JP2559747B2 - Olefin polymerization catalyst - Google Patents

Description

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

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.
Obtained by reacting with an organosilicon compound (2) having a —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. Disclosed is a method of polymerizing with the solid component obtained and a catalyst system formed from organoaluminum.

However, although the above problems are being solved by this proposal, there is a limit in the performance of the product polymer obtained, and further deterioration of the catalyst over time, the amount ratio of the titanium component and the organoaluminum compound used during the polymerization. There are still many points to be improved, such as restrictions on.

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

Component (A): Solid catalyst component obtained by contacting the following components (i) to (v), Component (i): Solid component containing tetravalent titanium, magnesium and halogen as essential components, Component (ii) ): General formula, (However, R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are 0 ≦ m ≦ 3 and 0 ≦, respectively.
a silicon compound represented by n ≦ 3 and 0 ≦ m + n ≦ 3), component (iii): general formula, Ti (OR ³ ) _4-l X _l (wherein R ³ is a hydrocarbon residue) Yes, X is halogen, l is 0 <l ≦
4), a component (iv): an organozinc compound, a component (v): a general formula, (However, R ⁴ is a hydrocarbon residue) A polymer silicon compound having a structure represented by the following formula: Component (B): 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. The reason why such a catalyst is used cannot be analyzed sufficiently, but 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 believed that this is due to the interaction between the organozinc compound (1) and the polymer silicon compound (v).

Further, a feature of the catalyst of the present invention is that the catalyst activity is extremely high. It is also possible to exert a catalytic activity that is about twice that of a conventionally known catalyst.

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

Component (A) Component (A) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (v). Here, "obtaining by contacting" does not mean that the target is only the ones listed (that is, the components (i) to (v)), but the coexistence of other purposeful components. Do not exclude

Component (i) Component (i) is a solid component containing tetravalent titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that other than the three listed components may contain a purposeful other element,
It is indicated that each of these elements may exist as any purposeful compound, and that these elements may exist as bonded to each other.

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,
54-131589, 55-75411, 55-90510, 55
-90511, 55-127405, 55-147507, 55-1
55003, 56-18609, 56-70005, 56-72001
No. 56-86905, No. 56-90807, No. 56-155206,
57-3803, 57-34103, 57-92007, 57-
121003, 58-5309, 58-5310, 585311
No. 58-8706, 58-27732, 58-32064,
58-32605, 58-67703, 58-117206, 58-
127708, 58-183708, 58-183709, 59-14
Those described in Japanese Patent Nos. 9905 and 59-149906 are used.

Examples of the magnesium compound used as the magnesium source in the present invention include magnesium halide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Among these magnesium compounds, magnesium halide is preferable.

In addition, the titanium compound serving as the titanium source has the general formula Ti (OR
⁵ ) _4-n X _n (wherein R ⁵ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents halogen,
n represents a number of 0 ≦ n ≦ 4. ). Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC
₂ H ₅ ) Cl ₃ , Ti (OC 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 (O-C 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 (O
_{C 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 , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] _{4 and the} like.

Further, it is also possible to use a molecular compound obtained by reacting TiX ' ₄ (here, X'represents halogen) with an electron donor described later. 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, 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 is 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.

Solid components used in the present invention include SiCl in addition to the above essential components.
_4, CH ₃ SiCl _3, silicon compounds such as methylhydrodiene _{polysiloxane, Al (OiC 3 H 7)} 3, AlCl 3, AlBr 3, Al
Aluminum compounds such as (OC ₂ H ₅ ) ₃ and Al (OCH ₃ ) ₂ Cl;
It is also possible to use other components such as boron compounds such as B (OC ₆ H ₅ ) ₃ , and these may remain in the solid components 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 in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acids. Examples thereof include oxygen-containing electron donors such as anhydrides, 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, cresols, xylenols, ethylphenols, propylphenols, cumylphenols, nonylphenols, naphthols, and other alkyl groups having 6 to 25 carbon atoms, (c) Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other C3 to C15 ketones, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphtholaldehyde and other C2 to C15 aldehydes Kind, (e)
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, toluyl Ethyl acid, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
C2-C20 such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate
Organic acid esters, (f) ethyl silicate, butyl silicate, inorganic acid esters such as silicic acid esters such as phenyltriethoxysilane, (to) acetyl chloride,
Benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isochlorophthaloyl and other acid halides having 2 to 15 carbon atoms, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, C2-C20 ethers such as diphenyl ether, acetic acid amides such as (li) acetic acid amide, benzoic acid amide and toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenz Examples thereof include amines such as ruamine, aniline, pyridine, picoline, and tetramethylethylenediamine, nitriles such as (l) acetonitrile, benzonitrile, and trinitrile. Two or more of these electron donors can be used. Of these, organic acid esters and acid halides are preferable, and phthalic acid esters and phthalic acid halides are particularly preferable.

The amount of each component used may be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The titanium compound may be used in a molar ratio of 1 × 10 ^{−4 to} 1000, preferably 0.01 to 10 with respect to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the molar amount of the compound is 1 × 10 ⁻ with respect to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{2 to} 1000, and more preferably in the range of 0.1 to 100. The amount of silicon, aluminum, and boron compounds used is 1 × 10 6 in molar ratio with respect to the amount of magnesium compound used above.
^It is preferably in the range of ^{-3 to} 100, and more preferably in the range of 0.01 to 1.

The amount of the electron-donating compound used is preferably in the range of 1 × 10 ⁻³ to 10 with respect to the amount of the above-mentioned magnesium compound used, and more preferably in the range of 0.01 to 5.

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

(A) A method in which a magnesium halide is optionally contacted with an electron donor and a titanium-containing compound.

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

(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, those represented by the following formula are suitable.

(Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, and n is the degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Of these, methylhydrogen Enpolysiloxane, 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 titanium tetraalkoxide and an electron donor, and a titanium compound is brought into contact with a solid component precipitated by a halogenating agent or a titanium halogen 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, etc., and then an electron donor and a titanium compound are brought into contact therewith as necessary.

(F) A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxymagnesium 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 component obtained by prepolymerizing the solid component by contacting it with olefins in the presence of an organoaluminum compound. Can also be used as

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. 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 prepolymerization, those generally known can be used.

As a specific example, 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 are preferable.
₄ H ₉ ) ₃ . 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.

Specific examples are: Al (C ₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) ₂ Cl combined, Al (iC ₄ H ₉ ) ₃ and Al (iC ₄ H ₉ ) ₂ Cl combined, Al ( C
₂ H ₅ ) ₃ and Al (C ₂ H ₅ ) _1.5 Cl _1.5 combined, Al (C ₂ H ₅ ) ₃ and A
One example is the combined use of l (C ₂ H ₅ ) ₂ Cl and Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ).

The amount of the organoaluminum component used during the prepolymerization is 1 / Al (molar ratio) with respect to the Ti component in the solid component (A).
-20, preferably 2-10. In addition to these, known electron donors such as alcohols, esters and ketones can 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.

Ingredient (ii) Ingredient (ii) used to produce ingredient (A) is
General formula (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). It is preferable that R ¹ and R ² are each a hydrocarbon residue of about 1 to 20, preferably 1 to 10. X is preferably chlorine, at least for economic reasons.

Specific examples include (CH ₃ ) Si (OCH ₃ ) ₃ and (CH ₃ ) Si.
_{(OC 2 H 5) 3,} (C 2 H 5) 2 Si (OCH 3) 2, (n-C 6 H 11) S
_{i (OCH 3) 3, (} C 2 H 5) Si (OC 2 H 5) 3, (n-C 10 H 21)
_{Si (OC 2 H 5) 3} , (CH 2 = CH) Si (OCH 3), Cl (CH 2) 3 Si
_{(OCH 3) 3, Si (} OCH 3) 4, Si (OC 2 H 5) 3 Cl, (C 2 H 5)
₂ Si (OC ₂ H ₅ ) ₂ , (C ₁₇ H ₃₅ ) Si (OCH ₃ ) ₃ , Si (OC
₂ H ₅ ) ₄ , (C ₆ H ₅ ) Si (OCH ₃ ) ₃ , Si (OCH ₃ ) ₂ Cl ₂ , (C
_{6 H 5) 2 Si (OCH} 3) 2, (C 6 H 5) (CH 3) Si (OCH 3) 2,
_{(C 6 H 5) Si (} OC 2 H 5) 3, (C 6 H 5) 2 Si (OC 2 H 5) 2, NC
_{(CH 2) 2 Si (OC} 2 H 5) 3, (C 6 H 5) (CH 3) Si (OC 2 H 5)
_{2, (n-C 3 H} 7) Si (OC 2 H 5) 3, (CH 3) Si (OC 3 H 7)
_{3, (C 6 H 5)} (CH 2) Si (OC 2 H 5) 3, 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 is a branched chain hydrocarbon residue having a secondary or tertiary carbon atom at the α-position of R ¹ and a carbon number of 3 to 20, particularly R ¹
Is a silicon compound having a tertiary carbon atom and a branched hydrocarbon residue having 4 to 10 carbon atoms.

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

Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti
_{(OC 2 H 5) 2 Cl} 2, Ti (OC 2 H 5) 3 Cl, Ti (O-iC 3 H 7) C
_{l 3, Ti (O-nC} 4 H 9) Cl 3, Ti (O-nC 4 H 9) 2 Cl 2, Ti (O
C 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} (O-C 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 , and the like.

Of these, preferred are TiCl ₄ , Ti (OC ₂ H ₅ ) Cl
₃ , Ti (OC ₄ H ₉ ) Cl ₃ , etc.

Ingredient (iv) Ingredient (iv) used to produce ingredient (A) is
General formula (Wherein R ⁶ is a hydrocarbon residue, X is a halogen or alkoxide group, and p is a number satisfying 0 ≦ p <2).

Specific examples include (CH ₃ ) ₂ Zn, (C ₂ H ₅ ) ₂ Zn, (iC
_{4 H 9) 2 Zn, (} nC 8 H 17) 2 Zn, (C 2 H 5) ZnCl, (nC
₄ H ₉ ) ZnCl, (CH ₃ ) Zn (OC ₂ H ₅ ), (C ₂ H ₅ ) Zn (OC
H ₃ ), etc.

Ingredient (v) Ingredient (v) used to produce ingredient (A) is
formula It is a polymer silicon compound having a structure represented by.

Here, R ⁴ is a hydrocarbon residue having about 1 to 10 carbon atoms, particularly about 1 to 6 carbon atoms. The polymerization degree of the polymer silicon compound is preferably such that the viscosity is about 1 to 100 centistokes.

Specific examples of the polymer silicon compound having such a structural unit include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, cyclohexylhydropolysiloxane, 1,1,3,3-
Examples thereof include tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane.

Production of Component (A) The contact conditions of the above-mentioned components (i) to (iii) may be arbitrary as long as the effect of the present invention is recognized,
Generally, the following conditions are preferred. Contact temperature is -50 to
The temperature is about 200 ° C, preferably 0 to 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 and pulverizing machine, and a method of contacting 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 (v) 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.

(A) Component (i) + {Component (ii) + Component (iii) + Component (iv) + Component (v)} (b) Component (i) + {Component (ii) + Component (iv) + Component ( v)} + component (iii) (c) component (i) + {component (iii) + component (iv) + component (v)} + component (ii) (d) component (i) + component (iii) + {Component (iv) + component (v) + component (ii)} (e) component (i) + component (v) + component (iv) + component (ii) + component (iii) (f) component (i) + Component (ii) + component (iv) + component (v) + component (iii) (g) component (i) + component (iv) + component (v) + component (iii) + component (ii) (ch) {Component (iii) + component (ii) + component (iv) + component (v)} + component (i) (i) component (i) + {component (ii) + component (iv) + component (v) + Component (iii)} + {component (ii) + component (iv) +
Component (v) + component (iii)} The component (i) to component (v) may be in any ratio as long as the effects of the present invention are observed, but generally, the following range is preferred. . The amount ratio of the component (i) and the component (ii) is such that the component (i) with respect to the titanium component constituting the component (i) is
i) The atomic ratio of silicon (silicon / titanium) is 0.01 to 1000
Is preferably in the range of 0.1 to 100, and more preferably in the range of 0.1 to 100.

The amount of component (iii) used is 0.01 to 1 in terms of atomic ratio of titanium of component (iii) to titanium component constituting component (i) (titanium (component (iii)) / {titanium (component (i))}.
A range of 00 is preferable, and a range of 0.1 to 20 is preferable. The amount of the component (iv) used is such that the atomic ratio of the organic zinc of the component (iv) to the titanium component constituting the component (i) (zinc /
Titanium) is preferably in the range of 0.01-100, preferably 0.1-
Within the range of 30. The amount of the component (v) used is the same as that of the component (i).
The atomic ratio (silicon / titanium) of the polymer silicon compound of component (v) with respect to the titanium component of (1) is in the range of 0.1 to 1000, preferably in the range of 1 to 100.

Component (B) Component (B) is an organoaluminum compound. As a specific example, Or (Here, R ⁷ and R ⁸ may be the same or different and have 1 carbon atom.
To about 20 hydrocarbon residues or hydrogen atoms, R ⁹ is a hydrocarbon residue, X is halogen, and n and m are each 0 ≦ n ≦
3, 0 <m <3. ). Specifically, (a) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum,
Trialkyl aluminums such as tridecyl aluminum, (b) diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, and other alkyl aluminum halides, (c) diethyl aluminum hydride, diisobutyl aluminum hydride, ( D) Aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as (Here, 1 ≦ a ≦ 3, R ¹⁰ and R ¹¹ are the same or different hydrocarbon residues having about 1 to 20 carbon atoms.)
It is also possible to use an alkylaluminum alkoxide represented by For example, combined use of triethyl aluminum and diethyl aluminum ethoxide, combined use of diethyl aluminum monochloride and diethyl aluminum ethoxide, combined use of ethyl aluminum dichloride and ethyl aluminum diethoxide, triethyl aluminum and diethyl aluminum ethoxide and diethyl aluminum chloride Can be used in combination.

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

[Use of catalyst / polymerization]

The catalyst of the present invention is, of course, applied to ordinary slurry polymerization, but is also applied to liquid phase solventless polymerization, solution polymerization, or gas phase polymerization method which uses substantially no solvent.
Further, it is also applied to a system in which continuous polymerization, batch polymerization or preliminary polymerization is carried out. The polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane,
Saturated aliphatic or aromatic hydrocarbons such as benzene and toluene may be used alone or as a mixture. The polymerization temperature is from room temperature to about 200 ° C., preferably 50 to 100 ° C., particularly 60 to 90 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time. 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 (where R is a hydrogen atom, or 1 to 10 carbon atoms)
Hydrocarbon residue of, and may have a branching group. ). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Ethylene and propylene are preferred. 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, diolefin, etc.) can also be performed.

Examples Example 1 [Production of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then MgCl ₂ was added.
0.4 _{mole, Ti (O-nC 4 H} 9) 4 was 0.8 mol introduced and reacted for 2 hours at 95 ° C.. 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 and introduce into flask at 70 ° C for 30 minutes.
The reaction was carried out at 0 ° C for 1 hour.

After the completion of the reaction, the resultant was washed with n-heptane. Then SiCl ₄ 2
After introducing 0 milliliter, the reaction was carried out at 80 ° C. for 6 hours. After completion of the reaction, it was thoroughly washed with n-heptane. The titanium content of this product was 1.21 weight percent.

50 milliliters of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then (CH ₃ ) ₃ as a silicon compound of the component (ii) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was introduced in 0.80 milliliter, then component (iii) TiCl ₄ 0.52 milliliter was introduced, and 0.5 g of diethyl zinc of component (iv),
Finally, 0.5 g of methylhydrogen polysiloxane was introduced and contacted at 30 ° C. for 2 hours. After contact, n
-Washed thoroughly with heptane to give component (A).

[Polymerization of propylene]

In a 1.5 liter stainless steel autoclave with agitation 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, and the temperature was increased and the pressure was increased. 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, 193.8 grams of polymer was obtained. One broth yielded 0.67 grams of polymer. All products II (hereinafter abbreviated as T-II) from boiling heptane extraction test
Was 99.0 weight percent. The MFR was 1.3 g / 10 min, and the bulk density of the polymer was 0.48 g / cc.

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

50 milliliters of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the component (i) obtained above was introduced, and then TiCl ₄ of the component (iii) was introduced.
0.40 milliliter was introduced and contact was performed at 100 ° C for 2 hours.
After the contact, the (CH ₃ ) ₃ CSi (CH ₃ ) OCH ₃ ) _{2 of} component (ii)
0.36 milliliter and component (iv) of diethyl zinc 0.
Introduced were 75 g and 1.0 g of methylhydrogenpolysiloxane, and they were contacted at 35 ° C. for 1 hour. After contact is over,
It was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Polymerization was carried out under the same conditions as in Example 1, except that the component (A) obtained above was used in the polymerization of propylene of Example 1 and the amount of triethylaluminum used as the component (B) was 125 mg. Natsuta.

As a result, 191.4 g of polymer was obtained, and T-II
= 99.0 weight percent, MFR = 1.7 g / 10 min, polymer bulk specific gravity = 0.48 g / cc.

Example 3 [Production of Component (A)] A fully dried and nitrogen-substituted 0.4 liter ball mill was filled with 40 12 mmφ stainless steel balls, and 20 g of MgCl ₂ and 12.4 milliliter of diethyl phthalate were introduced into this. Then, it was crushed by a rotary ball mill for 48 hours. After the completion of the pulverization, the mixed pulverized composition was taken out of the mill in a dry box. Then, 8.1 g of the ground composition was introduced into a flask that had been sufficiently replaced with nitrogen, 25 milliliters of n-heptane and 25 milliliters of TiCl ₄ were introduced, and the mixture was reacted at 100 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane. When a part of the obtained solid component [component (i)] was taken out and subjected to composition analysis, the Ti content was 3.43% by weight.

Next, 50 milliliters of sufficiently purified n-heptane was introduced into a flask which had been sufficiently replaced with nitrogen, and 5 g of the component (i) obtained above, and then 2.1 g of dimethyldimethoxysilane of the component (ii) were introduced. , Then ingredient (iii)
0.2 g of Ti (OC ₄ H ₉ ) Cl ₃ is introduced, 0.8 g of diisobutylzinc of component (iv) and 2.2 g of methylhydrogenpolysiloxane of component (v) are finally introduced, and 1
Contact was performed at 5 ° C for 2 hours. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1 except that the component (A) obtained above was used. As a result, 6
4.8 grams of polymer were obtained, T-II = 96.3 weight percent, MFR = 8.8 g / 10 min, polymer bulk specific gravity = 0.43 g / cc
It was.

Example 4 [Production of component (A)] 100 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced 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 the reaction, lower the temperature to 35 ° C and
15 milliliters of 3,5,7-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, 0.06 mol of SiCl ₄ was introduced at 20 ° C. for 30 minutes, and reacted at 50 ° C. for 3 hours. After completion of the reaction, it 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 (CH ₃ ) ₃ CSi (C
H ₃₎ (OCH _{3) 2} in place _{(CH 3) 3 CSi (CH} 3) (OC
Contact was performed under the same conditions as in Example 1 except that ₂ H ₅ ) ₂ 1.7 milliliter was used. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A).

[Polymerization of propylene]

Component (A) obtained above under the polymerization conditions of Example 1
The polymerization of propylene was carried out in the same manner as in Example 1 except that the amount of the component (A) was changed to 15 mg and the polymerization temperature was changed to 70 ° C.

The result was 82.2 grams of polymer, MFR = 8.7
g / 10 minutes, T-II = 96.9 weight percent, polymer bulk specific gravity = 0.47 g / cc.

Example 5 Component (A) was produced under the same conditions as in Example 1 except that ethyl benzoate was used instead of phthaloyl chloride in the production of component (A) of Example 1. Using this component (A), propylene was polymerized in the same manner as in Example 1.

The result was 61.4 grams of polymer, MFR = 6.8
g / 10 minutes, T-II = 93.9 weight percent, polymer bulk specific gravity = 0.43 g / cc.

Examples 6 to 10 In the same manner as in Example 1, except that the amounts and types of the components (ii) and (v) used in the production of the component (A) in Example 1 were changed to the compounds shown in Table 1. Polymerization of propylene was also carried out in the same manner as in Example 1 except that (A) was produced and the resulting component (A) was used. The results are shown in Table-2.

Example 11 [Production of component (A)] Component (i) was produced in the same manner as in Example 1.

50 milliliters of sufficiently purified n-heptane was introduced into a flask thoroughly replaced 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). (CH ₃ ) (OCH ₃ ) ₂ 0.30 milliliter, component (iii) TiCl ₄ 0.24 milliliter, component (iv) diethyl zinc 0.4 g, component (v) methylhydrogen polysiloxane 1.0 g were introduced, 30
Contact was carried out at 0 ° C for 1 hour. After the contact was completed, it was thoroughly washed with n-heptane. Then, the same amount of components (ii) to (v) as above
Was used to carry out the same contact as above, and was washed in the same manner as above to obtain the component (A).

[Polymerization of propylene]

Component (A) obtained above under the polymerization conditions of Example 1
Example 1 was repeated except that the polymerization temperature was changed to 80 ° C.
Polymerization was carried out under the same conditions as described above.

As a result, 201.4 g of the polymer was obtained, and T-II
= 99.1 weight percent, MFR = 1.3 g / 10 min, polymer bulk specific gravity = 0.48 g / cc.

Example 12 [Production of component (A)] 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 ℃,
Propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the completion of the polymerization, it was thoroughly 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 sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the above component (i) was introduced, and then 0.6 g of diethylzinc of the component (iv) and methyl of the component (v). 0.7 grams of hydrogen polysiloxane was contacted for 1 hour at 30 ° C. Then (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) _{2 of} component (ii)
0.3 milliliter was introduced and contacted at 40 ° C. for 1 hour.
Then, 0.35 milliliter of component (iii) TiCl ₄ was introduced,
Contact was carried out 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]

Component (A) obtained above under the polymerization conditions of Example 1
Example 1 except that the polymerization temperature was changed to 85 ° C.
Polymerization was carried out under the same conditions as described above.

As a result, 177.4 g of a polymer was obtained, and T-II was obtained.
= 99.3 weight percent, MFR = 1.4 g / 10 min, polymer bulk specific gravity = 0.45 g / cc.

Examples 13 to 14 Each of the components (A) prepared in Examples 1 and 11 was used for polymerization for 6 hours. However, as the polymerization conditions, the polymerization was carried out under the same conditions as in Example 1 except that the amount of triethylaluminum used as the component (B) was changed to 80 mg and the amount of the component (A) used was changed to 8 mg. . The results are shown in Table-3.

Comparative Example 1 In the production of the component (A) of Example 1, the component (iii)
The component (A) was produced in the same manner as in Example 1 except that TiCl _{4 of} Example 1 and the methylhydrogenpolysiloxane of the component (v) were not used. This component (A) was used, and propylene was polymerized in exactly the same manner.

As a result, 134.5 g of the polymer was obtained, and T-II
= 98.3 weight percent, MFR = 2.9 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. The results are shown in Table-3.

[Brief description of drawings]

FIG. 1 is intended to help the understanding of the technical content of the present invention regarding the Ziegler catalyst.

Claims (1)

(57) [Claims] 1. An olefin polymerization catalyst comprising the following components (A) and (B). Component (A): Solid catalyst component obtained by contacting the following components (i) to (v), Component (i): 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 (wherein R ¹ and R ² are hydrocarbon residues, X is halogen, and m and n are each 0 ≦ m ≦ 3. And 0 ≦
A silicon compound represented by n ≦ 3 and 0 ≦ m + n ≦ 3, component (iii): general formula, Ti (OR ³ ) _4-1 X ₁ (wherein R ³ is a hydrocarbon residue) And X is halogen, and 1 is 0 <1 ≦ 4), a titanium compound represented by the following formula: component (iv): organozinc compound, component (v): general formula, (Provided that R ⁴ is a hydrocarbon residue), a component (B) an organoaluminum compound.