JP2578406B2 - Method for producing α-olefin polymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for producing an α-olefin polymer. More specifically, the present invention relates to a method for producing an α-olefin polymer having the main characteristics of the catalyst used.

Prior Art Since the discovery of Ziegler-Natta catalysts (hereinafter referred to as Ziegler-type catalysts), regarding the polymerization of α-olefins,
Many suggestions have been made. A method in which a transition metal catalyst component is supported on magnesium halide for high activation (JP-B-47-41676) and a method in which an electron-donating compound is added for the purpose of improving stereoregularity (J. Polymn. Scien
ce.Polymer Lett. 3 , 855 (1965)) has been known for a long time.

In particular, many catalyst production methods have been proposed in which an electron-donating compound is contained in a titanium-supported solid catalyst component (Japanese Patent Publication No.
Nos. 53-46799, JP-A-54-94590, JP-A-58-117205,
58-117206, 59-149905, and 60-130607).

While these offer some improvement,
Each has some problems.

For example, many methods for producing a solid catalyst component containing magnesium, titanium and halogen as essential components have been proposed. In particular, a method for producing a solid catalyst component coexisting with an electron-donating compound for the purpose of improving stereoregularity has been proposed. Although many proposals have been made, further improvements in activity and stereoregularity are required.

As an improved technique, it has been proposed to coexist an electron-donating compound when an organoaluminum compound as a co-catalyst component is used (Japanese Patent Publication Nos. 52-39431, JP-A-56-139511, and JP-A-57-63310). No. each publication).

By these methods, the stereoregularity is improved. However, the amount of the electron donating compound used is increased, which not only increases the production cost, but also deteriorates the odor and quality of the polymer, and these electron donating compounds react with the organoaluminum compound. Because of its high properties, it has drawbacks such as poor polymerization stability and an increased amount of use, and further improvements are desired.

[Summary of the Invention]

SUMMARY OF THE INVENTION The present invention uses an organosilicon compound having a specific structure, the effect of which is not known at all in the known art, to provide an α-
This has been achieved by finding that stereoregular polymerization of olefins can be carried out.

That is, the method for producing an α-olefin polymer according to the present invention is characterized in that an α-olefin is brought into contact with a catalyst comprising a combination of the following components (A), (B) and (C) to carry out polymerization. Is what you do.

Component (A): a solid component containing tetravalent Ti, Mg and halogen as essential components. Component (B): General formula AlR _n X _3-n (where R is 1 carbon atom)
To 20 hydrocarbon residues, X is a hydrogen group, a halogen group, an alkoxy group or a siloxy group having 1 to 12 carbon atoms, and n is 0 <n ≦
Organoaluminum compound represented by 3) An organosilicon compound having a structural site represented by the following formula (provided that the organosilicon compound is Si—O—C or Si—N
When the compound does not contain a -C bond, and there is a bond other than a silicon-hydrogen bond in the structural unit, the bond is formed by bonding silicon with a _C1-20 alkyl group, a _C1-20 alkenyl group,
_6-20 phenyl group, C _1-20 haloalkyl group, siloxy group, aluminoxy group, C _1-20 thioalkoxy group, C _6-20 thiophenoxy group, halogen group or hydroxyl group), Or heptamethyl 3- (3-hydroxypropyl) trisiloxane.

Effect of the Invention The use of the organosilicon compound defined in the present invention, the effect of which has not been known at all, significantly improves the activity and stereoregularity, and furthermore, this compound has an effect on the organoaluminum compound. The organic aluminum compound hardly reacts under ordinary polymerization conditions, so that the organoaluminum compound has a small amount of decomposition and disappearance, so that it is possible to exhibit an effect in a substantially small amount. Deterioration can be improved.

The organosilicon compound defined in the present invention is An organosilicon compound having a structural site represented by the following formula (provided that the organosilicon compound is Si—O—C or Si—N
When the compound does not contain a -C bond, and there is a bond other than a silicon-hydrogen bond in the structural unit, the bond is formed by bonding silicon with a _C1-20 alkyl group, a _C1-20 alkenyl group,
_6-20 phenyl group, C _1-20 haloalkyl group, siloxy group, aluminoxy group, C _1-20 thioalkoxy group, C _6-20 thiophenoxy group, halogen group or hydroxyl group), Or heptamethyl 3- (3-
Hydroxypropyl) trisiloxane, which at first glance is similar to a compound having a carbon-oxygen bond such as siloxane or ether, but as is apparent from a comparative example described later, adjacent silicon atoms are Si- It is important to have an H bond, and the effect exerted by this difference is significantly increased.

With simple siloxanes or ethers, not only there is almost no effect of expressing stereoregularity, but also the activity may decrease,
Satisfactory effects cannot be obtained.

On the other hand, the organosilicon compound having the structure defined in the present invention can exhibit stereoregularity due to structural specificity, and can significantly improve the activity. further,
The organic aluminum compound hardly reacts under the usual polymerization conditions, so that the specified structure is maintained for a long time, and stable polymerization can be performed.

As described above, the effect of the present invention is based on the structure specificity of the organosilicon compound used, but the details of the reason for the effect are not clear.

[Specific description of the invention]

Catalyst The process for producing an α-olefin polymer according to the present invention is characterized by using a catalyst obtained by bringing components (A), (B) and (C) into contact.

Component (A) The component (A) is a titanium-containing Ziegler-type catalyst solid component in which magnesium, tetravalent titanium, and halogen are essential.

Examples of the magnesium compound used for producing the component (A) include metal magnesium, an alkyl magnesium halide obtained by reacting the metal magnesium with a halogenated hydrocarbon, a dialkyl magnesium, a magnesium halide, or magnesium hydroxide; Magnesium oxychloride, dialkoxymagnesium, alkoxymagnesium halide, organic acid magnesium,
And, a magnesium compound or the like obtained by reacting them with a halogenating agent can be used.

As the tetravalent titanium compound used for producing the component (A), a compound represented by the general formula Ti (OR ¹ ) _4-n X _n (where R ¹ is a hydrocarbon residue, preferably 1 to 4 carbon atoms) About 10; X represents a halogen; and n represents a number of 0n4).

Specific _{examples, 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 (OC 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 (OiC 4 H 9) Cl 3, Ti (OC 5 H 11) Cl 3, Ti (OC 2 H ₅ ) ₄ , Ti (O-nC ₃ H ₇ ) ₄ , Ti (O-nC ₄ H ₉ ) ₄ , Ti (O-iC ₄ H ₉ ) ₄ Ti (O-nC ₆ H ₁₃ ) ₄ , Ti (O -nC ₈ H _{17) 4,} Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] is _4, and the like.

Halogen, another essential component of component (A),
It is common to supply from these magnesium and / or titanium compounds.

Component (A) is well known as a solid component of a Ziegler-type catalyst, and its production method and production conditions are optional (details will be described later).

The mutual proportions of the components are such that magnesium / titanium (atomic ratio) is about 2 to about 100, especially about 4 to about 50, and halogen / titanium (atomic ratio) is about 5 to 200, especially about 5 to about 100. Are preferred.

Component (A) is one that essentially contains magnesium, tetravalent titanium and halogen. Here, “required” indicates that components that are not essential but can be used as needed may be included. Therefore, the component (A) may contain an electron donating compound or an auxiliary catalyst component.

As the electron donating compound, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides,
Acid halides, oxygen-containing electron donating compounds such as acid anhydrides, ammonia, amines, nitriles, isocyanates,
Examples include nitrogen-containing compounds such as amides and imines; sulfur-containing compounds such as thiols, thioethers, sulfates, and sulfonic acids; and silicon-containing compounds such as silicates, siloxanes, and silanols.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, diphenyl methanol, triphenyl methanol, etc. Alcohols having 1 to 20 carbon atoms, (b) phenol, cresol,
C6 to C25 phenols which may have an alkyl group such as xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol; (c) carbon such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone Ketones of number 3 to 15, aldehydes of carbon 2 to 15 such as (d) acetaldehyde, propionaldehyde, tolualdehyde, naphthaldehyde,
(E) Methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, ethyl propionate, ethyl n-butyrate,
Ethyl isobutyrate, ethyl isobutyrate, isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, ethyl phenylacetate, ethyl phenylbutyrate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, benzoate Cellosolve acid, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
Organic acid esters having 2 to 20 carbon atoms such as dineopentyl phthalate, γ-butyrolactone, γ-valerolactone, coumarin, phthalide, diethyl carbonate, etc., (f) methyl borate, ethyl borate, ethyl silicate, butyl silicate ,
Inorganic acid esters such as butyl phosphate, triethyl phosphite and diethyl phosphite, (g) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl C2-C25 ethers such as ether, ethylene glycol diphenyl ether, and 2,2-dimethoxypropane; C2-C20 acid amides such as (thi) acetic amide, benzoic amide, toluic amide; ) C2 to C20 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and phthaloyl isochloride; and C2 having two carbon atoms such as (nu) acetic anhydride and phthalic anhydride. And acid anhydrides of 20, (Le) monomethylamine, monoethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
C1-C20 amines such as aniline, pyridine, picoline, and tetramethylethylenediamine; (C) C2-C20 nitriles such as acetonitrile, benzonitrile, and trinitrile; (W) ethylthioalcohol, butylthioalcohol Thiols having 2 to 20 carbon atoms, such as phenylthiol, (f) diethyl thioether, and 4 to 20 carbon atoms such as diphenylthioether.
25 thioethers, (2) sulfuric acid esters having 2 to 20 carbon atoms, such as dimethyl sulfate and diethyl sulfate; (t) sulfonic acids having 2 to 20 carbon atoms, such as phenylmethylsulfone and diphenylsulfone; Methoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,
Phenyldimethylmethoxysilane, phenyldimethylmonoethoxysilane, triphenylmonomethoxysilane,
C2-C24 such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, lower alkyl silicate (especially ethyl silicate), etc.
And other silicon-containing compounds. Two or more of these electron donating compounds can be used. Preferred among these are cellosolve acetate, cellosolve benzoate, diheptyl phthalate, phthaloyl chloride, and ethyl silicate.

As the auxiliary catalyst component, metals, various halogen compounds, reducing compounds, and the like can be used.

Specifically, (a) metals such as silicon, aluminum, iron, zirconium, and zinc and metal-containing compounds;
Chlorine, bromine, iodine, iodine monochloride, iodine trichloride, iodine tribromide, aluminum chloride, phosphorus pentachloride, phosphorus trichloride, antimony pentachloride, antimony trichloride, tin chloride,
Halogen compounds such as silicon tetrachloride, dichloroethane, o-dichlorobenzene and chloroform; (c) triethylamylnium, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylhydrodienepolysiloxane, 1,
Examples thereof include reducing compounds such as 3,5,7-tetramethylcyclotetrasiloxane. The above electron donating compound and these auxiliary catalyst components can be used in combination. Also, two or more auxiliary catalyst components may be used.

The Ziegler-type catalyst solid component containing titanium, which essentially contains magnesium, titanium and halogen (component A), can be obtained by various preparation methods. Some specific preparation methods are as follows.

(A) MgX ₂ (magnesium halide) and alkoxytitanium or titanium halide are mixed and pulverized, and the obtained pulverized product is heated and contacted with an interhalogen compound in an inert solvent.

(B) MgX ₂ and an electron donating compound are mixed and pulverized, and the obtained pulverized product is brought into contact with a titanium halide in a liquid phase.

(C) MgX ₂ and AlX ₃ are mixed and pulverized, and the pulverized product is dissolved in hydrocarbon using a dissolving agent such as alcohol, ether, phosphate ester, or alkoxytitanium to obtain a hydrocarbon solution containing MgX _2. This is prepared and the solution is contacted with a halogen compound of titanium or silicon to precipitate a solid, and the precipitated solid is contacted with an alkoxytitanium halide or a titanium halide in a liquid phase. At this time, the contact with the electron donating compound can be performed simultaneously or sequentially.

(D) MgX ₂ is dissolved in a hydrocarbon solvent using butyl titanate, it is reacted with methylhydrodiene polysiloxane (having a viscosity of about 10 to 100) to precipitate a solid, and the precipitated solid containing this MgX ₂ Contact with a halide of silicon or titanium. Here, methylhydrogenpolysiloxane is It is a compound having a structural unit.

(E) The contact-treated product obtained in (d) is brought into contact with the electron-donating compound and titanium halide simultaneously or sequentially in a liquid phase.

(F) Metal magnesium is reacted with a halogenated hydrocarbon in ether (preparation of Grignard compound). A silicon halide is added to the resulting solution to precipitate a solid. The obtained precipitated solid is brought into contact with titanium halide in a liquid phase.

The feature of the present invention lies in a polymerization method using a specific silicon compound below, and as long as the titanium-containing solid component in which magnesium, titanium and halogen are present, a method for preparing the above-described titanium-containing solid component. However, the present invention is not limited to this.

Component (B) Component (B) is a compound represented by the general formula: AlR _n X _3-n (where R is a hydrocarbon residue having 1 to 20 carbon atoms;
X is a hydrogen group, a halogen group, an alkoxy group (1 to 12 carbon atoms), a siloxy group, and n is an organic aluminum compound represented by 0 <n ≦ 3.

Such an organoaluminum compound is specifically,
For example, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri isobutyl aluminum, tri n-hexyl aluminum, tri-isohexyl aluminum, tri n-octyl aluminum, diethyl aluminum hydride, diethyl aluminum n-propyl, diethyl aluminum se
c-butyl, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, diethylaluminum (tristrimethylsiloxide) and the like Can be Also, two or more of these organoaluminum compounds can be used in combination.

Component (C) Component (C) An organosilicon compound having a structural site represented by the following formula (provided that the organosilicon compound is Si—O—C or Si—N
When the compound does not contain a -C bond, and there is a bond other than a silicon-hydrogen bond in the structural unit, the bond is formed by bonding silicon with a _C1-20 alkyl group, a _C1-20 alkenyl group,
_6-20 phenyl group, C _1-20 haloalkyl group, siloxy group, aluminoxy group, C _1-20 thioalkoxy group, C _6-20 thiophenoxy group, halogen group or hydroxyl group), Or heptamethyl 3- (3-
(Hydroxypropyl) trisiloxane. Since the former organosilicon compound has the above-mentioned structural unit, it can be understood that silicon adjacent to a siloxy bond has one or more silicon-hydrogen bonds with each other. Functional groups such as ethers, esters, ketones, amines, amides, alcohols, halogens, and nitriles may be contained in the hydrocarbon residue bonded to silicon. In addition, the case where a siloxy compound as defined above is formed by a reaction in a system is also included.

Specifically, disiloxane, 1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-bis (chloromethyl) -1,3-dimethyldisiloxane, 1,3 −
Dichloro-1,3-dimethyldisiloxane, 1,3-dimethyl-1,3-diethyldisiloxane, 1,3-divinyl-1,3-
Dimethyldisiloxane, 1,3-bis (3-chloropropyl) dimethyldisiloxane, 1,3-bis (acetoxymethyl) -dimethyldisiloxane, 1,3-bis (3-hydroxypropyl) -1,3-dimethyl Disiloxane, 1,3-
Diethyldisiloxane, 1,1,3,3-tetraethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,1,1,3 ,
5,5-hexamethyltrisiloxane, 1,5-dichloro-1,
1,3-trimethyltrisiloxane, 1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,1,3,5-tetramethylcyclotrisiloxane, 3,5-triethylcyclotrisiloxane, 1,3,5-
Trivinylcyclotrisiloxane, 1,5-diphenyl-
1,3,5-trimethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,7-dichloro-1,1,3,
5,7,7-hexamethyltetrasiloxane, 1,1,3,5,7,7-
Hexamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7, tetraethylcyclo Tetrasiloxane, 1,3,5,7-tetrakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 1,3-bis (3-trimethylsiloxypropyl) -1,3-dimethyldisiloxane, 3,5,7,9-pentamethylcyclopentasiloxane, methylhydrogenpolysiloxane, heptamethyl 3- (3-hydroxypropyl) trisiloxane, and the like. Of these, 1,1,3,3
-Tetramethyldisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and heptamethyl 3- (3-hydroxypropyl) Trisiloxane and the like are preferred.

Formation of Catalyst The catalyst used in the present invention can be formed by bringing components (A), (B) and (C) into contact.

The proportions of each component can be varied over a wide range. Generally, the titanium atom in the component (A) is replaced by the component (B)
The organoaluminum compound of the formula (1) has a molar ratio of 1 to 1000, preferably 10 to 500, and the specific organosilicon compound of the component (C) also has a molar ratio to the titanium atom in the component (A).
It can be used at a rate of 0.1 to 1000, preferably 1 to 500.

The order of the contact or mixing of the components (A), (B) and (C), the number of times, and the method are arbitrary.

Polymerization of α-olefin Examples of the α-olefin used for the polymerization include ethylene (in the present invention, ethylene is treated as an α-olefin), propylene, 1-butene, 1-hexene, 4-methylpentene-1 and the like. Can carry out not only homopolymerization but also random copolymerization and block copolymerization of each other. As for copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can also be used as copolymerized olefins.

As the polymerization method, a so-called slurry polymerization method using an inert hydrocarbon such as hexane or heptane as a solvent, a liquid phase polymerization method using a liquefied monomer as a solvent, a gas phase polymerization method in which a monomer is present as a gas phase, and the like are possible. . In the case of the slurry polymerization method, there are very few soluble polymers having low stereoregularity and the organosilicon compound having a specific structure of the component (C) hardly causes a decomposition reaction. It can be used again for polymerization without treatment.

The polymerization temperature is generally about 20 to 150 ° C, preferably 40 to 100 ° C.
C., and the polymerization pressure is from atmospheric pressure to about 100 atm, preferably from atmospheric pressure to about 50 atm. The molecular weight control of the polymer is
It is carried out mainly by a method using hydrogen.

Experimental Example Example-1 [Production of Titanium-Containing Solid Component (A)] Into a 300 ml flask sufficiently purged with nitrogen, 50 ml of dehydrated and deoxygenated n-heptane was introduced, and then 0.1 mol of MgCl ₂ (magnesium chloride) was added. After introducing 0.2 mol of Ti (O-nBu) ₄ (tetrabutoxytitanium), the mixture was reacted at 90 ° C. for 2 hours to prepare a hydrocarbon solution of MgCl ₂ . Then, 12 ml of methyl halide diene polysiloxane (20 cps) was added and reacted at 40 ° C. for 3 hours. As a result, about 40 g of an off-white titanium / magnesium precipitated solid was deposited. When this titanium magnesium precipitated solid was sufficiently washed and analyzed, the precipitated solid contained 12.1% by weight of MgCl ₂ .

20 g (MgCl ₂ =
2.42g) sampled, 7.0ml of silicon tetrachloride
(0.06 mol) diluted in 25 ml of n-heptane at room temperature.
After dropwise addition over time, the reaction was further performed at 90 ° C. for 2 hours. After completion of the reaction, the mixture was washed twice with 200 ml of n-heptane, and the reaction was repeated twice at 20 ° C. for 2 hours with 20 ml of TiCl ₄ (titanium tetrachloride). Thereafter, 0.10 g of cellosolve acetate (cellosolve acetate / Mg = 0.025) was again added to a suspension slurry containing 20 ml of TiCl _4.
(Molar ratio) in 25 ml of an n-heptane solution was added dropwise at 50 ° C. over 30 minutes, and then reacted at 80 ° C. for 3 hours. After completion of the reaction, n
-Washing with heptane until no soluble titanium was observed, to obtain the target titanium-containing solid slurry.

When a part of the slurry was taken out and analyzed, it was found that the solid contained 4.51% by weight of titanium.

(Polymerization of propylene)

In a 1 liter autoclave equipped with a stirrer, 500 ml of dried and deoxygenated n-heptane, 1,1,3,3
-Tetramethyldisiloxane (Si-O-Si) (C) 73.5
mg, triethylaluminum (TEA) (B) 250 mg (Si-
O-Si / TEA = 0.25 mol ratio) and 0.5 mg in terms of titanium atoms from the titanium-containing solid component (A) were introduced in this order under a propylene atmosphere, and 150 ml of hydrogen was added to initiate polymerization. The polymerization was carried out under the conditions of propylene pressure of 7 kg / cm ² G, 70 ° C. and 3 hours. After completion of the polymerization, the remaining monomer was purged, the polymer slurry was separated, and the powder polymer was dried and the liquid was concentrated to obtain 162.5 g of a powder polymer and 1.6 g of a heptane-soluble polymer, respectively. The activity was 32.8 × 10 ⁴ gPP / gTi per titanium and 14,800 gPP / g solid catalyst per solid catalyst.

Stereoregularity of this powder polymer (hereinafter referred to as product II)
Was determined by a boiling n-heptane extraction test. Also, all
II (the ratio of the amount of the total boiling n-heptane-insoluble polymer to the total amount of the produced polymer) is the total II = the amount of the powder polymer × the product II
It can be obtained by a relational expression of / (amount of powder polymer + amount of liquid concentrated polymer) As a result, products II accounted for 98.0% and all IIs accounted for 97.0%
%Met. Further, the MI of the polymer was 3.4 g / 10 minutes, and the bulk density was 0.47 g / cc.

Example 2 [Production of Titanium-Containing Solid Component (A)] 20 g of titanium magnesium precipitated solid obtained in Example 1 (M
gCl ₂ = 2.42 g) was sampled in a 300 ml flask sufficiently purged with nitrogen, and 7.5 ml (0.65 mol) of silicon tetrachloride diluted in 25 ml of n-heptane was added dropwise.
The reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, n-heptane 30
Washed twice with 0 ml. Next, 0.0028 mol of phthaloyl chloride was mixed with 25 ml of n-heptane and introduced at 30 ° C. for 30 minutes.
The reaction was carried out at 2 ° C. for 2 hours. After completion of the reaction, n-heptane 300m
Washed twice with l. Next, 25 ml of TiCl ₄ was added, and 110 ° C.
For 3 hours. After the completion of the reaction, the resultant was thoroughly washed with n-heptane to obtain a target titanium-containing solid component (A) slurry. It was found that this solid contained 3.22% by weight of titanium.

(Polymerization of propylene)

In a 1 liter autoclave equipped with a stirrer, 500 ml of dried and deoxygenated n-heptane, 1,1,3,3
-73.5 mg of tetramethyldisiloxane (C), 250 mg of triethylaluminum (B) (Si-O-Si / TEA = 0.25 (molar ratio) and 0.3 mg in terms of titanium atoms from the titanium-containing solid component (A), The polymerization was started in this order under an atmosphere, and 200 ml of hydrogen was added to initiate polymerization, under the conditions of propylene pressure of 7 kg / cm ² G, 70 ° C. for 3 hours. As a result of processing
239.0 g of powder and 1.4 g of heptane-soluble matter were obtained. Also products
II was 98.1% and total II was 97.5%. MI is 1.2 (g / 10
Min) and the bulk density was 0.47 (g / cc). The results are shown in Table 1.

Examples -3 to 6 In the polymerization of propylene using the titanium-containing solid component (A) produced in Example 2, a silicon compound (C) was prepared.
Polymerization was carried out under the same conditions as in the polymerization of propylene in Example 2 except that the conditions were changed as shown in 1. Table-
Write it in 1.

Comparative Examples -1 to 5 In the polymerization of propylene using the titanium-containing solid component (A) produced in Example 2, the silicon compound (C) was changed as shown in Table 2 or was not used. Polymerization was performed under the same conditions as in Example-2. The results are shown in Table-2.

Example-7 [Production of Titanium-Containing Solid Component (A)] 20 g of the titanium-magnesium precipitated solid obtained in Example 1 (M
gCl ₂ = 2.42 g) was sampled into a 300 ml flask which was sufficiently purged with nitrogen, and 8.7 ml of silicon tetrachloride was introduced all at once.
The mixture was stirred at 70 ° C. for 1 hour, then heated to 70 ° C., and reacted for 1 hour. After the completion of the reaction, the resultant was washed twice with 300 mm of n-heptane. Next, after adding and dispersing 7.5 ml of silicon tetrachloride,
17 ml of tetrabutoxytitanium was added dropwise at 20 ° C. over 30 minutes,
Then, the mixture was heated to 70 ° C. and reacted for 2 hours. After the reaction,
Washed twice with 300 ml of n-heptane. 0.7 g of PCl ₅ after washing
The mixture was introduced, 25 ml of n-heptane was added, and the mixture was reacted at 80 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain an intended titanium-containing solid component (A) slurry. It was found that this solid contained 2.23% by weight of titanium.

(Polymerization of propylene)

Using the titanium-containing solid component (A), 73.6 mg of 1,1,3,3-tetramethyldisiloxane (C) and 250 mg of triethylaluminum (B) (Si-O-Si / TEA = 0.2 (molar ratio)) , And the above-mentioned titanium-containing solid component (A) were introduced in an order of 0.5 mg in terms of titanium atoms in a propylene atmosphere, and 200 ml of hydrogen was added to initiate polymerization. The polymerization was carried out under the conditions of propylene pressure of 7 kg / cm ² G, 70 ° C. and 3 hours. The results are shown in Table-3.

Comparative Examples -6 and 7 In the propylene polymerization of Example -7, all of Example -7 was carried out except that 55.9 mg of diisopropyl ether was used instead of 1,1,3,3-tetramethyldisiloxane or not used. Polymerization was carried out under the same conditions as described above. Table-
Write it in 3.

Example -8 anhydrous magnesium chloride [preparation of the titanium-containing solid component (A)] (MgCl ₂₎ 40g, ethyl benzoate
12ml Were filled in a vibrating mill pot having an inner volume of 1 liter (a stainless steel ball having a diameter of 25.5 mm occupying an apparent volume of 0.7 liter) under a nitrogen atmosphere and pulverized for 24 hours.

The resulting pulverized solid 5g aliquoted three-necked flask 200 ml, was added dry degassed n- heptane 50ml to form a slurry, and reacted 2 hours at added 90 ° C. The TiCl ₄ 10 ml. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain an intended titanium-containing solid component (A) slurry. In this solid
It was found that 0.72% by weight of titanium was contained.

(Polymerization of propylene)

Using the above titanium-containing solid component (A), propylene was polymerized under the same conditions as in Example-3. Table 4 shows the results.

Comparative Example-8 Using the titanium-containing solid component (A) obtained in Example-8, propylene was polymerized under the same conditions as in Example-8 except that the silicon compound (C) was not used. The results are shown in Table-4.

Examples-9 and 10 [Production of Titanium-Containing Solid Component (A)] In the production of the same pulverized solid as in Example-8, MgCl ₂ 5
For 0 g, cellosolve acetate 3.6 ml (0.05 vs. MgC
l ₂ molar ratio), except that addition of diheptyl phthalate 9.6 ml (0.05 vs. MgCl ₂ molar ratio) performs a reaction with TiCl ₄ in the same conditions, to obtain a slurry of the titanium-containing solid component of interest (A) . In these solids, 1.73% by weight, 1.
It contained 59% by weight of titanium.

(Polymerization of propylene)

Using these titanium-containing solid components (A),
Polymerization of propylene was carried out under the same conditions as in Example 3. Table 4 shows the results.

Comparative Examples -9 and 10 Using the titanium-containing solid components obtained in Examples -9 and 10, the polymerization of propylene was carried out using a silicon compound (C).
Was performed under the same conditions as in Examples -9 and 10, except that was not used. These results are shown in Table-4.

Example -11 thoroughly purged with nitrogen 300ml flask, dehydration and introduced deoxygenated n- heptane 50 ml, then MgCl ₂ (magnesium chloride) 0.1 mol of Ti (OBu) _{4 (titanium} tetrabutoxide) introducing 0.2 mole Thereafter, the mixture was reacted at 90 ° C. for 2 hours to prepare a hydrocarbon solvent of MgCl ₂ . Subsequently, when 12 ml of methyl hydrogen polysiloxane (20 cps) was added and reacted at 40 ° C. for 3 hours, about 40 g of an off-white titanium magnesium precipitated solid was precipitated. When this titanium magnesium precipitated solid was sufficiently washed and analyzed, the precipitated solid contained 12.1% by weight of MgCl ₂ .

20 g (MgCl ₂ = 2.
42 g) was sampled in a 300 ml flask sufficiently purged with nitrogen, 5.8 ml (0.05 mol) of silicon tetrachloride was diluted with 25 ml of n-heptane and added dropwise, and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 300 ml of n-heptane.
Next, 0.004 mol of phthaloyl chloride was mixed with 25 ml of n-heptane, introduced at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 2 hours. After the completion of the reaction, the resultant was washed twice with 300 ml of n-heptane.
Next, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a target titanium-containing solid component slurry. It was found that this solid contained 3.20% by weight of titanium.

Using the solid component (A) thus produced, 276.5 mg of heptamethyl-3- (3-hydroxypropyl) -trisiloxane (C) and 250 mg of triethylaluminum (B) (Si / Al = 0.5 molar ratio) , And the solid (A) were introduced in an order of 0.4 mg in terms of Ti atom under a propylene atmosphere, and 150 ml of hydrogen was added to initiate polymerization.
The polymerization was performed under the conditions of a propylene pressure of 7 kg / cm ² G / 75 ° C. for 3 hours. The results were as described in Table-5.

Example-12 1) Production of solid component (A) 20 g of titanium magnesium precipitated solid obtained in Example-11 (M
gCl ₂ = 2.42 g) was sampled, 8.7 ml of silicon tetrachloride was introduced at once, and the mixture was stirred at 20 ° C. for 1 hour. After completion of the reaction, n
-Washed twice with 300 ml heptane. Then, 7.5 ml of silicon tetrachloride was added to disperse the solid, and 17 ml of tetrabutoxytitanium was added dropwise at 30 ° C. over 30 minutes, followed by heating at 70 ° C. for 2 hours for reaction. After completion of the reaction, n-heptane
Washed twice with 300 ml. Next, 0.5 g of phosphorus pentachloride was added and reacted at 80 ° C. for 1 hour. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a target titanium-containing solid component slurry. It was found that this solid contained 2.80% by weight of titanium.

2) Polymerization of propylene Using the solid component (A), heptamethyl-3- (3
-Hydroxypropyl) -trisiloxane (C) to 276.
5 mg, 250 mg of triethylaluminum (B) (Si / Al =
0.5 mol ratio) and 0.5 mg of the above-mentioned contained solid component (A) in terms of Ti atom in a propylene atmosphere in this order,
The polymerization was started by adding 150 ml of hydrogen. The polymerization was carried out under the conditions of a propylene pressure of 7 kg / cm ² G / 70 ° C. for 3 hours. The results were as described in Table-5.

Comparative Examples 11 and 12 Instead of heptanemethyl-3- (3-hydroxypropyl) -trisiloxane (C) in the polymerization of propylene in Example-12, 1-methoxy-2-propanol 9 was used.
Polymerization was carried out under the same conditions as in Example 12 except that 8.7 mg was used or it was desired to use 8.7 mg. Table 5 shows the results.
It was as described in.

[Brief description of the drawings]

The figure is an example of a flowchart for helping to understand the technical contents of the present invention.

Continuation of the front page (56) References JP-A-58-111806 (JP, A) JP-A-60-67505 (JP, A) JP-A-60-31504 (JP, A)

Claims (1)

(57) [Claims] 1. A method for producing an α-olefin polymer, comprising contacting an α-olefin with a catalyst comprising the following components (A), (B) and (C) to polymerize the catalyst. Component (A): a solid component containing tetravalent Ti, Mg and halogen as essential components. Component (B): General formula AlR _n X _3-n (where R is 1 carbon atom)
To 20 hydrocarbon residues, X is a hydrogen group, a halogen group, an alkoxy group or a siloxy group having 1 to 12 carbon atoms, and n is 0 <n ≦
3, an organoaluminum compound represented by the formula: An organosilicon compound having a structural site represented by the following formula (provided that the organosilicon compound is Si—O—C or Si—N
When the compound does not contain a -C bond, and there is a bond other than a silicon-hydrogen bond in the structural unit, the bond is formed by bonding silicon with a _C1-20 alkyl group, a _C1-20 alkenyl group,
_6-20 phenyl group, C _1-20 haloalkyl group, siloxy group, aluminoxy group, C _1-20 thioalkoxy group, C _6-20 thiophenoxy group, halogen group or hydroxyl group), Or heptamethyl 3- (3-hydroxypropyl) trisiloxane.