JP2803290B2 - 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 using a specific component in combination, an olefin polymerization catalyst using the component as a transition metal component of a Ziegler catalyst, and an olefin polymer using the catalyst. The method relates to a method for producing the same.

When the solid catalyst component of the present invention is used as a transition metal component of a Ziegler type catalyst, particularly when an α-olefin is polymerized, a polymer having high activity and excellent stereoregularity can be obtained by reducing the derivation of a by-product polymer. It is possible to manufacture.

BACKGROUND OF THE INVENTION Conventionally proposed olefin polymerization catalysts comprising an organoaluminum and a fixed catalyst component containing titanium, magnesium and halogen as essential components have a very high activity, but the stereoregularity of the product polymer poses 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 the electron donating compound 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 terms of the performance of the resulting product polymer, and further, the deterioration of the catalyst with time, the amount of the titanium component and the amount of the organoaluminum compound used during the polymerization. There are still many points to be improved, such as restrictions on the ratio.

According to the proposal of Japanese Patent Application Laid-Open No. 62-187707, by using a special organic alkoxysilicon compound, the restriction on the amount of the organic aluminum compound used in the polymerization is considerably eliminated. However, for the purpose of controlling the molecular weight, producing a copolymer, and the like, there is a problem that the catalyst yield can always be obtained sufficiently high to omit the decontacting step, and further improvement is desired.

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

Component (i) Solid 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 20 carbon atoms)
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, and n is 1 ≦ a component (iii) an organoaluminum compound; a component (iv) a diene compound or a cyclic olefin compound.

Further, the present invention provides a catalyst for olefin polymerization characterized by combining the above-mentioned solid catalyst component for olefin polymerization [component (A)] with an organoaluminum compound [component (B)]. An object of the present invention is to provide 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. The problem of the known catalyst is solved.

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 use of the diene compound or the cyclic olefin compound of the component (iv) allows the component (i) to be disintegrated without disrupting the particle shape of the solid component (i). It is considered that the major reason is that the polymerization of iv) can form active sites with high activity and high stereoregularity uniformly and efficiently down to the order of primary particles. Therefore, it can be said that the present invention has an excellent effect which cannot be expected from the known art. DETAILED DESCRIPTION OF THE INVENTION Catalyst The α-olefin polymerization catalyst of the present invention is obtained by combining a specific component (A) and a specific component (B). It is a thing.

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

The solid component containing titanium, magnesium, halogen and tungsten as essential components used in the component (i) may be a known solid component containing titanium, magnesium and halogen, for example, JP-A-53-45688, JP-A-54-1988. Three
No. 894, No. 54-31092, No. 54-39483, No. 54-94591
Nos. 54-118484, 54-131589, 55-75411
No. 55-90510, No. 55-90511, No. 55-127405,
No. 55-147507, No. 55-155003, No. 56-18609, No. 5
6-70005, 56-72001, 56-86905, 56-90
807, 56-155206, 57-3803, 57-34103
No. 57-92007, No. 57-12003, No. 58-5309,
No. 58-5310, No. 58-5311, No. 58-8706, No. 58-27
No. 732, No. 58-32604, No. 58-32605, No. 58-67703
Nos. 58-117206, 58-127708, 58-183708
Nos. 58-183709, 59-149905, 59-149906 and the like, 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, magnesium carboxylate and the like. Can be

Among these, magnesium dihydride is preferable, and MgCl ₂ is particularly 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 having about 1 to 10 carbon atoms, X represents a halogen, and n represents a 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 ,
_{i (OC 2 H 5) 3} Cl, Ti (O-iC 3 H 7) Cl 3, Ti (O-nC 4 H 9)
_{Cl 3, T (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)
_{l 3, Ti (O-iC} 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl 3, Ti (OC 6 H 13) 3 , etc. Cl halogenated alkoxy titanium, 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 ) ₄ , tetraalkoxy titanium such as 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 ′ (here, X ′ represents halogen) can also be used. Specific examples include TiCl 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 C
_{OCl, 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 tetrahalides and alkoxytitanium halides are preferable, and particularly, Ti (OnC ₃ H ₇ ) ₄ , Ti (OnC ₄ H ₉ ) ₄ , Ti (OnC ₄ H ₉ ) ₂ Cl ₂ ,
Ti (OnC ₄ H ₉ ) Cl ₃ , TiCl _{4 and the} like are preferable.

As tungsten sources, WCl ₆ , WCL ₅ , WCl ₄ , WCl ₂ ,
Tungsten halides such as WBr ₆ , WBr ₅ , WCL ₂ , WI ₄ , WI ₂ , etc., tungsten oxyhalides such as WOCL ₄ , WO ₂ Cl ₂ , π (C ₅ H ₅ ) ₂ WH ₂ , WO ₆ etc. Tungsten oxide, K ₂ W
(OH) Cl ₅ , and the like. Among these, preferred are WCl ₆ , WCl ₅ , WCL _{4 and the} like, and particularly preferred is WC
L is _6.

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

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 hydropolysiloxane, polymeric silicon compounds such as phenyl hydropolysiloxane, Al
(OisoC ₃ H ₇ ) ₃ , AlCl ₃ , AlBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (O
Aluminum compounds such as CH ₃ ) ₂ Cl and B (OCH ₃ ) ₃ , B
It is also possible to use other components such as boron compounds such as (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ even if these remain as solid components such as silicon, aluminum and boron in the solid component. Good.

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, crosol, 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 in terms of a molar ratio with respect 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. Within 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 magnesium is treated with a phosphorus halide compound, and the resultant is contacted with a magnesium halide, an electron donor, a titanium halide-containing compound, and a tungsten-containing compound.

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

D. A method in which a magnesium compound is dissolved with a titaniumium 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 is represented by the general formula: R ¹ R ² _3- nSi (OR ³ ) _n (where R ¹ is A branched hydrocarbon residue, R ² is the same or different hydrocarbon residue as R ¹ , R ³ is 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 is preferably 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 has 1 to 20 carbon atoms, preferably 1 to
It is usually 10 aliphatic hydrocarbon groups, particularly preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

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

etc.

The component (iii) used for producing the solid catalyst component (A) for olefin polymerization of the present invention is an organoaluminum compound.

Specifically, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-
Trialkylaluminum such as n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, isobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride Chloride, haloalkylaluminum such as ethylaluminum dichloride, alkylaluminum hydride such as diethylaluminum hydride, diethylaluminum ethoxide, alkoxyalkylaluminum such as diethylaluminum phenoxide, methylaluminoxane, alkylaluminoxane such as ethylaluminoxane and isobutylaluminoxane are exemplified. Be done These can be used alone or as a mixture of two or more. Also, butyl lithium, butyl ethyl magnesium, cyethyl zinc,
It can be used as a mixture with an organometallic compound such as titanocene dimethyl, or as a complex with titanocene dichloride, titanocene dimethyl, zirconocene dimethyl, or the like.

Component (iv) is a diene compound having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a cyclic olefin compound having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms. Specifically, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,4-
Hexadiene, 1,5-hexadiene, methylhexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, divinylbenzene, divinylcyclohexane, diene compounds such as vinylcyclohexene, cyclopentene, Examples thereof include cyclic olefin compounds such as cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, dicyclopentadiene, norbornene, norbornenecarboxylic acid ethyl ester, cyclooctadiene, and bismethyloctahydronaphthalene. These can be used alone, or two or more can be mixed or used sequentially. Of these, 1,
Non-conjugated dienes such as 5-hexadiene, methylhexanediene, 1,6-heptadiene and divinylbenzene, and cyclic monoolefins such as norbornene and dimethyloctahydronaphthalene are preferred.

The contacting method and the amount of the components (i) to (iv) can be arbitrary, as long as the effects of the present invention are recognized.
Generally, the following conditions are preferred. Component (i) and component (i
The quantitative ratio of i) is the atomic ratio (silicon / titanium) of silicon of the component (ii) to the titanium component constituting the component (i).
It may be in the range of 01-1000, preferably in the range of 0.1-100.

Component (iii) The amount ratio to component (i) is in the range of 0.01 to 1000, preferably 0.1 to 300, in terms of the aluminum / titanium atomic ratio of the organoaluminum compound.

The quantitative ratio of the component (iv) to the component (i) is as follows:
Is in the range of 0.01 to 1000, preferably 0.1 to 100 by weight ratio of the component (iv) with respect to the solid amount of

The contact order of the components (i) to (iv) is not particularly limited,
For example, a method of bringing component (i) into contact with component (ii), then contacting with component (iii), and finally contacting with component (iv), contacting component (i) with component (iii), Ingredient (i
i), a method of contacting the component (iv) simultaneously or sequentially, a method of contacting the component (i) with the component (iv), and then contacting the component (ii) and the component (iii) simultaneously or sequentially, A method in which the component (ii) and the component (iii) are brought into contact with each other in advance, and then the component (iv) is brought into contact with the component (i), the component (i), (ii), (iii) and (iv).
Contact at the same time. 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-m Al (}} OR 7) m ( wherein R ⁵ and R ⁶ are the same or different carbon atoms which may be 20 about a hydrocarbon residue A group or a hydrogen atom, R ⁷ is a hydrocarbon residue, X is a halogen, n and m are each a number of 0 ≦ n <3, and 0 <m <3.) Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum Alkyl aluminum halides such as sesquichloride and ethyl aluminum dichloride; aluminum alkoxides such as (c) diethyl aluminum hydride, diisobutyl aluminum hydride, (d) diethyl aluminum ethoxide and diethyl aluminum phenoxide.

These (a) to other organometallic compound with an organoaluminum compound (c), 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 a polymerization solvent in the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, 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.

EXAMPLES 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 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then, 0.05 ml of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Then phthalic acid chloride was added to 25 ml of n-heptane.
003 mol were mixed, introduced into the flask at 90 ° C. for 30 minutes, and reacted at 94 ° 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 was 0.68 weight percent and the 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 (iv)
And 4 g of norbornene was introduced and contacted at 30 ° C. for 1 hour. Then, the mixture was cooled to 15 ° C, and 15.0 mmol of triethylaluminum diluted in n-heptane as the component (iii) was added dropwise at 15 ° C over 30 minutes. After dripping
The temperature was raised to 30 ° C. and reacted for 2 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane, and 4.7 g of the component (A) was recovered.
This component (A) contained 0.52% by weight of titanium.

(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 mg of the catalyst component (A) synthesized above was 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, 240.5 grams of a polymer was obtained. 0.49 g of polymer was recovered from the filtrate. Thus, the activity per catalyst was 16,000 grams polymer / gram solid catalyst and 309 × 10 ⁴ grams polymer / gram titanium per titanium atom. The MFR of this polymer was 1.1 g / 10 min, and the bulk specific gravity of the polymer was 0.412 g / ml. When the polymer density was measured by press molding, it was 0.9076 g / ml.

Example 2 [Production of Component (A)] 4 g of the component (i) obtained in Example 1 was purified n
- heptane 80 ml, thoroughly were introduced in a nitrogen-substituted flask, followed as component _{(ii) (CH 3) 3} CSi (C
H ₃₎ (OCH _{3) 2} and after introducing 2.7 mmole, under 15 ° C., was added dropwise over triethylaluminum 15.0 mmol, diluted in n- heptane as the component (iii) 30 minutes. After completion of the dropwise addition, the temperature was raised to 30 ° C., and the reaction was carried out for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. Next, 4 g of norbornene was introduced as the component (iv), and the mixture was contacted at 30 ° C. for 1 hour. After the completion of the contact, the solid component (A) was sufficiently washed with n-heptane.
2 grams were obtained. This component (A) contains 0.43 titanium.
Weight percent was included.

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

Example 3 [Production of Component (A)] Instead of using 0.003 mol of phthalic chloride as the solid component (i) of Example 1, cellosolve acetate 0.0 was used.
After using 04 moles, introduce 0.7 g of WCl ₆ and
By reacting for a time, a solid component (i) was obtained. In this solid component (i), titanium is 0.77% by weight,
Tungsten contained 3.5 weight percent.

Then, the solid component (i) obtained above was contacted with the component (ii), the component (iii) and the component (iv) under the same conditions as in Example 1 except that 4 g of the solid component (i) was used. As a result, 5.1 g of the component (A) was recovered. This component (A) contained 0.47% by weight of titanium.

(Polymerization of propylene)

Example 1 except that the solid component (A) obtained above was used.
Polymerization was carried out under the same conditions as in Example 1. Table 2 shows the results.

Comparative Examples 1-3 A solid component (A) was produced under the same conditions as in Example 1, except that the amounts of the components (ii), (iii) and (iv) were changed to the conditions shown in Table 1. Propylene polymerization was carried out in the same manner as in Example 1 except that this component (A) was used. The results are shown in Table 1.

Example-4 [Production of Component (A)] A 0.4 liter ball mill sufficiently dried and purged with nitrogen was charged with 40 stainless steel balls having a diameter of 12 mmφ, and MgCl ₂ was added thereto in an amount of gram, 2.0 ml of tetrabutoxy titanium, 3.0 ml of dibutyl phthalate and 20 ml of TiCl _{4 were} 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. Next, 6.0 g of the pulverized composition was introduced into a flask sufficiently purged with nitrogen, and further n-heptane 80 was added.
Milliliter and 1.0 g of WCl ₆ were introduced and reacted at 90 ° C. for 4 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. In the obtained solid component [component (i)], titanium is contained.
It contained 1.12 weight percent and 4.0 weight percent tungsten.

Next, the solid component (i) was brought into contact with the component (ii), the component (iii) and the component (iv) under the same conditions as in Example 1 except that 4 g of the solid component (i) obtained above was used. As a result, 5.4 g of the component (A) was recovered. This component (A) contained 0.76% by weight of titanium.

(Polymerization of propylene)

Polymerization was carried out under the same conditions as in Example 1 except that the solid component (A) obtained above was used. Table 2 shows the results.

Examples 5 to 8 A solid component (A) was produced under the same conditions as in Example 1 except that the components (ii), (iii) and (iv) were changed to the conditions shown in Table-2. The same polymerization as in Example 1 was carried out using each of the components (A). Table-Results
It is shown in FIG.

Examples -8 to 12 and Comparative examples -4 to 5 The solid component (A) was produced under the same conditions as in Example 1 except that the compounds shown in Table 3 were used as the component (iv). Propylene polymerization was carried out in the same manner as in Example 1 except that the component (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] A solid catalyst component for olefin polymerization obtained by contacting the following components (i), (ii), (iii) and (iv). Component (i) Solid containing titanium, magnesium, tungsten and halogen as essential components, Component (ii) Formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ is a C 3-20 A branched chain 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, component (iv) diene compound or cyclic olefin compound. 2. An olefin polymerization catalyst comprising a combination of the following compound (A) and component (B). Component (A): A solid catalyst component for olefin polymerization obtained by contacting the following components (i), (ii), (iii) and (iv): Component (i) Titanium, magnesium, tungsten and halogen are essential components solid containing as component (ii) general formula _{^{R 1 R 2 3-n Si}} (OR 3) n ( where, R ¹ is a branched hydrocarbon residue having 3 to 20 carbon atoms, R ² is R ¹ Or a hydrocarbon residue having 1 to 20 carbon atoms, R ³ represents a hydrocarbon residue having 1 to 20 carbon atoms, and n represents a number of 1 ≦ n ≦ 3). Component (iii) Organoaluminum compound, Component (iv) Diene compound or cyclic olefin 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): Component (i) , (Ii), a solid catalyst component for olefin polymerization obtained by contacting (iii) and (iv), component (i) a solid containing titanium, magnesium, tungsten and halogen as essential components, component (ii) a general formula R ¹ R ² _3- nSi (OR ³ ) _n (where R ¹ is a branched chain hydrocarbon residue having 3 to 20 carbon atoms, and R ² is the same as R ¹ or a carbon atom having 1 to 20 carbon atoms) A silicon compound represented by a hydrogen residue, R ³ represents a hydrocarbon residue having 1 to 20 carbon atoms, and n represents a number of 1 ≦ n ≦ 3), component (iii) organoaluminum compound, component (iv) ) Diene compounds or cyclic olefin compounds. Component (B): an organoaluminum compound.