KR960011549B1 - Prepolymerized olefin polymerization - Google Patents

Abstract

None.

Description

Prepolymerized catalyst

1 is a view showing processes of the olefin polymer production method using the prepolymerized catalyst [I] of the present invention.

The present invention relates to a prepolymerized catalyst capable of producing an olefin polymer having a high melt tension.

Olefin polymers such as polypropylene, high density polyethylene, and linear low density polyethylene (LLDPE) are excellent in mechanical properties such as stiffness and impact strength as well as transparency, and are conventionally molded into films by expansion molding, injection molding, extrusion molding, and the like. .

Such olefin polymers typically have low melt tension (MT), and therefore are difficult to form into a large container (eg, a bottle), or difficult to form into a liner of an electrical appliance, for example, by vacuum forming. . By the said restriction | limiting of a shaping | molding process, the molded article obtained is also limited. That is, despite the various excellent properties, the use of these olefin polymers is limited.

In addition, in the case of polypropylene, the felt tension is low, and when forming into a film by the expansion molding method, sagging occurs, and molding conditions are limited. In order to overcome these problems, in the conventional expansion molding method, a method of stabilizing bubbles by increasing melt tension by adding high pressure low density polyethylene or the like to polypropylene has been performed. However, this method may cause a decrease in the strength of the film and a decrease in the transparency of the film.

Therefore, when developing an olefin polymer having a high melt tension (for example, polypropylene), it is possible to manufacture a large-capacity container such as a bottle by blow molding, and to manufacture a liner of an electrical article by vacuum molding from the polymer. The use of olefin polymers can thus be further extended.

In addition, when molding an olefin polymer having a high melt tension into a film by expansion molding, bubbles may be stabilized and a molding speed may be increased.

For this reason, development of polyolefin polymers, such as polypropylene, a high density polyethylene, and a linear low density polyethylene with high melt tension, has been desired.

The present inventors have studied a high melt tension olefin polymer that meets the above requirements. As a result, a novel polymer obtained by copolymerizing an α-olefin and a polyene compound in a catalyst containing a transition metal compound catalyst component and an organometallic compound catalyst component is disclosed. The present invention has been completed by revealing that an olefin polymer having a high melt tension can be obtained by polymerizing olefins in the presence of a catalyst for olefin polymerization including a prepolymerized catalyst.

It is an object of the present invention to provide a novel prepolymerisation catalyst capable of producing high melt tension olefin polymers.

According to the present invention, an α-olefin and a polyene compound are contained in a catalyst containing (A) a transition metal compound catalyst component and (B) an organometallic compound catalyst component containing a metal selected from metals of Groups I to III of the Periodic Table. There is provided a prepolymerized catalyst (I) prepared by prepolymerizing these in an amount of 0.01 to 2,000 g per 1 g of the transition metal compound catalyst component.

The prepolymerized catalyst according to the present invention will be described in detail.

In the present invention, the term polymerization may be used in the sense including not only homopolymerization but also copolymerization, and the term polymer may be used in the meaning including not only homopolymer but also copolymer.

In FIG. 1, a process for producing an olefin polymer using the prepolymerized catalyst (I) of the present invention is described.

First, the transition metal compound catalyst component (A) used to prepare the prepolymerized catalyst (I) of the present invention will be described.

The transition metal compound catalyst component (A) used in the present invention is a compound containing a transition metal selected from Group III to Group VIII metals, preferably Ti, Zr, Hf, Nb, Ta, Cr, and V. It is a compound containing at least one transition metal selected from among them.

Examples of the transition metal compound catalyst component [A] include various catalyst components, and specifically, there are solid titanium catalyst components containing titanium and halogen.

More specifically, one example of the solid titanium catalyst component is a solid titanium catalyst component (A-1) which further contains titanium, magnesium and halogen and, if necessary, the electron donor (a).

Methods of preparing the solid titanium catalyst component (A-1) are described in detail in the following publications.

That is, the methods are disclosed in, for example, the following Japanese patent publications.

Specialty Offices 46-34092, Specialty Offices 53-46799, Specialty Offices 60-3323, Specialty Offices 63-54289, Japanese Patent Application Centers 1-261404, Japanese Patent Application Centers 1-2-2407, Specialty Offices 47-19794, Japanese Postal Services 47-46269, Specialty Offices 48-19794, 60-262803, 59-147004, 59-149004, 59-149911, 1-261308, 13-151211, 53-58495, 53-87990, 53-87990 206413, special place 58-206613, special place 58-125706, special place 63-68606, special place 63-69806, special place 60-81210, special place 61-403036, special place 51-281189, special place 50-126590, Special Office 51-92885, Special Public 57-45244, Special Office 57-26613. Special Office 61-5483, Special Office 56-811, Special Office 60-337804, Special Office 59-50246, Special Office 58-83006, Special Office 48-16986, Special Office 49-65999, Special Office 49-96482, Special Office 56-.39767, JP 56-32322, JP 55-29591, JP 53-146292, JP 57-63310, JP 57-63311, JP 57-63312, JP 62-273206. Special Place 63-69804, Special Place 61-21109, Special Place 63-264607, Special Place 60-23404, Special Place 60-44507, Special Place 60-158204, Special Place 61-55104, Special Place 2-28201, Special Place 58-196210, extraordinary 64-54005, extraordinary 59-149905, extraordinary 61-145206, extraordinary 63-302, extraordinary 63-225605, extraordinary 64-69610, extraordinary 1-168707, extraordinary 62- 104810, special place 62-104811, special place 62-104812, special place 62-104813

The solid titanium catalyst component (A-1) can be produced, for example, by contacting a titanium compound, a magnesium compound and, if necessary, the electron donor (a) with each other.

Examples of the titanium compound that can be used in the preparation of the solid titanium catalyst component (A-1) include tetravalent titanium compounds and trivalent titanium compounds.

As said tetravalent titanium compound, the compound represented by a following formula is mentioned.

Ti (OR) _n X _4-n

Wherein R is a hydrogen group, X is a halogen atom, and g is a number satisfying the condition of 0 ≦ g ≦ 4.

Specific examples of the compounds are as follows.

Tetrahalogenated titanium such as TiC1 ₄ , TiBr ₄ , Til _4. and the like;

Ti (OCH ₃ ) Cl ₃ ,

Ti (OC ₂ H ₅ ) Cl ₃ ,

Ti (On- C ₄ H ₉ ) Cl ₃ ,

Ti (OC ₂ H ₅ ) Br ₃ ,

Trihalogenated alkoxytitanium such as Ti (0-iso-C ₄ H ₉ ) Br ₃ ;

Ti (OCH ₃ ) ₂ Cl ₃ ,

Ti (OC ₂ H ₅ ) ₂ Cl ₃ ,

Ti (On- C ₄ H ₉ ) ₂ Cl ₃ ,

Dihalogenated dialkoxytitanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ , and the like,

Ti (OCH ₃ ) ₃ Cl ₃ ,

Ti (OC ₂ H ₅ ) ₃ Cl ₃ ,

Ti (On-C ₄ H ₉ ) ₃ Cl ₃ ,

Monohalogenated trialkoxytitanium titanium such as Ti (OC ₂ H ₅ ) ₃ Br, etc .;

Ti (OCH ₃ ) ₄ ,

Ti (OC ₂ H ₅ ) ₄ ,

Ti (Oiso -C ₄ H ₉ ) ₄ ,

Ti (0-2-ethylhexyl) ₄ ,

Tetraalkoxy titanium, such as these, is mentioned.

Of these, tetrahalogenated titanium is preferable, and titanium tetrachloride is particularly preferable, but these titanium compounds may be used alone or in combination of two or more kinds thereof. Moreover, these titanium compounds can be diluted and used for a hydrocarbon compound or halogenated hydrocarbon compounds.

As the trivalent titanium compound, titanium trichloride is employed.

Titanium trichloride obtained by reducing titanium tetrachloride by contact with hydrogen, a metal (i.e., a magnesium metal, an aluminum metal and a titanium metal) or an organometallic compound (i.e., an organic magnesium compound, an organic aluminum compound and an organic zinc compound) is preferably used. Used.

In the present invention, a magnesium compound having or without reducing ability may be used as the magnesium compound used for producing the solid titanium catalyst component [A-1].

Here, there is a compound represented by the following formula, for example, of a magnesium compound having a reducing ability.

X _n M _g R _2-n

Wherein n is a number satisfying the condition of 0 ≦ b ≦ 2; R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group; if n is 0, the two R's may be the same or different from each other; X is halogen.

Specific examples of the organic magnesium compound having a reduction or the like are as follows: dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octylbutyl magnesium and ethyl butyl magnesium Dialkyl magnesium compounds, such as these; Halogenated alkyl magnesium such as ethyl magnesium chloride, magnesium propyl chloride, magnesium butyl chloride, hexyl chloride, magnesium amyl chloride; Alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium; Butyl magnesium hydride and the like.

As a specific example of the magnesium compound which does not have a reduction etc., it is magnesium chloride. Magnesium halides such as magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, and ethoxy chloride. Alkoxy magnesium halides, such as isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; Aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxy magnesium, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethyl hexa hexamagnesium; Aryloxy magnesium, such as phenoxy magnesium and dimethylphenoxy magnesium; Carbonate of magnesium, such as magnesium laurate and magnesium stearate, is mentioned.

In addition, magnesium metal and magnesium hydride can be used as magnesium which does not have a reducing ability.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability as described above or a compound derived at the time of preparing the catalyst component. Magnesium Compounds Having No Reducing Capability To derive from magnesium compounds having reducing ability, for example, a magnesium compound having a reducing ability may be selected from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound, or an OH compound. What is necessary is just to contact with the compound which has a group or an active carbon-oxygen bond.

The magnesium compound with or without reducing ability may form a complex compound, a complex compound with another metal, such as aluminum, zinc, boron, beryllium, sodium and potassium, which will be described later, or with other metal compounds. It may be in the form of a mixture. In addition, the magnesium compounds may be used alone or in combination of two or more. In addition, the magnesium compound may be used in a liquid or solid phase. In the case where the magnesium compound used is in the solid phase, an alcon, a carboxylic acid, an aldehyde described later as the electron donor (a). It can be converted into a liquid phase using amines, metal acid esters and the like.

Various titanium compounds other than those described above may be used to prepare the solid titanium catalyst component (A-1), but those in the form of halogen-containing magnesium compounds among the finally obtained solid titanium catalyst component (A-1) are preferable. . Therefore, when using a magnesium compound which does not contain a halogen, it is preferable to make the said solid titanium catalyst component by making the compound react with the halogen containing compound intermediately. .

Among the various magnesium compounds, a magnesium compound having no reducing ability is preferable, and magnesium chloride, alkoxymagnesium chloride and aryloxymagnesium chloride are particularly preferable among them.

In the preparation of the solid titanium catalyst component (A-1), it is preferable to use the electron donor (a).

Examples of the electron donor (a) are as follows:

Oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid allides, esters of organic or inorganic acids, ethers, diethers, acid amides, acid anhydrides, and alkoxysilanes; Nitrogen-containing electron donors such as ammonia, amine, nitrile, pyridine, and isocyanate, more specifically, methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, C1-C18 alcohols, such as oleyl alcohol, benzyl alcohol, phenyl ethyl alcohol, cumyl alcohol, isopropyn alcohol, isopropyl benzyl alcohol, trichloro ethanol, trichloroethanol, and trichlorohexanol Halogen-containing alcohols; Phenols having 6 to 20 carbon atoms which may have lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 aldehydes such as benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate , Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl lactate, ethyl gil acetate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotoate, ethyl cyclohexanecarboxylate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate. Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate. Ethyl toluate, amyl toluyl acid, methyl ethyl benzoate, methyl aniseate, ethyl aniseate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone. C2-C18 organic acid ester, acetyl chloride, such as coumarin, a phthalide, and ethyl carbonate. Acid halides having 2 to 15 carbon atoms, such as benzoyl chloride, toluic acid zlotide, and aniseic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether Ethers having 2 to 20 carbon atoms: acid amides such as N, N-dimethacetamide, N, N-dimethylbenzamide and N, N-dimethyltoluamide; Amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethyleneamine, natrils such as acitrile, benzonitrile and trinitrile, pyridine, methylpyridine, ethylpyridine and dimethylpyridine Pyridines; Acid anhydrides, such as acetic anhydride, phthalic anhydride, and benzoic anhydride, are used.

As a more preferable organic acid ester, the polycarboxylate which has frame | skeleton of the following general formula is mentioned.

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶ are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ , R ⁴ are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group A hydrocarbon group, and at least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ¹ to R ⁶ are substituted, the substituent contains other atoms such as N, O, S, and the like. For example, C-0-C, COOR, COOH, OH, SO ₃ H, -CNC- , And NH ₂ and the like.

Specific examples of the polycarboxylates are as follows.

Aliphatic polycarboxylates, alicyclic polycarboxylates, aromatic polycarboxylates, and heterocyclic polycarboxylates. Preferred embodiments include n-butyl maleate, diisobutyl methyl maleate, di-n-hexylcyclohexene carboxylate, Diethyl nitrate, diisopropyltetrahydrophthalate, diethylphthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate and dibutyl 3,4-urandicarboxylate.

As said polycarboxylate, phthalates are preferable.

As said diether compounds, the compound represented by a following formula is mentioned. .

In the formula, n is an integer that satisfies the condition 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; R ¹ ~R ^26, preferably, any combination of from R ¹ ~R ²ⁿ can hyeonggeong a ring other than benzene ring and; The main chain may contain atoms other than carbon atoms.

The good example is as follows.

2,2-diisobutyl-1,3-dimethoxypropane,

2-isopropyl-2-isopentyl-1,3-dimethoxypropane,

2,2-dicyclohexyl-1,3-dimethoxypropane and,

2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,

The electron donor may be used in combination of two or more kinds.

The solid titanium catalyst component (A-1) that can be used in the present invention can be prepared by contacting the various compounds with inorganic and organic compounds containing silicon, phosphorus, aluminum, and the like, which are commonly used as carrier compounds.

The carrier compound may be Al ₂ O ₃ , SiO ₃ , B ₂ O ₃ , MgO. The resin and the like, such as CaO, TiO _2, ZnO, SnO _2, BaO, ThO and a styrene / divinyl jenjen copolymer is used.

Of these, Al ₂ O ₃ , SiO ₂ and styrene / divinyl benzene copolymers are preferred.

The solid titanium catalyst component [A-1] usable in the present invention is prepared by bringing the titanium compound and the magnesium compound (preferably with the electron donor 3) into contact with each other.

There is no particular limitation on the method for producing the solid titanium catalyst component (A-1) using the compounds, but an example of a method using a tetravalent titanium compound is briefly described below.

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

(2) A method in which a complex consisting of a magnesium compound and an electron donor (a) is brought into contact with an organometallic compound and then the reaction product is brought into contact with a titanium compound.

(3) A method in which a product obtained by contacting an inorganic carrier with an organic magnesium compound is brought into contact with a titanium compound. In this case, the product may be brought into contact with the halogen-containing compound electron donor (a) and / or the organometallic compound in advance.

(4) An inorganic or organic carrier carrying a magnesium compound is obtained from a mixture of a magnesium compound and an electron donor (and optionally a hydrocarbon solvent) with an inorganic or organic carrier, and the resulting carrier is brought into contact with the titanated hip water. How to let.

(5) A solution containing a magnesium compound and a titanium compound electron donor (and optionally a hydrocarbon solvent) is contacted with an inorganic or organic carrier to obtain a solid titanium catalyst component (A-1) carrying magnesium and titanium. Way.

(6) A method of bringing a liquid organic magnesium compound into contact with a halogen-containing titanium compound wave

(7) A method of bringing a liquid organomagnesium compound into contact with a halogen-containing compound and then contacting the product with the method and a titanium compound.

(8) A method of bringing an alkoxy group-containing magnesium compound into contact with a halogen-containing titanium compound.

(9) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor (a) is brought into contact with a titanium compound.

(10) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor (a) is brought into contact with an organometallic compound, and then the resulting product is brought into contact with a titanium compound.

(11) A method of contacting a magnesium compound, an electron donor (a) and a titanium compound in an arbitrary order, in this reaction, each component is reacted with a reaction aid such as an electron donor (a) and / or an organometallic compound or a halogen-containing silicon compound. It can be pretreated.

(12) A method of depositing a solid magnesium / titanium complex by contacting a liquid magnesium compound having no reducing ability with a titanium acid compound in the presence of an electron donor (a) as necessary.

(13) A method in which the reaction product obtained in the method (12) is further contacted with a titanium compound.

(14) A method in which the reaction product obtained in the method (11) or (12) is further contacted with an electron donor (a) and a titanium compound.

(15) A method of grinding a magnesium compound and a titanium compound (and, if necessary, an electron donor (a)) to obtain a solid, and treating the solid with a halogen, a halogen compound or an aromatic hydrocarbon. This method may include a step of pulverizing only the magnesium compound or the complex compound composed of the magnesium compound and the electron donor (a) or the magnesium compound and the titanium compound.

After the pulverization, the solid phase may be pretreated with a reaction aid and then treated with halogen or the like. Examples of the reaction aid include organometallic compounds and halogen-containing silicon compounds.

(16) A method of contacting a titanium compound with the titanium compound after milling the magnesium compound. In this case, an electron donor (a) or a reaction aid may be used at the time of grinding and / or connection.

(17) A method in which the compound obtained by any of the methods (11) to (16) is treated with a halogen, a halogen compound or an aromatic hydrocarbon.

(18) A method of contacting a metal oxide, an organic magnesium compound, and a halogen-containing compound with a titanium compound and an electron donor (a) as necessary.

(19) A method of bringing a magnesium compound, such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium into contact with a titanium compound and / or a halogen-containing hydrocarbon and, if necessary, the electron donor (a).

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and an alkoxy titanium into contact with a titanium compound and / or an electron donor (a). In this case, halogen-containing compounds such as halogen-containing silicon compounds can be further contacted as necessary.

(21) A method of contacting a liquid magnesium compound having no ringing capacity with an organometallic compound to precipitate a solid magnesium / metal (aluminum) complex, and contacting the complex with a titanium compound and an electron donor (a) as necessary.

The solid titanium catalyst component (A-1) is usually produced at a temperature of -70 to 200C, preferably -50 to 150 ° C.

The solid titanium catalyst component (A-1) thus obtained further contains titanium, magnesium, halogen, and preferably the electron donor (a).

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

The electron donor (a) usually contains an electron donor (a) / titanium (molar ratio) ratio of 0.01 to 100, preferably 0.05 to 50.

In the above, the solid titanium catalyst component (A-1) using the titanium compound has been described. However, a titanium substituted with zirconium, tantalum or chromium may be used in the titanium compound. As another example of the transition metal compound catalyst component (A-1), a conventionally known trichloride solid titanium catalyst component (A-1) can be mentioned.

The method for producing the trichloride catalyst (A-2) is, for example, Japanese Patent Application Laid-Open No. 63-17274, Japanese Patent No. 64-38409, Japanese Patent No. 56-34711, Japanese Patent No. 61-287904, Japanese Patent No. 63-75007 63-83106, 59-13630, Japan 63-108008, Japan 63-27508, Japan 57-70110, Japan 58-219207. Japanese Patent Laid-Open No. 1-144405, Japanese Patent Laid-Open No. 1-292011 and the like.

The titanium trichloride mentioned above can be illustrated as such a titanium trichloride catalyst component (A-2).

Such titanium trichloride can be used together with or after contact with the electron donor (a) and / or tetravalent titanium compound described above. In addition, a metallocene compound (A-3) can be used as the transition metal compound catalyst component (A).

The manufacturing method of such a metallocene compound (A-3) is Unexamined-Japanese-Patent No. 63-61010, 63-152608, and 63-264606. Special Publication 63-280703, Special Publication 64-6003, Special Publication 1-95110, Special Publication 3-62806, Special Publication 1-259004, Special Publication 64-45406, Special Publication 60-106808, Special Publication 60-137911, Special Publication 58-19309, special place 60-35006, special place 60-35007, special place 61-296008, special place 63-501369, special place 61-221207, special place 62-121707. JP-A 61-66206, JP-A 2-22307, JP-A 2-173110, JP-A 2-302410, JP-A 1-129003, JP-A 1-210404, JP-A 3-66710, JP-A 3-70710, JP-A 1-207248, 63-222177, 63-222178, 63-222179, 63-222179, 1-301704, 1-3 1-38989, 13-74412, 61-74412. 264010, JP-A 1-275609. Japanese Patent Application Laid-Open No. 63-251405, Japanese Patent Laid-Open No. 64-74202, Japanese Patent Application Laid-Open No. 2-41303, Japanese Patent Application Laid-Open No. 3-56508, Japanese Patent Application Laid-Open No. 3-70708, Japanese Patent Application Laid-Open No. 3-70709, and the like.

The metallocene compound (A-3) is represented by the following formula.

Wherein M is Zr, Ti. Hf, V. Nb. A transition metal selected from the group consisting of Ta and Cr, L is a ligand coordinated to the transition metal, at least one of L has a cyclopentadienyl skeleton and L other than a ligand having a cyclopentadienyl skeleton has 1 to 12 hydrocarbon groups, alkoxy groups, aryloxy groups, halogens. Trialkylsilyl group, SO ₃ R (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or hydrogen, and X is the valence of the transition metal.

As a ligand having a cyclopentadienyl skeleton, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group , An ethylcyclopentadienyl group, a methylethylcyclopentadienyl group, a propylcyclopentadienyl group, a methylpropylcyclopentadienyl group, and a butylcyclopentadienyl group. Alkyl-substituted cyclopentadienyl groups, such as a methylbutyl cyclopentadienyl group and a hexyl cyclopentadienyl group, and an indenyl group. 4,5,6,7-tetrahydroindenyl group and furoenyl group.

These may be substituted by halogen atom or trialkylsilyl group.

Alkyl-substituted cyclopentadienyl groups are most preferred among the ligands coordinated to the transition metal.

When the compound represented by the above formula has two or more ligands having a cyclopentadienyl skeleton, the two ligands having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, isopropylidene group and di Substituted alkylene groups such as phenylmethylene and the like may be bonded to each other through a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene, methylphenylsilylene and the like.

Ligands other than a ligand having a cyclopentadienyl skeleton are as follows.

C1-C12 hydrocarbon groups, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. can be illustrated; Specifically, the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like; As said cycloalkyl group, Cyclopentyl group, Cyclohexyl group, etc. are illustrated; As an aryl group, a phenyl group, a tolyl group, etc. are illustrated; Examples of the aralkyl group include benzyl group, neofill group and the like.

As an alkoxy group, a methoxy group, an ethoxy group, butoxy group, etc. are illustrated, A phenoxy group etc. are illustrated as an aryloxy group.

Examples of the halogen include fluorine, chlorine, bromine and iodine.

Examples of the ligand represented by SO ₃ R include p-toluene sulfonate, methanesulfonate, trifurmethanesulfonate, and the like.

In the case where the transition metal is tetravalent, the metallocene compound (A-3) having a ligand group having a ciclopentadiethyl skeleton can be represented more specifically by the following formula:

R ² _k R ² _I R ⁴ _m R ⁵ _n M

M is the above transition metal and R ² is a group (ligand) having a cyclopentadienyl skeleton. R ³ , R ⁴ and R ⁵ each represent a group having an cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group, a halogen, a trialkyl silyl group, SO ₃ R or hydrogen, k is an integer of 1 or more and k + l + m + n = 4.

Preferably having at least two cyclopentadienyl skeleton In the above formula _{^{R 2 k R 2 I R 4}} m R 5 n R 2, R 2 and R ^4, R ⁵ in the compound of the transition metal M and. That is, R ² and R ³ are each a group having a cyclopentadienyl skeleton. Groups having such a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups, or dimethylsilylene, diphenylsilylene and methylphenylsilylene And R ⁴ and R ⁵ are each cyclopentadienyl skeleton, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, or aryloxy group, halogen. Trialkylsilyl group, SO ₃ R or hydrogen.

Representative examples of the transition metal compound represented by the formula ML _x (M is zirconium) are as follows.

Bis (indenyl) zirconium dichromide,

Bis (indenyl) zirconium dichromide,

Bis (indenyl) zirconium bis (p-toluenesulfonate),

Bis (4,5,6,7-tetrahydroindenyl) zirconium dichromide,

Bis (fluoroenyl) zirconium dichromide,

Ethylenebis (indenyl) zirconium dichromide,

Ethylenebis (indenyl) zirconiumpromide,

Ethylenebis (indenyl) dimethylzylconium,

Ethylenebis (indenyl) demenylzylconium,

Ethylenebis (indenyl) methylzylconium monochloride,

Ethylenebis (indenyl) zirconiumbis (methanesulfonate),

Ethylenebis (indenyl) zirconiumbis (p-toluenesulfonate),

Ethylenebis (indenyl) zirconiumbis (trifurmethanesulfonate),

Ethylenebis (4,5,6,7-tetrahydro indenyl) zirconium dichromide,

Isopropylidene (cyclopentadienyl-purorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconiumbis (tripuroromethanesulfonate),

Dimethylsilylenebis (4,5.6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl-furorenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Methylphenyldiphenylsilylenebis (indenyl) zirconium dichloride,

Bis (cyclopentadienyl) zirconium dichloride,

Bis (cyclopentadienyl) zironium bromide,

Bis (cyclopentadienyl) methylzylconium monochloride,

Bis (cyclopentadienyl) ethylzylconium monochloride,

Bis (cyclopentadienyl) cyclohexylsiliconium monochloride,

Bis (ciflopentadienyl) phenylzylconium monochloride,

Bis (ciflopentadienyl) benzylkonium monochloride,

Bis (cyclopentadienyl) zirconium monochloride monohydride,

Bis (cyclopentadienyl) methylzylconium monohydride,

Bis (cyclopentadienyl) dimethylzylconium,

Bis (cyclopentadienyl) dimethylzylconium,

Bis (cyclopentadienyl) dibenzylconium,

Bis (cyclopentadienyl) zirconium methoxychloride,

Bis (cyclopentadienyl) zirconium ethoxychloride,

Bis (cylopentadienyl) zirconium bis (methanesulfonate),

Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate),

Bis (cyclopentadienyl) zirconium bis (trifurmethanesulfonate),

Bis (methylcyclopentadienyl) zirconium dichloride,

Bis (dimethylcyclopentadienyl) zirconium dichloride,

Bis (dimethylcyclopentadienyl) zirconium ethoxychloride,

Bis (dimethylcyclopentadienyl) zirconium bis (trifurmethanesulfonate),

Bis (ethylcyclopentadienyl) zirconium dichloride,

Bis (methylethylcyclopentadienyl) zirconium dichloride,

Bis (propylcyclopentadienyl) zirconium dichloride,

Bis (methylpropylcyclopentadienyl) zirconium diclide,

Bis (butylcyclopentadienyl) zirconium dichloride,

Bis (methylbutylcyclopentadienyl) zirconium dichloride,

Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),

Bis (trimethylcyclopentadienyl) zirconium dichloride,

Bis (tetramethylcyclopentadienyl) zirconium dichloride,

Bis (pentamethylcyclopentadienyl) zirconium dichloride,

Bis (hexylcyclopentadienyl) zirconium dichloride,

Bis (trimethylcyclopentadienyl) zirconium dichloride,

In the metallocene compound, the 2-substituted cyclopentadienyl groups include 1,2- and 1,3-substituted groups, and the 3-substituted cyclopentadienyl groups include 1,2,3- and 1, There are 2,4-substituted groups. In addition, alkyl groups such as propyl and butyl include n-, 1-, sec- and ter-isomers.

In addition, transition metal compounds obtained by substituting a titanium metal or hafnium, vanadium, niobium, tantalum or chromium in the above-described examples of the zirconium compounds may be used.

The compounds may be used alone or in combination. These compounds can be used diluted with a hydrocarbon or a halogenated hydrocarbon.

In the present invention, the ylconocene compound having a ligand having a central metal atom of zirconium and having at least two cyclopentadienyl skeletons is preferably used as the metallocene compound (A-3).

Such a metallocene compound may be supported on a carrier by contact with the clinical carrier compound.

Examples of the carrier compound which can be used in the present invention include inorganic carrier compounds such as SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ , BaO and ThO. and; And resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene and styrene / divinylbenzene copolymers.

The carrier compounds may be used in combination of two or more kinds.

Of these compounds, SiO ₂ , Al ₂ O ₃ , MgO are preferred.

Next, an organometallic polyconductor catalyst component [B] containing a metal selected from the metals of Groups I to III of the Periodic Table that can be used in the preparation of the prepolymerized catalyst (I) of the present invention will be described.

As the organometallic compound catalyst component [B], for example, an organoaluminum compound (B-1), an alkyl complex compound composed of a metal of Periodic Group 1 and aluminum, and an organometallic compound of Periodic Group II metal can be used. .

As such an organoaluminum compound, the organoaluminum compound represented by a following formula can be illustrated, for example;

As said organoaluminum compound (B-), the compound represented by a following formula can be used.

R ^a _n AIX _3-n

During food. R ^a is a hydrocarbon having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1-3.

In the above formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group and hexyl group. , Octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specifically as said organoaluminum compound, the following compounds are used.

Trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri 2-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 sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Alkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; Dialkyl aluminum hydrides, such as diethyl aluminum hydride and diisobutyl aluminum hydride.

R ^a _n AlY _3-n

Wherein R ^a is as defined above, Y is -OR ^b , -OSiR ^c ₃ , -OAlR ^d ₂ , -NR ^e ₂ , -SiR ^f ₃ , or -N (R ^g ) AlR ^h ₂ , n is 1 to 2 and R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc .: R ^e is hydrogen, methyl group, ethyl group, isopropyl group , Phenyl group, trimethylylsilyl group and the like; R ^f and R ^g are a methyl group, an ethyl group and the like, respectively.

Specifically as the organoaluminum compound (B-1), the following compounds are used.

(i) a compound of the formula R ^a _n Al (OR ^b ) _3-n ; Dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like;

(ii) a compound of the formula R ^a _n Al (OSiR ^c ₃ ) _3-n ; (C ₂ H ₅ ) ₂ AlOSi (CH ₃ ) ₄ , (iso-C ₄ H ₉ ) ₂ AlOSi (CH ₃ ) ₃ , (iso-C ₄ H ₉ ) ₃ AlOSi (C ₂ H ₅ ) _2, and the like;

(iii) ^a compound of Ra _n Al (OAlR ^d _n ) _3-n ; (C ₂ H ₅ ) AlOAl (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlOAl (iso-C ₄ H ₉ ) _2, and the like;

(iv) ^a compound of R ^a _n Al (NR ^a ₁ ) _3-n ; (C ₃ ) ₂ AlN (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlNHCH ₃ , (CH ₃ ) ₂ AlNH (C ₂ H ₅ ), (C ₂ H ₅ ) ₂ AlN (Si (CH ₃ ) ₃ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlN (Si (CH ₃ ) ₃ ) _2, and the like;

(v) ^a compound of Ra _n Al (SiR ^f ₂ ) _3-n ; (iso-C ₄ H ₉ ) ₂ AlSi (CH ₃ ) ₂ and the like;

(vi) compounds of the formula _{^{R a n Al [N (R}} a) -Al h 2) 3-n]; (C ₂ H ₉ ) AlN (CH ₃ ) Al (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlN (C ₂ H ₅ ) Al (iso-C ₄ H ₉ ) _2, and the like.

In the above-described organoaluminum compound (B-1), an organoaluminum compound represented by the formula R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , or R ^a _n Al (OAlR ^d ₂ ) _3-n is desirable.

As a complex alkylate of the metal of the periodic table group I and aluminum, the compound represented by a following formula can be illustrated.

M ¹ AlR ^j ₄

In formula, M <^1> is Li, Na or K, R <^j> is a C1-C15 hydrocarbon group.

Specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _4, etc. may be mentioned.

As an organometallic compound of the metal of group II of a periodic table, the compound represented by a following formula can be illustrated.

R ₁ , R ₂ , M ₂

In formula, R <_1> and R <_2> is a C1-C15 hydrocarbon group or halogen, respectively, and may mutually be same or different, except when both are halogen. M ₂ is Mg, Zn, Cd.

As a specific example, diethyl zinc diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, etc. are mentioned.

These compounds can be used in combination of 2 types.

Specific examples of the organoaluminum oxy compound (B-2) include aluminoxanes represented by the following formula (1) or (2).

In the formulas (1) and (2), R is a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group, an ethyl group, more preferably an ethyl group hydrocarbon group, and m is two or more, preferably 5 to It is an integer of 40. The aluminoxane used may be formed from alkyloxy aluminum units consisting of alkyl oxyaluminum units represented by the formula (OAl (R ¹ )) and alkyloxyaluminum units represented by the formula (OAl (R ² )). , R ¹ and R ² are each similar hydrocarbon groups as in the case of R, and R ¹ and R ² are groups different from each other.

In this case, the alumina formed from mixed alkyloxyaluminum units, usually containing at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol% of methyloxyaluminum units (OAl (CH ₃ )) Noxic acid is preferred. The organoaluminum oxy compound [B-2] to be used may be an existing aluminoxane or a benzene insoluble organoaluminum oxy compound as disclosed by the present applicant.

The aluminoxane can be prepared, for example, by the above methods.

(1) Hydrocarbon solvent suspensions such as compounds containing adsorbed water or salts containing crystal water such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and cerium chloride (1) A method of reacting with an organoaluminum compound such as this to recover the desired aluminoxane as a hydrocarbon solution containing the same.

(2) A method in which organic aluminum compounds such as trialkylaluminum are directly treated with water, ice, or steam in a solvent such as benzene, toluene, ethyl ether, or tetrahydrofuran.

(3) A method in which an organic aluminum compound such as trialkyl aluminum is reacted with an organic tin oxide in a solvent such as decane benzene or toluene.

The method (1) is preferable.

The aluminoxane may contain a small amount of organometallic components other than aluminum.

From the solution containing the recovered aluminoxane, the solvent or unreacted organoaluminum compound can be distilled off, and the remaining aluminoxane can be redissolved in the solvent.

As an organoaluminum compound used for the said aluminoxane solution manufacture specifically ,; Trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-sec-butyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, Trialkyl aluminums such as trioctyl aluminum and tridecyl aluminum; Tricycloalkyl aluminums such as tricyclohexyl aluminum and tricyclooctyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, or diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride or diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide or dimethyl aluminum ethoxide; And dialkyl aluminum aryl oxides such as diethyl aluminum phenoxide.

In addition, isoprenyl aluminum represented by the general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (x, y, z are each positive and z2x) may be used.

Among these, trialkyl aluminum is particularly preferable.

As a solvent used for the said alminoxane solution, Aromatic hydrocarbons, such as benzene, toluene, xylene, cumene, and cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane octane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methyl cyclopentane; Petroleum oils such as gasoline, carrosene and gas oil; Or halogenated hydrocarbons such as halides such as chlorides and bromide, in particular of the aromatic, aliphatic and alicyclic hydrocarbons.

In addition to these, ethers, such as ethyl ether and tetrahydrofuran, can also be used.

Of the solvents exemplified above, aromatic hydrocarbons are particularly preferred.

When the transition metal compound catalyst component [A] is a solid titanium catalyst component (A-1) or a titanium trichloride catalyst component (A-2), the organometallic compound catalyst component [B] is an organoaluminum compound (B -1) is preferred. In the case where the transition metal compound catalyst component [A] is a metallocene compound (A-3), the organometallic compound catalyst component [B] is preferably an organic aluminum oxy compound (B-2).

In the prepolymerization of the -olefin and the polyene compound to the catalyst containing the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B], the electron donor (a) or the following Electron donor (b) can be used.

The electron donor (b) is an organosilicon compound represented by the following formula.

R _n Si (OR ') _4-n

Wherein R and R 'are hydrocarbon groups and n is 0n4. As an organosilicon compound represented by the said general formula, the following compound is mentioned specifically ,.

Trimethylmethoxysilane, trimethylethoxysilane, dimethylmethoxysilina, dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane , Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenylethoxysilane, bis o-tolylmethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyl Diethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, Methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, r-chloropromethoxysilane, methyltriethoxysilane, ethyltriethoxy Silane, vinyltriethoxysilane, t-butyl Liethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, r-aminopropyl triethoxysilane, chlorotriethoxysilane, ethyltriisooxysilane, vinyltribu Methoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornenetrimethoxysilane, 2-norbornenetriethoxysilane, 2-norbornenemethyldimethoxysilane, ethyl silicate, Butyl silicate, trimethylphenoxysilane, methyltrialkyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclophene Tyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethyl Cyclopentyl) dimethoxysilane, dicyclopentyldiethoxy Silane, tricyclopentylethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmeth Methoxysilane, cyclopentyldiethylmethoxysilane, cyclopentylethoxysilane, and the like.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimeth Methoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornene triethoxysilane, 2-norbornenemethyl Dimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrioxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferable.

The organosilicon compounds may be used in combination of two or more kinds.

Moreover, the following can be used as an electron donor (b).

2, 6-substituted piperidine, 2, 5-substituted piperidine; Substituted methylenediamines such as N, N, N ', N'-tetramethylenediamine, N, N, N', and N'-tetraethylmethylenediamine; Nitrogen-containing electron donors such as substituted methylenediamines (ie, 1, 3-dibenzyl imidazolidine and 1, 3-dibenzyl-2-pephenylimidazolidine); Phosphites (ie triethyl phosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl-n-butyl phosphite and diethyl Phosphorus containing donors such as phenyl phosphite); And oxygen-containing electron donors such as 2, 6-substituted detrahydrofuran and 2, 5-substituted tetrahydropyran.

The electron donor [b] can be used in combination of two or more kinds.

The prepolymerized catalyst [I] according to the present invention is prepared by copolymerizing an α-olefin and a polyene compound on a catalyst containing the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B]. Prepolymerized catalyst [I] can be obtained.

The α-olefins usable in the present invention are α-olefins having 2 to 20 carbon atoms.

Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hensen, 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 and 1-eicosene.

These can be used individually or in combination.

The α-olefin used in the prepolymerization is the same as or different from the α-olefin used in the polymerization described later.

Among the α-olefins exemplified above, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-ecocene and the like are preferable.

Specific examples of the polyene compound and the like are as follows:

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-hexadiene, 1, 6-octadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9 -Decadiene, 1, 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-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1- Isopropenyl-3-vinylcyclopentane; Aromatic polyene compounds, such as divinylbenzene and vinyl isopropenylbenzene.

These can be used individually or in combination in alpha-olefin copolymerization.

Among the polyene compounds, a polyene compound having 7 or more carbon atoms having an olefinic double bond at the sock end is preferable, and an aliphatic or alicyclic polyene compound having an olefinic double bond at the sock end is more preferable.

Specific examples of the preferred polyene compound and the like include 1, 6-heptadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 13-tetradecadiene, 1, 5, 9-decatene , 1, 4-divinylcyclohexane, 1, 3-divinylcyclopentane, 1, 5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1, 4-diallylcyclohexane, and the like.

Among these, aliphatic polyene compounds having 8 or more carbon atoms, preferably 10 or more carbon atoms are preferable, and linear aliphatic polyene compounds having 10 or more carbon atoms are particularly preferable.

In the copolymerization of the α-olefin and the polyene compound, the combinations preferably used in the present invention are as follows: ethylene / 1, 7-octadiene, ethylene / 1, 9-decadiene, ethylene / 1, 13-tetra Decadiene, ethylene / 1, 5, 9-decatene, propylene / 1, 7-octadiene, propylene / 1, 9-decadienepropylene / 1, 13-tetradecadiene, propylene / 1, 5, 9- Decatriene, butene / 1, 9-decadiene, butene / 1, 5, 9-decatene, 4-methyl-1-pentene / 1, 9-decadiene, 3-methyl-1-butene / 1, 9-decadiene, 1-eicosene / 1,9-decadiene, propylene / 1, 4-divinylcyclohexane and butene / 1, 4-divinylcyclohexane.

In the present invention, when the α-olefin and the polyene compound are prepolymerized with the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B], the amount of the polyene compound is usually 1 mol of the α-olefin. Sugar, 0.0001-10 mol, Preferably it is 0.0005-5 mol, Especially preferably, it is 0.001-2 mol.

In the present invention, the prepolymerization can be carried out in the presence of an inert solvent described below.

In this prepolymerization, it is preferable to add the said monomer and a catalyst component in the said insoluble solvent, and to perform prepolymerization on comparatively mild conditions.

The prepolymerization can be carried out under conditions in which the resultant prepolymer is not dissolved or dissolved in the polymerization medium, but is preferably performed under conditions in which the resultant prepolymer is not dissolved in the polymerization medium.

More specifically, in the present invention, the prepolymerized catalyst [I] may be prepared by the following method.

(i) The transition metal compound catalyst component [A], the organometallic compound catalyst component [B], and, if necessary, the electron donor are brought into contact with each other in an inert solvent to prepare a catalyst, wherein the α-olefin A method of preparing a prepolymerized catalyst by copolymerizing a polyene compound with a polyene compound.

(ii) the catalyst is prepared by contacting the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B] and, if necessary, an electron donor with each other in a mixture of an α-olefin and a polyene compound, A method of preparing a prepolymerized catalyst by copolymerizing an α-olefin and a polyene compound.

Specific examples of the inert solvent are as follows:

Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohetan; Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as α-olefin chloride and chlorobenzene; And mixtures of the above hydrocarbons.

Among these, aliphatic hydrocarbons are preferable. The prepolymerization can be carried out by any of batch, semi-continuous and continuous methods.

In the prepolymerization, it is possible to use a catalyst of higher concentration than the catalyst concentration used in the polymerization.

The concentration of the catalyst component in the prepolymerization depends on the catalyst component used.

The amount of the transition metal compound catalyst component used (per 1 mol of polymerization) is usually about 0.001 to 5,000 mol, preferably about 0.01 to 1,000 mol, and more preferably 0.1 to 500 mmol in terms of transition metal atoms.

The organometallic compound catalyst component is used in an amount such that the amount of precopolymer produced is 0.1 to 2,000 g, preferably 0.03 to 1,000 g, more preferably 0.05 to 200 g per 1 g of the transition metal compound catalyst component. . That is, the amount of the organometallic compound catalyst component used is usually about 0.1 to 1,000 mol, more preferably about 0.5 to 500 mol, and more preferably 1 to 1000 mol per 1 mol of the transition metal atom contained in the transition metal compound catalyst component. to be.

When the electron donor is used in the prepolymerization, the amount of the electron donor is 0.01 to 50 mol, preferably 0.05 to 30 mol, more preferably 0.1 to 10 mol per mol of the transition metal atom contained in the transition metal compound catalyst component. to be.

The reaction temperature in the prepolymerization is usually about -20 + 100 占 폚, preferably about -20-80 占 폚, more preferably -10 ~ + 40 占 폚.

Molecular weight modifiers such as hydrogen can be used in the prepolymerization.

In the prepolymer catalyst [I] of the present invention, the total amount of the α-olefin and the polyene compound is added to 1 g of the transition metal compound catalyst component in the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B]. , 0.01 to 2,000 g, preferably 0.03 to 1,000 g, more preferably 0.05 to 200 g can be produced by copolymerization.

The prepolymerized catalyst [I] obtained above contains an α-olefin / polyene copolymer, and the α-olefin / polyene copolymer contains 99.999 to 50 mol% of structural units derived from α-olefin, Preferably it is 99.999-70 mol%, More preferably, it is 99.995-75 mol%, More preferably, it is 99.99-80 mol%, Most preferably, 99.95-85 mol%, and contains the structural unit derived from a polyene compound 0.001 to 50 mol%, preferably 0.001 to 30 mol%, more preferably 0.005 to 25 mol%, more preferably 0.01 to 20 mol%, most preferably 0.05 to 15 mol%.

The composition ratio in the said alpha olefin / polyene copolymer can be measured by the quantity of the alpha olefin and polyene compound consumed by the said prepolymerization reaction. Specifically, the structural unit [P] (mol%) is calculated as follows.

In the above formula, each symbol has the following meaning.

[P ₀ ]: number of moles of polyene compound supplied during the prepolymerization

[P _r ]: number of moles of unreacted polyene compound

[α ₀ ]: number of moles of α-olefin copolymerized during the prepolymerization

[α _r ]: number of moles of unreacted α-olefin

In the above formula, [α _r ] and [P _r ] can be obtained by measuring the α-olefin and the unreacted polyene compound remaining in the heavy mixing tank by gas chromatography or the like.

The prepolymerized catalyst is usually in suspension.

The prepolymerized catalyst on the suspension may be used in subsequent polymerization as it is, or the prepolymerized catalyst obtained by separating from the suspension may be used in subsequent polymerization.

When the prepolymerized catalyst in suspension is used at a subsequent medium pressure, the organometallic catalyst component [II] and the electron donor [III] can be used alone.

In the present invention, olefin may be prepolymerized in advance to the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B] prior to the prepolymerization.

(Alpha) -olefin (preferably polypropylene) can be used as said olefin.

When the said olefin is prepolymerized with the said catalyst component [A] and [B] beforehand, the following effect can be acquired, for example. In other words, when the olefins are prepolymerized to the catalyst components [A] and [B] in advance, a prepolymerized catalyst having excellent linearity such as particle size distribution and particle size distribution can be obtained.

As described above, when the olefin is polymerized or copolymerized using the prepolymerized catalyst [I], an olefin polymer of high melt tension can be obtained.

The catalyst for olefin polymerization using the prepolymerized catalyst is described below.

The olefin polymer catalyst is prepared from the prepolymerized catalyst [I] obtained above and the organometallic compound catalyst component [II] containing a metal selected from the metals of Groups I to III of the periodic table.

The catalyst for olefin polymerization can be formed from the prepolymerized catalyst [I], the organometallic compound catalyst component [II], and electron donor [III].

As the organometallic compound catalyst component [II] used here, one similar to the organometallic compound catalyst component [B] is used.

As the electron donor [III] used here, those similar to the electron donor (a) or the electron donor (b) are used. These electron donors (a) and (b) can be used in combination.

The catalyst for olefin polymerization may contain, in addition to the above components, other components useful for olefin polymerization.

In the olefin polymerization method, the olefin is polymerized or copolymerized in the presence of the catalyst for olefin polymerization as described above.

Examples of the olefins used here include the above-mentioned α-olefins having 2 to 20 carbon atoms.

In addition, the following compounds can be used.

Aromatic vinyl compounds such as styrene, substituted styrene (e.g. dimethyl styrene), allylbenzene, substituted aryl benzene (e.g. allyl toluene), vinylnaphthalene, substituted vinyl naphthalene, allyl naphthalene and substituted allylnaphthalene; Alicyclic vinyl compounds such as vinylcyclohexane, substituted vinylcyclohexane, vinylcyclopentane, substituted vinylcyclopentane, vinylcycloheptane, substituted vinylcycloheptane and allyl norbornene; Cyclopentane, cycloheptane, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1, 4, 5, 8-dimethino-1, 2, 3, 4a-5, 8 Cyclic olefins such as 8a-octahydronaphthalene; Silane-based unsaturated such as allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, and 1-trimethylsilin-1-decene Compounds; Polyene compounds described above; Said polyene compounds.

These can be used individually or in combination.

Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexane, dimethyl styrene, allyltrimethylsilane, allylnaphthalene, and the like are preferable.

The polymerization can be carried out by liquid phase polymerization or gas phase polymerization such as solution polymerization and suspension polymerization.

When the polymerization reaction is carried out in the form of a slurry polymerization method, the inert organic solvent can be used as the reaction solvent, or a liquid olefin can be used as the reaction solvent at the reaction temperature.

In the polymerization method, the amount of the prepolymerized catalyst [I] (per 1 mol of polymerization) is usually about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol in terms of transition metal atoms in the prepolymerized catalyst [I].

The amount of the organometallic compound catalyst component [II] used is usually about 1 to 2,000 mol, per 1 mol of the transition metal atoms contained in the prepolymerized catalyst [I] in the polymer. About 2 to 500 mol.

When the electron donor [III] is used, the amount of the electron donor [III] is usually about 0.001 to 10 mol, preferably 0.01 to 5 mol, per mol of the metal atom of the organometallic compound catalyst component [II].

When hydrogen is used in the polymerization, the molecular weight of the resulting polymer can be adjusted, and the obtained polymer has a high melt folw rate.

The conditions of the polymerization method vary depending on the olefins used, but in general, the polymerization is 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 usually at normal pressure to 100 kg / cm 2, preferably about 2 to 50 kg / cm 2.

The polymerization can be carried out batchwise, semicontinuously or continuously. The polymerization can also be carried out in two or more stages having different reaction conditions.

By such a polymerization method, a random copolymer or a block copolymer can be manufactured from the homopolymer of olefin or two or more types of olefins.

When performing the polymerization process of an olefin using the above-mentioned catalyst for olefin polymerization, the olefin polymer of a high melt tension can be obtained by high polymerization activity.

The olefin polymer obtained by the said method is the (alpha) -olefin / polyene copolymer and the (alpha) -olefin / polyene copolymer containing olefin polymer containing (ii) an olefin polymer.

The olefin polymer containing the α-olefin / polyene copolymer contains 0.001 to 99% by weight of the α-olefin / polyene copolymer (i), preferably 0.005 to 90% by weight, more preferably 0.01 to 88% by weight. And 99.999 to 1% by weight, preferably 99.995 to 10% by weight, more preferably 99.99 to 12% by weight of the olefin polymer (ii).

Among the olefin polymers, 0.001-15% by weight of the α-olefin / polyene copolymer (i), in particular 0.008-10% by weight, 99.999-85% by weight of the olefin polymer (ii), especially 99.992-90% The olefin polymer containing% is especially preferable.

The melt flow rate (MFR) of the olefin polymer measured by ASTM D1238 is 5000 g / 10 minutes or less, preferably 0.01 to 3000 g / 10 minutes, more preferably 0.02 to 2000 g / 10 minutes, most preferably 0.05 to 1000 g / 10 minutes.

Therefore, the olefin polymer has a high melt tension (MT).

In the olefin polymer of the present invention, the melt tension (MT) and the melt flow rate satisfy the following relationship.

For example, when the α-olefin / polyene copolymer (i) and olefin polymer (ii) constituting the olefin polymer are ethylene / polyene copolymer and polypropylene, respectively, the melt tension and melt flow rate of the olefin polymer Satisfies the following relationship.

Usually log [MT] ≧ −08log [MFR] +0.3; Preferably log [MT] ≧ −08log [MFR] +0.5; More preferably log [MT] ≧ −08log [MFR] +0.7; Particularly preferably log [MT] ≧ −08log [MFR] +0.8; Melt tension and melt flow rate of the olefin polymer when the α-olefin / polyene copolymer (i) is a copolymer of α-olefin and polyene having 3 or more carbon atoms and the olefin polymer (ii) is polypropylene in the olefin polymer Satisfies the following relationship:

Typically log [MT] ≧ −08log [MFR] +0.30; Preferably, log [MT] ≧ −08log [MFR] +0.35; More preferably, log [MT] ≧ −08log [MFR] +0.40; Furthermore, when the olefin polymer is composed of ethylene / polyene copolymer (i) and the polypropylene (ii), the density is about 0.92 g / cm 2, and the MFR is 1 g / 10 min, the melt tension of the olefin polymer is 2.5 g. Or more, preferably 3.5 g or more, more preferably 4.0 g or more, still more preferably 4.5 g or more, most preferably 5.0 g or more.

Intrinsic viscosity [(eta)] of an olefin polymer is 0.05-20 dl / g, Preferably it is 0.1-15 dl / g, More preferably, it is 0.2-13 dl / g or more when measured in decalin at 135 degreeC.

The melt tension (MT) and the intrinsic viscosity [η] of the olefin polymer also satisfy the following relationship.

For example, if the α-olefin / polyene copolymer (i) and the olefin polymer (ii) constituting the olefin polymer are ethylene / polyene copolymer and polypropylene, respectively, the melt tension and the ultimate viscosity of the olefin polymer may be as follows. To satisfy the relationship:

Typically, log [MT] ≥ 3.7 log [η]-1.5; Preferably, log [MT] ≥ 3.7 log [η]-1.3; More preferably log [MT] ≥3.7log [η] -1.1; Most preferably log [MT] ≧ 3.7 log [η] − 1.0; When the α-olefin / polyene copolymer (i) is an α-olefin / polyene copolymer having 3 or more carbon atoms and the olefin polymer (ii) is polypropylene in an olefin polymer, it is extreme with the melt tension of the olefin polymer. The viscosity satisfies the following relationship:

Typically log [MT] ≧ 3.7 log [η] − 1.50; Preferably log [MT] ≧ 3.7 log [η] − 1.45; More preferably, log [MT] ≧ 3.7 log [η] − 1.40; In addition, when the olefin polymer is composed of ethylene / polyene copolymer (i) and polyethylene (ii), the density is about 0.92 g / cm 2 and the intrinsic viscosity [η] is 1.8 dl / g, the melt tension of the olefin polymer is 2.5. g or more, preferably 3.5 g or more, more preferably 4.0 g or more, even more preferably 4.5 g or more, and most preferably 5.0 g or more.

The melt tension can be obtained by the following method.

Using an MT measuring instrument (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 7 g of the polymer was introduced into the silicone having a lower portion of the orifice and the piston, and the cylinder was melted at the polymer (α-polyolefin: 190 ° C, polypropylene: 230). ℃).

After 5 minutes, the piston was propagated downwards into 10 mm / min to extrude the molten polymer from the cylinder into the strand through an orifice on the bottom of the cylinder.

The extruded strand was stretched onto the filament and wound at a speed of 2.5 m / min by the poly of the load detector. In this step, the stress applied to the pulley was measured.

The value obtained is the melt tension of the polymer.

The melt tension of the olefin polymers obtained using the prepolymerized catalyst of the invention is higher than the olefin polymers produced by conventional methods. Moreover, the obtained olefin polymer is excellent in rigidity, transparency, mechanical strength (for example, impact strength), and an external appearance.

Therefore, when using the obtained olefin polymer, the film | membrane which has high transparency and high strength as well as the favorable external appearance, for example, without a fish eye etc. can be obtained.

The olefin polymer is also excellent in moldability such as expandability and can be molded into a film at high yield and at high speed. In addition, various molding methods, such as blow molding and vacuum molding, can be applied to the olefin polymer, thereby expanding the use of the polymer of the olefin.

An olefin polymer containing a large amount of the α-olefin / polyene copolymer in an olefin polymer provided by using the prepolymerized catalyst of the present invention can be preferably used as a master batch.

When using the obtained olefin polymer as a masterbatch, this olefin polymer has 15-99 weight% of alpha-olefin / polyene copolymer (i), Preferably it is 18-90 weight%, More preferably, it is 20-80 It is preferable to contain 85 to 1 weight%, Preferably it is 82 to 10 weight%, More preferably, it is 80 to 20 weight% of the said olefin polymer (ii).

The obtained olefin polymer can further contain various additives such as heat stabilizer, weather stabilizer, antistatic agent, antiblocking agent, lubricant, nucleating agent, pigment, dye, inorganic filler and organic filler as necessary.

The prepolymerized catalyst according to the present invention comprises the [A] transition metal compound catalyst component and the total amount of [alpha] -olefin and polyene compound in [B] organometallic compound catalyst component, the transition metal compound catalyst component [A ] A prepolymerized catalyst prepared by copolymerizing in an amount of 0.01 to 2,000 g per 1 g.

Polymerization or copolymerization of olefins in the presence of this prepolymerized catalyst yields a high melt tension olefin polymer.

Since the olefin polymer obtained above has a high melt tension, it can be molded into an expanded membrane of good appearance, high transparency, and high strength at high speed and high formability at high speed.

In addition, the olefin polymer can be molded by various molding methods such as blow molding, vacuum molding, pneumatic molding, calender molding, foam molding, extrusion molding, and stretching molding, and thus the use of the olefin polymer can be expanded.

Although the present invention is described in detail by the following examples, the present invention is not stable to these examples.

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 mixed, and it heated at 130 degreeC for 2 hours, and obtained the homogeneous liquid.

Next, 21.3 g of phthalic anhydride was added to this solution, mixed, and then stirred at 130 DEG C for 1 hour to dissolve phthalic anhydride in the solution.

The obtained homogeneous liquid was cooled to room temperature, and 75 ml of this homogeneous liquid was dripped at 200 ml of titanium tetrachloride maintained at -20 degreeC over 1 hour.

After this dropping was completed, the temperature of the resulting mixed liquid was raised to 110 ° C over 4 hours.

The temperature of the liquid mixture was raised to 110 degreeC.

When the temperature of the liquid mixture reached 110 ° C, 5/22 g of diisobutyl phthalate (DIBP) was added to the liquid mixture, and the obtained mixture was stirred at the same temperature for 2 hours.

After the completion of the reaction, the solid portion was recovered from the reaction liquid by high temperature filtration.

This solid portion was resuspended in 275 ml of titanium tetrachloride and the resulting suspension was further heated at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was recovered again by high temperature filtration.

This solid portion was washed well with decane and hexane at 110 ° C. until no free titanium compound was present in the solution.

The composition of the solid titanium catalyst component [A] -1 prepared above was stored as a decane slurry. A part of slurry was dried and the catalyst composition was examined. As a result, the composition of the obtained solid titanium catalyst component [A] -1 was 2.4 weight% of titanium, 60 weight% of chlorine, 20 weight% of magnesium, and 13.0 weight% of DIBP.

[Preparation of Prepolymerized Solid Titanium Catalyst Component [B] -1]

A 400 ml four-necked glass reactor equipped with a stirrer was charged with 200 ml of purified hexane, 6 mmol of triethylaluminum and 2.0 mmol of the solid titanium catalyst component [A] -1 (in terms of titanium atoms) obtained above in a nitrogen atmosphere. The propylene was then fed to the reactor at 20 ° C. for 1 hour at a rate of 6.4 l / h.

After the end of the propylene supply, the reactor was replaced with nitrogen, and the washing operation consisting of the supernatant liquid removal and the purification hexane addition and the purification hexane addition was performed twice. Next, the obtained reaction liquid was resuspended using purified hexane, and all the obtained suspension was transferred to the catalyst bottle, and the prepolymerized solid titanium catalyst component [B] -1 was obtained.

[Preparation of Prepolymerized Catalyst [1] -1]

In a 400 ml four-necked glass reactor equipped with a stirrer, 167 ml of purified hexane, 1 ml of 1.9-decadiene, 5 mmol of diethyl aluminum chloride, and 0.5 mmol of the solid titanium catalyst component [B] -1 (in terms of titanium atoms) obtained above were nitrogen. Charged in the atmosphere. Next, ethylene was supplied to the reactor at 0 degreeC, and supply was complete | finished when ethylene reaction volume was 13 l.

After the end of the ethylene supply, the reactor was replaced with nitrogen, and the washing operation was performed twice, which consisted of removing the supernatant and adding purified hexane. Next, the obtained reaction solution was resuspended using purified hexane, and all the obtained suspensions were transferred to a catalyst bottle to obtain a prepolymerized catalyst [1] -1.

In this process, ethylene and 1,9-decadiene were copolymerized in an amount of 15.3 g with respect to 1 g of the transition metal compound catalyst component.

[polymerization]

2 l autoclave was charged with 750 ml of purified n-nucleic acid, and 0.015 mmol Ti (tritium aluminum) 0.75 mmol, cyclohexylmethyldimethoxysilane (pre-polymerized catalyst [1] -1 (in terms of titanium atoms) obtained above) CMMS) 0.75 mmol was charged in 60 degreeC propylene atmosphere.

Further, 200 ml of hydrogen was introduced into the autoclave, the temperature in the autoclave was raised to 70 ° C, maintained at this temperature for 2 hours, and propylene polymerization was performed. The pressure of polymerization was maintained at 7 kg / cm 2 -G. After the polymerization was completed, the slurry containing the obtained solid was filtered and separated into a white powder and a liquid portion.

The yield of the white powder polymer was 362.6g on the basis of the dry amount, the extraction residue by boiling heptane was 98.34%. In addition, the white powder polymer had an MFR of 3.2 dg / min, a specific gravity of 0.45 g / ml, and a melt tension of 3.7 g. On the other hand, 1.7 g of solvent DYD polymers were obtained by concentrating the liquid phase. Thus, the activity was 24,300 g-pp / mM-Ti and white product II (T-1.1) was 97.9%.

The content of the ethylene / 1.9-decadiene copolymer of the olefin polymer obtained above was 0.17% by weight.

The results are shown in Table 1,

Example 2

[Preparation of Prepolymerized Catalyst [1] -2]

The prepolymerized catalyst [B] of Example 1 was used except that 0.5 mmol of diethyl aluminum chloride and 0.17 mmol (in terms of titanium atoms) of the prepolymerized catalyst [B] -1 were used, and the ethylene reaction amount was changed to 4.3 l. It carried out similarly to the polymerization method of] -1, and obtained the prepolymerized catalyst [1] -2.

In this step, ethylene and 1.9-decadiene were copolymerized in an amount of 15.4 g relative to 1 g of the transition metal compound catalyst component.

[polymerization]

An olefin polymer was obtained in the same manner as in the polymerization method of Example 1 except for using the prepolymerized catalyst [1] -2.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.18% by weight.

The results are shown in Table 1.

Example 3

[Preparation of Prepolymerized Catalyst [1] -3]

Prepolymerized catalyst [B] of Example 1, except that 1.5 mmol of diethyl aluminum chloride and 0.5 mmol (titanium atom equivalent) of the prepolymerized catalyst [B] -1 were used and the ethylene reaction amount was 13 l. It carried out similarly to the polymerization method of -1, and obtained the prepolymerized catalyst [1] -3.

In this step, ethylene and 1,9-decadiene were copolymerized in an amount of 15.3 g with respect to 1 g of the transition metal compound catalyst component.

[polymerization]

An olefin polymer was obtained in the same manner as in the polymerization method of Example 1 except for using the prepolymerized catalyst [1] -3.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.16% by weight.

The results are shown in Table 1.

Example 4

[polymerization]

Polymerization method of Example 1, except that triethylaluminum 1.88 mmol, CMMS 0.188 mmol, 0.0376 mmol of the prepolymerization catalyst [1] -3 (in terms of titanium atoms), and 400 ml of hydrogen were changed to 50 minutes. In the same manner as in the above, an olefin polymer was obtained.

The polymer tension obtained above could not be measured because its strands could not be stretched in the form of a single strand, therefore, after granulating the obtained white powder by the following method, the melt tension and melt flow rate of the polymer were measured. Measured.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.33 weight%.

The results are shown in Table 1.

[Granulation]

To 100 parts by weight of the white powder obtained above, 0.05 parts by weight of tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hyEHoscinnamate] methane, tris (mixed mono)- And 0.05 part by weight of di-nonylphenyl phosphite) and 0.1 part by weight of calcium stearate were mixed with each other, and the resulting mixture was granulated at 200 ° C. using an extrusion granulator (manufactured by Thermoplastic) having a screw diameter of 20 mm.

Example 5

[polymerization]

The polymerization of Example 1 was carried out except that triethylaluminum 0.94 mmol, CMMS 0.094 mmol, 0.0188 mmol of the prepolymerized catalyst [1] -3 (in terms of titanium atoms) and 300 ml of hydrogen were changed to 2 hours. It carried out similarly to the method and obtained the olefin polymer. After granulating the white powder of the polymer obtained above by the above method, the melt tension and the melt effective velocity of the polymer were measured.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.18 weight%.

The results are shown in Table 1.

Comparative Example 1

[polymerization]

Propylene polymerization was carried out in the same manner as in the polymerization method of Example 1, except that the prepolymerized solid titanium catalyst [B] -1 was used instead of the prepolymerized catalyst [1] -1.

The results are shown in Table 1.

Example 6

[Preparation of solid titanium catalyst component [A] -2]

4.8 g of commercially available magnesium chloride, 23.1 ml of 2-ethylhexyl alcohol, and 200 ml of decane were mixed, and heated at 140 ° C. for 3 hours to obtain a homogeneous liquid containing magnesium chloride. Next, a mixture of 7.1 ml of triethyl aluminum and 45 ml of decane was added to the solution and stirred at 20 ° C. for 30 minutes, and the resulting mixture was kept at that temperature for 1 hour. Then, the temperature of the mixture was raised to 80 ° C. over 1 hour, and the mixture was further heated at the same temperature for 1 hour.

Next, a mixture of 7.5 ml of diethyl aluminum chloride and 52 ml of decane was added dropwise to the mixture over 30 minutes, and the resulting mixture was heated again at 80 ° C. for 1 hour. The solid part produced in the reaction liquid was separated from the reaction liquid by filtration. Therefore, the solid component containing a reducing organic group was synthesize | combined.

The solid component obtained above was resuspended in 200 ml of decane, 3.75 mmol of 2-ethylhexacytitane trichloride was added to the obtained suspension, and these were reacted at 0 ° C for 1 hour. Next, the obtained reaction liquid was washed with decane to obtain solid titanium catalyst component [A] -2.

[Preparation of Prepolymerized Catalyst [1] -4]

In a 400 ml four-necked glass reactor equipped with a stirrer, 150 ml of purified hexane, 0.1 ml of 1,9-decadiene, 0.3 mmol of diethyl aluminum chloride, and the solid titanium catalyst component [A] -2 (in terms of titanium atoms) 0.1 mmol was charged in a nitrogen atmosphere. Next, ethylene was further supplied to the reactor at 30 ° C., and the methylene feed was terminated when the methylene reaction amount was 3 l. The reactor was nitrogen-substituted and the seeding operation which consists of removing supernatant liquid and adding refined hexane was performed twice. Next, the obtained reaction liquid was resuspended using purified hexane, and all the obtained suspension was transferred to the catalyst bottle, and the prepolymerized catalyst [1] -4 was obtained.

In the above step, the copolymerization amount of ethylene and 1,9-decadiene was 10.1 g with respect to 1 g of the transition metal compound catalyst component.

[polymerization]

2 g of aluminum chloride sufficiently substituted with nitrogen was charged with 150 g of sodium chloride as a dispersant, and the autoclave withstand pressure was reduced to 50 mmHg or less by using a vacuum pump for 2 hours while heating the autoclave at 90 ° C. The temperature of the autoclave was then lowered to room temperature and the autoclave was replaced with ethylene. Subsequently, 0.5 mmol of triethyl aluminum, 0.5 mmol of diethyl aluminum chloride, and 10 ml of 1-hexene were charged into the autoclave. After the reaction system was sealed, the temperature of the reaction system was raised to 60 ° C., and 1.2 kg / cm 2 of hydrogen was supplied to the reaction system.

While further applying pressure using ethylene, 0.003 mmol (in terms of titanium atoms) of prepolymerized catalyst [1] -4 obtained above were added to a reaction system at 70 ° C. During the polymerization, the temperature was 80 ° C. and the pressure was maintained at 8 kg / cm 2 by supplying ethylene gas. After the addition of the prepolymerized catalyst [1] -4, 40 ml of 1-hexene was fed to the reaction system over 1 hour using a pump. After addition to the prepolymerized catalyst [1] -4, the polymerization was terminated within 1 hour.

After the end of the polymerization, the contents of the autoclave were introduced into about 1 l of water. The obtained mixture was stirred for 5 minutes, and almost starch sodium chloride was dissolved, and only the polymer was suspended on the water surface. After recovering this polymer, the mixture was washed well with methanol and dried at 80 ° C. under reduced pressure overnight.

The ethylene / 1,9-decadiene copolymerization content of the olefin polymerization was 0.09% by weight.

The results are shown in Table 2.

Example 7

[Preparation of Prepolymerized Catalyst [1] -5]

A prepolymerized catalyst [1] -5 was obtained in the same manner as in the polymerization method of Example 6 except that 1.0 mmol of 1.9-decadiene was used.

In this process, ethylene and 1,9-decadiene were copolymerized in an amount of 11.0 g with respect to 1 g of the transition metal compound catalyst component.

[polymerization]

An olefin polymer was obtained in the same manner as in the polymerization method of Example 6 except that 1.5 kg / cm 2 of hydrogen was used and the prepolymerized catalyst [1] -5 was used.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.10% by weight.

The results are shown in Table 2.

Example 8

[Preparation of Prepolymerized Catalyst [1] -6]

The prepolymerized catalyst [1] -6 was obtained in the same manner as in the polymerization method of Example 6 except that the reaction amount of ethylene was 4.5 l.

In this process, 15.2 g of ethylene and 1,9-decadiene were copolymerized in an amount of 1 g of the transition metal compound catalyst component.

[polymerization]

An olefin polymer was obtained in the same manner as in the polymerization method of Example 7 except that the prepolymerized catalyst [1] -6 was used.

The ethylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.12% by weight.

The results are shown in Table 2.

Comparative Example 2

[Preparation of Prepolymerized Catalyst [B] -2]

In a 400 ml four-necked glass reactor equipped with a stirrer, 200 ml of purified hexane, 0.6 mmol of triethyl aluminum and 0.2 mmol of the solid titanium catalyst component [A] -2 (in terms of titanium atoms) obtained above were charged in a nitrogen atmosphere. The reactor was then further fed with ethylene at a rate of 7 l / h at 30 ° C. for 1 hour.

After the end of the ethylene supply, the reactor was replaced with nitrogen, and the washing operation was performed twice, which consisted of removing the supernatant and adding purified hexane. Next, the obtained reaction liquid was resuspended using purified hexane, and all the obtained suspension was transferred to the catalyst bottle, and the prepolymerization catalyst [B] -2 was obtained.

[polymerization]

An olefin polymer was prepared in the same manner as in the polymerization method of Example 6, except that 1.1 kg / cm 2 of hydrogen was used and instead of the prepolymerized catalyst [1] -4, the prepolymerized catalyst [B] -2 was used. Got it.

The results are shown in Table 2.

Example 9

[Preparation of Prepolymerized [1] -7]

In a 400 ml four-necked glass reactor equipped with a stirrer, 167 ml of purified hexane, 1 ml of 1,9-decadiene, 5 mmol of triethyl aluminum and 1 mmol of cyclohexylmethyldimethoxysilane (CMMS), the solid titanium catalyst component [A]-obtained above 0.5 mmol (1 in terms of titanium atoms) was charged in a nitrogen atmosphere. In the next reactor, propylene was further fed. When the propylene reaction amount was 8 l, the propylene supply was terminated.

After the end of the propylene supply, the reactor was replaced with nitrogen, and the washing operation was performed twice, which consisted of removing the supernatant and adding purified hexane. Next, the obtained reaction liquid was resuspended using purified hexane, and all the obtained suspension liquid was transferred to the catalyst bottle, and the prepolymerized catalyst [1] -7 was obtained.

In the above step, the copolymerization amount of propylene and 1,9-decadiene was 15.2 g based on 1 g of the transition metal compound catalyst component.

[polymerization]

2 l autoclave was charged with 750 ml of purified n-hexane, and further, 0.015 mmol of Ti (in terms of titanium atoms) obtained above, 0.015 mmol of Ti, 0.75 mmol of triethylaluminum, and cyclohexylmethyldimethoxysilane ( CMMS) 0.75 mmol was charged in a 60 ° C. propylene atmosphere.

Further, 200 ml of hydrogen was introduced into the autoclave, the temperature in the autoclave was raised to 70 ° C., maintained at this temperature for 2 hours, and propylene polymerization was performed. The pressure during polymerization was maintained at 7 kg / cm 2 -G. After the polymerization was completed, the slurry containing the obtained solid was filtered and separated into a white powder and a liquid portion.

The yield of the white powder polymer was 315.g on the basis of the dry amount, the extraction residue by boiling heptane was 98.89%. The white powder polymer had an MFR of 3.9 dg / min, a specific gravity of 0.46 g / ml, a melt tension of 0.85 g. On the other hand, 1.9g of solvent-soluble polymers were obtained by concentrating the said liquid component. Thus, the activity was 21,000 g-pp / mM-Ti and II (t-I.I.) In the white product was 98.3%.

The content of the propylene / 1,9-decadiene copolymer of the olefin polymer obtained above was 0.21% by weight.

The results are shown in Table 1.

Example 10

[Preparation of Prepolymerized Catalyst [1] -8]

A prepolymerized catalyst [1] -8 was obtained in the same manner as in the prepolymerization method of solid titanium catalyst component [A] -1 of Example 9, except that 5 ml of 1,9-decadiene was used.

In this process, propylene and 1,9-decadiene were copolymerized in an amount of 15.4 g with respect to 1 g of the transition metal compound catalyst component.

[polymerization]

An olefin polymer was obtained in the same manner as in the polymerization method of Example 9 except for using the prepolymerized catalyst [1] -8.

The propylene / 1,9-decadiene copolymer content of the olefin polymer obtained above was 0.27% by weight.

The results are shown in Table 3.

Claims (6)

(A) An organometallic compound catalyst component containing a transition metal compound catalyst component and a metal selected from the metals of Groups I to III of the periodic table, α-olefins and polyene compounds, the total amount of which is a transition metal compound A prepolymerized catalyst prepared by prepolymerization in an amount of 0.01 to 2,000 g per 1 g of catalyst component [A]. 2. The prepolymerized catalyst according to claim 1, wherein the transition metal compound catalyst component [A] is a compound containing at least one transition metal selected from Ti, Zr, Hf, Nb, Ta, Cr, and V. The prepolymerized catalyst according to claim 1, wherein the transition metal compound catalyst component [A] is a solid titanium catalyst component containing titanium and a halogen. The prepolymerized catalyst according to claim 1, wherein the transition metal compound catalyst component [A] is a metallocene compound containing a ligand having a cyclopentadienyl skeleton. The prepolymer catalyst according to claim 1, wherein the polyene compound is a polyene compound having an olefinic double bond at the sock end. The prepolymerized catalyst according to claim 1, wherein the polyene compound is an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms having an olefinic double bond at the sock end.