JP2615632B2 - Catalyst for olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention relates to olefins, particularly α-olefins having 3 or more carbon atoms, by using a specific catalyst.
When applied to the polymerization of, a highly stereoregular polymer can be advantageously produced under stable polymerization conditions for industrial production.

Background of the Invention Conventionally proposed olefin polymerization catalysts comprising organoaluminum and a solid catalyst component containing titanium, magnesium and halogen as essential components have an extremely high activity, but the stereoregularity of the product polymer poses a problem. In some cases, it was necessary to use an electron-donating compound during the polymerization.

However, such a catalyst using an electron-donating compound as the third component (external donor) can reduce the polymerization rate due to the reaction between the organoaluminum compound and the electron-donating compound, or increase the polymerization rate to increase the polymerization rate. When the temperature is increased, the above-mentioned reaction is accelerated. Therefore, it is limited to increase the polymerization temperature to increase the polymerization amount (production efficiency increase). Is difficult to control.

Accordingly, there is a need for a catalyst system which can solve the above problems and can produce a highly stereoregular polymer with a high catalyst yield without using an electron-donating compound as the third component (external donor).

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.

SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above points. That is, the present invention provides an olefin polymerization catalyst comprising the following components (A) and (B).

Component (A): a solid catalyst component obtained by contacting the following components (i) to (iv): Component (i): a solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii) ): General formula, R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are each O <m ≦ 3 and 0
≦ n ≦ 3 and 0 <m + n ≦ 3, and
Wherein the carbon at the α-position of R ¹ is a secondary or tertiary branched-chain hydrocarbon residue having 3 to 20 carbon atoms), component (iii): general formula, Ti (OR ³ ) _{4-l Xl} (where R ³ is a hydrocarbon residue, X is a halogen, l is 0 <l ≦ 4
Component (iv): an organoaluminum compound, Component (B): an organoaluminum compound.

Effect of the Invention The olefin polymerization catalyst of the present invention can produce a polymer having extremely high stereoregularity with high yield without using an electron donating compound (external donor) at the time of polymerization. Furthermore, in the polymerization using the olefin polymerization catalyst of the present invention, the problem of a decrease in the polymerization rate is solved, and the problem of the known catalyst such that no problem occurs even when the polymerization temperature is increased (about 75 to 90 ° C.). The point is eliminated. These features are extremely advantageous for industrial production and are important as catalyst features. Although the reason for such a catalyst cannot be sufficiently analyzed yet, the solid component of the component (i), the silicon compound of the component (ii), the titanium compound of the component (iii) and the component (iv) used in the present invention. It is thought to be due to the interaction of the organoaluminum compound of (1).

Further, a feature of the catalyst of the present invention is that the catalyst activity is extremely high. Conventionally, it is possible to obtain a catalyst activity about twice as high as that of a known catalyst.

DETAILED DESCRIPTION OF THE INVENTION [Catalyst] The catalyst of the present invention comprises a specific component (A) and a specific component (B).
Consisting of Herein, “consisting of” does not mean that the components are only those listed (ie, A and B) and does not preclude the coexistence of a purposeful third component.

Component (A) Component (A) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (iv). Here, “obtained by contact” does not mean that the object is only the indicated one (that is, only the components (i) to (iv)), and the coexistence of other components that is appropriate. Do not eliminate.

Component (i) Component (i) is a solid component containing tetravalent titanium, magnesium and halogen as essential components. Here, "contains as an essential component" means that it may contain other suitable elements in addition to the three components listed,
It indicates that each of these elements may be present as any purposeful compound, and that these elements may be present as mutually bonded.

Known solid components can be used. For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-31092.
No. 54-39483, No. 54-94591, No. 54-118484,
No. 54-131589, No. 55-75411, No. 55-90510, No. 55
-90511, 55-127405, 55-147507, 55-1
No. 55003, No. 56-18609, No. 56-70005, No. 56-72001
Nos. 56-86905, 56-90807, 56-155206,
No. 57-3803, No. 57-34103, No. 57-92007, No. 57-
No. 121003, No. 58-5309, No. 58-5310, No. 58-531
No. 58-8706, No. 58-27732, No. 58-32604, No.
58-32605, 58-67703, 58-117206, 58-
127708, 58-183708, 58-183709, 59-14
Nos. 9905 and 59-149906 are used.

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

Further, a titanium compound serving as a titanium source has a general formula Ti (O
R ⁴ ) _4-n X _n (where R ⁴ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents halogen,
n shows the number of 0 <= n <= 4. )). Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) C
_{l 3, Ti (OC 2 H} 5) 2 Cl 2, Ti (OC 2 H 5) 3 Cl, Ti (O-iC 3 H 7) Cl 3, T
i (O-nC ₄ H ₉ ) Cl ₃ , Ti (O-nC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O
_{C 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 ) 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, T
i (O-nC ₆ H ₁₃ ) ₄ , Ti (O-nC ₈ H ₁₇ ) ₄ , Ti (OCH ₂ CH (C ₂ H ₅ ) C
₄ H _9] is _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, 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, TiC
l ₄・ C ₆ H ₅ 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, preferred are TiCl
₄ , Ti (OEt) ₄ , Ti (OBu) ₄ , Ti (OBu) Cl _{3 and the} like.

The halogen source is usually supplied from the above-mentioned halogen compound of magnesium and / or titanium, but is supplied from a known halogenating agent such as a halide of aluminum, a halide of silicon, 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 , silicon compounds such as CH ₃ SiCl ₃ and methyl hydrogen polysiloxane, Al (OiC ₃ H ₇ ) ₃ , AlCl ₃ , AlBr ₃ , Al (OC ₂ H
₅ ) ₃ , aluminum compounds such as Al (OCH ₃ ) ₂ Cl, B (OC ₆ H ₅ ) ₃
It is also possible to use other components such as a boron compound such as, and these may remain in the solid component as components such as silicon, aluminum and boron.

Furthermore, when producing this solid component, it can also be produced 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 acids 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, (a) a compound having 1 carbon atom such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol;
To 18 alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenol, nonyl phenol, and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde , (E) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, chloroacetic acid Chill, dichloroacetic ethyl acetate, methyl methacrylate, ethyl crotonate, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc. Organic acid esters having 2 to 20 carbon atoms; (f) inorganic acid esters such as silicates such as ethyl silicate, butyl silicate, and phenyltriethoxysilane; (g) acetyl chloride;
Acid halides having 2 to 15 carbon atoms such as benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl isochloride, etc., (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, Ethers having 2 to 20 carbon atoms such as diphenyl ether, acetic acid amides such as (l) acetic acid amide, benzoic acid amide, and toluic acid amide; (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzide Examples thereof include amines such as ruamine, aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as (ル) acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used. Of these, organic acid esters and acid halides are preferred, and phthalic acid esters and phthalic halides are particularly preferred.

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 used is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 10, in terms of a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 ^{− in a} molar ratio to the amount of magnesium used irrespective of whether or not the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{2 to} 1000, preferably in the range of 0.1 to 100. The amount of silicon, aluminum and boron compound used is 1 × 10
The range is preferably from ^{-3 to} 100, and more preferably from 0.01 to 1.

The amount of the electron donating compound used is preferably in the range of 1 × 10 ⁻³ to 10 and more preferably in the range of 0.01 to 5 in terms of a molar ratio with respect to the amount of the magnesium compound.

The component (i) is produced using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor, for example, by the following production method.

(A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound.

(B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and is contacted with a magnesium halide, an electron donor, and a titanium halide-containing compound.

(C) A method of contacting a titanium halide and / or a silicon halide with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

(Where R represents a hydrocarbon residue having about 1 to 10 carbon atoms, and n represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes). Empolysiloxane, 1,3,5,7 tetramethylcyclotetrasiloxane,
Preferred are 1,3,5,7,9 pentamethylcyclopentasiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane, and the like.

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

(E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary.

(F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor.

As the catalyst component (i) used in the present invention, the solid component obtained as described above can be used as it is, or a prepolymerized component obtained by contacting this solid component with an olefin in the presence of an organoaluminum compound. Can also be used.

When component (i) is preliminarily polymerized, the conditions for prepolymerization of olefins for producing component (i) are not particularly limited, but generally the following conditions are preferred. The polymerization temperature is 0 to 80 ° C, preferably 10 to 60 ° C.
° C. The polymerization amount is 0.00 per gram of solid component.
It is preferred to polymerize 1 to 50 grams of olefins, more preferably 0.1 to 10 grams of olefins.

As the organoaluminum component at the time of the prepolymerization, generally known ones can be used.

Specific examples include Al (C ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (C ₅ H ₁₃ )
_{3, Al (C 8 H 17} ) 3, Al (C 10 H 21) 3, Al (C 2 H 5) 2 Cl, Al (iC 4 H 9)
₂ Cl, Al (C ₂ H ₅ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) and the like.

Of these, Al (C ₂ H ₅ ) ₃ and Al (iC ₄ H ₉ ) ₃ are preferred. It is also effective to use a combination of a trialkylaluminum and an alkylaluminum halide, or a combination of a trialkylaluminum, an alkylaluminum halide and an alkylaluminum ethoxide.

As a specific example, a combination of Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl, Al
Combined use of (iC ₄ H ₉ ) ₃ and Al (iC ₄ H ₉ ) ₂ Cl, Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ )
_1.5 Cl _1.5 , Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl and Al (C ₂ H ₅ )
₂ (OC ₂ H ₅ ).

The amount of the organoaluminum component used in the prepolymerization is 1 / Al (Ti molar ratio) with respect to the Ti component in the solid component (A).
-20, preferably 2-10. In addition, a known electron donor such as an alcohol, an ester or a ketone may be added during the prepolymerization.

Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene-1 and the like. It is also possible to make hydrogen coexist during the prepolymerization. Thus, the prepolymerized component (i) is obtained.

Component (ii) Component (ii) used to produce component (A) is represented by the general formula: R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are hydrocarbon residues X is halogen, and m and n are 0 <m ≦ 3 and 0, respectively.
≦ n ≦ 3 and 0 <m + n ≦ 3, and
Wherein the carbon at the α-position of R ¹ is a secondary or tertiary and is a branched chain hydrocarbon residue having 3 to 20 carbon atoms). R ¹ is such that the carbon at the α-position is tertiary and has 4 to 10 carbon atoms.
Preferably, R ² is 1
It is preferably about 20 to about 20, preferably 1 to 10, hydrocarbon residues. X is preferably chlorine at least from the viewpoint of economy.

As specific examples, Cl (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , Si (OC ₂ H ₅ ) ₃ C
l, Si (OCH ₃ ) ₂ Cl ₂ , _{CSi (CH 3) (OCH 3} ) 2, (CH 3) 3 CSi (HC (CH 3) 2) (OCH 3) 2, (CH 3)
₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C
_{2 H 5) CH-Si (} CH 3) (OCH 3) 2, ((CH 3) 2 CHCH 2) Si (OCH 3) 2, C 2 H
₅ C (CH ₃ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ ) (OC
_{2 H 5) 2, (CH} 3) 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H 5) 3, (C 2 H 5)
₃ CSi (OC ₂ H ₅ ) ₃ , (CH ₃ ) (C ₂ H ₅ ) CHSi (OCH ₃ ) _{3 and the} like.

Of these, preferred are branched or branched hydrocarbon residues having 3 to 20 carbon atoms, wherein the carbon at the α-position of R ¹ is secondary or tertiary, especially R ¹
Is a silicon compound having a tertiary carbon atom and a branched hydrocarbon residue having 4 to 10 carbon atoms.

Component (iii) Component (iii) used to produce component (A)
Is a titanium compound represented by the following general formula. Ti
(OR ³ ) _4-l X _l (where R ³ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, and l is a number satisfying 0 <l ≦ 4 Is shown.).

Specific examples include TiCl ₄ , TiBr ₄ , Ti (0C ₂ H ₅ ) Cl ₃ , Ti (O
C ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-iC ₃ H ₇ ) Cl ₃ , Ti (O-nC ₄ H
_{9) Cl 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) Cl 3, etc. Is raised.

Of these, preferred are TiCl ₄ , Ti (OC ₂ H ₅ ) C
l ₃ , Ti (OC ₄ H ₉ ) Cl ₃ , and the like.

Component (iv) Component (iv) used to produce component (A)
It is an organic aluminum compound. Examples of the organoaluminum which can be used during the prepolymerization of the component (i) described above can be used as they are, and they can be selected and used. Specific examples thereof include Al (C ₂ H ₅ ) ₃ and Al (iC ₄ H _9). ) ₃ , Al (nC ₄ H ₉ ) ₃ , Al (C ₅ H
₁₃ ) ₃ , Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₀ H ₂₁ ) ₃ , Al (C ₂ H ₅ ) Cl, Al (iC ₄ H
₉ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ),
And the like.

Production of Component (A) The contact conditions of the above-mentioned components (i) to (iv) may be any conditions as long as the effects of the present invention are recognized, but generally the following conditions are preferred. Contact temperature is -50 to 20
The temperature is about 0 ° C, preferably 0 to 100 ° C. Examples of the contact 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.
Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like.

The method of contacting the components (i) to (iv) when producing the component (A) is arbitrary as long as the effects of the present invention are recognized. For example, specific examples include the following.

(B) Component (i) + {Component (ii) + Component (iii) + Component (iv)} (b) Component (i) + {Component (iii) + Component (iv)} + Component (ii) (C ) Component (i) + Component (iii) + {Component (ii) + Component (iv)} (d) Component (i) + Component (iii) + Component (iv) + Component (i)
i) (e) Component (i) + component (iv) + component (ii) + component (ii)
i) (f) Component (i) + component (iv) + component (iii) + component (i
i) (g) Component (i) + {Component (ii) + Component (iii) + Component (iv)} + {Component (ii) + Component (iii) + Component (iv)} (H) Component (i) + Component (iii) + {component (ii) + component (iv)} + {component (ii) + component (iv)} (li) component (i) + {component (ii) + component (iii) + component ( iv) {+ {Component (ii) + Component (iv)} The ratio of the components (i) to (iv) can be arbitrary as long as the effects of the present invention can be recognized.
The following range is preferred. The quantitative ratio of the component (i) to the component (ii) is determined by the ratio of the component (i)
i) 0.01 to 1000 in silicon atomic ratio (silicon / titanium)
And preferably in the range of 0.1 to 100.

The amount of the component (iii) used is 0.01 to 100 in the atomic ratio of titanium of the component (iii) to the titanium component constituting the component (i) {titanium (component (iii)} / {titanium (component (i)}).
And preferably in the range of 0.1 to 20.
The amount of the component (iv) to be used is preferably in the range of 0.01 to 100, and more preferably in the range of 0.1 to 30 as an aluminum atomic ratio (aluminum / titanium) of the component (iv) to the titanium component constituting the component (i). It is.

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 ( where
R ⁵ and R ⁶ may be the same or different, and may be a hydrocarbon residue or a hydrogen atom having about 1 to 20 carbon atoms, R ⁷ may be a hydrocarbon residue, X
Is 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, ethylaluminum dichloride, etc., (c) diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, diethylaluminum phenoxide, etc. Aluminum alkoxide.

These (a) other organometallic compounds with an organoaluminum compound to (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 hydrocarbon residues having about 1 to 20 carbon atoms. )) Can 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.

[Use of catalyst / 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 using substantially 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 100 ° C., particularly 60 to 90 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner. In the case of slurry polymerization, the amount of component (A) used is preferably in the range of 0.0001 to 0.1 gram component (A) / liter solvent.

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 these polymerizations, up to 50% by weight, preferably up to 20% by weight, of the olefins can be copolymerized with ethylene, and up to 30% by weight of the olefins, especially ethylene, with respect to propylene. , Can be copolymerized. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefine, etc.) 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.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 milliliters of methylhydropolysiloxane (of 20 centistokes) were introduced, followed by a reaction 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 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom. Then, 25 ml of n-heptane was mixed with 0.4 mol of SiCl ₄ , 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 0.02 was added to 25 milliliters of n-heptane.
Mix 4 moles, introduce into flask at 70 ° C for 30 minutes, 9
The reaction was performed at 0 ° C. for 1 hour.

After the completion of the reaction, the resultant was washed with n-heptane. Then SiCl ₄ 2
The reaction was conducted at 80 ° C. for 6 hours by introducing 0 milliliter. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. It had a titanium content of 1.21 weight percent.

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently purged with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi as a silicon compound of the component (ii) 0.40 milliliters of (CH ₃ ) (OCH ₃ ) ₂ are introduced, then 0.52 milliliters of component (iii) TiCl ₄ ,
Further, 1.5 g of triethylaluminum of the component (iv) was introduced into each, and they were contacted at 30 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

In a 1.5 liter stainless steel autoclave with stirring and temperature control, 500 milliliters of fully dehydrated and deoxygenated n-heptane, 100 milligrams of triethylaluminum as component (B) and component (A) prepared above Was introduced, 60 ml of hydrogen were introduced, the temperature was raised and the pressure was increased, and the polymerization was carried out under the conditions of polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C., and polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 211.3 grams of a polymer was obtained. One filtrate yielded 0.45 grams of polymer. From the boiling heptane extraction test, all products II (hereinafter abbreviated as T-II) were 99.3%.
Weight percent. The MFR was 1.1 g / 10 minutes, and the bulk density of the polymer was 0.49 g / cc.

Example 2 [Production of component (A)] In the production of component (A) of Example 1, diheptyl phthalate was used instead of phthalic chloride, and SiCl ₄ 20
A solid component was produced in the same manner as in Example 1 except that the amount of TiCl ₄ used was changed to 25 milliliter instead of milliliter. The titanium content of the resulting solid component was 2.33 weight percent.

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 5 g of the component (i) obtained above and further 0.1 mL of the component (iii) TiCl ₄ .
40 milliliters were introduced and contacted at 100 ° C. for 2 hours. After contact completion, the components of (ii) a _{(CH 3) 3 CSi (CH} 3) (OCH 3) 2 0.36
Milliliters and 2.5 grams of component (iv) triethylaluminum were introduced and contacted at 40 ° C. for 1 hour. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

The polymerization was carried out under the same conditions except that the amount of the component (B), triethylaluminum, used in the polymerization of propylene in Example 1 was 125 mg.

223.7 grams of polymer were obtained, T-II = 99.1 weight percent, MFR = 1.2 g / 10 min, polymer bulk density = 0.48 g / cc
It was.

Example 3 [Production of Component (A)] 100 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 and 0.2 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After the reaction, lower the temperature to 35 ° C, and
-15 milliliters of tetramethylcyclotetrasiloxane were introduced and reacted for 5 hours. The resulting solid component was washed with n-heptane. Then, 50 ml of n-heptane was introduced into the flask which had been sufficiently purged with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then SiCl
₄ 0.06 mol was introduced at 20 ° C for 30 minutes and reacted at 50 ° C for 3 hours. After the completion of the reaction, the solid was washed with n-heptane to obtain a solid component (i) for producing the component (A). The titanium content in the solid component was 4.52 weight percent.

Using this component (i), the component (ii) (CH ₃ ) ₃ CSi (CH ₃ )
Contact was made under the same conditions as in Example 1 except that 1.8 milliliters of (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ was used instead of (OCH ₃ ) ₂ . After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

Under the polymerization conditions of Example 1, the amount of component (A)
Polymerization of propylene was carried out in the same manner as in Example 1 except that the polymerization temperature was 15 mg and the polymerization temperature was 70 ° C. As a result, 99
Grams of polymer, MFR = 6.3 g / 10 min, T-II
= 97.2% polymerization and specific gravity of polymer = 0.49 g / cc.

Example 4 In the production of the component (A) of Example 1, the component (A) was produced under the same conditions as in Example 1 except that ethyl benzoate was used instead of phthalic chloride. The polymerization of propylene was carried out in the same manner as in Example 1. As a result, 7
5.7 grams of polymer were obtained, MFR = 4.6 g / 10 min, T-
II = 95.5 weight percent, polymer bulk specific gravity = 0.43 g / cc
It was.

Examples 5 to 9 In the same manner as in Example 1 except that the amounts and types of the components (ii) and (iv) used in the production of the component (A) were the compounds shown in Table 1. (A) was produced, and propylene was polymerized in the same manner as in Example 1 except that each of the obtained components (A) was used. Table 1 shows the results.

Example 10 Production of Component (A) Production of component (i) was carried out in the same manner as in Example 1.

50 ml of sufficiently purified n-heptane was introduced into a flask sufficiently purged with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ CSi as a silicon compound of the component (ii) 0.25 milliliter of (CH ₃ ) (OCH ₃ ) ₂ , 0.26 milliliter of component (iii) TiCl ₄ , component (iv)
Of triethylaluminum was introduced and contacted at 30 ° C. for 1 hour. After the completion of the contact, the substrate was sufficiently washed with n-heptane. Next, the same contact as described above was repeatedly carried out on the obtained contact product using the same amount of the components (ii) to (iv) as described above. The obtained product was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

Polymerization was carried out under the same conditions as in Example 1 except that the polymerization temperature was changed to 80 ° C.
The result was 246.6 grams of polymer, T-II =
99.4 weight percent, MFR = 1.0 g / 10 min, polymer bulk specific gravity = 0.50 g / cc.

Example 11 [Production of component (A)] The component (i) was produced in the same manner as in Example 2.

Then the internal volume 1.5 with stirring and temperature control device
500 milliliters of sufficiently dehydrated and deoxygenated n-heptane, 2.2 grams of triethylaluminum, and 20 grams of the solid component obtained above were introduced into a stainless steel stirring tank of a little. Set the temperature in the stirring tank to 20 ° C,
Propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the completion of the polymerization, the resultant was sufficiently washed with n-heptane. A portion was taken out and the polymerization amount of propylene was examined. As a result, component (i) was found to be 1.08 g of propylene per gram of the solid component.

50 ml of fully purified n-heptane was introduced into a flask sufficiently purged with nitrogen, then 5 g of the above-mentioned component (i) and 3.0 g of triethylaluminum of the above-mentioned component (iv) were introduced, and the mixture was heated at 30 ° C. for 1 hour. Contacted.
Then, 0.25 milliliter of (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ of the component (ii) was introduced, and the mixture was contacted at 40 ° C. for 1 hour. Then, 0.35 milliliter of the component (iii), TiCl _4, was introduced and contacted at 30 ° C. for 1 hour. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Polymerization of propylene)

Polymerization was carried out under the same conditions as in Example 1 except that the polymerization temperature was changed to 85 ° C.
The result was 196.7 grams of polymer, T-II =
99.3 weight percent, MFR = 1.2 g / 10 min, polymer bulk specific gravity = 0.46 g / cc.

Examples 12 to 13 Polymerization was carried out for 6 hours using the component (A) prepared in Examples 1 and 11. However, as polymerization conditions,
Polymerization was carried out under the same conditions as in Example 1 except that the amount of the component (B) triethylaluminum was changed to 80 mg and the amount of the component (A) was changed to 7 mg. Table 2 shows the results.

Comparative Example 1 In the production of component (A) of Example 1, component (iii)
Component (A) was produced in exactly the same manner except that no TiCl ₄ was used. The polymerization of propylene was carried out in exactly the same manner. The result is 148.7 grams of polymer,
T-II = 99.0 weight percent, MFR = 1.9 g / 10 min, polymer bulk specific gravity = 0.46 g / cc.

Comparative Example 2 Using the component (A) produced in Comparative Example 1, polymerization was carried out under the same conditions as in Example 13 for 6 hours. Table 2 shows the results.

[Brief description of the drawings]

FIG. 1 is for assisting the understanding of the technical contents of the present invention regarding the Ziegler catalyst.

Claims (2)

(57) [Claims] An olefin polymerization catalyst comprising the following components (A) and (B). Component (A): a solid catalyst component obtained by contacting the following components (i) to (iv): Component (i): a solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii) ): General formula, R ¹ _m X _n Si (OR ² ) _4-mn (where R ¹ and R ² are a hydrocarbon residue, X is a halogen, and m and n are each 0 <m ≦ 3 and 0
≦ n ≦ 3 and 0 <m + n ≦ 3, and
Wherein the carbon at the α-position of R ¹ is a secondary or tertiary branched-chain hydrocarbon residue having 3 to 20 carbon atoms), component (iii): a general formula, Ti (OR ³ ) _{4 -1} X ₁ (where R ³ is a hydrocarbon residue, X is halogen, 1 is 0 <1 ≦ 4), Component (iv): an organoaluminum compound, Component ( B): Organoaluminum compound. 2. The silicon compound represented by the general formula of component (ii), wherein the carbon at the α-position of R ¹ is a tertiary carbon atom and is a branched hydrocarbon residue having 4 to 10 carbon atoms. The olefin polymerization catalyst according to claim 1,