JP2811863B2 - Solid catalyst component for olefin polymerization and use thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a solid catalyst component for olefin polymerization and its use. More specifically, the present invention relates to a solid catalyst component for olefin polymerization obtained by contacting a specific component, a catalyst using the component as a transition metal component of a Ziegler catalyst, and a method for producing an olefin polymer using the catalyst. is there.

When the solid catalyst component of the present invention is used as a transition metal component of a Ziegler-type catalyst and α-olefin is polymerized,
A polymer having high activity and excellent stereoregularity can be produced with less derivation of by-product polymers.

BACKGROUND OF THE INVENTION Conventionally proposed olefin polymerization catalysts comprising a solid catalyst component containing titanium, magnesium and halogen as essential components and an organoaluminum have extremely high activity, but the stereoregularity of the product polymer is a problem. Requires the use of an electron donating compound during polymerization.

However, such a catalyst using an electron-donating compound as the third component (external donor) has a problem that when the organoaluminum compound and the electron-donating compound react, the polymerization rate decreases, or the polymerization temperature increases. It is difficult to control the performance of the product polymer, including controlling the molecular weight of the product polymer, because it is difficult to increase the polymerization temperature and increase the polymerization amount (improving the production efficiency) because the reaction is promoted. There is a problem.

Further, in order to sufficiently maintain the stereoregularity, a substantial amount of an external donor is required. Therefore, if the decontact step is omitted, odor caused by the electron donating compound becomes a problem.

Therefore, in order to solve the above problems, it is desired to develop a catalyst system capable of producing a highly stereoregular polymer with a high catalyst yield without using an electron donating compound during polymerization.

Prior Art Japanese Patent Application Laid-Open No. 58-138715 discloses a titanium composite (1) containing no tetravalent titanium, magnesium, halogen and an electron donor as essential components without using an external donor.
An organosilicon compound (2) having an —O—C bond, in the presence of an organoaluminum compound, or by treating the titanium complex with an organoaluminum compound and then reacting with the organosilicon compound. A method of polymerizing with a catalyst system formed from the obtained solid component and organoaluminum is disclosed.

However, although the above problems have been solved by this proposal, there is a limit in the performance of the resulting product polymer, and furthermore, the catalyst deteriorates with time, and the ratio of the amount of the titanium component and the amount of the organoaluminum compound used during the polymerization is reduced. There are still many points to be improved, such as restrictions.

Also, according to the proposal of JP-A-62-187707, the restriction on the amount of the organic aluminum compound used during the polymerization was considerably eliminated by using a special organic alkoxysilicon compound. However, for the purpose of controlling the molecular weight, producing a copolymer, and the like, a sufficiently high catalyst yield has not always been obtained so that the decontacting step can be omitted, and a further improvement is desired.

SUMMARY OF THE INVENTION The present invention provides the following component (i), component (ii), component (ii)
The present invention provides a solid catalyst component for olefin polymerization obtained by contacting i) and component (iv).

Component (i) Solid component containing titanium, magnesium, tungsten and halogen as essential components, Component (ii) General formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ has 3 carbon atoms)
A branched hydrocarbon residue of 2020, R ² is the same as R ¹ or a hydrocarbon residue of 1 to 20 carbon atoms, R ³ is a hydrocarbon residue of 1 to 20 carbon atoms, n is A silicon compound represented by 1 ≦ n ≦ 3), component (iii) an organic aluminum compound or an organic zinc compound, and component (iv) an inorganic halogen or a metal halide compound.

Furthermore, the present invention provides a catalyst for olefin polymerization characterized by combining the above-mentioned solid catalyst component for olefin polymerization [component (A)] and an organoaluminum compound [component (B)] in the presence of the catalyst. And a method for producing an olefin polymer, characterized by polymerizing an olefin.

Effects of the Invention The olefin polymerization catalyst of the present invention can produce an olefin polymer having high activity and high stereoregularity without using an electron donating compound (external donor) at the time of polymerization. It is to solve the problems of the known catalyst.

These features are extremely advantageous for industrial production and are important as features of the catalyst. Although the reason why such an effect is exhibited has not yet been sufficiently analyzed, the active site is low when the inorganic halogen compound or the metal halide compound of the component (iv) acts on the active site having low activity or weak stereoregulatory power. It is presumed that high activity and high stereoregularity are a catalyst for producing an olefin polymer. Therefore, such excellent effects cannot be easily predicted from known techniques.

DETAILED DESCRIPTION OF THE INVENTION (Catalyst) The catalyst for olefin polymerization of the present invention comprises a specific component (A)
And component (B).

Component (A) Component (A) of the catalyst of the present invention is a solid catalyst component for olefin polymerization obtained by contacting the following components (i), (ii), (iii) and (iv). is there.

Solid components containing titanium, magnesium, halogen and tungsten as essential components used in component (i) are known solid components containing titanium, magnesium and halogen, for example, JP-A-53-45688 and JP-A-54-389.
No. 4, No. 54-31092, No. 54-39483, No. 54-94591,
No. 54-118484, No. 54-131589, No. 55-75411, No. 5
5-90510, 55-90511, 55-127405, 55-1
47507, 55-155003, 56-18609, 56-7000
No. 5, No. 56-72001, No. 56-86905, No. 56-90807,
Nos. 56-155206, 57-3803, 57-34103, 57
No.-92007, No.57-12003, No.58-5309, No.58-531
Nos. 0, 58-5311, 58-8706, 58-27732,
58-32604, 58-32605, 58-67703, 58-1
No. 17206, No. 58-127708, No. 58-183708, No. 58-183
Nos. 709, 59-149905, 59-149906, etc., which are treated with a tungsten compound.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. .

Among these, magnesium dihalide is preferable,
Particularly, MgCl ₂ is preferable.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR
^{4) _4-n} X _n (where R ⁴ is a hydrocarbon residue, preferably of the order of 1 to 10 carbon atoms, X is a halogen,
n shows the number of 0 <= n <= 4. )). Specific examples include titanium tetrahalides such as TiCl ₄ and TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O
_{C 2 H 5) 3 Cl,} Ti (O-iC 3 H 7) Cl 3, Ti (O-nC 4 H 9) C
_{l 3, Ti (O-nC} 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (OC
_{2 H 5) (OC 4 H} 9) 2 Cl, Ti (O-nC 4 H 9) 3 Cl, Ti (OC 6 H
_{5) Cl 3, Ti (O} -iC 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl 3, Ti
(OC ₆ H ₁₃ ) Alkoxy titanium halide such as Cl ₃ , Ti (OC _{2
H 5) 4, Ti (O} -nC 3 H 7) 4, Ti (O-nC 4 H 9) 4, Ti
_{(O-iC 4 H 9)} 4, Ti (O-nC 6 H 13) 4, Ti (O-nC 8 H
₁₇ ) Tetraalkoxy titanium such as ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] _{4 and the} like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ represents halogen) can also be used. Specific _{examples, TiC 4 · CH 3 COC 2} H 5, TiCl 4 · CH
₃ CO ₂ C ₂ H ₅ , TiCl ₄・ C ₆ H ₅ NO ₂ , TiCl ₄・ CH ₃ COCl, TiCl ₄・ C
_{6 H 5 COCl, TiCl 4 ·} C 6 H 5 CO 2 C 2 H 5, TiCl 4 · ClCOC 2 H 5, TiCl
₄ , C ₄ H ₄ O and the like.

Among these titanium compounds, Ti (OnC ₃ H ₇ ) ₄ , Ti
(OnC ₄ H ₉ ) ₄ , Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) Cl ₃ , TiC
such as l ₄ is preferable.

The tungsten compound serving as a tungsten source is WCl ₆ ,
WCl ₅ , WCl ₄ , WCl ₂ , WBr ₆ , WBr ₅ , WCl ₂ , WI ₄ , WI _2, etc., tungsten halide, WOCl ₄ , WO ₂ Cl _2, etc., tungsten oxyhalide, π− (C ₅ H ₅ ) ₂ WH ₂ , WO ₆ , K ₂ W (O
H) Cl _{5 and the} like. Preferred among these are
WCl ₆ , WCl ₅ , WOCl ₄ and the like.

The halogen source is usually supplied from the above-mentioned halogen compound of magnesium and / or titanium and / or the halogen compound of tungsten, but is supplied from a known halogenating agent such as a halide of aluminum and a halide of phosphorus. You can also.

The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid component used in the present invention includes SiCl
_4, CH ₃ SiCl _3, etc. silicon compound, methylhydrodiene polysiloxane, ethyl hydroperoxide di polysiloxane, phenyl hydroperoxide di Empoli polymeric silicon compounds such as _{siloxanes, Al (OisoC 3 H 7)} 3, AlCl 3, AlBr 3, Al
Aluminum compounds such as (OC ₂ H ₅ ) ₃ and Al (OCH ₃ ) ₂ Cl and boron compounds such as B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ Other components may be used, which may remain in the solid component as components such as silicon, aluminum and boron.

Further, when the solid component is produced, it can be produced by using an electron donor as an internal donor.

Examples of electron donors (internal donors) that can be used for producing the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acids. Examples include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
C 1 -C such as isopropylbenzyl alcohol
18 alcohols; phenols having 6 to 25 carbon atoms which may have an alkyl group, such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, and naphthol;
C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; C2 to C15 such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde
Aldehydes; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
C2-C20 such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters of the following; inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate and phenyltriethoxysilane; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl chloride 2 to 15 carbon atoms such as
C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, and diphenyl ether; acetate amides such as acetic acid amide, benzoic acid amide, and toluic acid amide Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used.

The use amount of each of the above components can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of the titanium compound and the amount of the tungsten compound to be used may be in the range of 1 × 10 ^{−4 to} 1000, respectively, preferably in a molar ratio to the amount of the magnesium compound to be used, preferably 0.01 to 0.01.
It is in the range of ~ 10. When silicon, aluminum and boron compounds are used as optional components, the amount thereof may be in the range of 1 × 10 ^{−3 to} 100 in terms of a molar ratio with respect to the amount of the above-mentioned magnesium compound, and is preferably 0.01 to 1
Is within the range.

When an electron-donating compound is used, its use amount is 1 × 10
^It may be in the range of ^-3 to 10, preferably in the range of 0.01 to 5.

The solid component used in the present invention can be produced by a known method, and among them, the following production method is preferable.

I. Perform co-milling of magnesium halide, electron donor, titanium-containing compound and tungsten-containing compound,
For example, hydrocarbons such as n-heptane and toluene, 1,2-
A method of treating with a specific solvent such as a halohydrocarbon such as dichloroethane, chlorobenzene and o-dichlorobenzene.

B. A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, a titanium-halogen-containing compound and a tungsten-containing compound are brought into contact therewith.

C. A method in which a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound is contacted with an electron donor, a titanium halide and a tungsten halide.

D. A method in which a magnesium compound is dissolved with titanium tetraalkoxide and an electron donor, and a tungsten compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halide compound.

Thus, a solid component (i) containing titanium, magnesium, tungsten and halogen as essential components is obtained.

The component (ii) to be brought into contact with the above component (i) to produce the component (A) of the catalyst of the present invention has a general formula: R ¹ R ² _3-n Si
(OR ³ ) _n (where R ¹ is a branched hydrocarbon residue, R ² is R
^A silicon residue represented by the same or different hydrocarbon residue as 1; R ³ represents a hydrocarbon residue; and n represents a number satisfying 1 ≦ n ≦ 3).

Here, R ¹ is preferably branched from a carbon atom adjacent to a silicon atom. In this case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example,
A phenyl group or a methyl-substituted phenyl group). More preferred R ¹ is ^one in which the carbon atom adjacent to the silicon atom, ie, the carbon atom at the α-position, is a secondary or tertiary carbon atom.

In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. The carbon number of R ¹ is usually 3 to 20, preferably 4 to 10. R ² has 1 to 20 carbon atoms, preferably 1 to
It is usually 10 branched or straight-chain aliphatic hydrocarbon groups. R ³ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms,
Is usually the case.

 Specific examples of the component (ii) are shown below.

The component (iii) used for producing the solid catalyst component (A) for olefin polymerization of the present invention is an organoaluminum compound or an organozinc compound. Specifically, organic zinc compounds such as diethyl zinc and dibutyl zinc, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, diethyl aluminum ethoxide, ethyl aluminum sesquichloride And organic aluminum compounds such as ethylaluminum dichloride and methylaluminoxane. Of these, organoaluminum compounds are particularly preferred.

Component (iv) is an inorganic or metal halide compound. Specifically, chlorine, bromine, iodine, iodine monochloride, halogen or interhalogen compounds such as iodine trichloride, boron chloride, aluminum chloride, silicon tetrachloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride,
Boron bromide, silicon tetrabromide, silicon tetraiodide, phosphorus tribromide, phosphorus pentabromide, arsenic pentachloride, tin tetrachloride, antimony pentachloride, titanium trichloride, titanium tetrachloride, molybdenum pentachloride, hexachloride Inorganic halogen compounds such as tungsten, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum chloride, ethyl aluminum dibromide, ethyl aluminum sesquibromide, diethyl aluminum bromide, diethyl aluminum iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl aluminum ion Organic metal halides such as dyed and the like are exemplified.
Among them, iodine, iodine trichloride, silicon tetrachloride, phosphorus pentachloride, organoaluminum halogen compounds and the like are preferable.

Component (i), component (ii), component (iii) and component (i
The contact method, amount and conditions of v) can be arbitrary as long as the effect is recognized, but the following conditions are generally preferred.

The quantitative ratio of the component (i) to the component (ii) may be in the range of 0.01 to 1000 in terms of the atomic ratio of silicon of the component (ii) to the titanium component constituting the component (i) (silicon / titanium), preferably It is in the range of 0.1-100. The amount ratio of component (iii) to component (i) is 0.01 to 300, preferably 0.1 to 100, in terms of the atomic ratio of metal in the organoaluminum compound or organozinc compound to the titanium component (metal / titanium). . The amount ratio of component (iv) to component (i) is in the range of 0.01 to 1000, preferably 0.1 to 300, in terms of the atomic ratio (halogen / titanium) of component (i) to titanium component.

The order of contact is not particularly limited. For example, (a) a method in which component (i) is brought into contact with component (ii), then with component (iii), and finally with component (iv); Contacting component (i) with component (ii) and then component (iii)
(C) contacting the component (i) with the component (iii), and then contacting the component (ii)
A method of simultaneously or sequentially contacting the component (iv),
(D) a method in which the component (i) is brought into contact with the component (iv), and then the components (ii) and (iii) are simultaneously or sequentially contacted. Contacting the contacted component with component (i) and then contacting component (iv)
And (f) components (i), (ii), (ii)
There is a method of contacting i) and (iv) simultaneously. There is no problem if a cleaning step is performed between each contact.

As the contact temperature, about -50 ~ 200 ℃, preferably,
0-100 ° C. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Examples of the inert diluent used in this contact include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

Component (B) Component (B) is an organoaluminum compound. Specific examples, R ⁵ _3-n AlX _{n ^{or, R 6 3- mAl (OR 7}} ) m ( wherein R ⁵ and R ⁶ are identical or different optionally having about 1 to 20 carbon atoms which may hydrocarbon residue Group or hydrogen atom, R ⁷ is a hydrocarbon residue, X
Is a halogen, n and m are respectively 0 ≦ n ≦ 3, 0 <m
<3. ). Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum;
Alkyl aluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminium dichloride, etc., (c) diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, diethylaluminum phenoxide, etc. Aluminum alkoxide.

These (a) to other organometallic compound with an organoaluminum compound (d), for example _{^{R 8 3-a Al (OR}} 9) a ( wherein 1 ≦ a ≦ 3, R ⁸ and R ⁹ are the same or different Which may be a hydrocarbon residue having about 1 to 20 carbon atoms.) May also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum chloride Are used in combination.

The amount of the component (B) used is such that the component (B) / component (A) is in the range of 0.1 to 1000, preferably 1 to 100 in weight ratio.

(Polymerization) The catalyst of the present invention can be applied not only to ordinary slurry polymerization but also to liquid-phase solventless polymerization, solution polymerization, or gas-phase polymerization which substantially uses no solvent. .
Further, the present invention is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is performed. As the polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane,
A single or a mixture of saturated aliphatic or aromatic hydrocarbons such as benzene and toluene is used. The polymerization temperature is from room temperature to about 200 ° C., preferably 50 to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner.

The olefins polymerized with the catalyst system of the present invention have the general formula R
-CH = CH ₂ (wherein R represents a hydrogen atom or a carbon atoms, 1 to 10
And may have a branched group. ). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Preferred are ethylene and propylene. In the case of these polymerizations, 50% by weight relative to ethylene, preferably
Up to 20 weight percent of the above olefins can be copolymerized, and up to 30 weight percent of the olefins, especially ethylene, can be copolymerized with respect to propylene. Copolymerization with other copolymerizable monomers (for example, aromatic olefins such as vinyl acetate, styrene, and divinylbenzene) can also be performed.

Experimental Example Example 1 [Production of Component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added.
0.1 mol, Ti a _{(O-nC 4 H 9)} 4 was 0.2 mol introduced and reacted for 2 hours at 95 ° C.. After completion of the reaction, the temperature was lowered to 40 ° C., and then 12 milliliters of methylhydropolysiloxane (of 20 centistokes) were introduced, and the reaction was performed for 3 hours.
The resulting solid component was washed with n-heptane. Then, n-purified in the same manner as above was placed in a flask sufficiently purged with nitrogen.
50 ml of heptane was introduced, and 0.03 mol of the solid component synthesized above was converted into Mg atoms. Then, 0.05 ml of SiCl ₄ was mixed with 25 ml of n-heptane and the mixture was mixed at 30 ° C.
It was introduced into the flask in 0 minutes and reacted at 70 ° C. for 3 hours.
After the completion of the reaction, the resultant was washed with n-heptane. Next, 0.003 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 90 ° C. for 30 minutes, and reacted at 95 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane.
Next, 0.5 g of WCl ₆ and 80 ml of heptane were introduced and reacted at 90 ° C. for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. The titanium content of the obtained solid is 0.68
Weight percent, tungsten content was 2.7 weight percent. This was used as component (i) for producing solid catalyst component (A).

Next, in a flask sufficiently purged with nitrogen, fully purified n
-80 ml of heptane were introduced, 4 g of component (i) obtained above were added thereto, and then (C) as component (ii)
2.7 mmol of H ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , component (ii)
After dilution in n-heptane as i), 15.0 mmol of triethylaluminum was added dropwise at 15 ° C. over 30 minutes. After completion of the dropwise addition, the temperature was raised to 30 ° C. and the reaction was carried out for 1 hour. Next, 1 g of iodine was added as a component (iv), and the mixture was further reacted at 30 ° C. for 1 hour. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a component (A). This component (A) contains titanium
0.65 weight percent was included.

(Polymerization of propylene)

In a 1.5 liter stainless steel autoclave with stirring and temperature control, 500 ml of fully dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum as component (B),
And 15 milligrams of the catalyst component (A) synthesized above were introduced. Then, 60 ml of H ₂ was introduced, the temperature was raised and the pressure was increased, polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C., polymerization time =
Polymerization was performed for 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration and the polymer was dried.

As a result, 131.5 grams of a polymer was obtained. 0.40 g of the polymer was recovered from the excess solution. Activity per catalyst thus 8,800 g polymer / g-solid catalyst, in per titanium atom was 135 × 10 ⁴ g polymer / g titanium. Of the resulting polymer
MFR = 2.7 g / 10 min, bulk specific gravity of the polymer was 0.466 g / milliliter. The polymer density measured by a press-molded product was 0.9084 g / cm ³ .

Comparative Examples 1-3 When producing the component (A) of Example 1, the components (iv),
Except not using component (iii) or component (ii), all were manufactured under the same conditions as in Example-1. Further, propylene was polymerized under the same conditions as in Example-1. The results are shown in Table 1.

Example-2 A 40 liter stainless steel ball having a diameter of 12 mm was filled in a 0.4 liter ball mill sufficiently dried and purged with nitrogen, and 20 g of MgCl ₂ , 2.0 ml of tetrabutoxy titanium, 3.0 ml of dibutyl phthalate, and TiCl were added. ₄ 2.0
Milliliter was introduced and pulverized by a rotary ball mill for 48 hours. After the completion of the pulverization, the mixed and pulverized composition was taken out of the mill in a dry box. Subsequently, 6.0 g of the pulverized composition, 80 ml of n-heptane, and 1.0 g of WCl ₆ were introduced into a flask sufficiently purged with nitrogen, and reacted at 90 ° C. for 4 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. The obtained solid component [component (i)] contained 1.12% by weight of titanium.

Next, 4 g of the solid component (i) obtained above was used, and (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was used as the component (ii).
2.7 mmol, 15.0 mmol of triethylaluminum as the component (iii), and 1.0 g of iodine trichloride were introduced.
The reaction was carried out at 2 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a component (A). This component (A) contained 0.81% by weight of titanium.

(Polymerization of propylene)

Polymerization was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. The results are shown in Table 1.

Comparative Example-4 The solid component (A) was prepared under the same conditions as in Example 2 except that 4 g of the component (i) obtained in Example 2 was used and no iodine trichloride was used as the component (iv). The propylene was produced and polymerized in the same manner as in Example 2 except that this component (A) was used. The results are shown in Table 1.

In preparation of Example -3 Ingredient preparation of (A)] Solid ingredients of Example -1 (i), instead of phthalic acid chloride 0.003 moles, after using cellosolve acetate 0.004 mol, WCl ₆ and 0.7 g introduction 70 ℃
For 4 hours to obtain a solid component (i).
The solid component (i) contained 0.77% by weight of titanium and 3.5% by weight of tungsten.

Next, the component (A) was brought into contact with the components (ii), (iii) and (iv) under the same conditions as in Example 1 except that 4 g of the solid component (i) obtained above was used. Obtained. This component (A) contained 0.70% by weight of titanium.

(Polymerization of propylene)

Polymerization was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. The results are shown in Table 1.

Comparative Example-5 A solid component (A) was produced under the same conditions as in Example 3 except that the component (iv) was not used, and propylene polymerization was carried out in the same manner as in Example 3 except that this component (A) was used. Was performed. The results are shown in Table 1.

Examples -4 to 8 and Comparative examples -6 to 7 A solid component (A) was produced under the same conditions as in Example 1 except that the compounds shown in Table 2 were used instead of iodine as the component (iv). Propylene polymerization was carried out in the same manner as in Example 1 except that the obtained component (A) was used. Table 2 shows the results.

Examples 9 to 12 and Comparative Examples 8 to 9 Using 4 g of the component (i) obtained under the same conditions as in Example 1, the components (ii), (iii) and (iv) are shown in Table-3.
By contacting under the following conditions, a solid component (A) was obtained. Further, propylene polymerization was carried out under the same conditions as in Example 1 except that each of the obtained components (A) was used. The results are shown in Table-3.

[Brief description of the drawings]

FIG. 1 is to assist in understanding the technical contents of the present invention relating to the Ziegler catalyst.

Claims (3)

(57) [Claims] (1) The following component (i), component (ii), component (ii)
A solid catalyst component for olefin polymerization obtained by contacting i) and component (iv). Component (i) Solid component containing titanium, magnesium, tungsten and halogen as essential components, Component (ii) General formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ has 3 to 3 carbon atoms)
20 is a branched hydrocarbon residue, R ² is the same as R ¹ or a hydrocarbon residue having 1 to 20 carbon atoms, R ³ is a hydrocarbon residue having 1 to 20 carbon atoms, n is 1 ≦ n ≦ 3), component (iii) organoaluminum compound or organozinc compound, component (iv) inorganic halogen or metal halide compound. 2. An olefin polymerization catalyst comprising a combination of the following components (A) and (B). Component (A): A solid catalyst component for olefin polymerization obtained by contacting the following components (i), (ii), (iii) and (iv). Component (i) Solid component containing titanium, magnesium, tungsten and halogen as essential components, Component (ii) General formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ has 3 to 3 carbon atoms)
20 is a branched hydrocarbon residue, R ² is the same as R ¹ or a hydrocarbon residue having 1 to 20 carbon atoms, R ³ is a hydrocarbon residue having 1 to 20 carbon atoms, n is 1 ≦ n ≦ 3), component (iii) organoaluminum compound or organozinc compound, component (iv) inorganic halogen or metal halide compound. Component (B): an organoaluminum compound. 3. A process for producing an olefin polymer, comprising polymerizing an olefin in the presence of a catalyst obtained by combining the following components (A) and (B). Component (A): a solid catalyst component for olefin polymerization obtained by bringing the following components (i), (ii), (iii) and (iv) into contact, component (i) titanium, magnesium, tungsten and halogen A solid component containing, as an essential component, component (ii) a general formula R ¹ R ² _3- nSi (OR ³ ) _n (where R ¹ has 3 to 3 carbon atoms)
20 is a branched hydrocarbon residue, R ² is the same as R ¹ or a hydrocarbon residue having 1 to 20 carbon atoms, R ³ is a hydrocarbon residue having 1 to 20 carbon atoms, n is 1 ≦ n ≦ 3), component (iii) organoaluminum compound or organozinc compound, component (iv) inorganic halogen or metal halide compound. Component (B): an organoaluminum compound.