WO1980001485A1 - Process for producing olefin polymer - Google Patents

Abstract

A process for producing a polyolefin having high polymerization activity and high molecular weight or a polyolefin, particularly polyethylene, having a wide molecular weight distribution adapted for extrusion or blow-molding, comprising the step of polymerizing olefin such as ethylene by the use of a catalyst system which comprises organic aluminum compound and solid catalyst component obtained by mixing or reacting organic oxygenated compounds or halides of metals such as (a) vanadium and (b) hafnium, or solid catalyst component obtained by mixing and reacting organic oxygenated compounds or halides of metals such as (A) vanadium, (B) hafnium and (C) titanium with (D) organic aluminum compound.

Description

 Description Title of invention

 Method of manufacturing refin polymer

Technical field

 The present invention relates to a method for producing an olefin polymer. More specifically, new catalysts or vanadium and vanadium compounds, including vanadium and vanadium compounds, have been introduced. Including new

A method for producing an olefin polymer using a catalyst

 o Background technology

 Conventionally, it is known to polymerize a non-native olefin such as ethylene using a so-called Ziegler catalyst comprising a transition metal compound and an organic aluminum compound. ]? For example, in the Japanese Patent Publication No. Sho 1 // = 2 <≤ 、, the mixture of tetravalent halogenogen titan and vanadium oxyalcoside is used. Is obtained from the eutectic obtained by reducing the reaction product with an organic aluminum compound and the organic aluminum compound.

Catalyst systems have been proposed. This catalyst system has a very high catalytic activity, and the resulting polymer has a narrow particle size distribution and a high bulk density. 4 (7

OMP1 WiPO.

, ¾NAT \ 0 ^ Has a very large advantage in

 However, the polymer obtained by this catalyst system had a narrow molecular weight distribution and was suitable for injection molding, but it was suitable for extrusion molding or pro-molding. However, it was not suitable for applications requiring a large space.

 As described above, multi-step polymerization and polymer blends are widely used as a method for producing a polymer with a wide molecular weight distribution using a catalyst having a high polymerization activity but a narrow molecular weight distribution. Methods have been proposed. However, each of these methods requires a large and complicated apparatus, and requires a high degree of technology to adjust the molecular weight ratio and mixing ratio of the polymer to be mixed.

It is known that two or more kinds of catalyst components are used in combination in order to produce a polymer having a wide molecular weight distribution. For example, T i OG ₂ , Zr C _4, etc. The catalyst may be a combination of a catalyst component for producing a polymer having a relatively high molecular weight and a catalyst component for producing a relatively low molecular weight which is usually used. The present inventors have also used a catalyst in which a titanium compound, a vanadimidic compound, and a zirconium compound are combined, as described in Japanese Patent Application No. 197 Therefore, a method for producing a polymer having a wide molecular weight distribution was proposed.

 Although this method is useful by itself, it is, however, not suitable for producing a polymer having a very wide molecular weight distribution.

Ο, ΜΡΙ In this case, the polymerization activity was still insufficient. In order to remedy this drawback, the olefins were polymerized under the same conditions, and both the catalysts giving relatively low molecular weight and the catalyst giving high molecular weight were highly active. In particular, it was necessary to increase the activity of a catalyst that gives a high amount of energy, which was conventionally low in activity.

 As a result of intensive studies on this point, the present inventors have found that a solid containing hafnium, vanadium, and halogen that gives a highly active and high-molecular-weight polymer is obtained. A catalyst was found. A method for polymerizing one-year-old refins, especially polyethylene, using hafnium's halogenogen is already known, but generally the polymerization activity is extremely low. Therefore, it was completely unsuitable for commercial production. The use of a hafnium compound in combination with a vanadium compound])), which significantly increases the polymerization activity and gives a higher molecular weight polymer. This must be said to be surprising.

 The present inventors have further developed a polymer having an extremely wide molecular weight distribution by using a combination of a vanadium-hafnium-based catalyst and a titanium-based catalyst. A method that can be produced based on the polymerization activity was found. According to this method, the amount ratio of the titanium compound, the vanadium compound, and the hafnimium conjugate in the catalyst is changed]), It describes the molecular weight distribution of the polymer obtained by one catalyst system.

OMP1 WiPO Ά The advantage is that it can be easily controlled. Disclosure of the invention

 The gist of the present invention is

(a) vanadium compounds selected from vanadium halogen compounds and organic oxygenated compounds; and (Ϊ) halogen halide compounds A solid catalyst component obtained by mixing and reacting a hafnium compound selected from a product and an organic oxygenated compound.

Or (A) a vanadium compound selected from the group consisting of a vanadium nitrogen compound and an organic oxygenated compound;

Hafnium compounds selected from organic compounds and organic oxygenated compounds; and (C) selected from dioxygen compounds and organic oxygenated compounds of titanium A solid catalyst component obtained by reacting the obtained titanium compound and the P) organic aluminum compound with a catalyst obtained by combining the organic aluminum compound component with the solid catalyst component. A method for producing an olefin polymer characterized by polymerizing the olefin.

 In order to explain the present invention in detail, the titanium compound, vanadium dimethyl compound and hafnium compound used for the preparation of the solid catalyst component in the present invention contain the organic oxygen of each metal. Selected from halogenated compounds and halogenated compounds. The term "organic oxygenated compound of metal" as used herein means that a molecule has at least / at least / metal-oxygen-organic bond in this order.

 Ji ',

OVP1 Means a compound. And / molecule warm! ) At least / piece

If it has a metal-oxygen-organic group bond of

A condensed compound having a genus-oxygen-metal bond

Good. It is possible to choose any of these

Yes, but generally have / ~ = 2 carbon atoms

And more preferably a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an aryl group, an aryl group, or an aryl group. Alkyl groups and the like are used. On the other hand, a metal halogen compound is a compound that is at least /

It means a compound having a halogen bond. And / molecule

At least one metal-halogen bond

If, condensed with a metal-oxygen-metal bond

It may be a compound. As this halogen atom,

Nitrogen, chlorine, bromine, and iodine can be used. This

Of these, the use of bromine or chlorine is preferred. And such organic oxygenated compounds and π-gen compounds are

The general formula [MeOa (0R) ¾X _C ] (where R is

And X represents the halogen atom described above, and Me is titanium, vanadium, or hafnium. a is d? ^ a ^ /, ¾clf ± 0≤ ~ b≤ ^^ ≤c≤ <DL ~ '> ^, and ax <2 + ti + c is equal to the valence of each metal. Is an integer of /

You. The compound represented by) is most preferred.

And a server Na di U beam compounds have the general formula ^{[VOa / i (ORi) TD 1} X 1 c 1 d 1 ( where, a ^1,, c ¹ each click ≤ a ¹ ≤ /, and υκ

OMP1

, WiPO, AT10 0≤ ^ ≤ ^ O≤ c ¹ ≤S, a ¹ X + ΐι ¹ + c ¹ Force S is a number that is equal to the valence of nonadium, and a ¹ is

Is an integer. ¹ is the number of carbon atoms / ~ = 2 k

/ Represents a hydrocarbon group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group. X ¹ represents a halogen atom. Value or price of Panamax di ©-time I arsenide compound represented by) is a good or arbitrariness, Chi jar of this, the general formula ^{VO (0R 2) a2 ^ _} a2 ( in the formula, a? Gu ^ _a 2 _≤ And R2 and _χ2 are the same as _Rl and _χ1 .) _And a _vanadium compound having the valency represented by the general formula V (OR ² )

(Wherein ring ² is the number of click ≤ ≤, R ^2, X ² is same as above.) Arbitrary favored the bets Ku valent vanadyl di U beam compounds represented by. As the halogen atom, chlorine and bromine are preferable. Is a these I匕合thereof, if e O key sialic breath Sa I De Yi _{j V0 (0- nC 4 H e} ) 3, V0 (0C 2 H 5) 3; old key leaves La Lee For example, VOC ₃ , V0Br ₃ ;

VO (OC ₆ H ₅ ) ₃ ;

VO (OG ₂ H ₅ ) ₂ Br, Y0 (0-nC ₄ H ₉ ) ₂ Br _% VO Γ OG ₂ H ₅ ) ₂ Gt _Λ

_{V0 (0-nC H g)} 2 C ^ V0 (0-nC 4 H 9) Br 2 Te Bok La Roh, La Lee de For example VBr _4, VC ₄ or the like is mentioned, et al. Are. Complexes with various Lewis bases such as VBr ^ .2 (butyl ether) may be used. Compounds containing several different organic groups or halogen atoms can be used, and some different vanadium compounds can be used.

B then '"..

_ ΟΓ.ίΡ! ヽ vii'o> The hafnium compound is represented by the general formula [HfOa ³ (OR ³ ) ¾ ³ X ³ c ³ d ³ (wherein a ³ ¾ ³ c ³ lf ± 0≤ ³ ≤ / 0≤ D ³ ≤ V-,

⁰ ≤ c ^z ≤ ^ and a ³ X <2 + T3 ³ + c ³ =

Is an integer of / ≤ d ³ ^. R ³ X ³ is the same as Ri X ¹ . )

A multivalent hafnium compound represented by is preferred,

—General formula Hf (0R ³ ) _A 4; ^ _ _A4 (where a ⁴ is ^ a ^

Number, R ³ X ³ is Ru same der to R ¹ _ X ^1. )

Particularly preferred are the tetravalent hafni umui dani compounds. Halogen

As atoms, chlorine and bromine are preferred. These compounds

And then it is, A Le co hexa Lee de e.g. _{Hf (0- nC 4 H 9)} 4

Hf (0C ₂ H ₅ ) ₄ ; Phenoxide such as Hf. (0C ₆ H ₅ ) ₄ ; Al

Breath La Lee de (1 example, if _{Hf (0-η-0 4} Η 9) 3 0 Hf (0 -η -. C 4 H g) 2

Br ₂ ; Tetrahalide such as HfC, HfBr ^;

Oral compounds such as HfOG _2. (This compound is usually

Used in the form of HfOC ₂ · 11 ₂ 0. ) And the like.

Various Lewis bases such as HfBr ₄ · ο2 (ethyl acetate)

A complex of and may be used. Several different organic groups

Or a compound containing a halogen atom.

Uses many different hafnium compounds

You can do it.

 However, as described in the above <Nadmium compound and

A solid catalyst component is prepared by mixing and reacting

If used, both compounds should be in the presence or absence of diluent

Contact in the presence. Temperature conditions during contact are particularly limited

WIPO, For example, it can be selected from the range of t t == 200 ° C., but usually around normal temperature. The pressure condition is not particularly limited, but may be around normal pressure. After contact, the two compounds are mixed, but the two compounds may be reacted simultaneously with or after the mixing. One small rather as also of and during contact the compound is rather was favored and the this that a liquid, one least for the well of both compounds for this has organic oxygen groups i.e. ORi, the OR ² or OR ³ / FOB Preferably, it is a compound. Therefore, when both compounds are solid, it is preferable to use a diluent so as to dissolve at least one of them. The resulting mixture or reaction product may be used as it is as a solid catalyst component, or a solid can be separated from the reaction product to be a solid catalyst component. In the case where a liquid substance is used as a diluent, the diluent is removed to precipitate a solid, and the obtained solid is separated to obtain a solid catalyst component. In addition, in a polymerization system, both compounds may be mixed or reacted to produce a solid catalyst component and, at the same time, combined with an organic aluminum compound component to provide a catalyst for olefin polymerization. it can. As a diluent, any of the usual inert hydrocarbon solvents can be used, but the number of carbon atoms is from ^ to. The use of two alkanes, cycloalkanes and aromatic hydrocarbons is preferred. Examples of these compounds include hexane, hebutane, hexopen hexan, benzene, tonolene, and xylene. Also use a polar solvent. As polar solvents, for example, ethylene chloride

 , Chlorbenzen, etc. "

 / Alcohols, carboxylic esters, air

Examples include tellurium and pyridin.

 In addition to the Bana-ji-U-Mich compound and the Ha-Fni-U-Mi dragon compound

The i "component to which the halogenating agent has been added is reacted to form a solid catalyst.

In particular, high activity and high molecular weight catalysts are obtained

It is preferred because it can be obtained. In this method, a halogenated pill

These include chlorine, bromine and other halogens;

、, 臭 匕 ァ レ レ 、, メ レ ア レ ア ゥ ゥ ゥ ゥ

 Lido, echinorenoremi

Digi-chloride, methyl-aluminum

 M / S / M / S

Halogen-containing anodized aluminum such as luminum monochloride

Silicon compounds, such as silicon tetrachloride and tin tetrachloride. Among these compounds, the halogen-containing aluminum imide compound, especially the general formula A! ^ _ _n (where, is the number of carbon atoms / ~ / = 2

X ⁴ represents a halogen atom, and II represents o≤n <J

The compound represented by) which represents the number of) is particularly preferred.

, X ⁴ are the same as those exemplified earlier for R ¹ and X ¹

Where n is the number of, /, /., <2

.

 Banaji Umyi Ridge, Hafni Umyi Ridge and Haloge

As a method for reacting the J component of the

Λ, W1FO, ν ", · A liquid material is prepared by mixing and reacting the dime compound and the hafdium compound in the presence or absence of a diluent to prepare a liquid substance, and then halogenate the liquid substance. Preferred is a method in which the catalyst is reacted and the solid catalyst component is separated from the reaction mixture. The mixing or reaction of the vanadium compound and the hafnium munich compound is carried out as described above, and the mixture or reaction is necessary so that the reaction mixture becomes liquid. The corresponding diluent is added. A reaction is performed by adding a halogenating agent to the obtained liquid, and the reaction is carried out if the mixture obtained as described above is sufficiently liquid in the absence of a diluent. Also, it is preferable to carry out the reaction in the presence of an inert solvent. As the inert solvent, an inert hydrocarbon solvent is usually used among those exemplified above as the diluent. When a polar solvent is used during the mixing or reaction of the vanadium compound and the hafnium compound, the polar solvent is distilled off under reduced pressure prior to the reaction with the halogenating agent. It may be removed by the above method, or the reaction with the halogenating agent may be carried out without removing it.

However, the reaction with the halogenating agent is carried out without the mixture of the vanadium munich compound and the hafnium compound to which the inert solvent has been added, or the reaction with the halogenating agent. , Preferably at room temperature to „2 C, more preferably at 0 ° C./s 0 C. The reaction may be performed at a temperature of C, and a solid insoluble in an inert solvent is obtained. Is separated and washed with an inert solvent. The second method for reacting the J component is as follows:

 Do not mix the components or perform the reaction simultaneously in an inert solvent.

There is a method. The reaction conditions are the same as those described above.

 However, although there is no particular limitation on the amount of ingredients used,

Banana against hafnium in the everlasting hajime

The atomic ratio of vanadium in the compound (V / Hf)

 /// 00 ≤ V / Hf ≤ / 00 preferably

 /// 0 ≤ V / Hf ≤ / 0

If a halogenating agent is used, the amount used should be

ナ ハ ノ フ ナ フ フ フ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ ナ

Atom of halogen contained in the agent for halogen

The ratio / (V + Hf)

 / ≤ / CV + Hf) ≤ / 00

 / ≤ X // (V + Hf) ≤ rO.

 The catalyst for vanadium-hafnium-based catalysts as described above

Pairs with Platinum-based Catalysts

To obtain a system catalyst, vanadium compounds and hafnium

Compounds, titanium compounds and organic aluminum compounds

The reaction is performed to prepare a solid catalyst component.

In here, it is a switch data Nihi compound of the general formula [TIOA ⁵

(OR ⁵ ) ¾5 X ⁵ c ⁵ ] d ⁵ (where a ⁵ , ¾ ⁵ and c ⁵ are 0 ≤ z ≤ / ^

Let a ⁵ X „2 + t ⁵ + c ⁵ = ^ with 0≤ ^ ⁵ ≤ ^ ^ 0≤ c ⁵ ≤ ii

Is a decimal number, and ⁵ is an integer of / ≤ d ⁵ ≤. R ^5, X ⁵ is

 Same as, ^. ) Represents a tetravalent titanium compound

W1PO, It is preferable to use a general formula Ti (on ⁶ ) _a e zj_ _a6 (where a ⁶ is a number that is q a6 ^, and X ⁶ is the same as R 上 記 above). The tetravalent titanium compounds mentioned are particularly preferred. Bromine is the most preferred halodan atom. These compounds include alcoholic acid

Ti (0G ₂ H ₅ ) ₄ , Ti (0-nC ₄ H ₉ ) ₄ ; phenoxyside

Ti (0C ₆ H ₅ ) ₄ ; Oxal alkoxide such as Ti0 (0C ₂ H ₅ ) ₂ ; Tetra halide such as TiC, iBr ₄ ; Oxide halide such as TiOC ^ _2, TiOBr _2, and c b gain emissions of Al co key Sa I de Yi J example, if _{Ti (0C 2 H 5) 2} G 2, Ti (0C 2 H 5) 2 Br 2

_{Ti (0-nG 4 H 9} ) 3 Br, T (0 - n - CH 9) 3 include C like mosquitoes. These compounds and species s complex of Le y scan bases, for example, IBR ₄ · 2 (Puchinore et one te le), using _{iBr 3 (0 -nC 4 H 9} ) · E chill § Se Te over preparative like You may. Compounds containing several different organic groups or halogen atoms can be used, and some different titanium compounds can be used.

In addition, the general formula [TiOqi (OHi ²⁾ _q ^2] q ³ (formula, is 0, 2 <q qi in the ^{z ≤ X + q 2:.} ? Number Let 's Ru door der], q ³ is = Ru integer der of 2≤ ≤. R ¹² is the same in.) at the indicated is rather small in the molecule and also / number of tetravalent having TiO-Ti bonds Ji data down § Honoré co la one DOO The condensate is a catalyst that forms a refined polymer with good extrudability, high bulk density, and low content of coarse and fine particles.oyPic Is preferred in that it gives These compounds include

The oligo sesame derived from the tantra alcohol box,

For example, titanium tetrakitide, titanium tetraethoxylate, titanium tetraproxide, titanium tetrakitoxide, etc. Condensation = 2 to a monomer. Also

Of course, mixtures of these condensates and mixed alcohols

It is also possible to use a condensate of

 On the other hand, the organic aluminum compound has a general formula

During Δ R ^ X ⁷ ₃ (wherein, R ⁷ is rather to preferred number / ~ J carbon is

/ ~ Number of hydrocarbon groups der 1) X ⁷ is Ru Ah at C B gain down atoms.

 Is the number of <. )

It is preferred to use a compound of the formula In addition, R ⁷ is

Quinole group, cyclone group quinole group, aryl group, aryl group

It is preferable to choose from alkyl groups and alkyl groups.

No. Is a X ⁷ chlorine, bromine, Yo U arsenide is like et be.

These compounds include A (C ₂ H ₅ ) ₃ , AZ (0 ₂ H ₅ ) ₂ C ^,

Α ₂ (C ₂ H ₅ ) ₃ C ₃ , A (C ₂ H ₅ ) ₂ C, A (C ₂ H ₅ ) ₂ Br

It is. The organic aluminum compound includes bromide.

Aluminum-dimethyl compounds are most preferred. Wrinkle, smell

Catalyst prepared using activated organic aluminum compound

The polymerization is carried out using the components in the presence of hydrogen in the polymerization reaction zone.

In this case, the molecular weight regulation effect of hydrogen is very large.

There are points. Such an organic aluminum bromide compound and

The general formula A Ϊ4ΒΓ ₃ (where R ⁸ is the number of carbon atoms / ~

OV.PI "W.PO = 2 preferably a hydrocarbon group of / to ό, where m is

This is the number of ku m i>. It is preferable to use an aluminum imide compound represented by the following formula: Further, R ⁸ is preferably selected from an alkyl group, a cycloalkyl group, an aryl group, an aryl group, and an aryl group. .

Is in these I匕合 _{thereof, A (GH 3) Br 2} , A_ (G 2 H 5) Br 2, AZ (i -G 4 Hn ") Br 2 ¾ KJ (nG 8 H 17) Br 2 _{^ A (C 2 H 5)} 2 Br,

A (C ₂ H ₅ ) ₂ Br, (CH ₃ ) .A ^ Br ₁ _ _5% (C ₂ H ₅ ) ₅ A Br ^

No. Among these, the organic dibromide aluminum dibromide compounds in which m is / in the general formulas such as AA (C ₂ H ₅ ) Br ₂ and A ^ (GH ₃ ) Br ₂ are shown. Use is preferred. Also, the use of several different organic aluminum compounds can result in the use of several different organic groups or organic aluminum compounds containing a halogen atom. It is also possible to use a My dagger. Aluminum trihalide and organic aluminum compounds can be used in combination. Among these, when a mixture of an organic aluminum dibromide compound and an organic aluminum dichloride compound is used, a catalyst having a special characteristic can be obtained. You. In other words, if the molecular weight distribution is too wide, it may cause unstable flow of the melt during melt molding.] Irrespective of the high extrudability, irregular patterns may be formed on the skin of the molded product. However, the olefin polymer obtained by using the catalyst produced by using the above mixture has a high molecular weight distribution and a high extrudability, but does not have a high meltability. Stable flow and success e 'K'

_ OMPI Irregular patterns may also appear on the skin of the shapes. However, as the organic aluminum dichloride compound,-in the general formula AR _λ shown above, it is assumed that X is chlorine in /

Compounds are listed. The mixing ratio of the two is in the range of /// 0 to / -0 by the atomic ratio of B i C.

~ Is preferred.

In the reaction, the components may be added and mixed in an arbitrary order and reacted. For example, a titanium compound, a vanadium compound, and a hafnium compound are mixed, and an organic aluminum compound is added to the obtained mixture or the reaction product to be reacted. Specifically, first, a titanium compound, a vanadium compound, and a hafnium compound are added and mixed. The order of addition of each compound can be arbitrarily selected. After mixing, a reaction may occur between the compounds. The temperature conditions during the addition are not particularly limited, ^ C to = 2 ° C, usually at normal temperature, and the pressure conditions are not particularly limited, and may be at normal pressure. Mixing can be performed in the presence or absence of a diluent, but it is preferred that the mixture be liquid (even a slurry). For this, if itself compounds are not liquid at mixing conditions, or if the amount is insufficient for the liquid compounds, and the arc Ru added diluent is a _c diluent Shi preferred, conventional inert Although all hydride solvents can be used, the use of alkanes having up to 2 carbon atoms, cyclopialkanes, and aromatic hydrocarbons is preferred.

 —, To

OMP1 WiKJ New These compounds include hexan, heptane, cyclohexan benzene, xylene, -xylene and the like. Also, a polar solvent can be used. These solvents include, for example, ethylene dike mouth light, alcohols of carbon ^ / to cf, esters of carboxylate, ethers of ethers. , Pyridin and the like. The addition of titanium, vanadium, and hafnium may be carried out as a solution of the polar solvent and the inert hydrocarbon solvent described above.

 Then, the mixture or the reaction product of the titanium compound, vanadium compound and hafnium mulphide compound obtained as described above is reacted with the organic aluminum compound. To prepare a solid catalyst component. The reaction with the organic aluminum compound can be carried out with the mixture obtained as described above or the reaction-even if the product is sufficiently liquid in the absence of a diluent, it is inert. Preferably, it is performed in the presence of a solvent. As the inert solvent, an inert hydrocarbon solvent is usually used among those exemplified above as the diluent. When a polar solvent is used for mixing, the polar solvent may or may not be removed by distillation under reduced pressure or other methods prior to the reaction with the organic aluminum compound. The reaction with the organic aluminum compound may be performed as it is.

 The reaction with an organic aluminum compound is carried out by the addition of an inert solvent to a titanium compound, a vanadium munich compound or a hafnium compound.

 υκ ヒ,

, :-

Mixture of 17 compounds or organic aluminum in the reactants

Add the compound, preferably at room temperature to << 20 O

The reaction may be carried out at a temperature of 0 ϊ to / 0 C.

Separates solids in an inert solvent as insoluble solids are obtained

Washing with inert solvent is preferred, but not separated

Can be used as is.

 The second method involves vanadium compounds and

After adding and mixing the zinc compound, the presence of an inert solvent

The lower organic aluminum compound was added to initiate the reaction.

The reaction is continued by adding a titanium compound.

And, preferably, separating the solid from the reaction mixture. —Reaction

Conditions conform to the method described above.

 The amount of each compound used is titanium compound and vanadium

Compound and the gram equivalent of each metal in the humid-palladium compound

Expressed sum, titanium compound, vanadium compound

In organic compounds, hafni munich compounds and organic aluminum munich compounds.

Of the sum u represented by the program equivalent of each

The ratio, or u / t, is preferably u / t>

 It is preferable to choose it. Where the Gram equivalent is

Gram equivalent = Gram atom of element Z Defined by valence of element

It is the amount to be done. If ¾>, the molecular weight distribution

The advantage is that it is particularly easy to produce a wide polymer.

is there. There is no particular upper limit on the value of u / t, but a value of up to about / is sufficient. Brominated organic aluminum When using gamma, it is preferable to use other halogens in a ratio of bromine and other halogens (mole ratio) / soil. . In addition, the amounts of titanium, palladium, and hafnium represented by Gram atoms should be set so as to satisfy the following expressions. I prefer to choose. Immediately, 0 / HfZTi f0, .H / H (Hf + Ti) ZV H / H, more preferably H = HH / i <cf, 0.0 <(Hf + Ti) / V </ 0.

When the value of Hf / Ti is within the above range, it is particularly easy to produce a polymer having a wide molecular weight distribution using this catalyst system.?, The value of (Hf + Ti) / V When the content is within the above range, there is an advantage that the polymerization activity of the catalyst system is particularly high.

 As described above, when the Panadium conjugate, the hafnium compound, the titanium compound, and the organic aluminum compound are reacted to prepare a solid catalyst component, Some of the hafdium compounds may be replaced with zirconium compounds. As such a zirconium compound, a halogen compound or an organic oxygenated compound is used.

C ZrOa ⁹ TOR ⁹ ¾9∑ ⁹ c ⁹ ] d ⁹ f where a ⁹ , ΐ ⁹ , and c ⁹ are a ⁹ /, 0 ≤ T ⁹ ≤ ϋ 0 ≤ ⁹ ≤ ¼ a ⁹ X «2 +" b ⁹ + c ⁹ = ^ the number der Let 's Ru ¾]?, is / ^ de ^ integer der of _Ru., χ9 is R ^1. X ¹ in the same. tetravalent Jill co-two represented by) The general formula Zi ^ ORiG) ^^^ (where a ¹⁰ is a number ≤ a ≤ and R ¹⁰ and X ¹⁰ are the same as R ¹ and X ¹

OMPI

UO is there. The tetravalent zirconium-myi conjugate represented by) is particularly preferred. Halogen is preferably chlorine or bromine. Is the these compounds, Al co key Size Lee de e.g. _{Zr (0-n- C 4 H} 9) 4 Zr (OC 2 H 5) 4; full d Roh key Size Lee de example if Zr (OC ₆ H ₅₎ *;. Tel breath leaves La y de e.g. _{Zr (0- nG 4) 3 Q} , JL Zr (OnC ^ Hg) 3 Br ^ Zr (0 -n-0 4 H o ") Br 2; Tetralide, for example, ZrC ^ ₄ ZrBr ₄ ; oxyhalogenated compound, for example, ZrOBr ₂ (this compound is usually used in the form of ZrOBr ₂ , cfH ₂₀ ). Complexes with various Lewis bases, such as ZrC ^ ₄ · o2 (ethynoleate acetate), may be used.Compounds containing several different organic groups or halogen atoms Alternatively, a number of different zirconium munich compounds can be used.

When a zirconium compound is used, the dose of each compound is determined by the atomic ratio of titanium, vanadium, zirconium, and platinum to each atom. (Zr + Hf) ZTi ratio in the range of 0.2 <(Ζτ + Εί / Ύ ± << Γ, (Ti + Zr + Hf) / VJ If 0.0ί <(Ti + Zr + Hf) / V <: / When the value of (Zr + Hf) / Ti is within the above range, the catalyst system has a wide molecular weight distribution, high extrudability, and causes abnormal flow during molding. It is particularly easy to produce a polymer so that when the (Ti + Zr + Hf) / V is within the above range, the polymerization activity of the catalyst system becomes particularly high. It also has advantages, including the amount of organic aluminum compound used. Formula ≤ ≤ (where r is the number of moles of the alkoxy group in the titanium compound, vanadium compound, zirconia compound, and hamphidic compound. A; is a titanium compound. A compound in a compound such as a pyridine compound, a zirconium compound, a hafnium compound and an organic aluminum compound. The sum of the logen atoms is expressed in terms of Gram atoms.).

If it is less than, the molecular weight distribution is narrow, and if it exceeds, the catalytic activity decreases, so that it is preferable. The quantity ratio of hafnium to ginoleconium is preferably in terms of the atomic ratio of Grams. / ≤ Zr / Hf ≤ / h, more preferably h. It is desirable that 2≤ Zr / Hf ≤ ^.

( 式中、 R¹¹はア ル キ ル基、 ァ リ ー ル又はシ ク ロ ア ル キ ル基を、 X¹¹ は ハ ロ ゲン原子を示 し、 は / 〜 の数を示す。 ） で表わ される化合物が挙げ ら れる。 具体的には ト リ エ チ ル ァ ノレ ミ ニ ゥ ム 、 ト リ ー η — プ ロ. ピノレ ア ノレ ミ ニ ゥ ム - ト リ ィ ソ ブチ ノレ ア ノレ ミ ニ ゥ ム な どの ト リ ァ ノレキ ノレ ア ル ミ 二 ゥ ムが好ま しい。 Next, as an organic aluminum compound used as a cocatalyst, for example, a general formula

(Wherein, R ¹¹ represents an alkyl group, aryl or cycloalkyl group, X ¹¹ represents a halogen atom, and represents the number of /). Examples include the compounds described above. To be more specific, there are tria-no-re-minimum, tri-η-pro-pinore-a-no-re-minimum and tri-no-reno-minimum and other tria-no-rea-no-mini. Normum is preferred.

 The usage ratio of the hydrocarbon-insoluble solid catalyst component and the organic aluminum compound is usually the atomic ratio of ΑZ (V + Ti + Hf) .When using the zirconium compound, A / ( V + Ti + Hf + Zr) in the atomic ratio 0./~/0, preferably ^. «2 ~

0.V.PJ

, C Used within the range of = 2.

 The polymerization of the olefins is carried out using the catalyst system thus prepared, and the olefins used are ethylene, propylene and the like. , One-buten / one-year-old / one-year-old / etc. Also, these orifices can be mixed and copolymerized.

However, it is advantageous for the production of ethylene homopolymers or copolymers of ethylene containing other monoolefins up to / by weight and preferably up to weight. It is. The polymerization reaction can be performed by either solution polymerization in an inert solvent or slurry polymerization, or gas-phase polymerization in the absence of a solvent! ) sell. The inert solvent is usually supplied in the presence of an inert solvent by supplying the olefin or mixture of olefins while maintaining the temperature and pressure at a given level. These include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and isooctane; cyclopentane; cyclohexene. '' 'Aromatic' hydrocarbons and the like are used such as alicyclic hydrocarbons such as san, benzene, and toluene. The polymerization reaction is usually performed at normal temperature to a temperature of 0 ° C and normal pressure.

 / 0 The pressure is selected from the range of atmospheric pressure.

 Further, when hydrogen is present in the polymerization reaction zone, the effect of controlling the molecular weight by hydrogen is large, and a polymer having a desired molecular weight can be easily obtained. The amount of hydrogen that must be present depends on the polymerization conditions and the desired molecular weight of the olefin polymer.

ΟΓ ΓΙ

Λ. W1P0 ' Since the amount varies depending on the amount and the like, it is necessary to appropriately adjust the amount to be introduced according to these. 'As described above, titanium compound, vanadium compound, hafnium compound and bromination; using solid catalyst component produced using organic aluminum compound In this case, the molecular weight control effect of hydrogen is particularly large. For example, the polymerization temperature? In the case of producing a polymer having a melt index of 0.3 to 0.0 with C, it is only necessary to add hydrogen of about J ″ // to the ethylene.

 As described above, according to the method of the present invention, the advantage that the catalyst system has a high polymerization activity is obtained, and in addition, the vanadium-hafnium system catalyst has a high molecular weight orifice. It has the advantage that a polymer can be obtained, and a vanadium-hafnium-titanium catalyst has a titanic compound, a panadimidic compound, a hafnium compound and By changing the ratio of the components of the organic aluminum compound, the molecular weight distribution of the obtained polymer can be easily adjusted. -The advantage of easily producing a olefin polymer having excellent moldability in molding can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. It is not specified.

 In the examples, the polymerization activity of the catalyst is as follows:

/ (f · catalyst) (Hi ") (^ / cd reference pressure). Melt index is ASTM · D · / 23S- · 7T The value was measured at a load of / 2 and the load was expressed as Ml. Furthermore, the outflow ratio (hereinafter abbreviated as PR) as a measure of the molecular weight distribution shows the shear stress dependence of the melt viscosity. in to value, ASTM · D · / 23S- - . J-7 according to the shear stress / 0 ⁶ dyne / ci and / click ⁵ dyne / d menu: NetBackup measured in Lee emissions de click scan ratio (Ml / 0 ^β / Μ1 / 0 ⁵ ), where is large and the molecular weight distribution is wide, and small is narrow.The density was measured according to ASTM D- / .

Example /

Dissolved vanadium tetrachloride J ^ and tetra-n-butoxy hanium 7 ·? ^ In hexane with J "0. After heating to 0 C, A A solution of (C ₂ H ₅ ) C in “J” weight hexane solution • 2 was added and reacted at the same temperature for 1 hour. The precipitate was washed with hexane to obtain a solid catalyst component. V / 0.0 weight, Hf ^. ヲ weight, CZ. ヲ weight, A

 It was weight.

Next, n-hexane S 0 0 πί and the above solid catalyst component 0 ^ -hythrisobutyral aluminum-mmo. Mmo were introduced into the / toichi-clave. <f J "C Element was introduced up to / Zc ^. Then, ethylene was supplied, and polymerization of ethylene 'was performed at a total pressure of -2 ^ f / d., And after / hour, ethanol was injected to stop the polymerization. The obtained polyethylene was //, the polymerization activity K was / 0/0, and Ml was 0 * 00, which was S / h.

Example ^2- / 0

 The vanadium compound and hafium compound described in Table / Table were dissolved in a predetermined amount of benzene in a predetermined amount, and various halogenating agents described in Table / Table were dissolved. After adding a benzene solution by weight of C, the mixture was stirred at C / hour. The resulting precipitate was washed with hexane to obtain a solid catalyst component. The analytical values are shown in Table / Table.

Next, hexane J "0 σ m £ is used for the autoclave of / z]), and the solid catalyst component obtained above is used, except that the solid catalyst component is used. et Ji Le emissions of polymerizing to put ¾ ivy. the results are shown in / Table. in the table, IiBu indicates Bruno Le Mas Le butyl Le group nC ₄ H _9, the same meanings also in the following Yes

"Ό o

Comparative example /

The polymerization of ethylene was carried out in the same manner as in Example 1, except that hafnium tetrachloride was used instead of the solid catalyst component in the polymerization of ethylene. Polymerization activity; ε was << 2. — S5— Comparative example

 In Example /, except that vanadium tetrachloride was not used at all, a solid catalyst component was obtained in the same manner as in Example /, and c was used as in Example // to obtain a solid catalyst component. The polymerization activity K was / /.

■ β one ^ ϋΗ,-"~, —,

, W1 0.

Ο, ΓΙ

WiPO Table / (continued) ヽ Solid catalyst analysis value Polymerization activity Μ No. V 番 Hf

(Weight (Weight) (Weight) K (// 0 ·) Example = 2/0. / 3 ^ 3. ¼ 0.0 / / Example ^ 9.3 / ¼s-. /? 9 0.002 Example? ^{3 1/2/0 0.00 /} s- example 50.3 ¥ ■ 0.2 7 9 0 0.00 / example / 7, 0 / / .7 V- ? .3 0.002 example 7 S 3/3/0 0.00 / example .6S- 3 Y-.? 7. evening / 220 0, 00 / S Example？? .7 / 36.3. ヲ / 0/0 0.000? Example z 33.0 S 3.0 730 0.003 Example /

 / JL ■ — Tokulebu 'II-Hexane 0 Ο-and j?

 The temperature rose to C. Hydrogen was introduced up to / H / d.

Next, Trinolmalbutokishinonajiru / .Z / ^, Shishio-daniha / Hafnium / ^ and Triisobutyrumiluminum-Ο.ε mmo ^ Was added, and a catalyst slurry was prepared. Ethylene was supplied, and ethylene polymerization was carried out at a total pressure of << 20 / erf. After / hour, ethanol was added to EE to stop the polymerization. The obtained polystyrene is 7 / and κ =

ク 分 であった。 ¥-0 0 M l = h. 《2

It was a minute.

Comparative example

 Polymerization of ethylene was carried out in the same manner as in Example 1 except that hafnium tetrachloride was not used at all, and no polymer was obtained.

Example / «2 ~ /

 (1) Preparation of solid catalyst component

ク ^ ^ ^ 四 四 ^ ^ 四 ^ ^ 四 ^ 四 ^ 四 四 四 四 四 四 四 四 四 四 ^ 四 四 四 四 四 四 四 四The hafnium tetanolmalbutoxide and benzene were mixed respectively in the amounts shown in Table 2 to obtain a homogeneous solution. Then add the amount of ethyl alumi-zum dichloride in the form of a benzene solution of 0.0 mot / in the amount shown in Table 2 at ク C, and add at άC / hr. followed by drying washed stirred _c formed precipitate to Bruno Le Mas Le in hexa down

• ¾ JK then A

O .'- '. PI A catalyst powder was obtained.

(2) Ethylene polymerization

 In the autoclave, n xan / cook cc was taken and the above catalyst powder was charged. After raising the temperature to C, hydrogen was introduced up to the specified pressure shown in Table 2, tris-butylindium aluminum 0.mmo was introduced together with ethylene, and the total pressure was increased. Changed to / erf. Ethylene absorption is observed with the introduction of ethylene, but additional ethylene is introduced to maintain the total pressure at // of, and ethanol is injected after / hour.] ? Polymerization was stopped. The results obtained are shown in Table.

Example / ~ . 0

 Various titanium, vanadium, and hafnimium ligations were mixed in the proportions shown in Table.

 In each of the examples, it was observed that heat generation and a change in color occurred simultaneously with the mixing, and that a reaction occurred between the respective compounds.

After mixing, the mixture was stirred at 0 ° C for 1 minute, and then the amount of benzene shown in Table 1 was added. Then, the aluminum conjugate shown in Table 1 was added to mot / l in the form of a benzene solution, and the mixture was stirred at ^ C for / hour.The formed precipitate was washed with normalhexane and dried to obtain a catalyst powder. ^ ^ And completely the same as Example / 2 except that hydrogen was introduced up to the pressures shown in Table 2. Polymerization of ethylene-lene was performed. The results are shown in Table 2 below. Example = 2

After dissolving tetrahydrochloride in nor-malbutanol as a hafni-umui dani product, excess nor-malbutanol is distilled off under reduced pressure. Using the obtained Hf (ΟηΒα) ₂ · nBOH, the obtained hafnium quinolmalbutoxychloride has the form of the norm. A catalyst powder was obtained in exactly the same manner as in Example Z = 2 except that the amount of sodium dichloride was used in the amount shown in Table 2.

The polymerization was carried out et Chi les down except that hydrogen was introduced in T. ⁷ 1 ^ Bruno or using this catalyst powder = 2 ^ is the total Ku as in Example / 2. The results are shown in Table 2 below.

Example << 22

Nozzle Trino Noremar Toxide 《20 mmo, Femme Tetrano Norema Tore Toxide 《2 mm mmo ^ and Benzenk? ^ Was mixed to obtain a homogeneous solution. Then, in ^ 0 C, add ethyl alminium dichloride <r mmo to the oi / l normal in the form of xan solution, and continue. Benzen << 2? ^ Was added to titanium tetrachloride J 0 mmo. After the addition of titanium tetrachloride, the mixture was stirred with J "C for / hour, and the resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder. Polymerization was carried out to obtain a polymer having a Ml content of 、 and a solid content of 2 = 220 0. Example 3

 When introducing and adding ethylene in the “polymerization of ethylene of Example 1”, butene-1 / was mixed and butene-2 / Z-ethylene in the gas phase during the polymerization reaction was added. The copolymerization of ethylene and butene — / was carried out in exactly the same manner as in Example 1 except that the molar ratio of the ethylene and butene was the same. The results obtained are shown in Table 1. In the obtained polymer, butenes / units of 0./mol-containing ethylene / butene-1 / copolymer It was united.

Comparative example

The mixture was mixed with titanium tetramoxide, 0 mmo ^, and mmo ^. After mixing, 4 benzenes? After adding ^ to make a homogeneous solution, add 0 mmo of ethyl aluminum dichloride in 6 in the form of a benzene solution of ¼0.00 / 1, and in C, Stirred for hours. The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder. This powder //? Use the trisobutyl aluminum. mmoz, hydrogen pressure. Z l ^ Zc ^, the total pressure ^ l ^ Zc ^ and the except the embodiment and o = 5 0 0 0 give all Ku the polymer subjected to the polymerization in the same manner, = 0, ¹ / 2.0 // 0 min, FR-Ji ". In the system without hafnium compound, the molecular weight distribution of the obtained polymer was narrow. Comparative example

 Titanium Tetra-no-Release 'Boot' Key Side o2 0 — mmo, Non-Fudium Tetra-Normal Multi-Side Tide >> 2 miiioz and And Ben Zeng? Was mixed to obtain a homogeneous solution. Then, in C, 2 ml of ethyl aluminum dichloride = 2 mmo was added dropwise in the form of a benzene solution of ¼0.0 mo / L,

6 / hr. The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder. Using this catalyst powder, polymerization was carried out in exactly the same manner as in Example 2 and polymer 2 ^^ fto1 = 200, MI =.

 / / H minutes, FR = «≤. Thus, when a vanadium compound is not used, the polymerization activity of the catalyst system is reduced.

0:,.

— —

Table 2 (continued) Hydrogen pressure polymer M

 Ti + Hf me, ft

 No.Hf / Ti ■ H

 V

/， 300 0. /0 70 実删 ,7 0.？ / .？ 3.0 S- .7 =2 =2, / 00 0. /ク ？ 0 実施例 0.？ / .？ / .2 .0 20 S- /， 600 0。c2 60 難例/ヲ 0 ·？ / .？ V-.0 ε .？ «2, 300 ？ 3 実施例《2 に。 2.0 3. 2, 000 0 , / ク Ad) ((/ min: Example = 2 / .0 2.0 3.9.0 23/2, / 00 0./0? Example "0 · <r / .. S-.73So2, 8-00 0.30 70 Difficult / 2.0 3.0 3.0? .7 / 3 Ά /, ΆΟΟ7 J "Actual leak //. 0 0.67 Ά.S-.7 / 2 /, ¥ -00 0, /7/Difficult""/.0 Ά.0 3.0 s- /

/, 300 0. / 0 70 execution, 7 0.? /.? 3.0 S- .7 = 2 = 2, / 00 0. 0 Example 0.? /.? / .2 .20 20 S- /, 6000. c2 60 Difficult example / ヲ 0 ·? /.? V-.0 ε.? «2,300? 3 Example <2. 2.0 3.2,000 000,

 ヽ

 0 2.0 ¥ ■, <f .7 232 2,000 (K? 0 Example 22 / .0 2.0 ¼.0 220 /,? 00 70 Real / / 0 2.0 3 · 9.0 236 o2, / evening 0 ./3?6

JiWlI 0 / .0 / .0 2.0 000 0.ΆΟ 2 夕 9.0 3.0 9.0 22 200 0, ΆΟ 63 Example = 2-

(1) Preparation of solid catalyst component

 M m m m 四 に に に に に 四 に に に に に mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo mo 2 mo After addition, the mixture was gradually caloried under ice-cooling to give a homogeneous liquid.

 Add benzene J to the homogeneous liquid to make a solution, and

After the temperature was raised to C, the ethyl aluminum jib mouth guide = 277 mmo was added in the form of a benzene solution, ^

 Stirred with C / hr. The resulting precipitate was washed with normanoxane and dried to obtain a catalyst powder.

 (2) Ethylene polymerization

 In a 2-node clave, n-hexane / cook cc and the above-mentioned catalyst powder = 2 cq were charged.

 After heating to mark C, hydrogen was introduced into ZCTT !, and trisopino real aluminum <.m if mmo was introduced together with ethylene, and the total pressure was changed to / ZCT !. . Ethylene absorption was observed with introduction of ethylene, but the total pressure was

 Ethylene was additionally introduced to maintain cA, and after 9 hours, the j9 polymerization was stopped by injecting ethanol.

 Ml = 0.0 ε 0? / / 0 / / polymer

 • I got f jr ^.

 K = »2 / /

ΟΛ'Ρ! — — Examples 2 to. Two

 Titanium Tetranol Molto Toxide, Natri Trinol Molto Toxide, Hafnium 'Tetranol Molto Toki The sides were mixed in the proportions shown in Table.

 After adding the amount of benzene shown in Table 4, add the amount of ethyl aluminum dibromide shown in Table J in Step C to form a volume of benzene solution. And stirred with ^ c / hr.

 The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder.

 The polymerization of ethylene was carried out in exactly the same manner as in Example 2 except that hydrogen was introduced up to the pressure shown in Table 2 using this powder = 2 ^. The results are shown in Table.

Example = 2 ヲ ~ "/ '

 A mixture of various titanium, natrium, and humid compounds in the proportions shown in Table o

 In each of the examples, particularly, in Example 30 and /, heat generation and change in color occurred simultaneously with mixing.]), And it was observed that a reaction occurred between the compounds. '

 After mixing, the mixture was stirred with C for 1 hour, and then the halo benzene shown in the table was added. Then, JC: The ethylene bromide shown in the table was added to J "Yodo was added dropwise in the form of a benzene solution and stirred for / hour. Generate

OMP3 The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder.

 Using this powder = 2 ^, polymerization of ethylene was carried out in exactly the same manner as in Example = 2 except that hydrogen was introduced up to the pressure shown in Table J. The results are shown in Table. Example = 2

 In Example 2, instead of the use of the etchant medium> / mmo] ?, the et al. A solid catalyst component was prepared in exactly the same manner as in Example c2 except that 0 mmox was used.

 Example 2 except that hydrogen was introduced up to the pressure shown in Table J using this solid catalyst component = 2 ^. Polymerization of ethylene was carried out in exactly the same manner as in 2. The results are shown in Table 0

Example5

 In the polymerization of ethylene in the example, when ethylene is introduced, butene-Z is mixed, and the molar ratio of butene1 // ethylene in the gas phase during the polymerization reaction is increased. Copolymerization of ethylene and butene-1 / was carried out in exactly the same manner, except that the pressure was increased.

The results obtained are shown in Table 3. The polymer obtained was as follows: 1-butene / 0-unit / ethylene-butene-1 / monomer-containing copolymer there were.

Μ 3 Table (continued)

レ .. υ Example

 Titanium trichloride Norema meltone Toxide 0 mmo, Nozil monochloride Renox malt Toxide «2 mmo, tetrasalt The mixture was mixed to prepare a homogeneous solution. Next, at 0 C, reduce the amount of triethylamine / 0 mmo to <0.0.

The solution was added dropwise in the form of a mo / l benzene solution, and the mixture was stirred at C / hour. The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder. Hf / Ti is

 (Ti + Hf) V was h and u / t was h.7 /.

 As a result of polymerizing ethylene in the same manner as in Example / except that the hydrogen pressure was Zed, Ml 0 /// 0,

A polymer of FR60 / 6 ^ was obtained. K was / 00.

Example "

 In the implementation lj, the ethyl aluminium dibromide was 77 mmo, and the et al.real niobium dibromide / <j * i7 ino and ethyl almiloid A solid catalyst component was prepared and polymerization was carried out in the same manner as in Example <2 ■ except that a mixture with dimethyl chloride (7 mmo ^) was used.

I got it. Ml 0.0 709 // 0 and polystyrene ヲ 0 of FR ヲ were obtained. K is << 2 /

,, Example

 (1) Preparation of solid catalyst component

 Titanium lanthanum toxin = 2 mm mmo and 《ジ ナ ナ ト fl fl Mixed with 2 mm mmo, then add zirconium tetrachloride mmo, and then add the final tetrachloride / mmo instantaneously. And added. After the addition, the mixture was stirred for 2 hours with C to obtain a uniform liquid. Benzene J 3 ^ is applied to this homogeneous liquid to form a benzene solution, and after heating to C, ethyl alminium dibromide o2 cf 6 mmo ^ was added in the form of a volumetric benzene solution and stirred at C / hr. Was の .6 ", (Zr + Hf) / Ti = /, (Ti + Zr + Hf) / Ύ = 2. The precipitate formed was washed with Normal hexane, It was used for polymerization in the form of normal hexanuclear slurry.

 (2) Compounding

 Take a 20-minute crane to the X-ray / 0t! ), The above solid. Catalyst component / 2?

? After raising the temperature to 0 C, hydrogen was introduced in the evening. ^ Then, Tritino Real Aluminum. ^ Mmo, butene-1 / ヲ 0 ^ was introduced together with the ethylene, and the total pressure was increased to / ≥§ ■ cd was performed. Ethylene absorption was observed with the introduction of ethylene, but additional ethylene was introduced to maintain the total pressure at / ZC? T !, and after a while, ethanol was injected. Stop polymerization — One

- did. The molar ratio of ethylene to butene / in the gaseous phase is on average /.d* mQ ^, and the ethylene-butene-1 / share weight of three cooks A coalescence was obtained and the polymerization activity K was / 7 ヲ ヲ?. Was 70 minutes, R was f and p was .9 /. Extrusion molding volume as a measure of extrudability is determined by one brander. 2 / D-type single screw extruder (diameter / /./female, L / D = o2 //, compression ratio = 3 Full-flight screwdriver and die have a diameter of 2 cubic meters and a clear skewed circular die) with a die temperature of 200 ϋ. The extruded amount was measured by the number of revolutions per minute and the extruded amount was divided by the number of revolutions (the number of revolutions per minute) to obtain the extrusion molding amount at the number of revolutions. The value was obtained.

 In addition, using an extrusion molding machine Modern EA Co., Ltd. (Modan Machinery Co., Ltd., Modan is a trademark) and a die with a radius of J "鹏 and a clearance of 2 /. , Set the temperature to C /: / 4 Ϊ:, 02: / δ-0 X 03; 200 ^ ：: 200 Ό ^ 3D: ο2 C C, and BUR:, „2; u The film was molded. The abnormal flow phenomenon of the molten polymer was visually observed.]? No abnormality was observed, and the obtained molded product was rough.

Example S 7

 (1) Preparation of solid catalyst component

In Example J ^, the amount of Hafni-Mich compound was calculated as / ^s-- , · ^ί: ' ^υ mmo, コ 物 / 量 o o o o o o o o o o o o o o o o o o o o o o o o o 2 o 2 2 A solid catalyst component was prepared in exactly the same manner as in Example J except that mmo. a; Zr =. evening, (Zr + Hf) ZTi = 8, and (Ti + Zr + Hf) / Y = 2.¼.

(2) Compounding

. hr と 良好であつ 。 溶融ポ リ マ ーの異常流動現象も認め られなかった。 押出成形性及び異常流動現象の有無の測定は実施例 3 と同様に しておこ ¾つた。 以下の実施例におい て も 同 じ。 Polymerization was carried out in exactly the same manner as in Example except that the amount of hydrogen introduced was 7.7 l ^ / c? 7! And the amount of butene was cf09. The molar ratio of ethylene to butene / in the gas phase was /.? Moz on average. = 2 to ^, an ethylene / butene / copolymer having a polymerization activity K of / 600 was obtained. Ml of this polymer is ク. The density was. ヲ ^ Zee. The result of the extrudability test is /

hr and good. No abnormal flow phenomenon of the molten polymer was observed. The measurement of the extrudability and the presence or absence of the abnormal flow phenomenon were performed in the same manner as in Example 3. The same applies to the following examples.

Example s-

(1) Preparation of solid catalyst component

The amount of the zirconium tyride is 0 mmoz, the amount of the no and the total zimudium is 0 mmoz, and the amount of ethyl alminium dipromide is 2 ? A solid catalyst component was prepared in exactly the same manner as in the example except that the amount was 6 mrno. = To (Zr + Hf) Ti = /., (I + Zr + Hf) / V =

2.0.

(2) Compounding

 Polymerization was carried out in exactly the same manner as in Example except that the amount of hydrogen introduced was .cndot.erf and the amount of butene / part was / '. The molar ratio of ethylene to butene-1 / in the gas phase is on average

であった。押出成 形性テ ス ト の結果は / ά f / rpm . lir の値が得られ 異常流動現象は全 く 認め られ ¾かった。 / .6 mo. An o2-q ethylene-butene- / copolymer was obtained, and the polymerization activity K was / f. Is Ml of this polymer 0.0 ε? // FR is ⁷⁰ minutes, and the density is ⁷⁰ .

Met. As a result of the extrudability test, a value of /άf/rpm.lir was obtained, and no abnormal flow phenomenon was observed.

(1) Preparation of solid catalyst component

· I click necked off la scan copolymers to switch data standard test preparative La Bruno Le Mas Le Bed bets - key Size Lee de Die Ma one _{Ti 2 0 (0llC H 9)} 6 and with the switch data down o2 mmo Navy Tri-Normanov Toxide 《2 oz.mmoz mixed, then zirconium tetrachloride.mmo, then nipple trachloride Id / mmo was added sequentially] 9. The mixture was stirred for 2 hours with C to obtain a uniform liquid. This level is applied to the liquid by applying benzene J to the benzene solution, heated to que C and then heated to ethyl alcohol mini jib mouth guide 230 mmo. In the form of an S-volume benzene solution, Stirred in evening C / hr. a; / r =., (Zr + Hf) ZTi = /, (Ti + Zr + Hf) / Y = 2. The resulting precipitate was washed with normal hexane and subjected to polymerization in the form of normal hexane slurry.

(2) Compound ―

 c20 The autocatalyst was prepared with a nonaluminous hexanox / 0 JL], and the solid catalyst component was charged with / 2 ^^.

? After raising the temperature to 0 C, hydrogen was introduced at 71 ^ / α 次 い で, and then the tritium ore minimum 0 8 ~ mmox _N- butene 1 /? 0 ^ was introduced along with the ethylene to bring the total pressure to /-kg./cd. Ethylene absorption was observed with the introduction of ethylene, but additional ethylene was introduced to maintain the total pressure at / Zcrf, and after 2 hours, ethanol was injected. ) The polymerization was stopped. The molar ratio of ethylene to butene-1 / in the gas phase was on average / mo ^. A copolymer of 370,000 V-butene-1 / copolymer was obtained, and the polymerization activity K was ///. Ml is. ^ // min, is 77, p = 0.? S-7 f / cc! ), And a test was conducted to evaluate the extrudability, and a value of /U/rm.3ar was obtained. The abnormal flow phenomenon of the molten polymer was visually observed] 9, and the obtained molded article was rough. Example C

 (1) Preparation of solid catalyst component

In Example wo, Ji motor emissions compound Chita - than replaced with © beam Te preparative La Lee Seo Bed B Bokisai de tetramer _{(Ti 4 0 3 (0-} iC 3 H 7) 10) All Ku similarly A solid catalyst component was prepared. / Te =,, (Zr + Hf) / Ti = / .¼ ^

 (Ti + Zr + Hf) / V = 2.Ά

 (2) Compounding

 What is the amount of introduced hydrogen? Z c, butene / volume is cT

 Polymerization was performed in exactly the same manner as in Example "ヲ" except that the molar ratio of ethylene to butene-1 / in the gas phase was /. ヲ moz ^ on average. The ethylene / butene / copolymer was obtained and the polymerization activity K was / 660.

 Ml is. ^ / / 、, 7 is 7, p = 0.? 6

 No CC. The results of the extrudability test are.

In f / r _V. hr, abnormal flow phenomena of melting port Li Ma over also was not Me sure.

Example " /

 (1) Preparation of solid catalyst component

 The amount of the dissolving compound is / mo, the amount of the nodifying compound is / mmo, and the amount of the ethyl aluminium dibromide. Example except that 2 ¼ 0 mmo ^

 A solid catalyst component was prepared in exactly the same manner as in 3). / ^ =

 .7, (Zr + Hf ^ / Ύ1 = /, 0 ^ (Ti + Zr + Hf) / Y = 2.0

-'

:, ν.Ρΐ

VA, WIPO Met. -

(2) Compounding

What is the amount of hydrogen introduced? Polymerization was carried out in exactly the same manner as in Example I except that the ratio of cd / butene / volume was set to / 00 ^. The molar ratio of ethylene to butene-1 / in the gas phase was /0.6 mo ^ on average. Thus, an ethylene / butene / copolymer of /0.0f was obtained, and the polymerization activity K was / h. Ml of this polymer is 0,07? / / 0), FR is 4 mm, density is. / CC. Results of extrusion moldability Te be sampled is / / T _V m - value of lav is obtained, abnormal - flow phenomenon was not observed all Ku. Industrial applicability

 As described above, the method of the present invention is particularly useful as a method for producing a polyolefin for extrusion molding or a single molding process, particularly for polyethylene. is there.

Claims

The scope of the claims (1) (a) Palladium compounds selected from vanadium halogen compounds and organic oxygenated compounds  () Hafnium compounds selected from halogenogen compounds and organic oxygen compounds  Is characterized in that a solid catalyst component obtained by mixing and reacting the components with an organic aluminum compound component is used to polymerize olefins using a catalyst. A method for producing a polymer.  (2) In the method described in claims (1) / (2), the solid catalyst component is a reaction mixture obtained by reacting a vanadium compound, a hafnium compound and a halogenogenating agent. A method for producing an olefin polymer, characterized in that the polymer is separated from a product.  (3) In the method described in Claims / Claim, the solid catalyst component is a mixture of the panadium compound and the hafnium compound in the presence or absence of a diluent. A halogenated agent is added to a liquid obtained by the reaction. A method for producing an olefin polymer characterized by being separated from a reaction mixture obtained by the reaction O (4) In the patented process ranging a <2 claim of claim, c b in gain down agent is Formula A RK_ _n (where ^ is the number of carbon atoms / Represents a hydrocarbon group of ~ / = 2, X ⁴ represents a halogen atom, and ϋ represents ≤ 11 <«? A method for producing an olefin polymer, characterized by being a compound represented by the following formula: (5) (Α) a vanadium compound selected from an organogen compound and an organic oxygenated compound of palladium;  (Ii) hafnium compounds selected from hafnium halogen compounds and organic oxygenated compounds;  (C) a titanium compound selected from halogenated compounds and organic oxygenated compounds of titanium and  Ρ) Organic aluminum compound  Is characterized by polymerizing olefins using a catalyst that combines a solid catalyst component obtained by reacting the compound with an organic aluminum compound component. Manufacturing method of coalescence. (6) In the method as set forth in the claims, the solid catalyst component may be a titanium compound, a vanadium compound and a hafdium compound in the presence or absence of a diluent. It is characterized by being separated from a reaction mixture obtained by adding and reacting an organic aluminum compound to a liquid obtained by mixing and reacting in the presence. A method for producing a refined polymer. (7) In the method described in the claim, the solid catalyst component may include a titanium compound, a vanadium compound, a hafnium compound, and an organic aluminum compound.ゥ formula (Wherein, is the sum of the halogen atoms in the titanium compound, the vanadium mulch compound, the hafni umi lig compound, and the organic aluminum mulch compound. Where t is the gram equivalent, where t is the total sum of each metal atom in the titanium conjugate, the vanadium munich compound, and the havani munich compound. Characterized in that it is obtained by reacting with an amount that satisfies the following formula:  (8) In the method described in the claim, the solid catalyst component comprises a titanium compound, a vanadium compound, a hadium compound and an organic aluminum compound. formula  2 <Hf / T i <if, k (Hf + T i / k (where T i, Hf and V represent titanium, hafnium and ba in each compound, respectively) (The amount of sodium atoms is expressed in terms of grams atoms.) The production of an olefin polymer characterized in that it is obtained by reacting with an amount that satisfies Law. (9) In the method described in Claims, an organic aluminum bromide compound is used as the organic aluminum compound used in preparing the solid catalyst component. And a method for producing an olefin polymer. (10) (A) Halogen compounds and organic oxygenation of vanadium Compound selected from the compound,  (B) a hafnium compound selected from a hafnium halogen compound and an organic oxygen compound, (〇) General formula [TiO¾i (0Ri2 _{) ci2} ] ₃ (where _q 2 is q. ≤ q ¹ ≤ /, = 2 <q ² ≤ and q ¹ X «2 + q ² = And a ³ is an integer of J q ³ ^ ^ R ¹² represents a hydrocarbon group having a carbon number of / 〜 = 2 k). Tetravalent titanium alcohol having one Ti-0-Ti bond,  P) Organic aluminum compounds and  (E) zirconium compounds selected from zirconia compounds and organooxygenated compounds  Characterized in that an orphan is polymerized by using a catalyst obtained by combining a solid catalyst component obtained by reacting the compound with an organic aluminum compound component. The method for producing the polymer. (11) In the method described in Claims (1) / (2), the amount of the zirconia compound used is such that the amount of the zirconia compound relative to the amount of hafnium in the compound of hafnium is reduced. Atomic ratio  A method for producing an olefin polymer, characterized in that (/ Zr / Hf) is ./ to /. α¾ In the method according to any one of paragraphs // to // of the patent application, the general formula V0 (0R ² ) _a ² X as _a Panadimid compound. ₂ or V (0R ² ) X (where R ² is a hydrocarbon group of carbon number / ~ / = 2 ぁ, X ² is a halogen atom] ?, a ² is the number of ≤-^, ≤ 3 and ² is A compound represented by the general formula Hf (0H ³ ) _a 4 _ _a4 (where R ³ is a prime number of carbon / hydrocarbon group der of ~ / = 2!), X 3 is Ah at c b gain down atom, a ⁴ is a Toku徵that you use the compound represented by the number der Ru) of click ≤ a ⁴ ≤ A method for producing refined polymers. 1PO