JPH06172448A - Olefinic polymer and its production - Google Patents

Abstract

(57) [Summary] [I] A transition metal compound catalyst component [A] and an organometallic compound catalyst component [B] containing a metal selected from Groups I to III of the periodic table are added to an olefin and a polyene compound. Is a prepolymerization catalyst prepared by prepolymerization in an amount of 0.01 to 2000 g per 1 g of the above component [A], and [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. In the presence of and ethylene or carbon number 3-2
An olefin polymer obtained by irradiating a polymer obtained by polymerizing or copolymerizing an olefin having an α-olefin of 0 as an essential component with radiation and a method for producing the same. [Effect] It is possible to produce an olefin polymer having a high melt tension.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymer having a high melt tension and capable of molding a large container by a blow molding method, a vacuum molding method or the like, and a method for producing the same.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymers represented by high-density polyethylene, linear low-density polyethylene, polypropylene and the like are excellent in transparency and mechanical strength such as rigidity and impact strength. Conventionally, it is formed into a film or the like by an injection molding method, an extrusion molding method, or the like.

By the way, since such an olefin polymer generally has a low melt tension (melt tension, MT), it can be molded into a large container (bottle, etc.) by, for example, blow molding, or lining of household electric appliances by vacuum molding. It was difficult to mold it. Due to such restrictions on molding, the molded products that can be manufactured are also limited, and the present application is limited in spite of having various excellent properties.

Further, when polypropylene or the like is formed into a film by the inflation molding method, the melt tension is low, so that there are problems that drawdown occurs and molding conditions are limited. For this reason, in conventional inflation molding, by blending polypropylene with a high-pressure low-density polyethylene or the like to increase melt tension, bubbles are stabilized during inflation molding. However, in such a method, the film strength and the transparency may be lowered.

Therefore, if an olefin polymer such as polypropylene or linear low density polyethylene having a high melt tension appears, a large container (bottle, etc.) is molded by blow molding using this olefin polymer. Since it becomes possible to form home electric appliances such as refrigerator linings by a vacuum forming method, applications of olefin-based polymers will be further expanded. When an olefin polymer having a high melt tension is formed into a film by an inflation molding method using the olefin polymer, the bubble can be stabilized and the molding speed can be increased.

Therefore, the advent of olefin polymers such as polypropylene, high-density polyethylene or linear low-density polyethylene having a high melt tension is desired.

The present inventors have conducted research for the purpose of obtaining an olefin polymer having a high melt tension in order to meet the above demands. As a result, a catalyst for olefin polymerization consisting of a transition metal compound catalyst component and an organometallic compound catalyst component, an olefin and a polyene compound are prepolymerized, and a prepolymerized catalyst in the presence of an organometallic compound catalyst component, ethylene. It has also been found that an olefin-based polymer obtained by polymerizing or copolymerizing an olefin containing an α-olefin having 3 to 20 carbon atoms as an essential component has a high melt tension.
Further research based on this finding revealed that it can be obtained by polymerizing or copolymerizing ethylene or α-olefin having 3 to 20 carbon atoms in the presence of the prepolymerization catalyst and the organometallic compound catalyst component as described above. When the polymer is irradiated with a specific amount of radiation, an olefin polymer having a higher melt tension is obtained, and such an olefin polymer has excellent moldability at the time of inflation molding, as well as a blow molding method and a vacuum molding method. The inventors have found that a large container and the like can be formed by such a method, and have completed the present invention.

In the presence of an organometallic compound catalyst component and a prepolymerization catalyst in which an olefin and a polyene compound have not been prepolymerized into an olefin polymerization catalyst comprising a transition metal compound catalyst component and an organometallic compound catalyst component, ethylene is added. Even if the polymer obtained by polymerizing or copolymerizing an α-olefin having 3 to 20 carbon atoms is irradiated with radiation, the effect of increasing the melt tension is small.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an olefin polymer having a high melt tension and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION The olefin polymer according to the present invention is an organometallic compound containing [I] [A] a transition metal compound catalyst component and [B] a metal selected from Group I to Group III of the periodic table. Olefin and polyene compound were added to the catalyst component in an amount of 0.0 per 1 g of the above [A] transition metal compound catalyst component.
Ethylene or carbon is present in the presence of a prepolymerized catalyst which is prepolymerized in an amount of 1 to 2000 g and an organometallic compound catalyst component containing a metal selected from [II] Group I to Group III of the periodic table. It is characterized in that a polymer obtained by polymerizing or copolymerizing olefins containing α-olefin of several 3 or more as an essential component is irradiated with radiation.

The method for producing an olefin-based polymer according to the present invention is an organic metal containing [I] [A] transition metal compound catalyst component and [B] a metal selected from Group I to Group III of the periodic table. An olefin and a polyene compound were added to the compound catalyst component in an amount of 0.0 per 1 g of the [A] transition metal compound catalyst component.
Ethylene or carbon is present in the presence of a prepolymerized catalyst which is prepolymerized in an amount of 1 to 2000 g and an organometallic compound catalyst component containing a metal selected from [II] Group I to Group III of the periodic table. It is characterized by polymerizing or copolymerizing olefins containing α-olefin of 3 or more as an essential component, and then irradiating the obtained polymer with radiation.

In the present invention, the radiation dose is preferably in the range of 0.1 to 100 Mrad as the absorbed dose of the polymer. Such an olefin polymer of the present invention has a high melt tension. Further, according to the method for producing an olefin polymer of the present invention, an olefin polymer having a high melt tension can be produced.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The olefin copolymer and the method for producing the same according to the present invention will be specifically described below.

In the present invention, the term "polymerization" means
The term "polymer" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymer but also copolymer.

First, the [A] transition metal compound catalyst component used in forming the prepolymerized catalyst [I] used in the present invention will be described. Used in the present invention [A]
As the transition metal compound catalyst component, there are III to VII of the periodic table.
A compound containing a transition metal selected from Group I can be mentioned, and a compound containing at least one transition metal selected from Ti, Zr, Hf, Nb, Ta, Cr and V is preferable.

Specific examples of such [A] transition metal compound catalyst components include solid titanium catalyst components containing titanium and halogen. More specifically, as an example of such a solid titanium catalyst component, a solid titanium catalyst component [A-1 containing titanium, magnesium, halogen and, if necessary, an electron donor (a) described later [A-1 ] Is mentioned.

The solid titanium catalyst component [A-1] is prepared, for example, by using a titanium compound, a magnesium compound and, if necessary, an electron donor (a), and bringing these compounds into contact with each other.

Examples of the titanium compound used for preparing the solid titanium catalyst component [A-1] include a tetravalent titanium compound and a trivalent titanium compound. Examples of the tetravalent titanium compound include compounds represented by the following general formula.

In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group, X is a halogen atom, and 0≤g≤4. Specific examples of such a tetravalent titanium compound include titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ and Ti
(OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H
₅ ) Trihalogenated alkoxytitanium such as Br ₃ and Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ and Ti (OC _{2
H 5) 2 Cl 2, Ti} (On-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2
Dihalogenated dialkoxy titanium such as Br ₂ ; Ti (O
_{CH 3) 3 Cl, Ti (} OC 2 H 5) 3 Cl, Ti (On-C 4 H 9) 3
Cl, Ti (OC ₂ H ₅ ) ₃ Br and other monohalogenated trialkoxy titanium; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ ,
_{Ti (On-C 4 H 9} ) 4, Ti (O-iso-C 4 H 9) 4, Ti (O-2-
Examples thereof include tetraalkoxy titanium such as ethylhexyl) ₄ .

Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

Titanium trichloride is used as the trivalent titanium compound. As such titanium trichloride, for example, titanium tetrachloride is reduced by bringing it into contact with hydrogen or a metal such as magnesium metal, aluminum metal, or titanium metal or an organometallic compound such as an organomagnesium compound, an organoaluminum compound or an organozinc compound. The titanium trichloride thus obtained is preferably used.

Examples of the magnesium compound used for preparing the solid titanium catalyst component [A-1] include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having reducing ability include organomagnesium compounds represented by the following general formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2 and R is hydrogen or carbon number 1
To 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different, and X is halogen.

Specific examples of the organomagnesium compound having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium, ethylbutylmagnesium. Alkyl magnesium halides such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride; alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium, octyl butoxy magnesium, etc. Examples include magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; Allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; Ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkyloxy magnesium such as; Phenoxy magnesium, Dimethylphenoxy magnesium, etc. Xymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability can be prepared by using a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound. It may be contacted with a compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability are the organic metal compounds described later, such as aluminum and zinc,
It may form a complex compound or a double compound with another metal such as boron, beryllium, sodium or potassium, or may be a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more kinds of the above compounds may be combined, and may be used in a liquid state or a solid state. When the magnesium compound is a solid, alcohols, carboxylic acids, aldehydes, amines, which will be described later as the electron donor (a),
It can be made into a liquid state by using metal acid esters or the like.

As the magnesium compound used for preparing the solid titanium catalyst component [A-1], many magnesium compounds other than those mentioned above can be used, but the finally obtained solid titanium catalyst component [A- In the above [1], it is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Of these, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferable.

An electron donor (a) is preferably used in the preparation of the solid titanium catalyst component [A-1]. Examples of such an electron donor (a) include alcohols, phenols, ketones, aldehydes, carboxylic acids,
Organic acid halides, organic acid or inorganic acid esters,
Ethers, diethers, acid amides, acid anhydrides,
Examples thereof include oxygen-containing electron donors such as alkoxysilane; and nitrogen-containing electron donors such as ammonia, amines, nitriles, pyridines and isocyanates.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone Acetaldehyde, propionaldehyde, octylaldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
Carbon number 2 to 1 such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarinphthalide, ethyl carbonate
Organic acid esters of 8; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, C2-C20 ethers such as diphenyl ether; acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine, Amines such as Ribenzylamine and Tetramethylethylenediamine; Nitriles such as Acetonitrile, Benzonitrile and Trinitrile; Pyridines such as Pyridine, Methylpyridine, Ethylpyridine, Dimethylpyridine; Acetic anhydride, Anhydrous Tal acid, and the like can be exemplified acid anhydride such as benzoic anhydride.

As the organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a preferred example.

[0033]

[Chemical 1]

(Wherein R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or It is an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴
And may be connected to each other to form a ring structure.
When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent is
Containing a heteroatom such as N, O, S, for example, C—O—C,
_{COOR, COOH, OH, SO 3} H, -C-N-C
It has a group such as-, NH ₂ . ) Specific examples of such polycarboxylic acid ester include aliphatic polycarboxylic acid ester, alicyclic polycarboxylic acid ester, aromatic polycarboxylic acid ester, and heterocyclic polycarboxylic acid ester. To be

Preferred specific examples include n-butyl maleate, diisobutyl methylmalonate, din-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, din-phthalate. Butyl, di-2-phthalate
Examples thereof include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Examples of particularly preferred polyvalent carboxylic acid esters include phthalic acid esters. Further, examples of the polyether compound include compounds represented by the following general formula.

[0037]

[Chemical 2]

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) As preferred specific examples, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1,3-dimethoxypropane etc. can be illustrated.

Two or more kinds of the above electron donors (a) can be used in combination. In addition, the solid titanium catalyst component [A-1] used in the present invention is an organic compound containing silicon, phosphorus, aluminum, etc. used as a carrier compound and a reaction aid in addition to the above-mentioned compound at the time of preparation. It may be prepared by contacting with an inorganic compound or the like.

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Zn
Resins such as O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene polymers are used. In this, Al ₂ O
₃ , SiO ₂ , and a styrene-divinylbenzene copolymer are preferable.

The solid titanium catalyst component [A-1] used in the present invention is prepared by bringing the above-mentioned titanium compound, magnesium compound and preferably the electron donor (a) into contact with each other.

The preparation method of the solid titanium catalyst component [A-1] using these compounds is not particularly limited, but the case of using a tetravalent titanium compound will be briefly described below with several examples. .

(1) A method in which a solution comprising a magnesium compound, an electron donor (a) and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, the titanium compound is contact-reacted. .

(2) A method in which a complex consisting of a magnesium compound and an electron donor (a) is subjected to a catalytic reaction with an organometallic compound and then a titanium compound is subjected to a catalytic reaction. (3) A method of contacting a titanium compound with a contact product of an inorganic carrier and an organomagnesium compound. At this time, the contact product was previously treated with a halogen-containing compound, an electron donor (a) and / or
Alternatively, it may be reacted with an organometallic compound.

(4) A magnesium compound-supported inorganic or organic carrier is obtained from a mixture of a solution containing a magnesium compound, an electron donor (a), and optionally a hydrocarbon solvent, and an inorganic or organic carrier. A method of contacting a titanium compound.

(5) magnesium compound, titanium compound,
A method of obtaining a solid titanium catalyst component [A-1] carrying magnesium and titanium by contacting a solution containing an electron donor (a), optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method in which an organomagnesium compound in a liquid state is subjected to a catalytic reaction with a halogen-containing titanium compound. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. (9) A method in which a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) is catalytically reacted with a titanium compound.

(10) A method in which a complex consisting of a magnesium compound containing an alkoxy group and an electron donor (a) is contacted with an organometallic compound and then reacted with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor (a) and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound.

(12) A liquid magnesium compound having no reducing ability is reacted with a liquid titanium compound in the presence of an electron donor (a), if necessary, to precipitate a solid magnesium-titanium complex. How to make.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor (a) and a titanium compound.

(15) A magnesium compound, a titanium compound and, if necessary, an electron donor (a) are pulverized to obtain a solid substance, which is treated with halogen, a halogen compound or an aromatic hydrocarbon. how to. This method may include a step of pulverizing only the magnesium compound, the complex compound consisting of the magnesium compound and the electron donor (a), or the magnesium compound and the titanium compound. In addition, after pulverization, a preliminary treatment with a reaction aid may be performed, and then a halogen treatment may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds.

(16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, an electron donor (a) or a reaction aid may be used during pulverization and / or contact / reaction.

(17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with a titanium compound and optionally an electron donor (a).

(19) A method of reacting a magnesium salt of an organic acid, a magnesium compound such as alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and, if necessary, an electron donor (a).

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor (a). At this time, if necessary, a halogen-containing compound such as a halogen-containing silicon compound may be further contacted.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) composite,
Then, a method of reacting the titanium compound and, if necessary, the electron donor (a).

Such solid titanium catalyst component [A-1]
Is usually -70 ° C to 200 ° C, preferably -50
It is carried out at a temperature of ℃ to 150 ℃. The solid titanium catalyst component [A-1] thus obtained contains titanium, magnesium, halogen and preferably the electron donor (a).

In this solid titanium catalyst component [A-1], the halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, and the magnesium / titanium (atomic ratio) is 1 to 100, It is preferably 2 to 50.

Preferably, the electron donor (a) is usually such that the electron donor (a) / titanium (molar ratio) is 0.01.
-100, preferably 0.05 to 50. Details of the method for preparing such a solid titanium catalyst component [A-1] are described in, for example, the following publications.

JP-B-46-34092, JP-B-53-46799, JP-B-60-3323, JP-B-63-54289, JP-A-1-61404
No. 1, JP-A 1-261407, JP-B 47-41676, JP-B 47-4
6269, JP-B-48-19794, JP-A-60-262803, JP-A-59-147004, JP-A-59-149911, JP-A-1-201308
JP-A-61-151211, JP-A-53-58495, JP-A-53-
87990, JP 59-206413, JP 58-206613, JP 58-125706, JP 63-68606, JP 63-69806
No. 60-81210, No. 61-40306, No. 51-2
81189, JP-A-50-126590, JP-A-51-92885, JP-B-57-45244, JP-B-57-26613, JP-B-61-5483,
JP-A-56-811, JP-B-60-37804, JP-B-59-50246
No. 58, JP-A-58-83006, JP-A-48-16986, JP-A-49-6
5999, JP-A-49-86482, JP-B-56-39767, JP-B
56-32322, JP-A-55-29591, JP-A-53-146292,
JP-A-57-63310, JP-A-57-63311, JP-A-57-63312
JP-A-62-273206, JP-A-63-69804, JP-A-61-
21109, JP 63-264607, JP 60-23404, JP 60-44507, JP 60-158204, JP 61-55104
No. 2, JP-A-2-28201, JP-A-58-196210, JP-A-64-5
4005, JP-A-59-149905, JP-A-61-145206, JP-A-63-302, JP-A-63-225605, JP-A-64-69610,
JP-A-1-168707, JP-A-62-104810, JP-A-62-1048
11, JP-A-62-104812, JP-A-62-104813 and the like.

As the catalyst component [A-1], the example of using a titanium compound has been described above. In the present invention, titanium is zirconium, hafnium, vanadium or niobium in the above titanium compound as the catalyst component [A-1]. ,
It can also be exemplified in place of tantalum or chromium.

In the present invention, as another example of the solid titanium catalyst component mentioned as the [A] transition metal compound catalyst component, a conventionally known [A-2] titanium trichloride-based catalyst component may be used.

As the titanium trichloride catalyst component [A-2], the above-mentioned titanium trichloride can be exemplified. Further, such titanium trichloride is used as the above-mentioned electron donor (a).
It can also be used with and / or after contacting with a tetravalent titanium compound.

Details of the method for preparing such [A-2] titanium trichloride-based catalyst component are described in, for example, the following publications. JP-A-63-17274
JP-A-64-38409, JP-A-56-34711, JP-A-61-2
87904, JP 63-75007, JP 63-83106, JP 59-13630, JP 63-108008, JP 63-27508
JP-A-57-70110, JP-A-58-219207, JP-A 1-1
44405, JP-A-1-292011, JP-A-1-292011 and the like.

Specific examples of the titanium trichloride catalyst component [A-2] include titanium trichloride. As this titanium trichloride, for example, titanium tetrachloride is reduced by bringing it into contact with hydrogen or a metal such as magnesium metal, aluminum metal, or titanium metal or an organometallic compound such as an organomagnesium compound, an organoaluminum compound or an organozinc compound. The titanium trichloride obtained is preferably used. Further, such titanium trichloride can be used together with the above-mentioned electron donor (a) and / or a tetravalent titanium compound, or after being brought into contact with them.

Further, in the present invention, [A-3] metallocene compound may be used as the [A] transition metal compound catalyst component. Specific examples of the [A-3] metallocene compound include compounds represented by the following general formula.

ML _x [wherein M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, L is a ligand coordinated to the transition metal, and at least One L is a ligand having a cyclopentadienyl skeleton, and Ls other than the ligand having a cyclopentadienyl skeleton have 1 to 1 carbon atoms.
2 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom Alternatively, it is a hydrogen atom, and x is the valence of the transition metal. ] As a ligand having a cyclopentadienyl skeleton, for example, a cyclopentadienyl group,
Methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group Group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group, and other alkyl-substituted cyclopentadienyl groups or indenyl groups , 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like can be exemplified. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula [I] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are alkylene such as ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. Containing a ligand having such a cyclopentadienyl skeleton [A-3]
When the valence of the transition metal is 4, the metallocene compound is more specifically represented by the following formula.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (wherein M is the above transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃ R groups, halogen atoms or hydrogen atoms. And k is an integer of 1 or more, and k + l + m + n = 4.) In the present invention, in the above general formula, R ² , R ³ and R ^{4 are used.}
And at least two of R ⁵ , namely R ² and R ³
A metallocene compound in which is a group (ligand) having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. It may be connected via. R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group,
An aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R, a halogen atom or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

It is also possible to use a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium in the zirconium compound as described above.

These compounds may be used alone,
You may use it in combination of 2 or more type. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. In the present invention, as the metallocene compound [A-3], a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used.

Details of the method for preparing such an [A-3] metallocene compound are described in, for example, the following publications. JP-A-63-61010, JP-A-63-1
52608, JP 63-264606, JP 63-280703, JP 64-6003, JP 1-95110, JP 3-62806,
JP-A 1-259004, JP-A 64-45406, JP-A 60-10680
8, JP-A-60-137911, JP-A-58-19309, JP-A-60
-35006, JP60-35007, JP61-296008, JP63-501369, JP61-221207, JP62-121
707, JP 63-66206, JP 2-22307, JP 2-
173110, JP2-302410, JP1-129003, JP1-210404, JP3-66710, JP3-70710, JP1-207248, JP63. -222177, JP-A-63-222178
No. 63-222179, No. 1-12407, No. 1-30
1704, JP-A-1-319489, JP-A-3-74412, JP-A-6
1-264010, JP 1-275609 A, JP 63-251405 A,
JP-A-64-74202, JP-A-2-41303, JP-A-2-131488
JP-A-3-56508, JP-A-3-70708, JP-A-3-7070
No. 9, etc.

The [A-3] metallocene compound as described above can also be used by supporting it on a carrier by bringing it into contact with a particulate carrier compound. As the carrier compound, SiO ₂ ,
Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO ₂ , Z
Inorganic carrier compounds such as nO, SnO ₂ , BaO and ThO, polyethylene, polypropylene, poly-1-butene, poly 4-
Resins such as methyl-1-pentene and styrene-divinylbenzene copolymer can be used.

These carrier compounds may be used in combination of two or more kinds. Of these, SiO ₂ , Al ₂
O ₃ and MgO are preferably used. Next, the [B] organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table used in the present invention will be described.

Such an organometallic compound catalyst component [B]
Are, for example, [B-1] organoaluminum compounds,
Complex alkyl compound of Group I metal and aluminum, Group II
Organometallic compounds of group metals can be used.

As such a [B-1] organoaluminum compound, an organoaluminum compound represented by the following general formula can be exemplified. R ^a _n AlX _3-n (In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. ) In the above general formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-
Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group. As such an organoaluminum compound, the following compounds are specifically used.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkyl aluminum such as ethylhexyl aluminum.

Alkenyl aluminum, such as isoprenyl aluminum. Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide.

Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide.

Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide.

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride. Further, as the [B-1] organoaluminum compound, a compound represented by the following general formula can also be used.

R^a _nAlY_3-n In the above general formula, R^aIs the same as above, and Y is −
OR^bGroup, -OSiR^c ₃Group, -OAlR^d ₂Group, -NR
^e ₂Group, -SiR^f ₃Group or -N (R^g) AlR^h ₂At the base
, N is 1 to 2 and R^b, R^c, R^dAnd R^hIs
Methyl group, ethyl group, isopropyl group, isobutyl group,
R is a cyclohexyl group, phenyl group, etc. ^eIs water
Elementary, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc., R^fAnd R^gIs
Examples include a methyl group and an ethyl group.

As the [B-1] organoaluminum compound, the following compounds are specifically used. (I) ^a compound represented by R ^a _n Al (OR ^b ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide; and (ii) R ^a _n Al (OSiR ^c ₃ ). A compound represented by _3-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
(SiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (iii)
_{^{R a n Al (OAlR d 2}} ) a compound represented by _3-n, for example, E
compounds represented by (iv) R ^a _n Al (NR ^e ₂ ) _3-n , such as t ₂ AlOAAlEt ₂ and (iso-Bu) ₂ AlOAl (iso-Bu) ₂ ; for example, Me ₂ AlNEt ₂ and Et ₂ AlNHMe, Me ₂ AlNHET
, Et ₂ AlN (Me ₃ Si) ₂ (iso-Bu) ₂ AlN (Me ₃ Si) _2, etc., (v) R ^a _n Al
A compound represented by (SiR ^f ₃ ) _3-n , for example, (iso-B
u) ₂ AlSiMe ₃ etc., (vi) R ^a _n Al [N (R ^g ) AlR
^h ₂ ] _3-n , for example, Et ₂ AlN (Me)
AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2, and the} like.

Further, as the above [B-1] organoaluminum compound, R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , R ^a _n
A preferable example is an organoaluminum compound represented by Al (OAlR ^d ₂ ) _3-n .

Examples of complex alkylated products of Group I metals and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na, K, and R ^j has 1 carbon atom)
~ 15 hydrocarbon groups. ) Specifically, LiAl (C _{2
H 5) 4, LiAl (C} 7 H 15) 4 and the like.

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula. R ^k R ^l M ² (In the formula, R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and they may be the same or different from each other, but they are not halogen. ² is M
g, Zn, and Cd. ) Specifically, diethyl zinc,
Diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, etc. are mentioned.

Two or more of these compounds can be used in combination. Specific examples of such a [B-2] organoaluminum oxy compound include aluminoxanes represented by the following general formulas (1) and (2).

[0094]

[Chemical 3]

(In the general formulas (1) and (2), R
Is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 to 40. . ) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) [wherein R ¹ and R ²
May be the same hydrocarbon group as R, and R ¹ and R ² represent different groups]. In that case, the methyloxyaluminum unit (OAl (C
H ₃ )) is 30 mol% or more, preferably 50 mol% or more,
Particularly preferably, an aluminoxane formed from mixed alkyloxyaluminum units contained in a proportion of 70 mol% or more is suitable.

The [B-2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound found by the present applicants. May be.

As the method for producing such aluminoxane, the following method can be exemplified. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted.

(2) A method in which water is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin compound such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of an organometallic component other than aluminum. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

Isoprenylaluminum represented by the following general formula can also be used. (I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z (In the formula, x, y and z are positive numbers and z ≧ 2x.) Of these, trialkylaluminum is particularly preferable. .

The above organoaluminum compounds may be used alone or in combination. As the solvent used in the production of aluminoxane, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and gas oil And hydrocarbon solvents such as halides, especially chlorinated compounds and brominated compounds of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, ethers such as ethyl ether and tetrahydrofuran. Of these, aromatic hydrocarbons are particularly preferably used.

In the present invention, when the [A] transition metal compound catalyst component is the [A-1] solid titanium catalyst component or the [A-2] titanium trichloride-based catalyst component, the [B] organometallic compound is used. The compound catalyst component is preferably a [B-1] organoaluminum compound, and when the [A] transition metal compound catalyst component is a [A-3] metallocene compound, the [B] organometallic compound catalyst component is , [B-2] organoaluminum oxy compound is preferable.

In preliminarily copolymerizing the [A] transition metal compound catalyst component and the [B] organometallic compound catalyst component with an α-olefin and a polyene compound,
If necessary, the above-mentioned electron donor (a) or the following electron donor (b) may be used.

As the electron donor (b), an organosilicon compound represented by the following general formula can be used. R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-
Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used.

These organosilicon compounds can be used in combination of two or more kinds. Further, in the present invention, as the electron donor (b), 2,6-substituted piperidines; 2,5-substituted piperidines; N, N, N ', N'-tetramethylmethylenediamine, N, N, N' Substituted methylenediamines such as N'-tetraethylmethylenediamine; Nitrogen-containing electron donors such as substituted methylenediamines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine, triethylphos Phosphorus-containing electron donors such as phosphites such as phyto, tri-n-propyl phosphite, tri-isopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite It is also possible to use oxygen-containing electron donors such as 2,2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.

Two or more kinds of the above electron donors (b) can be used in combination. In the present invention, when producing an olefin-based polymer, first, the above [A] transition metal compound catalyst component and [B] organometallic compound catalyst component are copolymerized with an olefin and a polyene compound to carry out preliminary polymerization. It forms the catalyst.

Examples of the olefin used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, and specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1- Pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. These olefins may be used alone or in combination.

Of these, ethylene is preferably used. The olefin used in the prepolymerization may be the same as or different from the α-olefin used in the main polymerization described later.

Specific examples of the polyene compound used for the prepolymerization include the following compounds.
4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 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, 6-methyl-
1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-
1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-
1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-
1,6-undecadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1, Aliphatic polyene compounds such as 13-tetradecadiene, 1,5,9-decatriene, butadiene and isoprene; vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, 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, 1,5-diallyl Cyclooctane, 1,3,4-trivinylcyclohexane, 1-allyl-4-
Isopropenyl cyclohexane, 1-isopropenyl-4-
Alicyclic polyene compounds such as vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane; aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene.

These polyene compounds are used alone or in combination in the copolymerization (prepolymerization) with olefin. In the present invention, among the polyene compounds as described above, polyene compounds having 7 or more carbon atoms and having olefinic double bonds at both ends are preferably used, and further have olefinic double bonds at both ends. An aliphatic or alicyclic polyene compound is more preferably used.

Specifically, 1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, 1,13-tetradecadiene,
1,5,9-decatriene, 1,4-divinylcyclohexane, 1,
3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane and the like are preferably used.

Of these, it is desirable to use an aliphatic polyene compound having 8 or more carbon atoms, preferably 10 or more carbon atoms, and particularly preferably a linear aliphatic polyene compound having 10 or more carbon atoms.

In the present invention, in copolymerizing (preliminarily polymerizing) the above olefin and polyene compound,
Ethylene / 1,7-octadiene, ethylene / 1,9-decadiene, ethylene / 1,1-3-tetradecadiene, ethylene / 1
5,9-decatriene, propylene / 1,9-decadiene, propylene / 1,5,9-decatriene, butene / 1,9-decadiene, 4-methyl-1-pentene / 1,9-decadiene, 3-methyl-
It is preferred to copolymerize with a combination of 1-butene / 1,9-decadiene, ethylene / 1,4-divinylcyclohexane and propylene / 1,4-divinylcyclohexane.

In the present invention, when the above [A] transition metal compound catalyst component and [B] organometallic compound catalyst component are copolymerized (prepolymerized) with an olefin and a polyene compound, the polyene compound is 1
It is generally used in an amount of 0.001 to 5 mol, particularly preferably 0.01 to 2 mol, based on mol.

In the present invention, the prepolymerization can be carried out in the coexistence of an inert solvent described below, and the above olefin, polyene compound and catalyst component can be added to the inert solvent and the polymerization can be carried out under relatively mild conditions. preferable. At this time, it may be carried out under the condition that the produced copolymer is dissolved in the polymerization medium, or it may be carried out under the condition that it is not dissolved, but it is preferably carried out under the condition that it is not dissolved.

Specific examples of the inert solvent used in the prepolymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane,
Examples thereof include alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these inert solvents, it is particularly preferable to use an aliphatic hydrocarbon.

The prepolymerization can be carried out in any of batch system, semi-continuous system and continuous system. In prepolymerization,
A catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.

The concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used, but the concentration of the [A] transition metal compound catalyst component is usually about 0.001 in terms of transition metal atom per liter of the polymerization volume. ~ 5000 mmol, preferably about 0.01-1000 mmol, particularly preferably 0.1-500 mmol.

[B] The organometallic compound catalyst component is [A]
0.01 to 2000 per 1 g of the transition metal compound catalyst component
g, preferably 0.03 to 1000 g, more preferably 0.05 to 200 g, is used in an amount such that a polymer is produced, and is usually about 1 mol per transition metal atom in the catalyst component [A] transition metal compound. It is used in an amount of 0.1 to 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol.

In the present invention, an electron donor similar to the above-mentioned electron donors (a) and (b) may be used in the prepolymerization, and the electron donor may be a [A] transition metal compound catalyst. 0.01 to 50 moles, preferably 0.05 to 30 moles, and more preferably 0.1 to 1 mole per transition metal atom in the component.
Used in an amount of 10 mol.

The reaction temperature in the prepolymerization is usually about -20.
It is desirable to be in the range of -100 to 100 ° C, preferably about -20 to 80 ° C, and more preferably -10 to 40 ° C. More specifically, the preparation of the prepolymerization catalyst is performed as follows.

(I) In an inert solvent, the catalyst component [A] transition metal compound catalyst component, [B] organometallic compound catalyst component and, if necessary, an electron donor are contacted in advance to form a catalyst,
A method of forming a prepolymerized catalyst by copolymerizing an olefin and a polyene compound with this catalyst.

(Ii) In the mixture of the olefin and the polyene compound, the catalyst component [A] transition metal compound catalyst, the catalyst component [B] organometallic compound and, if necessary, the electron donor are previously contacted to form a catalyst. Then, the catalyst is copolymerized with an olefin and a polyene compound to form a prepolymerized catalyst.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. The prepolymerization catalyst used in the present invention comprises the [A] transition metal compound catalyst component and [B] organometallic compound catalyst component
0.01 to 2000 per 1 g of the transition metal compound catalyst component
It is obtained by copolymerizing the above-mentioned olefin and polyene compound in an amount of g, preferably 0.03 to 1000 g, and more preferably 0.05 to 200 g.

The prepolymerized catalyst thus obtained is
An olefin / polyene copolymer, which is a copolymer of an olefin and a polyene compound (hereinafter, may be simply referred to as “olefin / polyene copolymer”), is contained in the olefin / polyene compound copolymer. , The structural units derived from olefins are from 99.999 to 50.
Mol%, preferably 99.999 to 70 mol%, more preferably 99.995 to 75 mol%, and further 99.99 to
The amount of the structural unit derived from the polyene compound is 0.0 in an amount of 80 mol%, particularly preferably 99.95 to 85 mol%.
01 to 50 mol%, preferably 0.001 to 30 mol%, more preferably 0.005 to 25 mol%, further preferably 0.01 to 20 mol%, and particularly preferably 0.05.
It is desirable that the content is ˜15 mol%.

Here, the proportion (molar fraction) of the structural units derived from the olefin in the above copolymer is measured as follows. [Mole Fraction Measuring Method] Hexachlorobutadiene 2.0 m
0.35 g of the copolymer was added to 1 and the mixture was heat-dissolved. After filtering this solution through a glass filter (G2), 0.5 ml of deuterated benzene was added to the filtrate to obtain N with an inner diameter of 10 mm.
Insert into MR tube.

A ¹³ C-NMR spectrum is measured at 120 ° C. using a GX-270 type NMR measuring device manufactured by JEOL Ltd. The cumulative number of times is 20,000 or more. From the ¹³ C-NMR spectrum obtained as described above, the peak intensity derived from a structural unit derived from an olefin (hereinafter simply referred to as a structural unit) and the peak intensity derived from the polyene compound structural unit or the sum of peak intensities. And the molar fraction of the olefin structural unit can be calculated from these.

Specifically, for example, the method of Bovey et al. (Ac
ademic Press P80 (1972)) and Ray et al.'s method (Macromole
cules, 10 , 773 (1977)) and the like can determine the amount of building blocks derived from olefins.

When the olefin-based copolymer does not dissolve in the above-mentioned hexachlorobutadiene, the amount of the olefin and polyene compound consumed during the polymerization is measured as described later to obtain the copolymer. Can be calculated. Specifically, the mol% [P mol%] of the structural unit derived from polyene is calculated as follows.

[0134]

[Equation 1]

(Where [P ₀ ] is the number of moles of the polyene compound supplied during polymerization [P _r ] is the number of moles of the unreacted polyene compound [α ₀ ]: The number of moles of the olefin supplied during the polymerization [α _r ]: number of moles of unreacted olefin) The above [α _r ] and [P _r ] are determined by measuring the unreacted olefin and polyene compound remaining in the polymerization vessel by using gas chromatography or the like. .

The prepolymerized catalyst obtained as described above is usually obtained in a suspended state. Such a prepolymerized catalyst can be used as it is in a suspended state in the polymerization in the next step, or the produced prepolymerized catalyst can be separated from the suspension and used.

The prepolymerized catalyst obtained in the above suspended state is
In the main polymerization step described below, it may not be necessary to further add [B] the organometallic compound catalyst component or the electron donor.

In the present invention, the olefin may be preliminarily polymerized with the [A] transition metal compound catalyst component and the [B] organometallic compound catalyst component prior to the above-mentioned prepolymerization.

As the olefin, the above-mentioned olefins are used. Of these, α-olefins are preferable, and propylene is more preferable. By polymerizing or copolymerizing an olefin using such a prepolymerization catalyst, an olefin polymer having a high melt tension can be obtained.

In the present invention, the olefin polymerization catalyst may contain other components useful for the polymerization of olefins, in addition to the above components. In the method for producing an olefin polymer according to the present invention, a prepolymerization catalyst [I] as described above and an organometallic compound catalyst component [II] containing a metal selected from Group I to Group III of the periodic table are used. The olefin is polymerized or copolymerized in the presence of As the organometallic compound catalyst component [II] used in this polymerization, the same organometallic compound catalyst component [B] as described above is used.

Specific examples of the olefin used in the main polymerization include ethylene and the above-mentioned α-olefin having 3 to 20 carbon atoms. Aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, substituted allylnaphthalenes, vinylcyclopentane, substituted vinylcyclopentanes, vinyl Cyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allyl norbornane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-
Cyclic olefins such as 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-
Examples thereof include silane unsaturated compounds such as butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, and 10-trimethylsilyl-1-decene, and the above-mentioned polyene compounds.

These are used alone or in combination. Among these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene, etc. It is preferably used.

In the present polymerization of the present invention, the amount of ethylene or α-olefin having 3 or more carbon atoms used varies depending on the type of olefin, the type of catalyst, etc., and therefore cannot be said to be a single value, but the final yield is obtained. In such an olefin polymer, it is preferable to use such an amount that the constitutional unit derived from ethylene or an α-olefin having 3 or more carbon atoms is contained in a proportion of 70 mol% or more. Specifically, for example, when copolymerizing ethylene and propylene, propylene is usually used in an amount of 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more.
It is used in an amount of more than mol% and copolymerized.

In the present invention, the constitutional unit derived from an olefin other than the α-olefin is contained in an amount of 30 mol% or less,
The amount is preferably 20 mol% or less, more preferably 15 mol% or less.
It may be contained in an amount of mol%.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization takes a reaction form of slurry polymerization, the reaction solvent may be the same solvent as the inert solvent used in the above-mentioned prepolymerization,
It is also possible to use olefins which are liquid at the reaction temperature.

In the polymerization method of the present invention, the prepolymerization catalyst [I] is usually about 0.001 to 100 mmol, preferably about 0, in terms of the transition metal atom in the prepolymerization catalyst per liter of the polymerization volume. Used in an amount of 0.005 to 20 mmol. In the organometallic compound catalyst component [II], the metal atom in the compound [II] is usually about 1 to 2000 mol, based on 1 mol of the transition metal atom in the prepolymerization catalyst in the polymerization system.
It is preferably used in an amount of about 2 to 500 mol.

Further, in the present invention, the same electron donors as the above-mentioned electron donors (a) and (b) can be used. The electron donor is usually used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound catalyst component [II].

If hydrogen is used during the polymerization, the molecular weight of the resulting polymer can be adjusted and a polymer having a high melt flow rate can be obtained. In the present invention, the polymerization conditions are different depending on the olefin used, but the polymerization is usually carried out under the following conditions.

The polymerization temperature is usually about 20 to 300 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is atmospheric pressure to 1 ° C.
00 kg / cm ² , preferably about ² to 50 kg / cm ² .

In the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In the present invention, in the present polymerization, a homopolymer of olefin may be produced, or a random copolymer or a block copolymer may be produced from two or more kinds of olefins. Specifically, polypropylene, poly (4-methyl-1-pentene), poly (1-butene), poly (3
-Methyl-1-pentene), a propylene-based random copolymer, a propylene-based block copolymer, a 4-methyl-1-pentene-based copolymer, and the like.

When the olefin polymerization method is carried out using the above olefin polymerization catalyst, an olefin polymer having a high melt tension can be produced with a high polymerization activity.

The olefin polymer thus obtained has a melt flow rate (MFR) measured according to ASTM D1238E of 5000 g / 10 minutes or less, preferably 0.01 to 3000 g / 10 minutes, More preferably 0.02 to 2000 g / 10 minutes, and particularly preferably 0.02.
It is in the range of 05 to 1000 g / 10 minutes.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.1.
˜15 dl / g, particularly preferably 0.2 to 13 dl / g.

Such an olefin polymer has a higher melt tension than conventional olefin polymers. It is generally known that the melt tension of an olefin polymer varies depending on the type of the olefin polymer and has a correlation with the melt flow rate of the olefin polymer. Therefore, the melt tension of the olefin polymer obtained as described above is difficult to unconditionally specify, but the melt tension (MT) and the melt flow rate (MFR) of the olefin copolymer are
And satisfy the following formula.

For example, when the olefin polymer formed by the main polymerization is polypropylene, log (MT) ≧ −0.8log (MFR) +0.5, preferably log (MT) ≧ −0.8log ( MFR) +0.6 More preferably, log (MT) ≧ −0.8log (MFR) +0.7 Particularly preferably, the formula represented by log (MT) ≧ −0.8log (MFR) +0.8 is satisfied. There is.

The melt tension (MT) of this olefin polymer is the melt flow rate (MF) as described above.
R) and the intrinsic viscosity ([η]) satisfy the following equation.

Log (MT) ≧ 3.7 log ([η])-1.3 Preferably log (MT) ≧ 3.7 log ([η])-1.2 More preferably log (MT) ≧ 3 .7log ([η])-1.1 Particularly preferably, log (MT) ≧ 3.7log ([η])-1.0 The melt tension is measured as follows.

Using the MT measuring device manufactured by Toyo Seiki Seisakusho,
Above the melting temperature of the polymer (190 for polyethylene)
C., 230.degree. C. in the case of polypropylene) are inserted into the cylinder in the order of orifice, polymer 7 g and piston. After 5 minutes, the piston is pushed down at a speed of 10 mm / min, and the molten polymer is pushed out through the orifice at the bottom of the cylinder. The extruded strand is drawn into a filament shape, passed through a pulley of a load detector, and wound up by a roller at a winding speed of 25 m / min. At this time, the stress applied to the pulley is measured, and this value is taken as the melt tension of the polymer.

The olefin polymer having a high melt tension according to the present invention (hereinafter referred to as "high MT olefin polymer") is obtained by irradiating the olefin polymer thus obtained with radiation. . When the above-mentioned olefin polymer is irradiated with radiation in this way, it becomes an olefin polymer having a higher melt tension.

The olefin polymer is preferably in the form of particles when irradiated with radiation, and the particle size is preferably 5 mm or less, preferably 0.1 to 4.5 mm. The particles are meant to include powders, flakes, granules and other forms.

When the olefin polymer is irradiated with radiation, the absorbed dose of the olefin polymer is 0.1 to 100 Mrad at a temperature not lower than the β dispersion temperature and not higher than the α dispersion temperature of the polymer. It is desirable to carry out so as to be 0.5 to 10 Mrad.

Here, the β-dispersion temperature of the olefin polymer means the temperature at which the molecular mobility of the entire molecular chain existing in a part other than the crystal part of the molecular chain in the polymer starts. Therefore, below this temperature, most of the molecular chains existing in other than the crystal part of the olefin polymer are in a glass state.

The α-dispersion temperature means the temperature at which the molecular mobility of the molecular chain in the crystal part of the olefin polymer starts. Therefore, above this temperature, the crystal part of the olefin polymer is in a softened state.

That is, in the present invention, the olefin polymer is irradiated with radiation in a state where the crystal part of the olefin polymer is robust and the molecular motion other than the crystal part is active, so that the part other than the crystal part is modified. This is very important. The reason for this is not clear, but usually the crystal part is composed of a molecular chain part without defects such as the central part of the molecular chain,
On the contrary, since it is configured to include many defect parts such as molecular end parts other than the crystal part, it is considered that the defect-free part is left as it is and the part containing many defect parts is modified by irradiation. .

Irradiation of the olefin polymer can be carried out in air, nitrogen gas, carbon dioxide gas or the like. In order to prevent gelation of the olefin polymer, the olefin polymer is treated under an inert atmosphere such as nitrogen gas. It is preferable to carry out.

Examples of the radiation used in the present invention include electron beams, β rays, γ rays, and the like, and examples of the radiation source include an electron beam irradiation device, a nuclear reactor, and radioactive isotopes. Among these, it is preferable to use an electron beam, and a commercially available electron beam irradiation device can be used.

In the present invention, the irradiation of radiation can be carried out in either a batch system or a continuous system, but a continuous system is preferred. When an olefin polymer is irradiated with radiation, active radicals are generated. The active radicals cause crosslinking of the olefin polymer and / or formation of free-end long-chain branches, and at the same time, decomposition of the olefin polymer also proceeds. Especially when the olefin polymer is polypropylene, unless a crosslinking agent and a crosslinking aid are added,
Decomposition of the olefin polymer is more likely to proceed than crosslinking and / or formation of long-chain branches. Further, even if a very small amount of oxygen is mixed, the decomposition of the olefin polymer is greatly promoted. Therefore, the MFR after irradiation with radiation is larger than the MFR before irradiation with radiation. However, as the MFR increases, the melt tension decreases, so it is desirable that the increase in MFR be as small as possible in order to obtain a high MT polyolefin. That is, it is preferable that the radiation dose is small. Generally, the modification effect is small when the radiation dose is small, but the high MT polyolefin of the present invention has a high modifying effect even when the radiation dose is small.

The olefin polymer which is irradiated with radiation may contain additives such as various stabilizers and pigments, but preferably, the olefin polymer which does not contain these additives is irradiated with radiation and then It is desirable to pelletize the olefin polymer with the additive.

At this time, the high M which has been subjected to the radiation treatment.
It is desirable that the T-olefin polymer is pelletized with a heat stabilizer as early as possible after the treatment to stabilize the radical residue generated by irradiation with radiation. Examples of the heat stabilizer used at this time include a phenol heat-resistant stabilizer, a phosphorus heat-resistant stabilizer, a sulfur heat-resistant stabilizer, an amine heat-resistant stabilizer, and the like. In the present invention, the phenol heat stabilizer is preferable. Further, a combined use system of a phenol heat resistance stabilizer and a phosphorus heat resistance stabilizer is particularly preferable.

When the high MT olefin polymer subjected to the irradiation treatment is left for a long period of time, residual active radicals cause cross-linking to form a gel component and inflation,
It causes formation of fish eyes during T-die film formation.

When the olefin polymer is thus irradiated with radiation, it becomes an olefin polymer having a high melt tension. The high MT olefin polymer of the present invention has a melt flow rate measured according to ASTM D1238E of 0.01 to 3000 g / 10 minutes, preferably 0.02 to 2000 g / 10 minutes, more preferably 0.02.
It is 5 to 1000 g / 10 minutes.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.1.
˜15 dl / g, particularly preferably 0.2 to 13 dl / g. Such a high MT olefin polymer has a higher melt tension than conventional olefin polymers.

The high MT olefin polymer of the present invention has a melt tension (MT) and a melt flow rate (MF).
R) satisfies the following formula. For example, when the high MT olefin polymer is polypropylene, log (MT) ≧ −0.8log (MFR) +0.5 is preferable, log (MT) ≧ −0.8log (MFR) +0.6 is further preferable. Satisfies log (MT) ≧ −0.8 log (MFR) +0.7, and particularly preferably satisfies the relationship represented by log (MT) ≧ −0.8 log (MFR) +0.8.

The melt tension (MT) of this high MT olefin polymer satisfies the relational expression with the melt flow rate (MFR) as described above, and is expressed by the following equation with the intrinsic viscosity ([η]). Meet

For example, when the high MT olefin polymer is polypropylene, log (MT) ≧ 3.7 log ([η])-1.3, preferably log (MT) ≧ 3.7 log ([η] ) -1.2, more preferably log (MT) ≧ 3.7 log ([η])-1.1, most preferably log (MT) ≧ 3.7 log ([η])-1.0. Meet a relationship.

Further, the high MT olefin copolymer obtained by the method of the present invention has a percentage of insoluble components not extracted by hot xylene of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less. It is particularly preferable that the amount is 3% by weight or less.

As described above, the high MT olefin polymer of the present invention has a higher melt tension than the olefin polymer obtained by the conventional method. Further, the high MT olefin polymer is excellent in rigidity, transparency, mechanical strength such as impact strength, and appearance. Therefore, by using such a high MT olefin polymer, it is possible to obtain a film having excellent appearance such as no fish eyes, excellent transparency, and high strength.

[0179]

The olefin polymer according to the present invention has a higher melt tension than the conventionally known olefin polymers. Further, according to the method for producing an olefin polymer according to the present invention, it is possible to produce an olefin polymer having a higher melt tension than conventionally known olefin polymers. Since such a high MT olefin polymer is excellent in inflation moldability, it is possible to produce an inflation film having a high yield and excellent in appearance, transparency, strength, etc. at high speed. Further, since this high MT olefin polymer can be molded by a molding method such as a blow molding method or a vacuum molding method which could not be conventionally applied due to lack of melt tension, the usage of the olefin polymer is expanded. Will be done.

[0180]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0181]

Example 1 [Preparation of solid titanium catalyst component [A-1]] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to obtain a uniform solution. Then, 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve the phthalic anhydride. After cooling the homogeneous solvent thus obtained to room temperature,
75 ml of this homogeneous solution was added dropwise to 200 ml of titanium tetrachloride kept at 20 ° C. over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, and thoroughly washed with decane at 110 ° C. and hexane at room temperature until no free titanium compound was detected in the solution. The solid titanium catalyst component [A-1] prepared by the above operation was stored as a hexane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [A-1] thus obtained was 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13.0% by weight of DIBP.

[Preliminary Polymerization of Solid Titanium Catalyst Component [A-1]] In a 400 ml four-necked glass reactor equipped with a stirrer, 200 ml of purified hexane, 6 mmol of triethylaluminum and the above solid titanium catalyst component in a nitrogen atmosphere were added. A-1] was added in an amount of 2.0 mmol in terms of titanium atom, and then propylene was fed to this reactor at a temperature of 20 ° C. at a rate of 6.4 l / hour for 1 hour.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane to make the total amount in the catalyst bottle. Transfer the liquid to the prepolymerization catalyst [B
-1] was obtained.

[Preparation of Prepolymerized Catalyst [I] -1] 400
In a four-necked glass reactor equipped with a stirrer, 167 ml of purified hexane, 1 ml of 1,9-decadiene, 5 mmol of diethylaluminum ethoxide, and the above prepolymerized catalyst [B-1] in a nitrogen atmosphere were added in an amount of 0.1. After adding 5 mmol, ethylene 1 was added at a temperature of 0 ° C. for 4 hours.
3 liters were fed to this reactor.

When the supply of ethylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane and the whole amount was put in a catalyst bottle. Liquid transfer and prepolymerization catalyst [I]
-1 was obtained.

[Polymerization] 750 ml of purified hexane was charged into an autoclave having an internal volume of 2 liters, and 0.75 mmol of triethylaluminum and cyclohexylmethyldimethoxysilane (CMM) were added in a propylene atmosphere at 60 ° C.
S) (0.75 mmol) and the prepolymerized catalyst [I] -1 (0.015 mmol) in terms of titanium atom were charged.

200 ml of hydrogen was introduced, the temperature was raised to 70 ° C., and this was held for 2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 7 kg / cm ² G. After completion of the polymerization, the slurry containing the produced solid was filtered to separate a white powder and a liquid phase part. The yield of the white powdery polymer after drying was 326.4.
g, extraction residual rate with boiling heptane is 98.2%, MFR
Was 1.7 dg / min, apparent bulk specific gravity was 0.45 g / ml, and melt tension was 8.0 g. On the other hand, by concentrating the liquid phase part, 1.3 g of a solvent-soluble polymer was obtained. Therefore, the activity was 21,800 g-PP / mM-Ti and the I.V. I. (Total-II) was 97.8%.

The results are shown in Table 1. [Radiation Irradiation] As the electron beam irradiation device, "Curetron" manufactured by Nisshin High Voltage was used.

To 30 g of the above powdery polymer was added tetrakis [methylene-3 (3,5-t-butyl-4-hydroxyphenyl)].
Propionate] Methane (Ciba Geigy Irganox101
After adding 3 mg of 0) and powder blending, the bottom area is 1
A polyethylene bag of 00 cm ² (10 cm × 10 cm) was filled so that the height was uniform.

This was placed on the conveyor of the above-mentioned electron beam irradiation apparatus and passed through an electron beam beam generated at an acceleration voltage of 200 kV in a nitrogen atmosphere. The absorbed dose of the powdery polymer at this time was 8 megarads. After the electron beam irradiation, the powdery polymer had an MFR of 3.6 dg / min and a melt tension of 6.4 g.

The results are shown in Table 2.

[0192]

Example 2 [Polymerization] 750 ml of purified hexane was charged into an autoclave having an internal volume of 2 liters, and 0.75 mmol of triethylaluminum, 0.75 mmol of cyclohexylmethyldimethoxysilane (CMMS) and a preliminary were added in a propylene atmosphere at 25 ° C. Polymerization catalyst [I] -1 was charged in an amount of 0.015 mmol in terms of titanium atom.

The supply of propylene gas was stopped and the supply of a mixed gas of ethylene 7 mol% -propylene 93 mol% was started. 250 ml of hydrogen was introduced, the temperature was raised to 60 ° C., and this was kept for 1.5 hours to carry out propylene-ethylene copolymerization. The pressure during the polymerization was kept at 7 kg / cm ² G.

The results are shown in Table 1. [Radiation irradiation] The same procedure as in Example 1 was carried out using the obtained copolymer.

The results are shown in Table 2.

[0196]

Example 3 [Preparation of Prepolymerized Catalyst [I] -3] Purified Hexane 167
ml, 7-methyl-1,6-octadiene (5 ml), diethylaluminum chloride (5 mmol) and the prepolymerization catalyst [B-1] (0.5 mmol in terms of titanium atom),
Example 1 except that 13 liters of ethylene were reacted
Prepolymerization is carried out in the same manner as above, and the prepolymerization catalyst [I]-
Got 3.

[Polymerization] Polymerization was carried out in the same manner as in Example 1 except that the prepolymerization catalyst [I] -3 was used.

The results are shown in Table 1. [Radiation irradiation] The same procedure as in Example 1 was carried out using the obtained copolymer.

The results are shown in Table 2.

[0200]

Comparative Example 1 [Polymerization] Except that the prepolymerization catalyst [B-1] was used.
Propylene polymerization was carried out in the same manner as in Example 1.

The results are shown in Table 1. [Radiation irradiation] The same procedure as in Example 1 was carried out using the obtained copolymer.

The results are shown in Table 2.

[0203]

Comparative Example 2 [Polymerization] Except that the prepolymerization catalyst [B-1] was used.
Propylene-ethylene copolymerization was carried out in the same manner as in Example 2.

The results are shown in Table 1. [Radiation irradiation] The same procedure as in Example 1 was carried out using the obtained copolymer.

The results are shown in Table 2.

[0206]

[Table 1]

[0207]

[Table 2]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (6)

[Claims] 1. An olefin and a polyene compound are added to an organometallic compound catalyst component [I] [A] transition metal compound catalyst component and [B] a metal selected from Group I to Group III of the periodic table. An organic compound containing a prepolymerized catalyst prepared by prepolymerization in an amount of 0.01 to 2000 g per 1 g of the transition metal compound catalyst component [A], and a metal selected from Group I to Group III of the periodic table. An olefin-based polymer, characterized in that a polymer obtained by polymerizing or copolymerizing an olefin containing ethylene as an essential component in the presence of a metal compound catalyst component is irradiated with radiation. 2. An olefin and a polyene compound are added to an organometallic compound catalyst component containing [I] [A] transition metal compound catalyst component and [B] metal selected from Group I to Group III of the periodic table. An organic compound containing a prepolymerized catalyst prepared by prepolymerization in an amount of 0.01 to 2000 g per 1 g of the transition metal compound catalyst component [A], and a metal selected from Group I to Group III of the periodic table. A polymer obtained by polymerizing or copolymerizing an olefin having an olefin having 3 or more carbon atoms as an essential component in the presence of a metal compound catalyst component, and irradiating the polymer with radiation. Polymer. 3. A radiation dose in the range of 0.1 to 100 Mrad as an absorbed dose of the polymer.
The olefin-based polymer described in 1. 4. [I] [A] a transition metal compound catalyst component and [B] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table containing an olefin and a polyene compound. An organic compound containing a prepolymerized catalyst prepared by prepolymerization in an amount of 0.01 to 2000 g per 1 g of the transition metal compound catalyst component [A], and a metal selected from Group I to Group III of the periodic table. A method for producing an olefin-based polymer, which comprises polymerizing or copolymerizing an olefin containing ethylene as an essential component in the presence of a metal compound catalyst component, and then irradiating the obtained polymer with radiation. 5. [I] [A] a transition metal compound catalyst component and [B] an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table containing an olefin and a polyene compound. An organic compound containing a prepolymerized catalyst prepared by prepolymerization in an amount of 0.01 to 2000 g per 1 g of the transition metal compound catalyst component [A], and a metal selected from Group I to Group III of the periodic table. An olefin polymer characterized by polymerizing or copolymerizing an olefin having an olefin having 3 or more carbon atoms as an essential component in the presence of a metal compound catalyst component, and then irradiating the obtained polymer with radiation. Manufacturing method. 6. A radiation dose in the range of 0.1 to 100 Mrad as an absorbed dose of the polymer.
The method for producing an olefin-based polymer according to 1.