JP3357191B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an olefin polymer. More specifically, the present invention provides
An α-olefin having 3 to 12 carbon atoms is subjected to stereoregular polymerization to have a melt flow rate (MFR) of 30 to 1000 g /
The present invention relates to a method for producing an olefin polymer having high activity and high stereoregularity even when producing a polymer as large as 10 minutes (relatively small in molecular weight).

[0002]

2. Description of the Related Art Solid components containing titanium, magnesium, halogen and, if necessary, an electron donating compound,
An α-olefin having 3 or more carbon atoms is stereoregularly polymerized using an olefin polymerization catalyst comprising an organometallic compound component of the Groups I to III of the periodic table and, if necessary, an electron-donating compound component. It is known to produce olefin polymers. Further, although an organozinc compound is known as an organometallic component, a catalyst using the same is not used recently because the activity thereof is insufficient.
In recent years, when molding a polyolefin polymer, an improvement in molding speed has been required in order to improve a molding cycle from the viewpoint of economy. For this purpose, the molecular weight of the polymer is small, in other words, the melt flow rate (MF
R) must be large, but even when the molecular weight is small, conventional high stereoregularity is required. If the polyolefin polymer is not a highly stereoregular polymer, 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 a 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, MFR = 1) can be obtained. (MFR = 50), the stereoregularity of the target polymer is reduced under the conditions for producing the polymer, for example, the conditions in which the amount of hydrogen added to the polymerization system is changed. 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, problems such as a large decrease in catalytic activity and an increase in cost of the catalyst are considered. Is inevitable. Therefore, it is desired to provide a production method capable of obtaining a polymer having high activity and high stereoregularity without using a large amount of hydrogen or an electron donor in a place where the molecular weight of the polymer is relatively small.

[0004]

The problem to be solved by the present invention is to solve the above-mentioned problems, and the present invention provides a polymer having a high activity and a high stericity at a relatively small molecular weight of the produced polymer. An object of the present invention is to provide a catalyst from which a polymer having regularity can be obtained.

[0005]

SUMMARY OF THE INVENTION [Summary] The object of the present invention is to provide a solution to these problems, and it is intended that the activity of the catalyst is sufficiently high and the content of the polar vinyl monomer is high. The present invention relates to a method for producing a copolymer having a high water content. That is, in the method for producing an olefin polymer of the present invention, an α-olefin having 3 to 12 carbon atoms is stereoregularly polymerized in the presence of a catalyst to obtain a melt flow rate (MFR) of 3.
A method for producing an olefin polymer of 0 to 1000 g / 10 minutes, wherein the catalyst used comprises the following components (A), (B) and (C). Component (A): titanium, magnesium and halogen containing as essential components, and the silicon compound solid for stereoregular polymerization of olefins comprising a containing catalyst component general formula R ¹ R ² represented by the following general formula _3-n Si (OR ³ ) _n (where R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, R ² is a hydrocarbon residue which is the same as or different from R ¹ , R ³ is a hydrocarbon residue, n represents the number of 1 ≦ n ≦ 3, respectively shown) component (B): represented organoaluminum compound formula R ⁴ _3-m AlX _m (here is the following general formula, R ⁴ represents a hydrocarbon residue having 1 to 20 carbon atoms;
Represents hydrogen or a halogen, and m represents a number satisfying 0 ≦ m ≦ 2. Component (C): an organozinc compound represented by the following general formula: General formula R ⁵ R ⁶ Zn (where R ⁵ and R ⁶ each independently has 1 carbon atom
~ 20 hydrocarbon residues)

[0006]

According to the present invention, a polymer having high activity and a relatively small molecular weight of the target polymer, namely, MF
30 to 1000 g / 10 min at R, preferably 50 to 50 g
Even with a polymer in the range of 0 g / 10 minutes, a polymer having high stereoregularity can be produced. The reason why such an effect is exhibited is not clear, but the use of an organozinc compound makes it possible to obtain a desired polymer having a large 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)> component (A) used in the present invention include titanium, containing magnesium and a halogen as essential components, and a silicon compound represented by the following general formula in the solid catalyst component comprising a free is there. 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 a hydrocarbon identical or different from R ¹ ) R ³ is a hydrocarbon residue, n is a number of 1 ≦ n ≦ 3, respectively. First, here, “containing as an essential component” for Ti, Mg and halogen means that In addition to the three components of the indications, it may contain other suitable elements, each of these elements may exist as any suitable compound, and these elements are mutually bonded It may indicate that it may be present as a result.

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

The magnesium compound used as a magnesium source in the present invention includes magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Is raised. Of these, magnesium dihalide and dialkoxymagnesium are preferred.

The compound serving as a titanium source has a general formula T
i (OR⁷)_4-pX_p(Where R ⁷Is a hydrocarbon residue,
It preferably has about 1 to 10 carbon atoms, and X is
And p is a number satisfying 0 ≦ p ≦ 4).
Compounds. As a specific example, TiCl_Four,
TiBr_Four, Ti (OC_TwoH_Five) Cl_Three, Ti (OC _Two
H_Five)_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti (O
-IC_ThreeH₇) Cl_Three, Ti (O-nC_FourH₉) C
l_Three, Ti (O-nC_FourH₉)_TwoCl_Two, Ti (OC_Two
H_Five) Br_Three, Ti (OC_TwoH_Five) (OC_FourH₉)_TwoC
1, Ti (O-nC _FourH₉)_ThreeCl, Ti (OC₆H
_Five) Cl_Three, Ti (O-iC_FourH₉)_TwoCl _Two, Ti
(OC_FiveH₁₁) Cl_Three, Ti (OC₆H₁₃) Cl_Three, T
i (OC_TwoH_Five)_Four, Ti (O-nC_ThreeH₇)_Four, Ti
(O-nC_FourH₉)_Four, Ti (O-iC _FourH₉)_Four, T
i (O-nC₆H₁₃)_Four, Ti (O-nC₈H₁₇)_Four,
Ti [OCH_TwoCH (C_TwoH_Five) C_FourH₉]_FourEtc.
I can do it.

Further, TiX '_Four(Where X 'is a halogen
Molecular compound obtained by reacting an electron donor described later on
The material can also be used as a titanium source. Such a minute
Specific examples of the child compound include TiCl_Four・ CH_ThreeCOC
_TwoH_Five, TiCl_Four・ CH_ThreeCO_TwoC_TwoH_Five, TiCl
_Four・ C₆H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl, T
iCl_Four・ C₆H_FiveCOCl, TiCl_Four・ C₆H_FiveC
O_TwoC_TwoH_Five, TiCl_Four・ ClCOC_TwoH_Five, TiC
l_Four・ C_FourH_FourO and the like. Also, TiCl_Three(T
iCl_FourTo H_TwoReduced with Al metal
Or reduced with an organometallic compound, etc.
Mu), TiBr_Three, Ti (OC _TwoH_Five) Cl_Two, TiC
l_Two, Dicyclopentadienyl titanium dichloride
It is also possible to use a titanium compound such as These titanium
Among compounds, TiCl_Four, Ti (OR⁷)_Four(here
R⁷Is the same as above), especially Ti (OC_FourH₉)_Four, Ti
(OC_TwoH_Five) Cl_ThreeAre preferred. Halogen is described above
Of magnesium and / or titanium
Is usually supplied from the source, but other halogen sources,
For example, AlCl_Three, AlBr_Three, (C_TwoH_Five) AlC
l_Two, (C_TwoH_Five) AlCl, Al (OCH_Three)_TwoC
l, etc. aluminum halides and SiCl_Four, S
i (CH_Three) Cl_Three, Such as silicon halide, PC
l_FiveHalides such as phosphorus, WCl₆, MoCl_Fiveetc
Can also be supplied from known halogenating agents such as
You. Halogen contained in the catalyst component is fluorine, chlorine,
It may be bromine, iodine or a mixture thereof,
Is preferably 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. (OR
⁷ ) ₄ (R ⁷ is the same as defined above) and a hydrocarbon solvent containing alkylhydropolysiloxane (alkyl having 1 to 10 carbon atoms), preferably having a degree of polymerization such that the viscosity becomes 1 to 100 centistokes; And a solid component obtained by precipitating a solid, more preferably a solid component obtained by contacting the 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 for production, and the use of an internal donor is preferred. Examples of electron donors (internal donors) that can be used for producing this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids, ethers, acid amides, and acid anhydrides. And 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,
C6-C2 which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, and naphthol;
Phenols having 5 to 15 carbon atoms, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone;
C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, trialdehyde and 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 ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
Organic acid esters having 2 to 20 carbon atoms such as phthalide and ethylene carbonate; and acid halides having 2 to 15 carbon atoms such as (f) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and isophthaloyl chloride. Ethers having 2 to 20 carbon atoms such as (g) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; (thi) acetic acid amide, benzoic acid amide, toluic acid amide and the like Acid amides, amines such as (li) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine,
(Nu) Nitriles such as acetonitrile, benzonitrile and tolunitrile, and the like. Two or more of these electron donors can be used. Among these, preferred are organic acid esters and acid halides, and particularly preferred are phthalic acid esters, cellosolve acetate and phthalic acid halides.

The component (A) used in the present invention comprises:
In which also have containing a silicon compound represented by a specific general formula. Here, it is Ru confirmed <br/> silicon compound Ingredient (A) is contained therein when analyzed by gas chromatography is of structures tables in substantially the general formula. The silicon compound used for producing the component (A) in the present invention has a general formula R ¹ R ² _3- nSi (OR ³ ) _n (where R ¹ is a branched aliphatic hydrocarbon residue or An alicyclic hydrocarbon residue, R ² represents a hydrocarbon residue the same as or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3). Things. The silicon compound may be a mixture of a plurality of compounds of the above formula.

When R ¹ is a branched aliphatic hydrocarbon residue, it is preferable that R ¹ is branched from a carbon atom adjacent to a silicon atom. In this 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 preferred R ¹ is ^one in which 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 preferred. When R ¹ is a branched aliphatic hydrocarbon residue, the number of carbon atoms is usually 3 to
20, preferably 4 to 10. When R ¹ is an alicyclic hydrocarbon residue, the number of carbon atoms is usually 5 to 20, preferably 5 to 10. R ² is usually a branched or straight-chain saturated aliphatic hydrocarbon residue having 1 to 20, preferably 1 to 10 carbon atoms which is the same 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 ,
_{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 may contain optional components as required in addition to the above-mentioned essential components. Can be mentioned. (A) Vinyl silane compound As the vinyl silane compound, monosilane (SiH ₄ )
At least one hydrogen atom is vinyl (CH ₂ ＣＨCH
-) And some of the remaining hydrogen atoms are replaced by halogen (preferably Cl), alkyl (preferably having 1 to 12 carbon atoms), aryl (preferably phenyl), etc. More specifically, CH ₂ ＣＨCH—SiH ₃ , CH ₂ ＣＨCH—SiH ₂ (CH ₃ ), CH ₂ ＣＨCH—SiH (CH ₃ ) ₂ , CH ₂ ＣＨCH—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 ＣＨCH—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. Of these, vinyl silane, vinyl alkyl silane (alkyl having 1 to 12 carbon atoms) and vinyl halogenated silane containing no oxygen are preferable.

(B) Organometallic compounds of metals of Groups I to III of the periodic table The organometallic compounds of metals of Groups I to III of the periodic table include:
It has at least one organic group-metal bond. As the organic group in that case, about 1 to 10 carbon atoms, preferably 1 to
About 6 hydrocarbyl groups are typical. The remaining valences (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group may be hydrogen, halogen, hydrocarbyloxy (hydrocarbyl groups having 1 to 1 carbon atoms). About 10, preferably 1 to 6
Degree) or the metal via 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
Organic lithium compounds such as -butyllithium and tert-butyllithium; organic magnesium compounds such as (ii) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, butylmagnesium chloride, and tert-butylmagnesium bromide; (c) diethylzinc and dibutyl Organic zinc compounds such as zinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride,
Organoaluminum compounds such as methylaluminoxane are exemplified. Among them, 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. When these optional components are used, the effect of the present invention, that is, the activity and the stereoregularity are further increased.

Production of Component (A) The component (A) is prepared by bringing the components constituting the component (A) or, if necessary, the above-mentioned optional components into contact with each other in a stepwise or temporary manner, and intermediate and / or Finally, an organic solvent,
For example, it can be prepared by washing with a hydrocarbon or halohydrocarbon, which is a preferred method. In such a case, a solid product containing Ti, Mg and halogen as essential components is first produced, and the solid product is brought into contact with the silicon compound of the above general formula (a two-stage method). In the process of producing a solid product containing a halogen as an essential component, a method of producing the component (A) at once by allowing the silicon compound to be present (in other words, a one-step method) is also possible. The preferred scheme is the former.

The contact condition of each component constituting the above-mentioned component (A) may be any condition as long as the effects of the present invention are recognized, but generally the following conditions are preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.,
It is. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium agitating / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halogenated hydrocarbons, polysiloxanes and the like. Component (A)
The amount of each component constituting can be used arbitrarily as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of the titanium compound to be used is 1 × 10 ⁻⁴ to 1 in a molar ratio to the amount of the magnesium compound to be used.
000, preferably 0.01 to 10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. The range is preferably from ^{-2 to} 1000, and more preferably from 0.1 to 100. 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). When the vinylsilane compound is used, the amount of the vinylsilane compound used is 0.001 to 10 in terms of a molar ratio to the titanium component constituting the component (A).
00, more preferably 0.01 to 10
It is within the range of 0. When the aluminum and boron compounds are used, the amount thereof is preferably in the range of 1 × 10 ^{−3 to} 100, preferably in the range of 0.01 to 1, in a molar ratio with respect to the amount of the magnesium compound. It is. When the electron donating compound is used, the amount of the electron donating compound is 1 × 10
The range is preferably from ^-3 to 10 and more preferably from 0.01 to 5.

The component (A) used in the method of the present invention is as follows. Titanium, magnesium and halogen containing as essential components, and the following stereospecific polymerization solid catalyst component of the general made have containing a silicon compound represented by the formula olefin general formula _{^{R 1 R 2 3-n Si}} ( OR ³ ) _n (where R ¹ , R ² , R ³ and n are as defined above).

The titanium, magnesium, halogen and an electron donor, consisting particularly preferably contains chloride phthalic acid, compound selected from phthalic acid esters and cellosolve acetate, as essential components, and has free of the above silicon compound-olefin Solid Catalyst Component for Stereoregular Polymerization of Water

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

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

The solid obtained by co-grinding the magnesium dihalide, the titanium compound and the silicon compound described above is treated with a vinylsilane compound and / or a periodic table I-
The solid catalyst component as described above, which is produced by bringing an organometallic compound of a Group III metal into contact.

<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 (where R ⁴ represents a hydrocarbon residue having 1 to 20 carbon atoms;
Represents hydrogen or halogen, and m represents a number satisfying 0 ≦ m ≦ 2.) Specific examples of such a compound include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum Alkyl aluminum halides such as trialkylaluminum, tridecyl aluminum, (ii) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) diethylaluminum hydride,
Examples include diisobutylaluminum hydride, (d) aluminum alkoxide such as diethylaluminum ethoxide and diethylaluminum phenoxide.

[0032] These (a) to other organometallic compound with an organoaluminum compound (c), for example R ⁸ _3-q Al
(OR ⁹ ) _q (where 1 ≦ q ≦ 3, R ⁸ and R ⁹ may be the same or different and are a hydrocarbon residue having about 1 to 20 carbon atoms). You can also. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride Can be used in combination.

<Component (C)> The component (C) used in the present invention is an organozinc compound represented by the following general formula. Formula R ⁵ R ⁶ Zn (where R ⁵ and R ⁶ each independently have 1 to 1 carbon atoms)
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)> The amounts of components (A), (B) and (C) used in the present invention are optional as long as the effects of the present invention are recognized. In general, the following range is preferable. The amount of component (B) used is such that component (B) / component (A) is in the range of 0.1 to 1000, preferably 1 to 100 in weight ratio. Component (C) is used in a molar ratio of component (C) /
Component (B) is 0.01 to 100, preferably 0.05
-10, more preferably 0.1-2.

<Use of Catalyst / Polymerization> The catalyst according to the present invention can be applied not only to ordinary slurry polymerization, but also to liquid-phase solventless polymerization, solvent polymerization or gas-phase polymerization which substantially uses no solvent. It also applies to law. Also, continuous polymerization,
The present invention is also applicable to a system of performing batch polymerization or prepolymerization. As a polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane, benzene,
A single or mixture of a saturated aliphatic or aromatic hydrocarbon such as toluene is used. The polymerization temperature is from room temperature to 150
C., preferably 50 to 100 ° C., and the polymerization pressure is from atmospheric pressure to about 300 kg / cm ² , preferably from atmospheric pressure to
Was 50 kg / cm ^2, it is possible to use hydrogen as a molecular weight regulator at that time.

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

The α-olefins to be polymerized by the catalyst system of the present invention have the general formula R—CH−CH ₂ (where R is 1 carbon atom).
To 10 hydrocarbon residues, which may have a branched group)
It is represented by Specifically, there are olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Preferred is propylene. In addition to the homopolymerization of these α-olefins, copolymerisation, for example up to 30% by weight, based on propylene and propylene, of the abovementioned olefins, in particular ethylene,
Can be carried out. Copolymerization with other copolymerizable monomers (eg, 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 minutes, but the effect is relatively small, and the MFR is usually 30 to 10
The effect of the present invention is great when 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 sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2_TwoTo 0.4 mol and Ti
(O-nC_FourH ₉)_FourAt a temperature of 95 ° C.
Allowed to react for hours. After completion of the reaction, the temperature was lowered to 40 ° C.
Ide methylhydropolysiloxane (20 centistoke
48 ml), and react for 3 hours
Was. The resulting solid component was washed with n-heptane. About
Purify in the same manner as described above into a flask
50 ml of n-heptane was introduced and synthesized as described above.
The solid component was introduced in an amount of 0.24 mol in terms of Mg atoms.
Then, SiCl was added to 25 ml of n-heptane._Four0.
Mix 4 mol and introduce into flask at 30 ° C for 30 minutes
Then, the mixture was reacted at 70 ° C. for 3 hours. After the reaction, n-hep
Washed with tan. Then, as a silicon compound (t-C_Four
H₉) (C_TwoH_Five) Si (OCH_Three)_Two2.6 ml
And contacted at 20 ° C. for 2 hours. N-Hep after contact
This was thoroughly washed with a tan to obtain the component (A). Take part
And analyzed for composition, the Ti content was 2.7 wt.
%, (T-C_FourH₉) (C_TwoH_Five) Si (OCH_Three)_Two
Content = 6.9 wt%.

[Polymerization of Propylene] In a 1.5-liter stainless steel autoclave having a stirring and temperature control device, 500 mL of n-heptane sufficiently dehydrated and deoxygenated was added as an AlEt
₃ of 100 mg, 108 mg of diethyl zinc as the component (C) and 1 component of the component (A) prepared above.
Five milligrams and then hydrogen were introduced, the temperature was raised and the pressure was increased, and the polymerization operation was performed under the conditions of polymerization pressure = 5 kg / cm ² G, polymerization temperature = 70 ° C., and polymerization time = 2 hours. After polymerization,
The obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 187.4 grams of a polymer was obtained. The hydrogen concentration in the gas phase of the polymerization tank was 5.8.
vol%. Also, 0.18 grams of polymer was obtained from the filtrate. From the boiling heptane extraction test,
All products I. I (hereinafter abbreviated as TII) was 98.2% by weight. 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 in Example 1, the concentration of hydrogen in the polymerization tank was 8.8 without using diethyl zinc as the component (C).
Polymerization was carried out in exactly the same manner except that the content was 1 vol%. 1
62.5 grams of polymer were obtained and the T.I. I = 9
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 Component (A) of 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 1.2m
Component (A) was prepared in exactly the same manner, except that 3.3 grams of 1 and (iC ₄ H ₉ ) ₃ Al were used. When a part was taken out and analyzed for composition, the Ti content was 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] Under the polymerization conditions for the polymerization of propylene in Example 1, the polymerization temperature was 75 ° C., and the component (B) was used.
As Al (C ₂ H _{5) 3} 125 mg, except for using each of 135 mg of diethyl zinc as the component (C), was exactly the same polymerization as in Example 1. The hydrogen concentration in the gas phase of the polymerization tank was 5.9 vol%. The result is 207.2 grams of polymer,
TI. I = 98.5% by weight, MFR = 55.2 g / 1
At 0 minute, the polymer bulk specific gravity was 0.49 g / cc.

Example 3 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2_TwoTo 0.4 mol and Ti
(O-nC_FourH ₉)_FourAt a temperature of 95 ° C.
Allowed to react for hours. After completion of the reaction, the temperature was lowered to 40 ° C.
Ide methylhydropolysiloxane (20 centistoke
48 ml), and react for 3 hours
Was. The resulting solid component was washed with n-heptane. About
Purify in the same manner as described above into a flask
50 ml of n-heptane was introduced and synthesized as described above.
The solid component was introduced in an amount of 0.24 mol in terms of Mg atoms.
Then, SiCl was added to 25 ml of n-heptane._Four 
Mix 0.4 mol and lead to flask at 30 ° C for 30 minutes
And reacted at 70 ° C. for 3 hours. After the reaction is completed,
Washed with butane. Then 25 milliliters of n-heptane
And 0.024 mol of phthalic acid chloride,
Introduce into flask at 0 ° C for 30 minutes and react at 90 ° C for 1 hour
I responded. After the completion of the reaction, the resultant was washed with n-heptane. Next
With SiCl_Four Introduce 10 milliliters and at 80 ° C
Allowed to react for hours. After the reaction, wash thoroughly with n-heptane.
It was purified to obtain a solid component for producing the component (A). This
Had a titanium content of 1.24% by weight.

Into a flask sufficiently purged with nitrogen, 50 ml of sufficiently purified n-heptane was introduced, then 5 g of the solid component obtained above, 0.5 ml of vinyltrimethylsilane as an optional component and silicon as an optional component. 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 into each, and they were contacted at 95 ° C. for 2 hours. After the completion of the contact, the components were thoroughly washed with n-heptane to obtain Component (A). When a part thereof was taken out and subjected to composition analysis, titanium content = 1.62 wt%, (t-C ₄ H
_{9) (n-C 8 H} 17) Si (OCH 3) 2 content = 5.7
wt%.

[Polymerization of Propylene] In a 1.5-liter stainless steel autoclave having a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, triethyl aluminum (component (B ₁ )) ) 125 milligrams, 135 milligrams of diethylzinc (component (C)) and 10 milligrams of component (A) produced above, then hydrogen was introduced, the temperature was raised and the pressure increased, polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75
The polymerization operation was performed under the conditions of ° C and a polymerization time of 2 hours. The hydrogen concentration in the gas phase was 6.7 vol%. After the polymerization, the obtained polymer slurry is separated by filtration,
The polymer was dried. As a result, 236.8 g of a polymer was obtained. Also, 0.21 g of polymer was obtained from the filtrate. From the boiling heptane extraction test, all products I.I. I (hereinafter abbreviated as TII) is 98.
5 percent by weight. MFR = 77.4 / 10
The polymer bulk specific gravity was 0.48 g / cc.

Example 4 [Production of Component (A)] Substituted with sufficiently purified nitrogen 5
In a 00 ml flask, add Mg (OC _TwoH_Five)_Two
20 grams, 100 milliliters of purified toluene
And then TiCl_Four Introduce 60 ml, 7
The temperature was raised to 0 ° C., and then 8.6 ml of cellosolve acetate was added.
Then, the temperature was raised to 100 ° C. and the reaction was carried out for 3 hours. Anti
After completion of the reaction, the reaction was thoroughly washed with n-heptane. So
After, further TiCl_FourIntroduce 100 ml,
The reaction was performed at 110 ° C. for 3 hours. After the reaction is completed, n-hepta
After washing thoroughly with a solid, a solid for producing the component (A) is obtained.
The ingredients. As in the synthesis of component (A) of Example-3,
Add 50 milliliters of n-heptane to a well-purified flask.
And then 5 grams of the solid component obtained above,
As a silicon compound (cyclo-C_FiveH₉)_TwoSi
(OCH_Three)_Two1.2 ml, and then
(C_TwoH_Five)_Two0.4 g Zn and dimethyl high
Introduce 1.0 g of drosiloxane, 2 hours at 50 ° C
Contact. After the contact is completed, the product is charged with n-heptane.
Then, the mixture was washed to obtain component (A). This is the composition analysis
Roller, titanium content = 2.3 wt%, (cyclo-C
_FiveH₉)_TwoSi (OCH_Three)_TwoContent = 9.8 wt%
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.
%, Except that the polymerization was carried out in the same manner. 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 was sufficiently replaced by nitrogen, 0.4.
Liter ball mill with 1.6mm inner diameter steel
23 balls were introduced and anhydrous MgCl_Two20 grams,
(T-C_FourH ₉) (CH_Three) Si (OCH_Three)_Two3.
2 ml and TiCl_Four1.5 ml
Each was introduced and pulverized in a 20 ° C. atmosphere for 48 hours.
After pulverization is completed, take out from the mill to produce component (A).
For the solid component. Then, with fully purified nitrogen
Purify well in the replaced 500 ml flask
100 ml of the n-heptane thus obtained was mixed with the solid component described above.
5 grams and 0.5 ml of vinyltrichlorosilane
The mixture was introduced in a small amount and contacted at 50 ° C. for 2 hours. End of contact
After that, the contact material was thoroughly washed with n-heptane to remove the components.
(A). When the composition was analyzed, the titanium content
= 2.2 wt%, (t-C_FourH₉) (CH_Three) Si (O
CH_Three)_TwoContent = 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) was used. 15
mg, the polymerization temperature was 65 ° C., and the polymerization operation was carried out in exactly the same manner except that 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 minutes, polymer bulk specific gravity = 0.42 (g / c
c).

Comparative Example 2 Polymerization was carried out in exactly the same manner as in Example 1 except that the hydrogen concentration was changed to 10.5 vol% under the polymerization conditions of Example 3 without using diethyl zinc as the component (C). Was performed. 19
4.5 grams of polymer were obtained and the 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 exactly the same manner as in Example 2 except that the hydrogen concentration was changed to 12.6 vol% under the polymerization conditions of Example 4 without using diethyl zinc as the component (C). Was performed. 12
6.3 grams of polymer were obtained and the T.I. I = 97.
1% by weight, MFR = 89.1 g / 10 min, and polymer bulk specific gravity = 0.44 g / cc.

Comparative Example 4 Polymerization was carried out in the same manner as in Example 3, except that the hydrogen concentration was changed to 8.7 vol% under the polymerization conditions of Example 5 without using dibutyl zinc as the component (C). Was performed. 73.
1 gram of polymer was obtained and the T.I. I = 96.8% by weight, MFR = 35.2 g / 10 min, polymer bulk specific gravity =
It was 0.43 g / cc.

Examples 6 to 10 [Production of component (A)] The procedure of Example 4 was repeated except that the silicon compound of component (ii) was changed as shown in Table 1. The production was carried out in exactly the same manner as in Example 4, to obtain the component (A).

[Polymerization of Propylene] The polymerization of propylene in Example 4 was repeated except that the amounts of the components (B) and (C) used were changed as shown in Table 1.
The polymerization was carried out in exactly the same manner as described above. Table 1 shows the results.

[0055]

[Table 1]

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

Comparative Examples 5 to 7 In the polymerization of propylene in Comparative Example 2, polymerization was carried out in exactly the same manner as in Comparative Example 2 except that the hydrogen concentration was changed as shown in Table 2. Table 2 shows the results.

[0058]

[Table 2]

[Brief description of the drawings]

FIG. 1 is for assisting understanding of the technical contents of the present invention relating to a Ziegler catalyst. >

Claims (1)

(57) [Claims] An α-olefin having 3 to 12 carbon atoms is subjected to stereoregular polymerization in the presence of a catalyst to obtain a melt flow rate (MF).
R) a process for producing an olefin polymer having a content of 30 to 1000 g / 10 minutes, wherein the catalyst used comprises the following components (A), (B) and (C): Manufacturing method of coalescence. Component (A): titanium, magnesium and halogen containing as essential components, and the silicon compound solid for stereoregular polymerization of olefins comprising a containing catalyst component general formula R ¹ R ² represented by the following general formula _3-n Si (OR ³ ) _n (where R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, R ² is a hydrocarbon residue which is the same as or different from R ¹ , R ³ is a hydrocarbon residue, n represents the number of 1 ≦ n ≦ 3, respectively shown) component (B): represented organoaluminum compound formula R ⁴ _3-m AlX _m (here is the following general formula, R ⁴ represents a hydrocarbon residue having 1 to 20 carbon atoms;
Represents hydrogen or a halogen, and m represents a number satisfying 0 ≦ m ≦ 2. Component (C): an organozinc compound represented by the following general formula: General formula R ⁵ R ⁶ Zn (where R ⁵ and R ⁶ each independently has 1 carbon atom
~ 20 hydrocarbon residues)