JPH0867710A - Production of olefin polymer - Google Patents

Abstract

PURPOSE: To obtain a polymer having a high stereoregularity and a high melt flow rate by polymerizing an α-olefin using a catalyst comprising a specific organosilicon compound containing Ti, Mg, and a halogen, an organoaluminum compound, and an organozinc compound. CONSTITUTION: A 3-12C α-olefin is stereoregularly polymerized using a catalyst comprising a component (A) containing Ti, Mg, a halogen, and an Si compound represented by formula I (wherein R<1> us a branched aluphatic or alicyclic hydrocarbon group; R<2> is the same as R<1> or another hydrocarbon group; R<3> is a hydrocarbon group; and 1<=n<=3), an organic Al compound (B) represented by formula II (wherein R is a 1-20C hydrocarbon group; X is H or a halogen; and 0<=m<=2), and an organic Zn compound (C) represented by formula III (wherein R<5> and R<6> each is a 1-20C hydrocarbon group) to produce an olefin polymer having a melt flow rate of 30-1,000 g/10 min. This catalyst does not need a large amount of hydrogen. It is highly active in the polymerization of molecules having a low mol.wt. It gives a highly stereoregular polymer. The amounts of the ingredients (A), (B), and (C) are preferably such that the (B) to (A) weight ratio is 1-100 and the (C) to (B) molar ratio is 0.1-2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an olefin polymer. More specifically, the present invention provides
Melt flow rate (MFR) is 30 to 1000 g / by stereoregular polymerization of α-olefin having 3 to 12 carbon atoms.
The present invention relates to a method that enables production of an olefin polymer having high activity and high stereoregularity even when producing a polymer as large as 10 minutes (having a relatively small molecular weight).

[0002]

2. Description of the Related Art A solid component containing titanium, magnesium, halogen, and optionally an electron donating compound,
Using an olefin polymerization catalyst comprising an organometallic compound component of Group I to III of the periodic table and, if necessary, an electron donating compound component, an α-olefin having 3 or more carbon atoms is stereoregularly polymerized, It is known to produce olefin polymers. Further, although an organozinc compound is known as an organometallic component, a catalyst using this is not used recently because of its insufficient activity.
In recent years, when molding a polyolefin polymer, it is required to improve the molding speed in order to improve the molding cycle from the viewpoint of economy. For that purpose, the polymer has a small molecular weight, in other words, the melt flow rate (MF).
It is necessary that R) is large, but even when the molecular weight is small, high stereoregularity as usual is required. This is because unless the polyolefin polymer has high stereoregularity, it is difficult to obtain sufficient performance required as a molding material, for example, rigidity.

However, in the case of a conventionally known catalyst, a polymer having high stereoregularity can be obtained when producing a polymer having a relatively large molecular weight (for example, MFR = 1), but a polymer having a small molecular weight (for example, Under the conditions for producing MFR = 50), for example, under the condition that the amount of hydrogen added to the polymerization system is changed, the stereoregularity of the desired polymer is lowered. Therefore, in order to solve the above problems, for example, a method of using a large amount of an electron-donating compound as an external donor is conceivable, but in that case, there are problems such as a large decrease in catalyst activity and an increase in catalyst cost. Is unavoidable. Therefore, it is desired to provide a production method capable of obtaining a polymer having high activity and high stereoregularity in a polymer having a relatively small molecular weight without using a large amount of hydrogen or an electron donor.

[0004]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to solve the above-mentioned problems. The present invention has a high activity and a high steric property at a relatively small molecular weight of the polymer produced. It is intended to provide a catalyst capable of obtaining a polymer having regularity.

[0005]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present inventors have reached the present invention by discovering that the above-mentioned problems can be solved by using a specific catalyst. That is, in the method for producing an olefin polymer of the present invention, a melt flow rate (MFR) is 3 by stereoregularly polymerizing an α-olefin having 3 to 12 carbon atoms in the presence of a catalyst.
In the method for producing an olefin polymer of 0 to 1000 g / 10 min, the catalyst to be used is composed of the following component (A), component (B) and component (C). Component (A): Solid catalyst component for stereoregular polymerization of olefins containing titanium, magnesium and halogen as essential components, and substantially containing a silicon compound represented by the following general formula in that form General formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, and R ² is the same or different hydrocarbon residue as R ^1. , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3) Component (B): Organoaluminum compound represented by the following general formula R ⁴ _3-m AlX _m ( Here, R ⁴ is a hydrocarbon residue having 1 to 20 carbon atoms,
Represents hydrogen or halogen, and m represents a number of 0 ≦ m ≦ 2) Component (C): an organozinc compound represented by the following general formula R ⁵ R ⁶ Z _n (where R ⁵ and R ⁶ independently has 1 carbon atom
~ 20 hydrocarbon residues).

[0006]

EFFECTS OF THE INVENTION According to the present invention, a polymer having high activity and having a relatively small molecular weight, that is, MF, is obtained.
R: 30 to 1000 g / 10 minutes, preferably 50 to 50
A polymer having a high stereoregularity can be produced even with a polymer in the range of 0 g / 10 minutes. Although the reason why such an effect is exhibited is not clear, the use of an organozinc compound is to obtain a desired polymer having a high MFR and a high stereoregularity by adding a small amount of hydrogen.

[0007] The catalyst used in the specific description method of the present invention invention is made of the following components (A), component (B) and component (C). <Component (A)> The component (A) used in the present invention contains titanium, magnesium and halogen as essential components, and substantially contains a silicon compound represented by the following general formula in that form. It is a solid catalyst component. General formula R ¹ R ² _3-n Si (OR ³ ) _n (wherein R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, and R ² is a hydrocarbon which is the same as or different from R ^1. A residue, R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3) First, here, regarding Ti, Mg and halogen, “containing these as essential components” means In addition to the three listed components, other purposeful elements may be included, and each of these elements may exist as any purposeful compound, and these elements are bound to each other. It may indicate that it may exist as an item.

The solid component itself containing titanium, magnesium and halogen is known. For example, JP-A Nos. 53-45688, 54-3894, and 54-
31092, 54-39483, 54-945.
No. 91, No. 54-118484, No. 54-13158.
No. 9, No. 55-75411, No. 55-90510,
55-90511, 55-127405, 5
5-147507, 55-155003, 56
-18609, 56-70005, 56-72
001, 56-86905, 56-90807.
56-155206, 57-3803, 57-34103, 57-92007, 57-.
121003, 58-5309, 58-531
0, 58-5311, 58-8706, 5
8-27732, 58-32604, 58-3
2605, 58-67703, 58-1172.
06, 58-127708, 58-18370.
No. 8, No. 58-183709, No. 59-149905.
No. 59-149906, etc. are used.

As the magnesium compound used as the magnesium source in the present invention, magnesium dihalide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, carboxylates of magnesium, etc. Can be given. Among these, magnesium dihalide and dialkoxy magnesium are preferable.

The compound serving as the titanium source has the general formula T
i (OR⁷)_4-pX_p(Where R ⁷Is a hydrocarbon residue,
Preferably, it has about 1 to 10 carbon atoms, and X is a ha
Is a gen, and p is a number 0 ≦ p ≦ 4)
Compounds. As a specific example, TiCl_Four,
TiBr_Four, Ti (OC₂H_Five) Cl₃, Ti (OC ₂
H_Five)₂Cl₂, Ti (OC₂H_Five)₃Cl, Ti (O
-IC₃H₇) Cl₃, Ti (O-nC_FourH₉) C
l₃, Ti (O-nC_FourH₉)₂Cl₂, Ti (OC₂
H_Five) Br₃, Ti (OC₂H_Five) (OC_FourH₉)₂C
l, Ti (O-nC _FourH₉)₃Cl, Ti (O-C₆H
_Five) Cl₃, Ti (O-iC_FourH₉)₂Cl ₂, Ti
(OC_FiveH₁₁) Cl₃, Ti (OC₆H₁₃) Cl₃, T
i (OC₂H_Five)_Four, Ti (O-nC₃H₇)_Four, Ti
(O-nC_FourH₉)_Four, Ti (O-iC _FourH₉)_Four, T
i (O-nC₆H₁₃)_Four, Ti (O-nC₈H₁₇)_Four,
Ti [OCH₂CH (C₂H_Five) C_FourH₉]_FourEtc.
You can

Further, TiX '_Four(Where X'is a halogen
(Indicated by a
An object can also be used as a titanium source. Such a minute
Specific examples of the child compound include TiCl_Four・ CH₃COC
₂H_Five, TiCl_Four・ CH₃CO₂C₂H_Five, TiCl
_Four・ C₆H_FiveNO₂, TiCl_Four・ CH₃COCl, T
iCl_Four・ C₆H_FiveCOCl, TiCl_Four・ C₆H_FiveC
O₂C₂H_Five, TiCl_Four・ ClCOC₂H_Five, TiC
l_Four・ C_FourH_FourO etc. are mentioned. Also TiCl₃(T
iCl_FourTo H₂Reduced with, and reduced with Al metal
, Or reduced with an organometallic compound, etc.
Mu), TiBr₃, Ti (OC ₂H_Five) Cl₂, TiC
l₂, Dicyclopentadienyl titanium dichloride
It is also possible to use titanium compounds such as These titanium
TiCl among other compounds_Four, Ti (OR⁷)_Four(here
R⁷Are the same as above), especially Ti (OC_FourH₉)_Four, Ti
(OC₂H_Five) Cl₃Etc. are preferred. Halogen is above
Halogenated compounds of magnesium and / or titanium
Is normally supplied from other sources, but other halogen sources,
For example AlCl₃, AlBr₃, (C₂H_Five) AlC
l₂, (C₂H_Five) AlCl, Al (OCH₃)₂C
l, etc. Aluminum halide or SiCl_Four, S
i (CH₃) Cl₃, Etc. Silicon halides, PC
l_FivePhosphorus halides such as WCl₆, MoCl_Fiveetc
Can also be supplied from known halogenating agents such as
It Halogen contained in the catalyst component is fluorine, chlorine,
It may be bromine, iodine or a mixture thereof,
Particularly preferred is chlorine.

The component (A) used in the present invention can be obtained by contacting a solid component produced by using the above-mentioned magnesium compound and titanium compound with the above-mentioned silicon compound, preferably magnesium dihalide and Ti. (OR
⁷ ) ₄ (R ⁷ is the same as above) in a hydrocarbon solvent containing alkylhydropolysiloxane (alkyl having 1 to 10 carbon atoms), preferably having a polymerization degree such that the viscosity is 1 to 100 centistokes, Is a solid component obtained by contacting with to precipitate a solid, more preferably a solid component obtained by contacting this solid component with a halogenating agent, particularly preferably silicon tetrachloride.

Further, when producing this solid component,
An electron donor can also be used as an internal donor and can be manufactured, and the use of an internal donor is preferable. Examples of electron donors (internal donors) that can be used to produce this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid esters, ethers, acid amides, and acid anhydrides. Examples thereof include oxygen-containing electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as isopropylbenzyl alcohol, (b) phenol, cresol,
6 to 2 carbon atoms which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol and naphthol
5 phenols, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other ketones having 3 to 15 carbon atoms, (d)
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, trialdehyde, naphthaldehyde,
(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, cyclohexane, ethyl carboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate. Methyl toluate, ethyl toluate, amyl triylate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
C2 to C20 organic acid esters such as phthalide and ethylene carbonate, (f) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthalic acid halide and other acid halides having 2 to 15 carbon atoms Ethers having 2 to 20 carbon atoms such as (to) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc., (thi) acetic acid amide, benzoic acid amide, toluic acid amide, etc. Amides such as acid amides, (ri) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine,
(N) Nitriles such as acetonitrile, benzonitrile, tolunitrile, and the like can be mentioned. Two or more kinds of these electron donors can be used. Among these, organic acid esters and acid halides are preferable, and phthalic acid esters, acetic acid cellosolve esters and phthalic acid halides are particularly preferable.

The component (A) according to the present invention substantially contains the silicon compound represented by the specific general formula in that form. Here, "comprising substantially in that form" means that when the component (A) is analyzed by gas chromatography, the silicon compound contained therein is substantially of the structure represented by the general formula. It means that you can confirm that it is a thing. Now, the silicon compound used for producing the component (A) in the present invention is represented by the general formula R ¹ R ² _3-n Si (OR ³ ) _n (wherein R ¹ is a branched aliphatic hydrocarbon residue or An alicyclic hydrocarbon residue, R ² represents a hydrocarbon residue which is the same as or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3). It is a thing. The silicon compound may be a mixture of two or more compounds of the above formula.

When R ¹ is a branched aliphatic hydrocarbon residue, it is preferably branched from a carbon atom adjacent to a silicon atom. In that case, the branching group is preferably an alkyl group, a cycloalkyl group or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group). More preferable R ¹ is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferable. When R ¹ is a branched aliphatic hydrocarbon residue, the carbon number is usually 3 to
20, preferably 4 to 10. When R ¹ is an alicyclic hydrocarbon residue, the carbon number is usually 5 to 20, preferably 5 to 10. R ² is usually a branched or linear saturated aliphatic hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 which is the same as or different from R ¹ . R ³ is usually an aliphatic hydrocarbon residue, preferably an aliphatic hydrocarbon residue having 1 to 10 carbon atoms.

Specific examples of the silicon compound used in the present invention are as follows. (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH
₃ ) ₃ CSi (CH (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 , (C
H ₃ ) (C ₂ H ₅ ) CHSi (CH ₃ ) (OC
_{H 3) 2, ((CH} 3) 2 CHCH 2) 2 Si (OCH
₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (CH ₃ )
(OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (C
_{H 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 , (CH ₃ ) ₂ CH (CH
₃ ) ₂ CSi (CH ₃ ) (OCH ₃ ) ₂ , ((CH ₃ )
₃ C) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ )
₂ CSi (OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ C
Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ CSi (O-tC
₄ H ₉ ) (OCH ₃ ) ₂ , (iC ₃ H ₇ ) ₂ Si (OC
_{H 3) 2, (iC 3} H 7) 2 Si (OC 2 H 5) 2,
(IC ₄ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ ) ₃ C
_{(C 6 H 13) Si (} OC 4 H 9) 2, (CH 3) 3 C
_{(C 5 H 9) Si (} OiC 3 H 7) 2, (C 5 H 9) 2
Si (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OC
₂ H ₅ ) ₂ , (C ₅ H ₉ ) ₂ (CH ₃ ) Si (OC
_{H 3) 2, (C 5} H 9) (iC 4 H 9) Si (OC
_{H 3) 2, (C 6} H 11) Si (CH 3) (OC
H ₃ ) ₂ , (C ₆ H ₁₁ ) Si (OCH ₃ ) ₂ , (C ₆ H
₁₁ ) (iC ₄ H ₉ ) Si (OCH ₃ ) ₂ , (iC
₄ H ₉ ) (secC ₄ H ₉ ) Si (OCH ₃ ) ₂ , (i
_{C 4 H 9) (iC 3} H 7) Si (OC 5 H 11) 2, HC
(CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) (OC
H ₃ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (OC
H ₃ ) ₃ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (OC
₂ H ₅ ) ₃ ,

[0018]

Embedded image

As described above, the component (A) of the present invention contains an optional component in addition to the above-mentioned essential components, if necessary, but the following are applicable as such an optional component. Compounds of (A) Vinylsilane compound As the vinylsilane compound, monosilane (SiH ₄ ) is used.
Where at least one hydrogen atom is vinyl (CH ₂ = CH
-) And some of the remaining hydrogen atoms are replaced with halogen (preferably Cl), alkyl (preferably having from 1 to 12 carbon atoms), aryl (preferably phenyl), etc. and shows a structure, more _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si _{(CH 3) 3, CH 2} = CH-SiCl 3, CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) H, CH 2 = CH-SiCl (C 2 H 5) _{2, CH 2 = CH-Si} (C 2 H 5) 3, CH 2 = CH-Si (CH 3) (C 2 H 5) 2, CH 2 = CH-Si (C 6 H 5) (CH 3) _{2, CH 2 = CH-Si} (CH 3) 2 (C 6 H 4 CH 3), (CH _{2 = CH) (CH 3)} 2 -Si-O-Si (CH
₃ ) ₂ (CH = CH ₂ ), (CH ₂ = CH) ₂ SiCl
₂ , (CH ₂ ═CH) ₂ Si (CH ₃ ) _{2 and the} like can be exemplified. Of these, vinylsilane, vinylalkylsilane (alkyl having 1 to 12 carbon atoms) and vinylhalogenated silane that do not contain oxygen are preferable.

(B) Organometallic compounds of metals of groups I to III of the periodic table As organometallic compounds of metals of groups I to III of the periodic table,
It has at least one organic group-metal bond. In that case, the organic group has about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
Approximately 6 hydrocarbyl groups are typical. The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is satisfied by an organic group is a hydrogen atom, a halogen atom, a hydrocarbyloxy group (a hydrocarbyl group has 1 to 1 carbon atoms). About 10, preferably 1-6
Degree), or the metal through an oxygen atom (specifically, in the case of methylalumoxane)

[0021]

Embedded image

Others are satisfied. Specific examples of such an organometallic compound include (a) methyllithium, n
-Organolithium compounds such as butyllithium and tert-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, butylmagnesium chloride, tert-butylmagnesium bromide and other organomagnesium compounds, (c) diethylzinc and dibutyl Organozinc compounds such as zinc, (d) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, diethyl aluminum ethoxide, ethyl aluminum sesquichloride, ethyl aluminum dichloride,
Examples include organic aluminum compounds such as methylaluminoxane. Among these, the organoaluminum compound is
Particularly, a trialkylaluminum compound is preferable. The above optional components (a) and (b) can be used alone or in combination of two or more. Using these optional components, the effect of the present invention, namely the activity and stereoregularity, becomes greater.

Production of Component (A) The component (A) is prepared by contacting each component constituting the component (A), or optionally the above-mentioned optional components with each other in a stepwise or temporary manner, and in the middle and / or between them. Finally an organic solvent,
It can be produced, for example, by washing with hydrocarbons or halohydrocarbons, which is the preferred production method. In that case, a solid product containing Ti, Mg and halogen as essential components may be first produced and then contacted with the silicon compound represented by the general formula (so-called two-step process), or Ti, Mg and It is also possible to use a method (so-called one-step method) for producing the component (A) all at once by making the silicon compound already exist in the process of producing a solid product containing halogen as an essential component. The preferred method is the former.

The contact conditions of the respective components constituting the above-mentioned component (A) may be arbitrary as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is about -50 to 200 ° C, preferably 0 to 100 ° C,
Is. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, polysiloxanes and the like. Ingredient (A)
The amount of each of the components constituting the above may be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of titanium compound used is 1 × 10 ^-4 to 1 in molar ratio with respect to the amount of magnesium compound used.
The range of 000 is good, and the range of 0.01 to 10 is preferable. When a compound therefor is used as a halogen source, the amount used is 1 × 10 6 in molar ratio with respect to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. The range of ^{-2 to} 1000 is preferable, and the range of 0.1 to 100 is preferable. The amount of the silicon compound used is in the range of 0.01 to 1000, preferably 0.1 to 100 in terms of the atomic ratio of silicon to the titanium component constituting the component (A) (silicon / titanium). The amount of the vinylsilane compound used is 0.001 to 10 in terms of molar ratio to the titanium component constituting the component (A).
The range of 00 is good, and more preferably 0.01 to 10.
It is within the range of 0. When the aluminum and boron compounds are used, the amount thereof used is preferably in the range of 1 × 10 ^{−3 to} 100, preferably 0.01 to 1 in terms of molar ratio with respect to the amount of the magnesium compound used. Is. When the electron-donating compound is used, its amount is 1 × 10 6 in molar ratio with respect to the amount of the above-mentioned magnesium compound.
^It is preferably in the range of ^-3 to 10 and more preferably in the range of 0.01 to 5.

Component (A) used in the above-mentioned method of the present invention
Is as follows. Solid catalyst component for stereoregular polymerization of olefins containing titanium, magnesium and halogen as essential components, and substantially containing a silicon compound represented by the following general formula in the form thereof: R ¹ R ² _{3 -n} Si (OR ³ ) _n (wherein R ¹ , R ² , R ³ and n are defined as above).

Titanium, magnesium, halogen and an electron donor, particularly preferably a compound selected from phthalic acid chloride, phthalic acid ester and cellosolve acetate, is contained as an essential component, and the above silicon compound is substantially contained in the form thereof. A solid catalyst component for stereoregular polymerization of an olefin contained.

In a hydrocarbon solvent containing Ti (OR ⁷ ) ₄ (R ⁷ is preferably a hydrocarbon residue having 1 to 10 carbon atoms) and magnesium dihalide, an alkylhydropolysiloxane (alkyl having 1 to 10 carbon atoms) is added. A halogenating agent, particularly preferably silicon tetrachloride, is brought into contact with the solid component obtained by contacting the solid component with a polymerization degree such that the viscosity is from 1 to 100 centistokes, and an electron donor and silicon are further added. A solid catalyst component as described above prepared using a compound.

The above solid catalyst prepared by contacting with a halogenating agent in the above, and further using a vinylsilane compound and / or an organometallic compound of Group I to III metal of the periodic table, an electron donor and a silicon compound. component.

A solid obtained by co-milling a magnesium dihalide, a titanium compound and the above silicon compound is added to a vinylsilane compound and / or I to
The solid catalyst component as described above, which is produced by contacting an organometallic compound of Group III metal.

<Component (B)> The component (B) used in the present invention is an organoaluminum compound represented by the following general formula. R ⁴ _3-m AlX _m (wherein R ⁴ is a hydrocarbon residue having 1 to 20 carbon atoms,
Represents hydrogen or halogen, and m represents a number of 0 ≦ m ≦ 2. Specific examples of such a compound include (a) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, and trioctyl aluminum. , Tridecyl aluminum, trialkyl aluminum, etc., (b) diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc. alkyl aluminum halides, (c) diethyl aluminum hydride,
Aluminum alkoxides such as diisobutylaluminum hydride, (d) diethylaluminum ethoxide, and diethylaluminum phenoxide are available.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as R ⁸ _3-q Al
(OR ⁹ ) _q (wherein 1 ≦ q ≦ 3, R ⁸ and R ⁹ are the same or different hydrocarbon residues having about 1 to 20 carbon atoms) are used together. You can also For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride. It can be used in combination with.

<Component (C)> The component (C) used in the present invention is an organozinc compound represented by the following general formula. The general formula R ⁵ R ⁶ Zn (wherein R ⁵ and R ⁶ are each independently a carbon number of 1 to 1).
20, preferably a hydrocarbon residue having 1 to 10 carbon atoms. ) Specific examples of such a compound include (CH ₃ ) ₂ Zn,
(C ₂ H ₅ ) ₂ Zn, (iC ₃ H ₇ ) ₂ Zn, (iC _{4
H 9) 2 Zn, (nC} 4 H 9) 2 Zn, (C 5 H 11) 2
_{Zn, (C 6 H 13)} 2 Zn, (CH 3) (C 2 H 5) Z
n, (C ₈ H ₁₇ ) ₂ Zn and the like.

<Amounts of Components (A), (B) and (C) Used> The amounts of components (A), (B) and (C) of the present invention are arbitrary as long as the effects of the present invention are observed. However, in general, the following ranges are preferred. The amount of the component (B) used is within the range of 0.1 to 1000, preferably 1 to 100, by weight ratio of the component (B) / component (A). The amount of the component (C) used is a molar ratio of the component (C) /
The component (B) is 0.01 to 100, preferably 0.05.
-10, and more preferably 0.1-2.

<Catalyst Use / Polymerization> The catalyst of the present invention can be applied not only to ordinary slurry polymerization but also to liquid phase solvent-free polymerization, solution polymerization or gas phase weight polymerization substantially without solvent. It also applies to legality. Also, continuous polymerization,
It can also be applied to batch polymerization or prepolymerization. As the polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbons such as toluene may be used alone or as a mixture. Polymerization temperature is from room temperature to 150
° C. approximately, preferably 50 to 100 ° C., the polymerization pressure is atmospheric pressure ~300kg / cm ^2, preferably about atmospheric pressure to
It is 50 kg / cm ² , and hydrogen can be used as a molecular weight regulator at that time.

The amount of hydrogen used is such that the concentration in the gas phase portion of the polymerization tank is 3 to 50 vol in terms of hydrogen / olefin volume percent.
%, Preferably 5 to 30 vol%, more preferably
It is within the range of 7 to 20% by volume. If the concentration is too low, the target polymer having a small molecular weight cannot be obtained, and if it is too high, the molecular weight is too small, which is not practical. Further, in order to control the stereoregularity of the obtained polymer, a known electron-donating compound such as ester, ether or amine can be used as the third component during the polymerization. In the case of slurry polymerization, the amount of the component (A) used is 0.001 to 0.
A range of 1 gram, component (A) / liter solvent is preferred.

The α-olefins polymerized by the catalyst system of the present invention have the general formula R--CHCH ₂ (where R is 1 carbon atom).
10 to 10 hydrocarbon residues, which may have a branching group)
Is represented by. Specific examples include olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Preferred is propylene. Besides homopolymerization of these α-olefins, copolymerizations such as propylene and up to 30% by weight, based on propylene, of the above olefins, especially ethylene,
Can be copolymerized with. Copolymerization with other copolymerizable monomers (for example, vinyl acetate, diolefin, etc.) can also be performed. The olefin polymer obtained by the method of the present invention can be produced with high activity and high stereoregularity even in a polymer having an MFR of less than 30 g / 10 min, but the effect is relatively small, and the MFR is usually 30 to 10
The effect of the present invention is great in producing a polymer of 00 g / 10 min, preferably 50 to 500 g / 10 min.

[0038]

【Example】

 Example-1 [Production of component (A)] In a flask thoroughly replaced with nitrogen,
200 ml dehydrated and deoxygenated n-heptane
Was introduced, and then MgCl₂0.4 mol and Ti
(O-nC_FourH ₉)_FourWas introduced at 0.8 mol, and 2
Allowed to react for hours. After the reaction was completed, the temperature was lowered to 40 ° C. and then
Ide methylhydropolysiloxane (20 centistoke
48 ml) and let them react for 3 hours
It was The solid component produced was washed with n-heptane. Just
In a flask thoroughly replaced with nitrogen, and purify in the same manner as above.
50 ml of n-heptane was introduced and synthesized as above.
0.24 mol of the obtained solid component was introduced in terms of Mg atom.
Then add 25 ml of n-heptane to SiCl_Four0.
Mix 4 moles and introduce into flask at 30 ℃ for 30 minutes
Then, the mixture was reacted at 70 ° C. for 3 hours. After the reaction is completed, n-hep
Washed with tan. Then as a silicon compound (t-C_Four
H₉) (C₂H_Five) Si (OCH₃)₂2.6 ml
It was put in and contacted at 20 ° C. for 2 hours. After contact, n-hep
It was thoroughly washed with tongue to obtain a component (A). Take a part
When taken out and subjected to compositional analysis, Ti content = 2.7 wt
%, (T-C_FourH₉) (C₂H_Five) Si (OCH₃)₂
Content = 6.9 wt%.

[Polymerization of Propylene] In a stainless steel autoclave having an internal volume of 1.5 liter equipped with a stirrer and a temperature controller, sufficiently dehydrated and deoxygenated n-heptane was added as 500 ml of the component (B) to AlEt.
100 mg of ₃ and 108 mg of diethylzinc as component (C) and 1 (A) prepared above
Then, 5 mg of hydrogen was introduced, the temperature was raised, and the pressure was raised to carry out a polymerization operation under the conditions of polymerization pressure = 5 kg / cm ² G, polymerization temperature = 70 ° C., and polymerization time = 2 hours. After polymerization,
The polymer slurry obtained was separated by filtration and the polymer was dried. As a result, 187.4 g of polymer was obtained. The hydrogen concentration in the gas phase of the polymerization tank was 5.8.
It was vol%. Further, 0.18 g of polymer was obtained from the filtrate. From the boiling heptane extraction test,
All products I. I (hereinafter abbreviated as T-I.I) was 98.2 weight percent. The MFR was 48.3 g / 10 minutes, and the polymer bulk specific gravity was 0.48 g / cc.

Comparative Example-1 In the polymerization of propylene of Example-1, the hydrogen concentration in the polymerization tank was 8. without using diethylzinc as the component (C).
Polymerization was performed in exactly the same manner except that the amount was 1 vol%. 1
62.5 grams of polymer were obtained, T-I. I = 9
It was 7.3% by weight, MFR = 45.4 g / 10 min, and polymer bulk specific gravity = 0.47 g / cc.

Example-2 [Production of Component (A)] In the production of the component (A) of Additional Example-1, (t-C ₄ H ₉ ) (C
_{2 H 5) Si (OCH 3} ) 2 in the place (t-C
₄ H ₉ ) (n-C ₆ H ₁₁ ) Si (OCH ₃ ) ₂ 1.2 m
Component (A) was prepared in exactly the same manner, except that 3.3 g of 1 and (iC ₄ H ₉ ) ₃ Al were used. When part of the composition was taken out and analyzed for composition, Ti content = 2.9.
_{wt%, (t-C 4} H 9) (n-C 6 H 11) Si (OC
The H ₃ ) ₂ content was 10.7 wt%.

[Polymerization of Propylene] The polymerization temperature was 75 ° C. and the component (B) was changed under the polymerization conditions for the polymerization of propylene of Example-1.
Polymerization was carried out in the same manner as in Example-1 except that 125 mg of Al (C ₂ H ₅ ) ₃ was used as the component and 135 mg of diethylzinc was used as the component (C). The hydrogen concentration in the gas phase of the polymerization tank was 5.9 vol%. The result was 207.2 grams of polymer,
T-I. I = 98.5% by weight, MFR = 55.2 g / 1
At 0 minutes, the bulk density of the polymer was 0.49 g / cc.

Example-3 [Production of component (A)]
200 ml dehydrated and deoxygenated n-heptane
Was introduced, and then MgCl₂0.4 mol and Ti
(O-nC_FourH ₉)_FourWas introduced at 0.8 mol, and 2
Allowed to react for hours. After the reaction was completed, the temperature was lowered to 40 ° C. and then
Ide methylhydropolysiloxane (20 centistoke
48 ml) and let them react for 3 hours
It was The solid component produced was washed with n-heptane. Just
In a flask thoroughly replaced with nitrogen, and purify in the same manner as above.
50 ml of n-heptane was introduced and synthesized as above.
0.24 mol of the obtained solid component was introduced in terms of Mg atom.
Then add 25 ml of n-heptane to SiCl_Four 
Mix 0.4 mol and transfer to a flask at 30 ℃ for 30 minutes.
It was put in and reacted at 70 ° C. for 3 hours. After completion of the reaction,
It was washed with putan. Then n-heptane 25 millilitres
Mixture of 0.024 mol of phthalic acid chloride and 7
Introduce into the flask at 0 ℃ for 30 minutes, and let it react at 90 ℃ for 1 hour.
I responded. After completion of the reaction, it was washed with n-heptane. Next
With SiCl_Four 6 ml at 80 ° C by introducing 10 ml
Allowed to react for hours. After the reaction is complete, wash thoroughly with n-heptane.
It was used as a solid component for producing component (A) by purification. This
Its titanium content was 1.24% by weight.

50 ml of sufficiently purified n-heptane was introduced into a flask thoroughly replaced with nitrogen, then 5 g of the solid component obtained above was introduced, and 0.5 ml of vinyltrimethylsilane as an optional component and silicon. the compound _{(t-C 4 H 9)} (n-C 8 H 17) Si
0.5 ml of (OCH ₃ ) ₂ and Al (C
1.7 g of ₂ H ₅ ) ₃ was introduced, and the mixture was contacted at 95 ° C. for 2 hours. After the contact was completed, it was thoroughly washed with n-heptane to obtain a component (A). When a part of it was taken out and the composition was analyzed, titanium content = 1.62 wt%, (t-C ₄ H
_{9) (n-C 8 H} 17) Si (OCH 3) 2 content = 5.7
It was wt%.

[Polymerization of Propylene] In a stainless steel autoclave having an internal volume of 1.5 liter equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxidized n-heptane and triethylaluminum (component (B ₁ ) ) 125 mg, diethyl zinc (component (C)) 135 mg and component (A) produced above 10 mg, then hydrogen was introduced, the temperature was raised and the pressure was increased, and the polymerization pressure was 5 kg / cm ² G and the polymerization temperature. = 75
Polymerization was carried out under the conditions of ° C and polymerization time = 2 hours. The hydrogen concentration in the gas phase was 6.7 vol%. After the polymerization is completed, the obtained polymer slurry is separated by filtration,
The polymer was dried. As a result, 236.8 grams of polymer was obtained. In addition, 0.21 g of the polymer was obtained from the filtrate. From the boiling heptane extraction test, all products I.V. I (hereinafter abbreviated as T-I.I) is 98.
It was 5 weight percent. MFR = 77.4 / 10
Minutes, the polymer bulk specific gravity was 0.48 g / cc.

Example 4 [Production of Component (A)] 5 Substituted with Well Purified Nitrogen
In a 00 ml flask, place Mg (OC ₂H_Five)₂
20 g, 100 milliliters of purified toluene
Then TiCl_Four Introduce 60 ml, 7
Raise the temperature to 0 ° C, then add 8.6 milliliters of cellosolve acetate.
Introduced in torr, heated to 100 ° C. and reacted for 3 hours. Anti
After completion of the reaction, the reaction product was thoroughly washed with n-heptane. So
And then TiCl_FourIntroduce 100 ml,
The reaction was carried out at 110 ° C for 3 hours. After the reaction, n-hepta
Solid to produce component (A) after thorough washing with
As an ingredient. Similarly to the synthesis of the component (A) of Example-3,
Add 50 milliliters of n-heptane to a well-purified flask.
Torr, then 5 grams of the solid component obtained above was introduced,
As a silicon compound (cyclo-C_FiveH₉)₂Si
(OCH₃)₂Introduced 1.2 ml, and
(C₂H_Five)₂0.4 g Zn and dimethyl high
Introduce 1.0 gram of dorosiloxane at 50 ° C for 2 hours
Contacted. After the contact was completed, the product was filled with n-heptane.
It was washed for minutes to obtain the component (A). The composition analysis of this
Around, titanium content = 2.3 wt%, (cyclo-C
_FiveH₉)₂Si (OCH₃)₂Content = 9.8 wt%
It was.

[Polymerization of Propylene] Under the polymerization conditions of Example-3, the hydrogen concentration in the gas phase of the polymerization tank was adjusted to 8.3 vol.
Polymerization was performed in exactly the same manner except that the percentage was changed to%. As a result, 158.4 g of a polymer was obtained, and T-I. I
= 98.0 wt%, MFR = 81.7 g / 10 min, and polymer bulk specific gravity = 0.44 (g / cc).

Example-5 [Production of Component (A)] The internal volume of the material was sufficiently replaced with nitrogen to give an internal volume of 0.4.
Made of steel with an inner diameter of 1.6 mm in a liter ball mill
Introducing 23 balls, anhydrous MgCl₂20 grams,
(T-C_FourH ₉) (CH₃) Si (OCH₃)₂3.
2 ml and TiCl_Four1.5 ml
Each was introduced and crushed in an atmosphere of 20 ° C. for 48 hours.
After crushing, take out from the mill to produce component (A)
To be a solid component. Then with fully purified nitrogen
Thoroughly purify in a replaced 500 ml flask.
100 ml of n-heptane was added to the above solid solution.
5 grams and 0.5 milliliters of vinyltrichlorosilane.
Lilith was introduced and contacted at 50 ° C. for 2 hours. End of contact
After completion, wash the contacted material thoroughly with n-heptane to
(A). When the composition of this was analyzed, the titanium content
= 2.2 wt%, (t-C_FourH₉) (CH₃) Si (O
CH₃)₂Content = 8.3 wt%.

[Polymerization of Propylene] Under the polymerization conditions of Example-3, 125 mg of triisobutylaluminum was used as component (B), 57 mg of dibutylzinc was used as component (C), and the amount of component (A) used was 15
Polymerization was carried out in exactly the same manner except that the amount was changed to mg, the polymerization temperature was changed to 65 ° C., and the hydrogen concentration in the gas phase of the polymerization tank was changed to 4.8 vol%. As a result, 89.6 g of a polymer was obtained, and T-I. I = 97.7 wt%, MFR =
33.6 / 10 min, polymer bulk specific gravity = 0.42 (g / c
It was c).

Comparative Example-2 Polymerization was carried out in the same manner as in Example-1 except that the component (C), diethylzinc, was not used and the hydrogen concentration was set to 10.5 vol% under the polymerization conditions of Example-3. Was done. 19
4.5 grams of polymer were obtained, T-I. I = 97.
6% by weight, MFR = 75.8 g / 10 min, and polymer bulk specific gravity = 0.48 g / cc.

Comparative Example-3 Polymerization was carried out in the same manner as in Example-2, except that the component (C), diethylzinc, was not used and the hydrogen concentration was 12.6 vol% under the polymerization conditions of Example-4. Was done. 12
6.3 grams of polymer were obtained, T-I. I = 97.
1% by weight, MFR = 89.1 g / 10 minutes, and bulk density of polymer = 0.44 g / cc.

Comparative Example-4 Polymerization was carried out in the same manner as in Example-3 except that the dibutylzinc as the component (C) was not used and the hydrogen concentration was 8.7 vol% under the polymerization conditions of Example-5. Was done. 73.
1 gram of polymer was obtained, T-I. I = 96.8 wt%, MFR = 35.2 g / 10 min, polymer bulk specific gravity =
It was 0.43 g / cc.

Examples 6 to 10 [Production of Component (A)] In the production of the component (A) of Example-4, except that the silicon compound of the component (ii) was changed as shown in Table-1. The same production process as in Example-4 was carried out to obtain a component (A).

[Polymerization of Propylene] In the polymerization of propylene of Example-4, except that the amounts of the component (B) and the component (C) used were changed as shown in Table-1, Example-2
Polymerization was carried out in exactly the same manner as in. The results are shown in Table-1.

[0055]

[Table 1]

Examples-11 to 13 Polymerization of propylene in Example-3 was carried out in the same manner as in Example-3 except that the hydrogen concentration was changed as shown in Table-2. The results are shown in Table-2.

Comparative Examples 5 to 7 Polymerization of propylene of Comparative Example-2 was carried out in the same manner as Comparative Example-2 except that the hydrogen concentration was changed as shown in Table-2. The results are shown in Table-2.

[0058]

[Table 2]

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[Procedure amendment]

[Submission date] December 6, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A melt flow rate (M) obtained by stereoregularly polymerizing an α-olefin having 3 to 12 carbon atoms in the presence of a catalyst.
In the method for producing an olefin polymer having an FR of 30 to 1000 g / 10 min, the catalyst used is composed of the following components (A), (B) and (C). How to make a coalesce. Component (A): Solid catalyst component for stereoregular polymerization of olefins containing titanium, magnesium and halogen as essential components, and substantially containing a silicon compound represented by the following general formula in that form General formula R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, and R ² is the same or different hydrocarbon residue as R ^1. , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3) Component (B): Organoaluminum compound represented by the following general formula R ⁴ _3-m AlX _m ( Here, R ⁴ is a hydrocarbon residue having 1 to 20 carbon atoms,
Represents hydrogen or halogen, and m represents a number of 0 ≦ m ≦ 2) Component (C): an organozinc compound represented by the following general formula R ⁵ R ⁶ Z _n (where R ⁵ and R ⁶ independently has 1 carbon atom
~ 20 hydrocarbon residues).