethylene-1,2-
Bis [2,4,7-trimethyl- (1-indenyl)]
Zirconium dichloride, dimethylsilylene bis [2
-Methyl- (1-indenyl)] zirconium dichloride, dimethylsilylenebis [2-ethyl- (1-indenyl)] zirconium dichloride, dimethylsilylenebis [2-i-propyl- (1-indenyl)] zirconium dichloride, dimethylsilylene Screw [2
4,7-trimethyl- (1-indenyl)] zirconium dichloride, dimethylsilylenebis [2-methyl-
4-phenyl- (1-indenyl)] zirconium dichloride, dimethylsilylenebis [2-methyl-4-
(1-naphthyl)-(1-indenyl)] zirconium dichloride, dimethylsilylenebis [2-methyl-
4,5-benzo (1-indenyl)] zirconium dichloride, dimethylsilylene (1-indenyl) [2-
Methyl- (1-indenyl)] zirconium dichloride, dimethylsilylene (1-indenyl) [2-ethyl- (1-indenyl)] zirconium dichloride, dimethylsilylene (1-indenyl) [2-isopropyl- (1-indenyl)] Zirconium dichloride, dimethylsilylene (9-fluorenyl) [2-methyl-4
-(1-naphthyl)-(1-indenyl)] zirconium dichloride.

Other preferred metallocene compounds (b) include those represented by the following formula (II).

[0048]

Embedded image

Cp ^** is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group cross-linked to L by Q. Q is a hydrocarbon group having 1 to 20 carbon atoms or a silylene group. When Q is a hydrocarbon group having 1 to 20 carbon atoms, it is preferably an ethylene group, a substituted ethylene group, a methylene group, or a substituted methylene group. When Q is a silylene group, preferably a dimethylsilylene group, a methylethylsilylene group, a diethylsilylene group, a dialkylsilylene group such as di-n-butylsilylene group, a diarylsilylene group such as diphenylsilylene group, or a methylphenylsilylene group. It is an alkylarylsilylene group.

L is any ^one of NR ¹ , PR ¹ , BR ¹ , O and S, and is preferably NR ¹ . R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a silyl group. M is Ti or Zr, and X ¹ and X ² are hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy, or amide, which may be different from each other or may be the same.

Specific examples of the metallocene compound represented by the formula (II) include dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) titanium dichloride and dimethylsilylene (phenylamide)
(Tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (methylamide) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (benzylamide) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (phenylphosphide) ) (Tetramethylcyclopentadienyl) titanium dichloride,
1,2-ethylene (t-butylamide) (tetramethylcyclopentadienyl) titanium dichloride,
2-ethylene (phenylamide) (tetramethylcyclopentadienyl) titanium dichloride, 1,2-ethylene (methylamide) (tetramethylcyclopentadienyl) titanium dichloride, 1,2-ethylene (benzylamide) (tetramethylcyclo Pentadienyl) titanium dichloride, 1,2-ethylene (phenylphosphide) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (t-
Butylamide) (t-butylcyclopentadienyl) titanium dichloride, dimethylsilylene (phenylamide) (t-butylcyclopentadienyl) titanium dichloride, dimethylsilylene (methylamide) (t
-Butylcyclopentadienyl) titanium dichloride, dimethylsilylene (benzylamide) (t-butylcyclopentadienyl) titanium dichloride, dimethylsilylene (phenylphosphide) (t-butylcyclopentadienyl) titanium dichloride, 1,2
-Ethylene (t-butylamide) (t-butylcyclopentadienyl) titanium dichloride, 1,2-ethylene (phenylamide) (t-butylcyclopentadienyl) titanium dichloride,

1,2-ethylene (methylamide) (t-
Butylcyclopentadienyl) titanium dichloride, 1,2-ethylene (benzylamide) (t-butylcyclopentadienyl) titanium dichloride,
2-ethylene (phenyl phosphide) (t-butylcyclopentadienyl) titanium dichloride, dimethylsilylene (t-butylamide) (fluorenyl) titanium dichloride, dimethylsilylene (phenylamide) (fluorenyl) titanium dichloride, dimethylsilylene (methylamide) (Fluorenyl) titanium dichloride, dimethylsilylene (benzylamide)
(Fluorenyl) titanium dichloride, dimethylsilylene (phenylphosphide) (fluorenyl) titanium dichloride, 1,2-ethylene (t-butylamido) (fluorenyl) titanium dichloride, 1,
2-ethylene (phenylamide) (fluorenyl) titanium dichloride, 1,2-ethylene (methylamide) (fluorenyl) titanium dichloride, 1,2
-Ethylene (benzylamide) (fluorenyl) titanium dichloride, 1,2-ethylene (phenyl phosphide) (fluorenyl) titanium dichloride,

Dimethylsilylene (t-butylamide)
(Tetrahydrofluorenyl) titanium dichloride, dimethylsilylene (phenylamide) (tetrahydrofluorenyl) titanium dichloride, dimethylsilylene (methylamide) (tetrahydrofluorenyl)
Titanium dichloride, dimethylsilylene (benzylamide) (tetrahydrofluorenyl) titanium dichloride, dimethylsilylene (phenylphosphide)
(Tetrahydrofluorenyl) titanium dichloride, 1,2-ethylene (t-butylamide) (tetrahydrofluorenyl) titanium dichloride, 1,2-
Ethylene (phenylamide) (tetrahydrofluorenyl) titanium dichloride, 1,2-ethylene (methylamide) (tetrahydrofluorenyl) titanium dichloride, 1,2-ethylene (benzylamide) (tetrahydrofluorenyl) titanium dichloride,
1,2-ethylene (phenyl phosphide) (tetrahydrofluorenyl) titanium dichloride.

In the present invention, the metallocene compound (b) specifically exemplified above is obtained by replacing zirconium with titanium or titanium with zirconium,
It is also possible to use one obtained by replacing chloride with another halide, a hydrocarbon group such as a methyl group or a benzyl group, or a hydride.

When the above-mentioned preferred compounds are used as the metallocene compound (b), even when the ethylene-α-olefin copolymer elastomer having a high α-olefin content is produced in the step (B), the composition is easily formed into particles. You can get things.

The cocatalyst component (c) of the present invention is a compound which forms a metallocene catalyst upon contact with the metallocene compound (b), and specifically includes an aluminoxane, an organoaluminum compound having at least one halogenated aryl group. 1 selected from organic boron compounds
That is all.

As the aluminoxane, known ones can be used, and are obtained by reacting one or more trialkylaluminums with water.
Specific examples include methylaluminoxane, ethylaluminoxane, butylaluminoxane, and isobutylaluminoxane obtained from one type of trialkylaluminum, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane obtained from two types of trialkylaluminum.

As the co-catalyst component (c), it is also possible to use a mixture of a plurality of the above-mentioned components or a component modified with trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum dichloride or the like. Among these, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane are preferable, and methylaluminoxane and methylisobutylaluminoxane are particularly preferable.

As the organoaluminum compound having at least one halogenated aryl group, tris (3,3
4,5-trifluorophenyl) aluminum, tris (pentafluorophenyl) aluminum, dimethylaniliniumtetrakis (pentafluorophenyl) aluminate and the like.

As the organic boron compound, an ionic compound represented by the following formula (III) can be used. [A] ⁺ · [BR ² R ³ R ⁴ R ⁵ ] ^- (III) In the formula, [A] ⁺ represents a monovalent cation, specifically, a proton, an ammonium ion such as pyridinium or dimethylanilinium, Carbenium ions such as trimethylcarbenium, triphenylcarbenium and tropylium; oxonium ions such as trimethyloxonium and triethyloxonium; phosphonium ions such as triphenylphosphonium and tri (methylphenyl) phosphonium; Cenium ion, silver (I)
Ions.

R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen, an alkoxy group, an aryloxy group,
An aluminum oxy group, an amide group, or a hydrocarbon group having 1 to 30 carbon atoms, at least one of which is an alkoxy group, a phenoxy group, an amide group,
-30 hydrocarbon groups. 1-30 carbon atoms
Specific examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, and naphthyl group; 2-fluorophenyl group; Phenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group,
2,6-difluorophenyl group, 3,5-difluorophenyl group, 3,4-difluorophenyl group, 2,3,4
-Trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group,
2,4,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group,
2,3,4,6-tetrafluorophenyl group, 2,3
5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-trifluoromethyl group, 3-trifluoromethyl group, 4-trifluoromethyl group, 2,3-bis (trifluoromethyl) phenyl group, 2, 4-bis (trifluoromethyl) phenyl group, 2,5-bis (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 3,4-bis (trifluoromethyl) phenyl group, 2,3,4-tris (trifluoromethyl) phenyl group, 2,3,5-tris (trifluoromethyl) phenyl group, 2,3,6-tris (Trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 2,4,5-tris (trifluoromethyl) phenyl Group, 3,4,5-tris (trifluoromethyl) phenyl group, 2,3,4,5-tetrakis (trifluoromethyl) phenyl group, 2,3,4,
6-tetrakis (trifluoromethyl) phenyl group,
It is a 2,3,5,6-tetrakis (trifluoromethyl) phenyl group, a pentakis (trifluoromethyl) phenyl group, or a halogenated aromatic hydrocarbon group obtained by substituting these fluorines with another halogen.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an i-propoxy group, a 2,2,2-trichloroethoxy group, a 2,2,2-trifluoroethoxy group,
1,1,3,3,3-hexafluoro-i-propoxy group and the like. Examples of the aryloxy group include a phenoxy group, a tolyloxy group, a 3,4,5-trifluorophenoxy group, a pentafluorophenoxy group, and the like. Examples of the aluminum oxy group include a dimethyl aluminum oxy group, a diethyl aluminum oxy group, a diisobutyl aluminum oxy group, and the like. Among these, preferred are an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, and a halogenated aryloxy group, and particularly preferred are fluorinated aromatic groups such as a pentafluorophenyl group. Is a group hydrocarbon group.

Other boron compounds that can be used as the cocatalyst component (b) are nonionic compounds represented by the following formula (IV).

R ² R ³ R ⁴ B (IV) wherein R ² , R ³ and R ⁴ are the same as those described above, and are preferably an alkyl group, a halogenated alkyl group, an aromatic hydrocarbon group, Halogenated aromatic hydrocarbon group,
It is a halogenated aryloxy group, particularly preferably a fluorinated aromatic hydrocarbon group such as a pentafluorophenyl group.

Preferred among these boron compounds are dimethylanilinium tetrakispentafluorophenylborate, triphenylcarbenium tetrakispentafluorophenylborate, triethyloxonium tetrakispentafluorophenylborate, tropylium tetrakispentafluorophenylborate. Borat,
Trispentafluorophenylborane, tris (3,
4,5-trifluorophenyl) borane, tris (2,
3,5,6-tetrafluorophenyl) borane and tris (pentafluorophenoxy) borane.

Next, the amounts of the metallocene compound (b) and the co-catalyst component (c) in the present invention will be described.
In the present invention, the amount of the metallocene compound (b) to be added is not particularly limited. In particular, in order to suppress aggregation of the polymer particles and to produce a composition having a high elastomer content in a particulate form with high productivity, the amount of (b) used is preferably 1 μm.
mol to 10,000 μmol, more preferably 5 μmol
~ 5,000 μmol, more preferably 20 μmol
~ 1,000 μmol, most preferably 50 μmol ~ 50
The range is 0 μmol.

When the above-mentioned titanium halide supported on magnesium halide catalyst is used as the nonmetallocene catalyst (a), the molar ratio (a3) / electron donor component (a3) used in the production of the catalyst and the metallocene compound (b) is used. (B) is preferably 2,000 or less. In this case, the activity of the metallocene catalyst is particularly good, more preferably 1,000.
Or less, more preferably 500 or less, and most preferably 200 or less.

When the metallocene compound (b) is added as a solution or a slurry in the present invention, its concentration is in the range of 0.01 to 500 mmol / l. In particular, in order to suppress aggregation of the polymer particles, and to produce a composition having a high elastomer content in a particulate form with good productivity, preferably 0.05%
~ 200 mmol / l, more preferably
The range is from 0.1 to 100 mmol / l. Particularly when the addition is performed in the absence of liquid propylene, 0.1 to 50
A range of mmol / l is preferred.

In the case where (c) is aluminoxane, the amount of the co-catalyst component (c) to be added is one of the metallocene compound (b)
It is 1 to 100,000 μmol for Al atoms relative to μmol. In order to obtain higher polymerization activity, preferably 10 to
10,000 μmol, more preferably 50 to 5,000 μmo
1, most preferably in the range of 100 to 1,000 μmol.

When (c) is an organoboron compound or an organoaluminum compound having at least one halogenated aryl group, its addition amount is usually from 0.01 μmol to 10,000 per 1 μmol of the metallocene compound (b).
μmol. In order to obtain a higher polymerization activity, preferably 0.1 to 1,000 μmol, more preferably 0.3 to
500 μmol, most preferably 0.8-100 μmol
Range.

In the present invention, it is also possible to use other organoaluminum compounds other than those described in (c) as components other than those described above. Examples of such organoaluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, trinormalpropylaluminum, triisobutylaluminum, and trihexylaluminum; dialkylaluminum halides such as diethylaluminum dichloride and ethylaluminum dichloride; and alkylaluminum dihalides. And dialkylaluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide, and phenoxide.

As described above, the step (A) is carried out in the presence of either the metallocene compound (b) or the co-catalyst component (c).
And then adding the other, and producing an elastomer in step (B), whereby the composition comprising the elastomer with the metallocene catalyst and the propylene polymer with the Ziegler-Natta catalyst is mixed with the particles without mechanical mixing. It can be manufactured in a shape.

[0073]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. The metallocene compound (b) and the promoter component (c) used in the examples are as follows.

[Metallocene compound (b)] (b-1): Dimethylsilylene (t-butylamide)
(Tetramethylcyclopentaenyl) titanium dichloride, (b-2): ethylene-1,2-bis (1-indenyl) hafnium dichloride, (b-3): dimethylsilylenebis [2-methyl-4-
(1-naphthyl) -1-indenyl] zirconium dichloride, (b-4): bis (n-butylcyclopentadienyl)
Zirconium dichloride, (b-5): dimethylsilylene bis (9-fluorenyl) zirconium dichloride, (b-6): dimethylsilylene (9-fluorenyl)
[2-methyl-4- (1-naphthyl) -1-indenyl] zirconium dichloride,

[Co-catalyst component (c)] (c-1): tris (pentafluorophenyl) borane, (c-2): dimethylanilinium tetrakis (pentafluorophenyl) borate, (c-3): methylaluminoxane .

In Examples and Comparative Examples, the ratio between the propylene polymer and the elastomer in the propylene polymer composition was determined by the following method. That is, about 2 g of the propylene polymer composition is accurately weighed (this is referred to as W
(G). ) Was dissolved in 250 ml of boiling xylene under a stream of nitrogen. Thereafter, the solution was cooled to 25 ° C. and left for 30 minutes, and the formed precipitate was promptly filtered. About 20 to 100 ml of the obtained filtrate (the composition 1
When the content of the elastomer in 00 parts by weight is expected to exceed 40 parts by weight, 20 to 30 ml and 20 to 30 ml are used.
If it is expected to be 40 parts by weight, it is desirable to collect it in the range of 30 to 50 ml, and if it is expected to be less than 20 parts by weight, it is desirable to collect it in the range of 50 to 100 ml. ) And collect this (L (m
x) The xylene was evaporated by placing it in an aluminum container whose constant weight was determined and heating it in a nitrogen stream.
The weight of the evaporation residue was determined (m (g)), and the elastomer content x in 100 parts by weight of the propylene polymer composition was determined by the following equation. X (parts by weight) = m × 250 × 100 / (W × L)

The content of the elastomer by the non-metallocene catalyst in the produced elastomer was determined as follows. That is, a propylene polymer composition is produced under the same conditions except that a metallocene compound is not separately used, and the ratio P = w2 / w of the elastomer amount w2 to the propylene polymer amount w1 obtained by the above method is used.
Find 1 Using this value, the content x of the elastomer by the nonmetallocene catalyst contained in 100 parts by weight of the propylene polymer was determined by the following equation. x (parts by weight) = (100−X) × P

The composition of the elastomer in the produced elastomer by the non-metallocene catalyst was determined to be the same value as the composition of the elastomer in the composition used in the above calculation of x. The composition of the elastomer by the metallocene catalyst was a calculated value obtained by subtracting the contribution of the elastomer by the non-metallocene catalyst from the measurement results of all the elastomers.

The composition of the propylene polymer and the elastomer (the ratio of the ethylene component, the propylene component, and the butene component) was measured using FT-IR, and the composition was determined from a calibration curve prepared from a sample having a known composition.

Further, the properties of the polymer composition particles obtained in Examples and Comparative Examples were determined by selecting particles having a minimum diameter of 5 mm or more contained in 1 g of the propylene polymer composition, and measuring the total weight thereof. From this, the content (% by weight) of the particles having the shortest diameter of 5 mm or more was determined, and the evaluation was evaluated as ◎ when less than 1% by weight, ○ when 1 to 5% by weight, and Δ when more than 5% by weight.

Preparation of Nonmetallocene Catalyst (1) Preparation of Solid Titanium Catalyst Component (A): After sufficiently replacing a 200 ml three-necked flask equipped with a thermometer and a stirrer with nitrogen, 1.11 g (9.47 mmol) of diethoxymagnesium ,
10 ml of toluene and 0.46 m of di-n-butyl phthalate
1 (1.73 mmol) and stirred at 70 ° C. for 2 hours. Thereafter, the mixture is cooled to room temperature, and 50 ml of TiCl ₄ is dropped from the dropping funnel over 1 hour. After the completion of dropping, 110
C., and reacted for 2 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature, washed several times with 200 ml of n-hexane, and dried under reduced pressure at 50 to 60 ° C. for 30 minutes to obtain a solid titanium catalyst component (A).

Preparation of polymerization catalyst: An organoaluminum compound (a) was added to 10 mg of the solid titanium catalyst component prepared above.
1.5 mmol of triethylaluminum as 2) and 0.3 mmol of cyclohexylmethyldimethoxysilane as an electron donor component (a3) were added to prepare a nonmetallocene catalyst.

Preparation of Nonmetallocene Catalyst (2) To 15 mg of the solid titanium catalyst component described in the nonmetallocene catalyst (1) were added 10 mmol of triethylaluminum as the organoaluminum compound (a2) and cyclohexylmethyl as the electron donor component (a3). A nonmetallocene catalyst was prepared by adding 5 mmol of dimethoxysilane.

Example 1 1) Step (A): Production of Propylene Polymer Using Nonmetallocene Catalyst (1) In a 1.5 L internal volume autoclave equipped with a magnetic stirrer, the above nonmetallocene catalyst (1) and (b- 1) 2mm
ol / l methylene chloride solution (5 ml), propylene (8 mol) and hydrogen (730 ml) (volume at normal pressure)
Introduced. Raise the internal temperature of the autoclave to 70 ° C,
The polymerization was started.

2) Step (B): Production of Elastomer Using Metallocene Catalyst After the above step (A) was carried out for 60 minutes, the step (c-1) -2
7.5 mmol / l hexane solution and 0.5 mol /
1 ml of a triisobutylaluminum (hereinafter abbreviated as TIBA) toluene solution, which had been previously mixed, was added. After removing the liquid propylene, propylene gas and ethylene gas were newly added at a partial pressure of 3 kg / each.
to maintain cm ² and 12 kg / cm ^2, intermittently introduced to produce elastomeric by polymerizing for 90 minutes at 70 ° C., the propylene polymer composition 138 was obtained in the form of particles (polymerization of metallocene catalyst Activity 1472g / mmol ・
h).

The obtained propylene polymer contained 72 parts by weight of the propylene polymer and 28 parts by weight of the elastomer (of which the proportion of the elastomer obtained by the nonmetallocene catalyst was 43% by weight of the total elastomer). . Table 1 shows the reaction conditions of the step (A), Table 2 shows the reaction conditions of the step (B), and Table 3 shows the results.

Example 2 1) Step (A): Production of Propylene Polymer Using Nonmetallocene Catalyst In a 1.5 L internal volume autoclave equipped with a magnetic stirrer, the above nonmetallocene catalyst (1) and (b-1) were mixed. 1 mmol
After adding 20 ml of a 1 / l toluene solution,
730 ml (volume at normal pressure) were introduced. The internal temperature of the autoclave was raised to 75, and polymerization was performed for 60 minutes.

2) Addition of metallocene compound and / or cocatalyst component After the above step (A) was completed by adding a small amount of methanol, liquid propylene was removed, and remaining methanol was removed under reduced pressure. Thereafter, a mixture of 1 ml of a 0.5 mol / l toluene solution of TIBA and 30 ml of a 1 mmol / l hexane solution of (c-1) in advance was added into an autoclave.

[0089] 3) Step (B): After preparation 2) above elastomeric metallocene-catalyzed, 1 Butengasu and ethylene gas its partial pressure respectively 6 kg / cm ² and 7 kg / cm ²
Was introduced intermittently and polymerized at 75 ° C. for 120 minutes to produce an elastomer, thereby obtaining 127 g of a propylene polymer composition in the form of particles. Table 1 shows the reaction conditions.
2 and Table 3 shows the results such as the content and composition of the propylene polymer and the elastomer.

Example 3 1) Step (A): Production of Propylene Polymer by Nonmetallocene Catalyst In a 1.5 L internal volume autoclave equipped with a magnetic stirrer, the above nonmetallocene catalysts (1) and (b-1) were prepared. 1mm
ol / l toluene solution 10 ml, propylene 8 mol and hydrogen 730 ml (volume at normal pressure)
Introduced. Raise the internal temperature of the autoclave to 70 ° C,
The polymerization was carried out for 60 minutes.

2) Addition of metallocene compound and / or co-catalyst component After the above step (A), propylene is removed and TIBA
2 ml of 0.5 mol / l toluene solution and (c-2)
12 ml of a 1 mmol / l toluene solution of was mixed in advance.

[0092] 3) Step (B): After preparation 2) above elastomeric metallocene-catalyzed, 1 Butengasu and ethylene gas its partial pressure respectively 6 kg / cm ² and 7 kg / cm ²
Was introduced intermittently and polymerized at 70 ° C. for 120 minutes to produce an elastomer, and 141 g of a propylene polymer composition was obtained in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 4 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 3 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 5 The same procedure as in Example 2 was carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Examples 6 to 8 The same procedures as in Example 3 were carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 9 1) Step (A): Production of Propylene Polymer by Nonmetallocene Catalyst In a 1.5-L autoclave equipped with a magnetic stirrer, 8 mol of propylene, 730 ml of hydrogen (volume at normal pressure) and After introducing 0.5 ml of a 10 mmol / l methylene chloride solution of (b-4), the internal temperature of the autoclave was reduced to 7%.
The temperature was raised to 0 ° C. The non-metallocene catalyst (1) was injected with ethylene to initiate polymerization. During the polymerization, ethylene was fed intermittently to maintain its partial pressure at 0.3 kg / cm ² .

2) Step (B): Production of Elastomer Using Metallocene Catalyst After the above step (A) was carried out for 60 minutes, the step (c-3)
12 ml of a 00 mmol / l toluene solution was added. Then removing the liquid propylene was started manufacturing elastomer newly propylene gas and ethylene gas introduction 7 kg / cm ² and 8 kg / cm ^2, respectively partial pressures.
Polymerization was carried out at 70 ° C. for 90 minutes while intermittently introducing the propylene gas and the ethylene gas so that the partial pressures of the propylene gas and the ethylene gas maintained the above values, to obtain 119 g of a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 10 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 3 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 11 1) Step (A): Production of propylene polymer using nonmetallocene catalyst In a 1.5-liter autoclave equipped with a magnetic stirrer, 8 mol of propylene, 730 ml of hydrogen (volume at normal pressure) and After introducing 40 ml of a 0.5 mmol / l toluene solution of (b-5), the internal temperature of the autoclave was raised to 60 ° C.
Temperature. The non-metallocene catalyst (1) was injected with ethylene to initiate polymerization. During the polymerization, ethylene was supplied intermittently to maintain its partial pressure at 0.3 kg / cm ² .

2) Step (B): Production of Elastomer Using Metallocene Catalyst After the above-mentioned step (A) was carried out for 60 minutes, 0.5% of TIBA was added.
2 mol / l toluene solution and 5 of (c-3)
A premixed 8 ml of a 00 mmol / l toluene solution was added. Next, liquid propylene was removed, and propylene gas and ethylene gas were newly added at 5 kg / c, respectively.
With the introduction of m ² and 10 kg / cm ² , the production of the elastomer was started. While intermittently introducing the partial pressures of propylene gas and ethylene gas so as to maintain the above values, 7
Polymerized at 0 ° C. for 240 minutes to obtain a propylene polymer composition 149
g was obtained in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 12 A propylene polymer composition was obtained in the form of particles using the non-metallocene catalyst (2) and in the same manner as in Example 2 except for the conditions shown in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 13 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 3 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 14 The same procedures as in Example 1 were carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 15 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 2 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 16 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 3 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 17 The procedure of Example 2 was repeated except for the conditions described in Tables 1 and 2 to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Example 18 A propylene polymer composition was obtained in the form of particles in the same manner as in Example 1 except for the conditions described in Tables 1 and 2. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Examples 19 to 20 The same procedure as in Example 3 was carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Examples 21 to 22 The same procedures as in Example 1 were carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Examples 23 to 24 The same procedures as in Example 3 were carried out except for the conditions described in Tables 1 and 2, to obtain a propylene polymer composition in the form of particles. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Comparative Example 1 1) Step (A): Production of Propylene Polymer Using Nonmetallocene Catalyst In a 1.5-liter autoclave equipped with a magnetic stirrer, 8 mol of propylene and 730 ml of hydrogen (volume at normal pressure) were used. Then, the internal temperature of the autoclave was raised to 50 ° C. Next, the non-metallocene catalyst (1), TIBA
2 ml of a 0.5 mol / l toluene solution of (b-1)
After adding 0.1 ml of a toluene solution of 0.1 mmol / l and 0.2 ml of a 2 mmol / l solution of toluene in (c-2), 30
Polymerization was performed for minutes.

2) Step (B): Production of Elastomer by Metallocene Catalyst After the polymerization is completed, liquid propylene is removed, and propylene gas and ethylene gas are newly added at a partial pressure of 7 kg each.
/ Cm ² and 8 kg / cm ^{2 were} introduced to start the production of the elastomer. While intermittently introducing propylene gas and ethylene gas so that the partial pressures maintain the above values, polymerization was performed at 70 ° C. for 240 minutes to obtain 142 g of a propylene polymer composition in a lump. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

Comparative Example 2 1) Step (A): Production of Propylene Polymer Using Nonmetallocene Catalyst The above nonmetallocene catalyst (1) was charged into a 1.5 L autoclave equipped with a magnetic stirrer.
730 ml (volume at normal pressure) were introduced. Next, the internal temperature of the autoclave was raised to 70 ° C.
Polymerization was performed for 60 minutes.

2) Step (B): Production of Elastomer by Metallocene Catalyst After removing liquid propylene, 0.5 mol /
1 ml of a toluene solution, 2 ml of a (b-2) 2 mmol / l toluene solution and 500 mmol of a (c-3)
A mixture of 10 ml of a toluene solution in advance was added. Its partial pressure of propylene gas and ethylene gas then is introduced ² 3 kg / cm ² and 12 kg / cm, respectively started manufacturing elastomer. Polymerization was performed at 70 ° C. for 120 minutes while intermittently introducing propylene gas and ethylene gas so that the partial pressures maintained the above values, to obtain 118 g of a propylene polymer composition in a lump. The results such as the content and composition of the propylene polymer and the elastomer are as shown in Table 3.

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

According to the method of the present invention, the step (A) of producing a propylene polymer using a nonmetallocene catalyst (a) in the presence of either the metallocene compound (b) or the cocatalyst component (c) is described. After the addition, the other is added and the elastomer is produced in the step (B), whereby the composition comprising the elastomer with the metallocene catalyst and the propylene polymer with the Ziegler-Natta catalyst is formed into particles without mechanical mixing. It can be manufactured.

Claims (10)

[Claims] 1. A step (B) of producing an elastomer with a catalyst comprising at least a metallocene compound (b) and a co-catalyst component (c) after the step (A) of producing a propylene polymer using a nonmetallocene catalyst (a). The step (A) in the presence of one of the metallocene compound (b) and the co-catalyst component (c), and then performing the step (B) by adding the other. A method for producing a propylene polymer composition, comprising: 2. The method according to claim 1, wherein the step (A) is performed in the presence of one of the metallocene compound (b) and the cocatalyst component (c), and then the other is added in the absence of liquid propylene. The method for producing a propylene polymer composition according to claim 1, wherein B) is performed. 3. The metallocene compound (b) is added in an amount of 0.1 μmo per 1 kg of the propylene polymer produced in the step (A).
The method for producing a propylene polymer composition according to claim 1, wherein the propylene polymer composition is added in a range of 1 to 100,000 μmol. 4. The method according to claim 1, wherein the metallocene compound (b) is used at a concentration of 0.01.
The method for producing a propylene polymer composition according to any one of claims 1 to 3, wherein the propylene polymer composition is added in the form of a solution or a slurry of up to 500 mmol / l. 5. The metallocene compound (b) having a concentration of 0.1
The method for producing a propylene polymer composition according to claim 4, wherein the propylene polymer composition is added as a solution or slurry having a concentration of -50 mmol / l. 6. The nonmetallocene catalyst (a) comprises a solid titanium catalyst component (a1) containing magnesium, titanium, halogen and an electron donor as essential components, an organoaluminum compound (b2) and an electron donor catalyst component (a3). )
The method for producing a propylene polymer composition according to any one of claims 1 to 5, comprising: 7. The method for producing a propylene polymer composition according to claim 6, wherein the molar ratio (a3) / (b) between the electron donor component (a3) and the metallocene compound (b) is 2,000 or less. 8. The method for producing a polypropylene resin composition according to claim 1, wherein the metallocene compound (b) is a compound containing hafnium metal. 9. The metallocene compound represented by the following general formula (I): (Wherein Cp and Cp ^* are hydrocarbon groups having a cyclopentadienyl skeleton bridged by Q, and Cp,
At least one of Cp ^* is an indenyl group or a substituted indenyl group, Q is a hydrocarbon group having 1 to 20 carbon atoms or a silylene group, M is Ti or Zr, X ¹ and X ² are hydrogen, halogen , A hydrocarbon group having 1 to 20 carbon atoms, alkoxy or amide, which may be different from each other or may be the same. The method for producing a propylene polymer composition according to any one of claims 1 to 7, which has a structure represented by the formula: 10. A metallocene compound represented by the following general formula (II): (Where Cp ^** is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group cross-linked to L by Q; L is NR ¹ , PR ¹ , BR ¹ , O or S; R ¹ is a hydrocarbon group having 1 to 20 carbon atoms; M is Ti or Zr , X ¹ and X ² are hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or amide, which may be different from each other or may be the same.) 8. The method for producing a propylene polymer composition according to any one of items 7 to 7.