JPH07666B2 - α-olefin polymerization method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a catalyst for polymerization of α-olefin. More specifically, the present invention is
Further, the present invention relates to an α-olefin polymerization catalyst suitable for efficiently producing an α-olefin polymer having excellent particle characteristics and high stereoregularity even in a long-term polymerization.

(Prior Art) Conventionally, as a catalyst for stereoregular polymerization of an olefin, for example, a combination of a titanium halide and an organoaluminum compound such as triethylaluminum or diethylaluminum chloride is industrially used. well known. Also, as a highly active and highly stereoregular polymerization catalyst, many catalyst systems have been proposed which are composed of a solid component composed of an inorganic or organic magnesium compound, titanium halide and a carboxylic acid ester, triethylaluminum and an electron donor. The inventors of the present invention have previously described Japanese Patent Publication Sho 57
-9567, 60-11924, 62-5925, JP-A-58-104903 and the like, a halogen-containing magnesium solid obtained by reacting an organomagnesium component with a chlorosilane compound containing a Si-H bond. We have proposed a catalyst system consisting of a halogen compound of titanium, an aromatic carboxylic acid ester, and an organoaluminum compound, and found that a polymer having high activity and high stereoregularity can be obtained.

Furthermore, the solid component obtained by reacting and / or pulverizing the halogen-containing magnesium solid with a titanium halide or carboxylic acid ester, or by further treating with a tetravalent titanium compound, and an alkoxysilane and an organoaluminum compound are obtained. It has been found that the catalyst has less tendency for the activity of the catalyst to decay over time in the polymerization. (Refer to JP-B-60-11924) (Problems to be Solved by the Invention) The present invention relates to an improvement of the catalyst for polymerization of α-olefin proposed in JP-B-60-11924. The catalyst synthesized by using the above-mentioned prior art previously proposed by the present inventors has already been able to produce a polymer having sufficiently high activity and stereoregularity, however, in recent years, the activity has been further increased. The development of catalysts with high stereoregularity is desired, and it is required to have high activity and high stereoregularity even in polymerization at higher temperatures, especially for improvement of heat removal efficiency of polymerization and application to gas phase polymerization process. Has been done. In addition, there is a need to develop a catalyst that does not decrease in activity with the passage of polymerization time because it is applied to so-called block polymerization, which has a relatively long residence time in the polymerization machine.

In response to these requirements, the above-mentioned catalysts of the prior art are insufficient in terms of particle characteristics, stereoregularity of polymer powder in high temperature polymerization (for example, 75 ° C. or higher in propylene polymerization), and activity maintenance in long-term polymerization. There was a problem.

(Means for Solving Problems) As a result of diligent studies on these points, the present inventors have made a magnesium-containing solid by reacting an organomagnesium component containing an alkoxy group with a chlorosilane compound having an H—Si bond. The solid component obtained by contacting this solid with a titanium halide and / or an aromatic carboxylic acid ester in the presence of a chlorinated hydrocarbon solvent, or further treated with a titanium halide. By using a catalyst system consisting of the solid component obtained in this way, an organoaluminum compound and an alkoxysilane, it has excellent particle characteristics even at higher polymerization temperatures and even for a longer period of time, and has a high stereoregularity. The present invention has been achieved by finding that a coalesce can be efficiently produced.

That is, the present invention provides (A), (i), (i) the general formula (M) α (Mg) β (R ¹ ) _p (R ² ) _q (OR ³ ) _r (where M is the periodic table I Metal atoms belonging to Group ¹ to Group II, R ¹ , R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms, and α, β, p, q and r are numbers satisfying the following relationships.

Organomagnesium component soluble in a hydrocarbon solvent represented by 0 ≦ α, 0 <β, 0 ≦ p, 0 ≦ q 0 <r / (α + β) ≦ 1.0 kα + 2β = p + q + r (where k is a valence of M) (Ii) General formula H _a SiCl _b R ⁴ _{4- (a + b)} (wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and a and b
Is a number that satisfies the following relationship.

The solid component obtained by reacting with a chlorosilane compound having a Si—H bond represented by 0 <a, 0 <b, a + b ≦ 4) is (b) a general formula Ti (OR ⁵ ) _m D _4-m (formula In the formula, R ⁵ is a hydrocarbon group having 2 to 10 carbon atoms, D is a halogen atom, and m is a number satisfying the relationship of 0 ≦ m <4. A solid catalyst component obtained by contacting in the presence of a chlorinated hydrocarbon solvent, or a solid catalyst component further treated with the component (b), (B) a general formula AlR ⁶ _n Z _3-n (wherein R ⁶ Is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom,
Halogen atom, hydrocarbyloxy group or siloxy group, n is a number satisfying the relation of 0 <n ≦ 3) (C) General formula R ⁷ _s Si (OR ⁸ ) _4-s (wherein R ⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms, and s is 0 ≦ s
<A number satisfying the relation of 4), wherein the catalyst comprises (A), (B) and (C) is used.

The present invention will be described in detail below.

The general formula (M) α (Mg) β (R ¹ ) _p (R ² ) _q (OR ³ ) _r (wherein α, β,
The organomagnesium component (i) of p, q, r, M, R ¹ , R ² and R ³ has the above-mentioned meanings.

Relational expression of symbols α, β, p, q, r p + q + r = mα + 2
β indicates the stoichiometry of the valence of the metal atom and the substituent.

This compound is an organomagnesium complex compound containing an alkoxy group soluble in a hydrocarbon solvent, and an organomagnesium complex compound soluble in a hydrocarbon solvent and an alcohol having a hydrocarbon group represented by R ³ above. Can be prepared by a method of reacting with or a method of mixing an organomagnesium complex compound soluble in a hydrocarbon solvent and a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ³ which is soluble in a hydrocarbon solvent. .

The organic magnesium complex compound soluble in the hydrocarbon solvent used here will be described.

The hydrocarbon group represented by R ¹ to R ² in the organomagnesium complex compound soluble in the hydrocarbon solvent represented by the general formula (M) α (Mg) β (R ¹ ) _p (R ² ) _q is an alkyl group. A group, a cycloalkyl group or an allyl group, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, decyl,
Examples thereof include cyclohexyl and phenyl groups, and preferably
R ¹ is an alkyl group.

When α> 0, a metal element belonging to Group I to Group III of the periodic table can be used as the metal atom M.
Lithium, sodium, potassium, beryllium, zinc,
Examples thereof include boron and aluminum, with aluminum and zinc being particularly preferable.

The ratio β / α of magnesium to the metal atom M can be set arbitrarily, but is preferably in the range of 0.1 to 30, particularly preferably 1 to 20.

The relationship between the symbols α, β, p, and q is represented by the formula p + q = kα + 2β, which indicates the stoichiometry between the valence of the metal atom and the substituent.

These organomagnesium compounds or organomagnesium complexes are represented by the general formula: R ¹ ₂ Mg (R ¹ is as defined above)
And an organometallic compound represented by the general formula, MR ² _k or MR ² _k-1 H (M, R ² and k have the above-mentioned meanings), hexane, heptane and cyclohexane. It can be obtained by reacting at room temperature to 150 ° C. in an inert hydrocarbon medium such as benzene, toluene.

Further, when a certain organomagnesium compound with α = 0 is used, for example, when R ¹ is sec-butyl or the like and R ³ is an alkyl group having a side chain at the 2 position, it is soluble in a hydrocarbon solvent. And such compounds also give favorable results when used in the present invention.

The general formula (M) α (Mg) β (R ¹ ) _p (R ² ) _q (O
In R ³ ) _r , the relationship between R ¹ and R ² when α = 0 and OR ³ which is an alkoxy group are shown below.

First, regarding the relationship between R ¹ and R ² when α = 0, it is recommended that the relationship be one of the following three groups (1), (2), and (3).

(1) At least one of R ¹ and R ² is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably
Both R ¹ and R ² have 4 to 6 carbon atoms, and at least one of them is a secondary or tertiary alkyl group.

(2) R ¹ and R ² are alkyl groups having different carbon atoms, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ² is an alkyl group having 4 or more carbon atoms. Be a base.

(3) At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, and preferably both R ¹ and R ² are alkyl groups having 6 or more carbon atoms.

Hereinafter, these groups will be specifically shown. In (1), as the secondary or tertiary alkyl group having 4 to 6 carbon atoms, sec-butyl, tert-butyl, 2-methylbutyl, 2
-Ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl, etc. are used, and se
c-Butyl is particularly preferred.

Next, in (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group and a propyl group, and the ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group and an octyl group, and a butyl group and a hexyl group are particularly preferable.
Examples of the alkyl group having 6 or more carbon atoms in (3) include a hexyl group, an octyl group, a decyl group, a phenyl group, and the like. An alkyl group is preferable, and a hexyl group is particularly preferable.

Generally, increasing the number of carbon atoms of the alkyl group makes it easier to dissolve in a hydrocarbon solvent, but the viscosity of the solution tends to increase,
It is not preferable in terms of handling to use an alkyl group having a longer chain than necessary.

Next, the alkoxy group (OR ³ ) contained in the organomagnesium component used in the present invention will be described.

The hydrocarbon group represented by R ³ is preferably an alkyl group having 3 to 10 carbon atoms or an allyl group. Specifically, for example, n-propyl, n-butyl, sec-propyl, s
Examples include ec-butyl, tert-butyl, amino, 2-methylpentyl, 2-ethylhexyl, octyl, decyl and phenyl groups.

For the reaction of a hydrocarbon-soluble organomagnesium component with an alcohol, the reaction is carried out by an inert reaction medium, for example, hexane, an aliphatic hydrocarbon such as heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, cyclohexane, It can be carried out in an aliphatic hydrocarbon such as methylcyclohexane or a mixed solvent thereof. Regarding the reaction sequence, either a method of adding an alcohol to the organomagnesium component, a method of adding the organomagnesium component to the alcohol, or a method of adding both of them at the same time can be used.

The reaction ratio between the hydrocarbon-soluble organomagnesium component and the alcohol is not particularly limited as long as it remains in the hydrocarbon solvent after the reaction.

Next, (ii) the general formula H _a SiCl _b R ⁴ _{4- (a + b)} (wherein a, b,
The H-Si bond-containing chlorosilane compound represented by R ⁴ is as described above).

The hydrocarbon group represented by R ⁴ in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, Examples thereof include cyclohexyl and phenyl groups, preferably alkyl groups having 1 to 10 carbon atoms, and lower alkyl groups such as methyl, ethyl and propyl are particularly preferred. Further, a and b are numbers larger than 0 that satisfy the relationship of a + b ≦ 4, and particularly, b is preferably 2 or 3.

These compounds include HSiCl ₃ , HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl _2n -C ₃ H ₇ , HSiCl _2iso -C ₃ H ₇ , HSiCl _2n -C ₄ H ₉ , HSiCl ₂ C ₆ H. ₅ , HSiCl ₂ (4-Cl-C ₆ H ₄ ), HSiCl ₂ CH = CH ₂ , HSiCl ₂ CH ₂ C ₆ H ₅ , HSiCl ₂ (1-C ₁₀ H ₇ ), HSiCl ₂ CH ₂ CH = CH ₂ , H ₂ SiClCH ₃ , H ₂ SiClC ₂ H ₅ , HSiCl (CH ₃ ) ₂ , HSiCl (C ₂ H ₅ ) ₂ , HSiClCH ₃ (iso-C ₃ H ₇ ), HSiClCH ₃ (C ₆ H ₅ ), HSiCl (C ₆ H ₅ ) _{2 and the} like, and a chlorosilane compound composed of a mixture of these compounds and a compound selected from these compounds is used, and trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichloro are used. Silane and the like are preferable, and trichlorosilane and monomethyldichlorosilane are particularly preferable.

Next, an organomagnesium component (i) soluble in a hydrocarbon solvent
The reaction between the chlorosilane compound and the chlorosilane compound (ii) will be described.

In the reaction, a chlorosilane compound is previously added to an inert reaction medium such as an aliphatic hydrocarbon such as n-hexane and n-heptane, an aromatic hydrocarbon such as benzene, toluene and xylene, and an alicyclic carbon such as cyclohexane and methylcyclohexane. Hydrogen, or chlorinated hydrocarbon such as 1,2-dichloroethane, o-dichlorobenzene, dichloromethane,
Alternatively, it is preferable to use after diluting with these mixed media. The reaction temperature is not particularly limited, but is preferably in the range of 40 ° C. or higher and lower than the boiling point of the reaction medium in order to accelerate the reaction.

The ratio of both components in the reaction is 0.01 to 100 mol, particularly preferably 0.1 to 10 mol of the chlorosilane compound to 1 mol of the organomagnesium compound (based on magnesium).
A molar range is preferred.

The solid component obtained by the above reaction is separated by filtration or decantation method, and then thoroughly washed with an inert solvent such as n-hexane or n-heptane to remove unreacted substances or by-products. It is preferable. Further, it is possible to employ a method in which after washing once or more with a chlorinated hydrocarbon solvent, sufficient washing with an inert solvent such as hexane is carried out.

Next, the titanium compound represented by the general formula Ti (OR ⁵ ) _m D _4-m (wherein R ⁵ and m have the above-mentioned meanings) will be described.

The hydrocarbon group represented by R ⁵ in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group,
Examples thereof include ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl and phenyl groups, with an alkyl group being particularly preferred. Specific examples include, for example, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium chloride, and the like. Particularly preferred is titanium tetrachloride.

The aromatic carboxylic acid ester used in the present invention is preferably an aromatic carboxylic acid monoester or diester. As a preferred specific example, for example, methyl of a monocarboxylic acid such as benzoic acid, P-toluic acid or P-anisic acid,
Esters such as ethyl, propyl and butyl, and dimethyl phthalate, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-iso-butyl, di-n-heptyl,
Examples thereof include dicarboxylic acid diesters such as di2-ethylhexyl and dioctyl. Further, these aromatic carboxylic acid esters may be used alone or in combination.

The solid component (a) used for preparing the solid catalyst component (A) in the present invention may be contacted with the titanium compound (b) and the aromatic carboxylic acid ester (c) as follows.
(I) A method of simultaneously contacting (a), (b), and (c), (II) First, after contacting (a) and (b),
Method of contacting (C), (III) In advance (A) and (C)
And (IV), and (IV)
Although any of the methods of contacting (b) and (c) and then contacting (a) can be used, it is a feature of the present invention that a chlorinated hydrocarbon solvent is allowed to coexist at that time. Is one.

In particular, it is preferable to coexist in the final step of each contacting method.

Preferred contact methods are (I), (II) and (III)
And the method (I) is particularly preferable.
Further, as the contact means, any means such as a method of contacting with the solid component (a) in the liquid phase or the gas phase, a combination of contact in the liquid phase or the gas phase and pulverization to contact the solid component (a), etc. Can also be used.

The effect of the present invention can be further increased by further treating the solid catalyst component prepared by any of the above methods with the titanium compound (b).

Next, the preferable methods (I), (II) and (III) described above will be specifically described.

A method for simultaneously contacting (I) the solid component (a) with the titanium compound (b) and the aromatic carboxylic acid ester (c) will be described.

Examples of chlorinated hydrocarbons coexisting as a reaction medium include dichloromethane, 1,2-dichloroethane, n-butyl chloride, n-amyl chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethylene, 1,1,2,2-
Tetrachloroethane, 1,2-dichlorobenzene and the like can be mentioned, or a mixed medium thereof can be used, but among them, 1,2-dichloroethane, n-butyl chloride and 1,2-dichlorobenzene are preferable.

The temperature at the time of contact and the concentration of the titanium compound are not particularly limited, but coexistence of a chlorinated hydrocarbon, which is one of the features of the present invention, is essential, and its upper limit is naturally restricted by the amount of the reaction medium used. However, in order to accelerate the reaction at the time of contact, it is preferable that the temperature is 80 ° C. or higher and the titanium compound concentration is 2 mol / liter or higher.

Further, the amount of the reaction medium used is preferably in the range of 0.1 to 2.0, particularly preferably in the range of 0.2 to 1.0, when expressed by the volume ratio to the titanium compound.

The ratio of the titanium compound and the aromatic carboxylic acid ester to the solid component (a) at the time of contact is not particularly limited, but preferably 1 mol of the titanium compound is used per 1 mol of magnesium contained in the solid component (a). ~ 100
Moles, particularly preferably in the range of 5 to 50 moles, for aromatic carboxylic acid esters 0.01 to 1.0 moles,
Particularly preferably, the range of 0.05 mol to 0.3 mol is recommended.

It is also possible to carry out the contact with the above-mentioned solid component (a) by using pulverization. As the crushing method, a known mechanical crushing means such as a rotary ball mill, a vibrating ball mill, an impact ball mill or the like can be adopted. Grinding time is 0.5-100
Time, preferably 1 to 30 hours, crushing temperature 0 to 20
It is in the range of 0 ° C, preferably 10 to 150 ° C.

(II) First, a method of bringing the solid component (a) into contact with the titanium compound (ii) and then bringing into contact with the aromatic carboxylic acid ester (iii) will be described.

As the method for bringing the solid component (a) and the titanium compound (b) into contact with each other, the same method as the above-mentioned method (I) can be used, but here, the titanium compound itself is used without using an inert medium. One of the preferred methods is to bring them into contact with each other as a medium.

Regarding the ratio of the titanium compound (c) to the solid component (a), 1 mol to 100 mol of the titanium compound to 1 mol of magnesium contained in the solid component (a),
It is particularly preferably in the range of 5 to 50 mol. The contact temperature is not particularly limited, but in order to accelerate the reaction
A range of 40 ° C. or higher and lower than the boiling point of the reaction medium is preferable. The contact product obtained by the above reaction is separated by filtration or a decantation method, and then thoroughly washed with an inert solvent such as n-hexane or n-heptane, and then contacted with the aromatic carboxylic acid ester (c). However, the solid component (a) and the titanium compound (b) are brought into contact with each other, and subsequently, in the presence of a sufficient excess amount of the titanium compound with respect to the aromatic carboxylic acid ester, and the chlorinated hydrocarbon content. A method of contacting an aromatic carboxylic acid ester in the presence thereof is also preferable. The ratio of the aromatic carboxylic acid ester (C) to the contact product is not particularly limited, but preferably 0.01 mol of the aromatic carboxylic acid ester to 1 mol of magnesium contained in the solid component (A) before contact. A range of 1.0 mol, particularly preferably 0.05 to 0.3 mol is recommended. The contact temperature is not particularly limited, but is preferably in the range of 40 ° C. or higher and lower than the boiling point of the reaction medium in order to accelerate the reaction.

After separating the contact product, an aromatic carboxylic acid ester (c)
As a method of contacting with, a chlorinated hydrocarbon is used as a reaction medium. Preferred examples of chlorinated hydrocarbons include 1,2-dichloroethane, o-dichlorobenzene, n
-Butyl chloride, dichloromethane, or the like, or a mixed medium thereof is preferably used for contact.

The ratio of the two components in contact with each other is 1 mol of magnesium contained in the contact product and aromatic carboxylic acid ester.
The range of 0.01 to 1.0 mol is preferable, and more preferably 0.1 to 0.
A range of 5 moles is preferred. The contact product obtained by the above reaction is preferably separated by filtration or decantation, and then thoroughly washed with an inert solvent such as n-hexane or n-heptane.

(III) First, the method of contacting the solid component (a) with the aromatic carboxylic acid ester (c) and then the titanium compound (b) will be described.

As a method of contacting the solid component (a) with the aromatic carboxylic acid ester (c), an inert medium, for example, an aliphatic hydrocarbon such as n-hexane or n-heptane as a reaction medium, benzene, toluene, xylene or the like is used. Alicyclic hydrocarbons such as aromatic hydrocarbons, cyclohexane and methylcyclohexane,
Alternatively, it is a preferable method to contact by using a chlorinated hydrocarbon such as 1,2-dichloroethane, o-dichlorobenzene, dichloromethane, or a mixed medium thereof, but among them, an aromatic hydrocarbon and a chlorinated hydrocarbon Is preferred as the inert medium.

The ratio of both components in contact with each other is preferably 0.01 to 1.0 mol of aromatic carboxylic acid ester per 1 mol of magnesium contained in the solid component (a), more preferably 0.1.
A range of up to 0.5 mol is preferred.

The reaction temperature is not particularly limited, but is preferably in the range of 40 ° C. or higher and lower than the boiling point of the reaction medium in order to accelerate the reaction. The contact product obtained by the above reaction is separated by filtration or decantation, and then n-hexane and n-hexane are added.
It is preferable to sufficiently wash with an inert solvent such as heptane to remove unreacted substances or by-products.

Next, as a method of contacting with the titanium compound (b),
The method of contacting in the presence of a chlorinated hydrocarbon solvent of the method shown in (I) above can be used.

In addition, the ratio at the time of contact is 1 to 10 mol of titanium compound (b) with respect to 1 mol of magnesium contained in the contact product.
It is in the range of 0 mol, particularly preferably in the range of 5 to 50 mol.

It is also one of the preferred methods of the present invention to further treat the solid component obtained by (I), (II) or (III) with the titanium compound (II). The contact method is (I
It is preferable to use the method of contacting the titanium compound itself as a medium in the method of I).

After the above contact or treatment, it is preferable to thoroughly wash with an inert medium such as n-hexane, n-heptane, toluene or cyclohexane to remove unreacted substances or by-products. It is also a preferable method to wash with a chlorinated hydrocarbon such as 2-dichloroethane and then to wash thoroughly with an inert medium such as hexane.

Regarding the composition and structure of the solid catalyst component (A) in the present invention obtained by these contact or treatment,
Although it depends on the type of starting material and the contact conditions, it was found from the compositional analysis value that the solid catalyst contained about 1 to 10% by weight of titanium and had a specific surface area of 50 to 300 m ² / g.

The general formula used as the component (B) is AlR ³ _n Z _3-n (wherein R is
⁶ , Z and n have the above-mentioned meanings. ) Will be described.

First, as the aluminum halide alkyl compound,
Dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, di-iso-butyl aluminum chloride, di-n-hexyl aluminum chloride, di-iso-hexyl aluminum chloride,
Di (2-ethylhexyl) aluminum chloride, di-
n-decyl aluminum chloride, methyl-iso-butyl aluminum chloride, ethyl-iso-butyl aluminum chloride, methyl aluminum sesquichloride,
iso-butyl aluminum sesquichloride, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples include iso-butylaluminum dichloride, diethylaluminum bromide, diethylaluminium iodide and the like, and mixtures thereof.

Next, as a trialkylaluminum compound, trimethylaluminum, triethylaluminum, tri-n
-Propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, tri-iso-
Butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum, tri-n-dodecyl aluminum, tri-n-hexadecyl aluminum, and the like, and mixtures thereof.

Next, as the hydrocarbyloxyaluminum alkyl compound, usually, a trialkylaluminum compound and carbinol can be reacted and used. As carbinol, methyl alcohol, ethyl alcohol,
n- to iso-propyl alcohol, n-, iso-, se
c to tert-butyl alcohol, n-, iso-, sec-
To tert-amyl alcohol, phenol, cresol and the like.

The ratio of carbinol to be reacted with the trialkylaluminum compound is 0.1 to 1 mol, preferably 0.2 to 0.9 mol, based on 1 mol of the trialkylaluminum.

As the siloxy group-containing aluminum alkyl compound,
Usually, it can be used by reacting a trialkylaluminum compound with silanol or siloxane.

As the silanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, a hydrolyzate of chlorosilane, and polysilanols can be used.

Examples of the siloxane include methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, propyl hydrogen polysiloxane, butyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, dimethyl polysiloxane, methyl ethyl polysiloxane, and methylphenyl polysiloxane. To be

The ratio of silanol or siloxane to be reacted with the trialkylaluminum compound is 0.1 to 2 moles, preferably 0.2 to 1.5 moles, and particularly preferably 0.2 to 1.2 moles based on 1 mole of trialkylaluminum. Is recommended.

By using these alkylaluminum compounds in combination with the above-mentioned solid catalyst component (A) and the below-mentioned alkoxysilane compound (C), a catalyst system having high activity and high stereoregularity can be obtained. The highest performance can be achieved by using a dialkylaluminum halide.

Next, the alkoxysilane compound as the component (C) used in the present invention will be described.

This compound has the general formula R ⁷ _s Si (OR ⁸ ) _4-3 (wherein R ⁷ , R ⁸ and s
Has the above-mentioned meaning. ).

First, the _{^{Si (OR 3) 4, Si}} (OCH 3) 4, Si (OC 2 H 5) 4, Si (On-C 3 H 7) 4, Si (Oiso-C 3 H 7) 4, Si (On-C ₄ H ₉ ) ₄ , Si (Osec-C ₄ H ₉ ) _{4 and the} like.

RSi (OR ′) ₃ includes CH ₃ Si (OCH ₃ ) ₃ , C ₂ H ₅ Si (OC ₂ H ₅ ) ₃ , nC ₄ H ₉ Si (OCH ₃ ) ₃ , nC ₅ H ₁₁ Si (OCH _{3 ) 3, C 6 H 5 Si} (OCH 3) 3, C 6 H 5 CH 2 Si (OCH 3) 3, CH 2 = CHSi (OCH 3) 3, CH [Si (OCH 3) 3] 3, (CH ₃ O) ₃ SiCH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CCl ₃ Si (OCH ₃ ) _{2, CH 3 CHClSi (OCH 3} ) 3, CH 2 ClCH 2 Si (OCH 3) 3, CH 3 Si (OC 2 H 5) 3, C 2 H 5 Si (OC 2 H 5) 3, nC 3 H 7 Si (OC ₂ H ₅ ) ₃ , n
-C ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , nC ₅ H ₁₁ Si (OC ₂ H ₅ ) ₃ , cyclo-C ₆ H ₁₁ Si
_{(OC 2 H 5) 3,} C 6 H 5 Si (OC 2 H 5) 3, CH 2 = CHSi (OC 2 H 5) 3, CH3CH = CHSi (OC 2 H 5) 3, CH2 = CHCH2Si (OC 2 _{H 5) 3, (C 2} H 5 O) 3 SiCH 2 Si (OC 2 H 5) 3, CH [Si (OC 2 H 5) 3] 3, CF 3 C 6 H 4 Si (OC 2 H 5) _{3, CH 2 ClSi (OC 2} H 5) 3, CCl 3 Si (OC 2 H 5) 3, CH 2 ClCH 2 Si (OC 2 H 5) 3, CH 2 ClCHClSi (OC 2 H 5) 3, CH 2 _{= CHSi (Oiso-C 3 H} 7) 3, (iso-C 3 H 7 O) 3 SiCH 2 Si (Oiso-C 3 H 7) 3, CH 3 CHClSi (Oiso-C 3 H 7) 3, CH 2 _{ClCH 2 Si (Oiso-C 3} H 7) 3, CH 3 Si (OnC 4 H 9) 3, C 2 H 5 Si (OnC 4 H 9) 3, C 6 H 5 Si (OnC 4 H 9) 3, CH ₂ ＝ CHSi (OnC ₄ H ₉ ) ₃ , (nC ₄ H ₉ O) ₃ SiCH ₂ Si (OnC ₄ H ₉ ) ₃ , CH ₃ CHClSi (OnC ₄ H ₉ ) ₃ , CH ₂ ＝ CClSi (OnC ₄ H ₉ ) ₃ , CH ₃ Si (Oiso-C ₄ H ₉ ) ₃ , CH ₂ = CHSi (O-iso-C ₄ H ₉ ) ₃ , (iso-C ₄ H ₉ O) ₃ SiCH ₂ Si (O-iso _{-C 4 H 9) 3, CH} 3 CHClSi (O-iso-C 4 H 9) 3, CH 2 = CClSi (O-iso-C 4 H 9) 3, CH 3 Si (Osec-C 4 H 9) ₃ , CH ₂ = CHSi (O-sec-C ₄ H ₉ ) ₃ , (sec-C ₄ H ₉ O) ₃ SiCH ₂ Si ( O-sec-C ₄ H ₉ ) ₃ , CH ₃ CHClSi (O-sec-C ₄ H ₉ ) ₃ , CH ₂ = CClSi (O-sec-C ₄ H ₉ ) ₃ , C ₆ H ₅ Si (O- _{sec-C 4 H 9) 3} , CH 3 Si (O-tert-C 4 H 9) 3, C 6 H 5 Si (O-tert-C 4 H 9) 3, and the like.

R ₂ Si (OR ′) ₂ includes (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si (OCH ₃ ) ₂ , (nC ₃ H ₇ ) ₂ Si (OCH ₃ ) ₂ , (NC ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , (CH ₃ ) (C ₂ H ₅ ) Si (OC ₂ H ₅ ) ₂ , (CH ₃ ) (C ₆ H ₅ ) Si (OC ₂ H ₅ ) ₂ , CH ₃ SiCl _{(OC 2 H 5) 2,} C 2 H 5 SiH (OC 2 H 5) 2, include _{(C 2 H 5) 2 Si} (OC 2 H 5) 2 and the like.

R ₃ SiOR ′ includes (CH ₃ ) ₃ SiOCH ₃ , (C ₂ H ₅ ) ₃ SiOCH ₃ , (CH ₃ ) ₃ SiOC ₂ H ₅ , and (CH ₃ ) ₂ (nC ₃ H ₇ ) SiOC ₂ H _{5 , (CH 3) 2 (C} 6 H 5) SiOC 2 H 5, (C 2 H 5) 3 SiO-nC 3 H 7, (CH 3) 3 SiO-nC 4 H 9, but and the like, preferably CH ₃ Si (OC ₂ H ₅ ) ₃ , C ₂ H ₅ Si (OC ₂ H ₅ ) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H _{5
Si (OC 2 H 5) 3} , nC 3 H 7 Si (OC 2 H 5) 3, nC 4 H 9 Si (OC 2 H 5) 3, n-
_{C 5 H 11 Si (OC 2} H 5) 3, is _{(C 6 H 5) 2 Si} (OCH 3) 2, Si (OC 2 H 5) 4. These alkoxysilanes may be used alone or as a mixture, and may be in the form of a reaction product or an adduct with an organoaluminum compound, or may be used in combination with a complex compound such as an ether, an ester or an amine.

The use ratio of the catalyst components (A), (B) and (C) in the present invention is 1 to 3,000 millimoles in terms of aluminum atoms in (B), relative to 1 g of the solid component (A). It is preferably in the range of 5-1000 mmol, and (C) is (C)
It is preferably used in the range of 0.01 to 1000 mmol, preferably 0.05 to 100 mmol, in terms of silicon atoms.

These catalyst components (A), (B) and (C) may be used by bringing them into contact with each other at the time of polymerization, or may be used by contacting them in advance before the polymerization. Only the person may be freely selected and contacted. The contact may be in an inert gas atmosphere or an olefin atmosphere.

The present invention relates to α-olefins such as propylene, butene-
Suitable for use in olefins such as 1, pentene-1,4-methyl-pentene-1,3-methyl-butene-1, especially propylene for stereoregular polymerization at higher temperatures. Further, the activity is hardly decreased with the lapse of polymerization time, and it is suitable for so-called block polymerization, in which the α-olefin is copolymerized with ethylene or another olefin and has a relatively long residence time in the polymerization machine.

Further, in order to control the molecular weight of the polymer, it is possible to add hydrogen, halogenated hydrocarbon or an organometallic compound which easily causes chain transfer.

As the polymerization method, usual suspension polymerization, polymerization in a liquid monomer, and gas phase polymerization are possible. Particularly, in the polymerization of the present invention, it can be preferably used for polymerization in a liquid monomer and gas phase polymerization which are carried out at a relatively high polymerization temperature.

In suspension polymerization, a catalyst is introduced into a reactor together with a polymerization solvent such as hexane and an aliphatic hydrocarbon such as heptane.
1 to 1 of olefins such as propylene in an inert gas atmosphere
Polymerization can be carried out at a temperature of room temperature to 150 ° C. by press-fitting to 20 kg / cm ² . In the polymerization in a liquid monomer, the olefin can be polymerized using a liquid olefin as a polymerization solvent under the condition that the catalyst is a liquid olefin such as propylene. For example, in the case of propylene, room temperature to 90 ° C
It is possible to carry out the polymerization in liquid propylene under the pressure of 10-45 Kg / cm ² at the temperature of. On the other hand, in gas phase polymerization, under the condition that olefin such as propylene is a gas, in the absence of a solvent at a pressure of 1 to 50 kg / cm ² , at a temperature condition of room temperature to 120 ° C., contact between an olefin such as propylene and a catalyst is carried out. It is possible to carry out the polymerization by taking measures such as mixing with a fluidized bed, a moving bed, or a stirrer so as to improve the above.

EXAMPLES Hereinafter, the present invention will be described by way of examples. The boiling heptane extraction residue used in the examples means the percentage of the extraction residue after the polymer is extracted with boiling n-heptane for 6 hours with respect to the weight of the polymer before extraction. It is meant.

Example 1 (1) Synthesis advance triethylaluminum and synthesized composition formula from dibutylmagnesium alkoxy group-containing organomagnesium component _{AlMg 6 (C 2 H 5)} 3 (nC 4 H 9) 12 organomagnesium complex component 250 mmol represented by An n-heptane solution containing (based on magnesium) was placed in a 1-liter flask sufficiently replaced with nitrogen, cooled in an ice bath and stirred, while n-butyl alcohol 11.4cc was added from a dropping funnel.
(125 mmol) was slowly added dropwise over 1 hour to react, and further reacted at room temperature for 1 hour with stirring. A relatively viscous colorless and transparent solution was obtained, which was analyzed to find that the solution contained 0.48 mol of n-butoxy group per mol of Mg and had a magnesium concentration of 1.0 mol / liter.

(II) Synthesis of Magnesium-Containing Solid by Reaction with Chlorsilane Compound Trichlorosilane (HSiCl ₃ ) was added as a 1 mol / 1 n-heptane solution to a 1-liter flask that had been sufficiently replaced with nitrogen.
500 mmol was charged, the temperature was maintained at 65 ° C. with stirring, the total amount of the n-heptane solution of the above-mentioned alkoxy group-containing organomagnesium component was added over 1 hour, and the mixture was further reacted at 65 ° C. for 1 hour with stirring. The white solid produced was separated, washed thoroughly with n-hexane and dried to give a white solid (A
-1) 29.5 g was obtained. As a result of analyzing this solid substance, in 1 g of the solid, Mg7.45 mmol, CL14.2 mmol, butoxy group
It contained 1.92 mmol and had a specific surface area of 218 m ² / g measured by the BET method.

(III) Synthesis of solid catalyst component In a 500 cc flask sufficiently replaced with nitrogen, the above (II)
The solid obtained in 10 g, titanium tetrachloride (200 cc) and 1.2 dichloroethane (50 cc) were added, and di-n-butyl phthalate (2.0 c) was added.
c (7.5 mmol) was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. After the reaction, a solid was collected by filtration, and this solid was further collected.
It was suspended in 200 cc of titanium tetrachloride and reacted at 120 ° C. for 2 hours with stirring. After completion of the reaction, the solid is separated by heating and the heat
-Thoroughly washed with heptane, and further washed with n-hexane, and then made into a solid catalyst component (B-
1). When a part of this was taken and analyzed, the Ti content in the solid catalyst component was 2.1% by weight.

(IV) Polymerization in liquid propylene Hydrogen gas was introduced into a 1.5 liter autoclave that had been thoroughly nitrogen-substituted and vacuum dried so that the MFI of the produced polymer was 5 and 350 g of liquefied propylene was introduced, and the temperature was adjusted to 80 7 mg of n-hexane slurry (B-1) containing the solid catalyst component in terms of solid catalyst component, 1.2 mmol of triethylaluminum and 0.12 mmol of phenyltriethoxysilane were added to the autoclave at 80 ° C with stirring.
Polymerization was carried out for 4 hours to obtain 201 g of a polymer.

The activity per 1 g of the solid catalyst component was 28700 g-PP / g-Solid, and the activity per unit time was 7170 g-PP / g-Solid · hr. The boiling n-heptane extraction residue of this polymer is 97.5.
%, And the bulk density of the polymerized powder was 0.48 g / cc.

Comparative Example 1 An n-hexane slurry containing a solid component (C-3) was obtained in the same manner as in Example 1 except that 1.2 dichloroethane was not used. When analyzed, the solid catalyst component
It contained 2.5% by weight of Ti component per gram.

(III) Polymerization in liquid propylene Hydrogen gas was introduced into a 1.5 liter autoclave, which had been sufficiently purged with nitrogen and vacuum dried, so that the MFI of the produced polymer was 5, and further 350 g of liquefied propylene was introduced, and then the temperature was adjusted to 80 The solid catalyst component n-hexane slurry (C-3) containing solid catalyst component 7 mg, triethylaluminum 1.2 mmol and phenyltriethoxysilane 0.12 mmol was added to the autoclave at 80 ° C under stirring.
Polymerization was carried out for 4 hours to obtain 122 g of a polymer.

The activity per 1 g of the solid catalyst component was 17400 g-PP / g-Solid, and the activity per unit time was 4350 g-PP / g-Solid · hr. The boiling n-heptane extraction residue of this polymer was 96.2
%, And the bulk density of the polymerized powder was 0.32 g / cc.

Example 2 In the synthesis of the (I) alkoxy group-containing organomagnesium component in Example 1, the amount of n-butanol used was 22.8.
Organomagnesium was synthesized under the same conditions as in Example 1 except that cc (250 mmol) was changed, and the solution contained 0.96 mol of butoxy groups per 1 mol of Mg and had an alkoxy group content of 1.0 mol / liter as the Mg concentration. The ingredients are obtained.

As a result of synthesizing a solid catalyst component in the same manner as in Example 1 below, an n-hexane slurry (B-3) of a solid catalyst component containing 3.2 wt% of Ti component was obtained.

(IV) Polymerization in liquid propylene Hydrogen gas was introduced into a 1.5 liter autoclave that had been thoroughly nitrogen-substituted and vacuum dried so that the MFI of the produced polymer was 5 and 350 g of liquefied propylene was introduced, and the temperature was raised to 80 ° C. The solid catalyst component n-hexane slurry (B-3) containing the solid catalyst component (7 mg), triethylene aluminum 1.2 mmol and phenyltriethoxysilane 0.12 mmol was added to the autoclave and the mixture was stirred at 80
Polymerization was carried out at 4 ° C for 4 hours to obtain 236 g of a polymer.

The activity per 1 g of the solid catalyst component was 33700 g-pp / g-Solid, and the activity per unit time was 8420 g-pp / g-Solid · hr. The boiling n-heptane extraction residue of this polymer was 97.0.
%, And the bulk density of the polymerized powder was 0.47 g / cc.

Example 3 In the polymerization using the solid catalyst component (B-3) synthesized in Example 2, the monomer used was changed to butene-1,
Polymerization was carried out under the same conditions as in Example 1 except that the polymerization temperature was changed to 50 ° C. As a result, polybutene-1 polymer 95
g, and the activity per 1 g of the solid catalyst component was 13600 g-PP / g-Sol.
id and the activity per unit time is 3400 g-PP / g-Solid
It was hr. The boiling diethyl ether extraction residue of this polymer was 97.5%, and the bulk density of the polymer powder was 0.43 g / cc.
Met.

Example 4 (III) The solid catalyst of Example 2 was synthesized under the following conditions.

Add the above (II) to a 500 cc flask with sufficient nitrogen substitution.
The solid obtained in 10 g, titanium tetrachloride (200 cc) and 1.2 dichloroethane (50 cc) were added, and di-n-butyl phthalate (2.0 c) was added.
c (7.5 mmol) was added and the mixture was reacted at 100 ° C. for 10 hours with stirring. After the reaction, the solid was collected by heating, thoroughly washed with hot n-heptane, further washed with n-hexane, and then used as a solid catalyst component (B-5) as an n-hexane slurry.
When a part of this was taken and analyzed,
The Ti content was 2.8% by weight. This solid catalyst component (B-
4) was used and polymerized in the same manner as in Example 1 to obtain 247 g of a polymer.

The activity per 1 g of the solid catalyst component was 35300 g-PP / g-Solid, and the activity per unit time was 8820 g-PP / g-Solid · hr. The boiling n-heptane extraction residue of this polymer is 9
7.5%, and the bulk density of the polymerized powder was 0.47 g / cc.

Examples 5 to 7 Solid catalyst components (B-6 to B-8) were prepared in the same manner as in Example 1 except that the substances shown in Table 1 were used as the alkoxy-containing organomagnesium component used in Example 2.
Was synthesized and evaluated for polymerization in the same manner as in Example 1.
Got the result.

Examples 8 to 11 In the synthesis of the solid catalyst component of Example 2, except that the substances shown in Table 1 were used as the aromatic carboxylic acid ester,
In the same manner as in Example 1, solid catalyst components (B-9 to B
-12) was synthesized and polymerized in the same manner as in Example 1 to obtain the results shown in Table 2.

Examples 12 to 14 In polymerization in liquid propylene using the solid catalyst component (B-3) synthesized in Example 2, the same except that the organoaluminum compound and the alkoxysilane compound used are changed to the compounds shown in Table 3. Polymerization was performed under the conditions of and the results shown in Table 3 were obtained.

Example 15 A solid catalyst component (B-13) was obtained in the same manner as in Example 1 except that the chlorinated hydrocarbon solvent used in the synthesis of the solid catalyst component of Example 2 was changed to n-butyl chloride. It was Using this solid catalyst component, polymerization was carried out in the same manner as in Example 1 to obtain 238 g of polymer.

The activity per 1 g of the solid catalyst component was 34000 g-PP / g-Solid, and the activity per unit time was 8500 g-PP / g-Solid · hr. The boiling n-heptane extraction residue of this polymer is 96.5.
%, And the bulk density of the polymerized powder was 0.45 g / cc.

(Effect of the invention) When the solid catalyst component is synthesized as in the present invention, the solid catalyst component obtained by carrying out in the coexistence of a chlorinated hydrocarbon solvent provides high stereoregularity. The particle size characteristics of the obtained polymer can be improved while maintaining the high activity.

In this regard, it is an effect that cannot be expected by those skilled in the art at all.

By using the catalyst of the present invention, for example, even in a polymerization at a high polymerization temperature such as 80 ° C. in propylene polymerization, an α-olefin polymer having excellent particle size characteristics and high stereoregularity can be obtained. It can be obtained in high yield.

[Brief description of drawings]

 The figure is a flow chart illustrating aspects of the present invention.

Claims (1)

[Claims] 1. (A) (a) (i) General formula (M) α (Mg) β (R ¹ ) p (R ² ) q (OR ³ ) r (where M is a periodic table I The metal atoms belonging to Group 3 to Group III, R ¹ , R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms, and α, β, p, q and r are numbers satisfying the following relationships. Organic magnesium soluble in a hydrocarbon solvent represented by 0 ≦ α, 0 <β, 0 ≦ p, 0 ≦ q 0 <r / (α + β) ≦ 1.0 kα + 2β = p + q + r (where k is a valence of M) Component and (ii) General formula H _a SiCl _b R ⁴ _{4- (a + b)} (In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and a and b
Is a number that satisfies the following relationship. 0 <a, 0 <b, a + b ≦
4) The solid component obtained by reacting with a chlorosilane compound having a Si—H bond is represented by (b) the general formula Ti (OR ⁵ ) _m D _4-m (wherein R ⁵ has 2 to 8 carbon atoms). 10 hydrocarbon groups, D is a halogen atom, m is a number satisfying the relationship of 0 ≦ m <4), and (c) an aromatic carboxylic acid ester and a chlorinated hydrocarbon solvent. A solid catalyst component obtained by contacting in the presence of a solid catalyst component, or a solid catalyst component further treated with the component (b), (B) a general formula AlR ⁶ _n Z _3-n (wherein R ⁶ has 1 to 1 carbon atoms). 20 hydrocarbon groups, Z is a hydrogen atom, a halogen atom, a hydrocarbyloxy group or a siloxy group, n is a number satisfying the relationship of 0 <n ≦ 3), and (C) a general formula R ⁷ _s Si (OR ⁸ ) _4-s (wherein R ⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms, and s is 0 ≦
An alkoxysilane compound represented by the formula: s <4, wherein the catalyst comprises (A), (B) and (C).