JP2001048928A - Catalyst for polymerizing propylene and method for polymerizing propylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymerization catalyst which enables the highly active production of the polypropylene which has high stereo-regularity and sufficient effects for improving melt tension and spiral flow and can contribute to the shortening of molding cycles and the reduction in the production costs of large moldings, and to provide a method for polymerizing the propylene. SOLUTION: This catalyst for polymerizing propylene comprises the following components (A), (B) and (C). The component (A): a solid component containing titanium, magnesium and a halogen as essential components and used for the polymerization catalyst. The component (B): an organic aluminum compound component. The component (C): an organic compound of the formula (R1 to R10 are each a substituent having at least one element selected from carbon, hydrogen, oxygen, halogens, nitrogen, sulfur, phosphorus, boron and silicon; R7 and R8 may together form a ring; R9 and R10 may also together form a ring).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization catalyst and a polymerization method capable of obtaining a propylene polymer having a high melt tension and excellent moldability. Therefore, the crystalline polypropylene obtained by the present invention can be suitably used for blow molding, sheet molding, and injection molding.

[0002]

2. Description of the Related Art Polymers used for sheet molding, blow molding and the like are required to have a high melt tension, which requires a wide molecular weight distribution. Also in injection molding, high melt tension is required to improve the appearance of the molded product.

[0003] Conventionally, TiCl ₃ -based catalysts have been used for producing polymers having a high melt tension. However, the use of a TiCl ₃ -based catalyst generally has a problem that the activity is low and the stereoregularity is inferior, so that the amount of the attack polymer produced is large and the rigidity of the product is not sufficiently high.

[0004] In order to solve these problems, polypropylene having high activity and high stereoregularity can be produced.
Various studies have been made to produce a polymer having a wide molecular weight distribution and a high melt tension using a gCl ₂ supported catalyst.

However, regarding the molecular weight distribution, T
It is narrower than iCl ₃ -based catalysts, and the melt tension is not sufficiently high. Thus, there is a problem that the molding processability is poor in sheet molding and blow molding, and the molding appearance is poor such as a flow mark in injection molding. Was.

Accordingly, for molding requiring high melt tension such as blow molding and sheet molding, MgC
It failed to provide a suitable polymer in the production method using l ₂ supported catalyst.

Under these circumstances, the present inventors have found that MgCl
Various attempts have been made to improve _2- supported catalysts. As a result, it has been found that by using a compound having two or more ether bonds and having a specific structure, the melt tension can be further increased, and the present invention has been achieved.

The catalysts utilizing two or more ether bond-containing compounds are described in JP-A-3-294302 and JP-A-3-294302.
294304 and 3-706 are disclosed. However, these known ether bond-containing compounds do not have the effect of increasing the melt tension, and therefore have not been able to obtain the effects of improving flowability and spiral flow.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and a propylene polymer suitable for a molding method such as sheet molding, blow molding, injection molding or the like by using a MgCl ₂ supported catalyst. Is provided.

That is, the present invention provides a propylene polymer having high activity, high stereoregularity, sufficient effects of improving the melt tension and the spiral flow, and contributing to shortening the molding cycle and reducing the cost of large molded products. The present invention provides a polymerization catalyst and a polymerization method that can be used.

[0011]

The present invention provides a propylene polymerization catalyst comprising the following components (A), (B) and (C): Component (A): titanium, magnesium, Solid component for polymerization containing halogen as an essential component Component (B): Organoaluminum compound component Component (C): Organic compound represented by the following general formula 1 General formula 1

[0012]

Embedded image (R ¹ to R ¹⁰ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and R ⁷ and R ⁸ and R ⁹ and R ^{9 10} may form a ring together) and the polymerization of propylene in the presence of the above-mentioned propylene polymerization catalyst.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a combination of specific components (A), (B) and (C). Here, the term “combined” does not mean that the components are only those listed, that is, only the component (A), the component (B), and the component (C). Does not exclude coexistence of other components within a range not to impair the above.

(A) Solid catalyst component The component (A) of the catalyst of the present invention is a solid component for stereoregular polymerization of propylene containing titanium, magnesium and halogen as essential components. is there.

Here, "contained as an essential component" means that, in addition to the three components mentioned above, other suitable elements may be contained, and each of these elements may be any suitable compound. And that these elements may be present as being bonded to each other.

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 mentioned.

Among these, magnesium dihalide,
Dialkoxy magnesium, and the like of ^{_{Mg (OR 16) 2 - p}} X p
(Here, R ¹⁶ is a hydrocarbon group, preferably having 1 to 1 carbon atoms.
X is about 10, X is halogen, and p is 0 ≦
p ≦ 2. ) Is preferred.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR ¹⁷ ) _{4 -qX q} (where R ¹⁷ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms; Represents a halogen, and q is 0 ≦ q ≦ 4).

As a specific example, TiCl_Four, TiBR
_Four , Ti (OC_TwoH_Five) Cl_Three, Ti (OC_TwoH_Five)_TwoC
l_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti (O-iso-C_Three
H₇) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (O
-N-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH _Five) BR_Three, Ti
(OC_TwoH_Five) (On-C)_FourH₉)_TwoCl, Ti (On
-C_FourH₉)_ThreeCl, Ti (OC₆H_Five) Cl_Three, Ti (O-
iso-C_FourH₉)_TwoCl_Two, Ti (On-C_FiveH₁₁) C
l_Three, Ti (On-C₆H₁₃) Cl_Three, Ti (OC
_TwoH_Five)_Four, Ti (On-C_ThreeH₇)_Four, Ti (On-C
_FourH₉)_Four, Ti (O-iso-C _FourH₉)_Four, Ti (On-
-C₆H₁₃)_Four, Ti (On-C₈H₁₇)_Four, Ti (OC
H_TwoCH (C_TwoH_Five) C_FourH₉)_FourAnd the like.

Further, TiX '_Four(Where X 'is a halogen
It is. ) By reacting with an electron donor described below
The compound can also be used as a titanium source. like that
Specific examples of the molecular compound include TiCl_Four・ CH_ThreeCOC
_TwoH_Five, TiCl_Four・ CH_ThreeCO _TwoC_TwoH_Five, TiCl_Four・ C₆
H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl, TiCl_Four・ C ₆
H_FiveCOCl, TiCl_Four・ C₆H_FiveCO_TwoC_TwoH_Five, TiC
l_Four・ ClCOC_TwoH_Five, TiCl_Four・ C_FourH_FourO etc.
It is.

TiCl ₃ (including TiCl ₄ reduced with hydrogen, reduced with aluminum metal, reduced with an organometallic compound, etc.), TiB
It is also possible to use titanium compounds such as R ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , dicyclopentadienyl-titanium-dichloride, and cyclopentadienyl-titanium-trichloride.

Among these titanium compounds, TiC
_{l 4, Ti (O-n} -C 4 H 9) 4, Ti (OC 2 H 5) Cl
_{3 and the} like are preferred.

Halogen is the above-mentioned magnesium and
(Or) is supplied from titanium halides
Other, but common, halogen sources, such as AlCl_ThreeEtc.
Aluminum halide or SiCl_FourEtc. of silicon
Halide, PCl_Three, PCl _FiveHalogenation of phosphorus
Object, WCl₆Halides such as MoC
l _FiveKnown halo such as halides of molybdenum
It can also be supplied from a gentizing agent.

The halogen contained in the solid component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid components used in the present invention include Al (OC ₂ H ₅ ) ₃ and Al (0-iso-C) in addition to the above essential components.
Aluminum compounds such as ₃ H ₇ ) ₃ and Al (OCH ₃ ) ₂ Cl, and B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆
H ₅₎ It is also possible to use a boron compound such as or other components ₃ such as, no problem is that they remain in the solid component as a component of aluminum and boron and the like.

Further, when producing this solid component,
It can also be prepared using an electron donor as an internal donor. Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides,
Examples thereof include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate.

More specifically, (a) a compound having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol and isopropylbenzyl alcohol; Alcohols, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol,
C6 to C2 which may have an alkyl group such as naphthol
5 phenols, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde naphthaldehyde, etc. Aldehydes having 2 to 15 carbon atoms, 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, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, α-valerolactone, coumarin, organic acid monoester such as phthalide, or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate,
Dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-
1,2-dimethylcarboxylate, cyclopropane-
Organic acid esters having 2 to 20 carbon atoms of organic acid polyvalent esters such as 1,2-dicarboxylic acid-di-n-hexyl and diethyl 1,1-cyclobutane-dicarboxylate, (f) ethyl silicate, butyl silicate , Inorganic acid esters such as silicate esters such as phenyltriethoxysilane,
(G) C2-C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl isochloride, etc., (h) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl Ethers having 2 to 20 carbon atoms such as ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as (ii) acetic acid amide, benzoic acid amide and toluic acid amide;
(Nu) methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Amines such as aniline, pyridine, picoline, tetramethylethylenediamine, nitriles such as (ル) acetonitrile, benzonitrile, tolunitrile, (ヲ) 2
-Ethoxymethyl-ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, 3-ethoxy-2-S-butylpropionic acid Alkoxy ester compounds such as ethyl and ethyl 3-ethoxy-2-t-butylpropionate, (W) ethyl 2-benzoylbenzoate, 2- (4′-methylbenzoyl)
Examples include ketoester compounds such as ethyl benzoate and ethyl 2-benzoyl-4,5-dimethylbenzoate.

Two or more of these electron donors can be used. Among these, organic acid ester compounds and acid halide compounds are preferred, and phthalic acid diester compounds, cellosolve acetate compounds and phthalic acid dihalide compounds are particularly preferred.

Further, as described above, in the production of the component (A) of the present invention, an optional component may be contained as necessary in addition to the above-mentioned essential component. Suitable compounds include the following compounds.

(A) Vinyl silane compound As the vinyl silane compound, monosilane (SiH ₄ )
At least one hydrogen atom is a vinyl group (CH ₂ ＣC
H-), and some of the remaining hydrogen atoms are halogen (preferably Cl), alkyl groups (preferably hydrocarbon groups having 1 to 12 carbon atoms), aryl groups (preferably phenyl), alkoxy groups (Preferably an alkoxy group having 1 to 12 carbon atoms) and a structure substituted with others.

More specifically, CH ₂ ＣＨCH—SiH ₃ ,
_{CH 2 = CH-SiH 2 (} CH 3), CH 2 = CH-SiH
_{(CH 3) 2, CH 2} = CH-Si (C 2 H 5) 3, CH 2 =
CH—Si (CH ₃ ) ₂ (C ₂ H ₅ ), CH ₂ ＣＨCH—Si
_{(CH 3) (C 2 H} 5) 2, CH 2 = CH-Si (n-C 4 H
_{9) 3, CH 2 = CH} -Si (C 6 H 5) 3, CH 2 = CH-
_{Si (CH 3) (C 6} H 5) 2, CH 2 = CH-Si (C
H ₃ ) ₂ (C ₆ H ₅ ), CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C _{6
H 4 CH 3), (CH} 2 = CH) (CH 3) 2 Si-O-S
i (CH ₃ ) ₂ (CH ＝ CH ₂ ), (CH ₂ ＣＨCH) ₂ Si
H ₂ , (CH ₂ ＣＨCH) ₂ Si (CH ₃ ) ₂ , (CH ₂ ＣC
H) ₂ Si (C ₆ H ₅ ) _{2 and the} like.

(B) Organometallic compounds of metals of Groups I to III of the periodic table It is also possible to use organometallic compounds of metals of Groups I to III of the periodic table. Periodic Table I used in the present invention
The organometallic compounds of Group III-III metals have at least one organic group-metal bond. As the organic group in that case, a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms is representative.

In an organometallic compound in which at least one of the valences is filled with an organic group, the remaining valences of the metal (if any) are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl is number of 1 to 20, preferably about (specifically, -O-Al (CH ₃ in the case of methyl alumoxane) the metal through the 1-6 degree), or oxygen atom -) is satisfied otherwise.

Specific examples of such an organometallic compound include the following compounds. (A) organic lithium compounds such as methyllithium, n-butyllithium and tert-butyllithium; (C) Organic zinc compounds such as diethyl zinc and dibutyl zinc, (d) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri n-hexyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, diethyl aluminum ethoxide, ethyl aluminum sesquichloride And organoaluminum compounds such as ethylaluminum dichloride and methylalumoxane.

Of these, organoaluminum compounds are particularly preferred. The optional components (a) and (b) are 1
Species or a combination of two or more can be used. When these optional components are used, the effect of the present invention is further increased.

Production of Component (A) The component (A) is obtained 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, to form an intermediate and / or intermediate component. Alternatively, it can be produced by finally washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent.

In this case, a solid product containing titanium, magnesium and halogen as essential components is first produced, and the solid product is brought into contact with the above-mentioned optional components (a two-stage process). In the process of preparing a solid product containing halogen as an essential component, it is also possible to adopt a method of producing the component (A) at once by allowing the above-mentioned optional component to be present at once (that is, a one-step method). The preferred scheme is the former.

The conditions for contacting the components constituting the component (A) may be any conditions 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.
It is. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The ratio of the amounts of the components constituting the component (A) can be arbitrary as long as the effects of the present invention are recognized, but generally the following ranges are preferred.

The amount of the titanium compound used is 0.0001 in mol ratio to the amount of the magnesium compound used.
It is good to be in the range of -1000, preferably 0.01-10.
Within the range. When a compound for that purpose is used as a halogen source, the amount of the compound used may be 0.01 mol ratio to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen or not. It is good to be in the range of -1000, preferably in the range of 0.1-100.

When the vinylsilane compound is used, the amount of the vinylsilane compound to be used is m
The ol ratio is preferably in the range of 0.001 to 1000, and more preferably 0.01 to 100.

When the aluminum and boron compounds are used, the amount thereof is preferably in the range of 0.001 to 100, more preferably 0.01 to 1, in terms of mol ratio to the amount of the magnesium compound. Is within.

When the electron donor is used, the amount of the electron donor is mol to the amount of the magnesium compound.
The ratio is preferably in the range of 0.001 to 10, preferably 0.1.
It is in the range of 01-5.

The component (A) is produced by contacting a titanium component, a magnesium component and a halogen, if necessary, using other components such as an electron donor, for example, by the following production method.

(A) A method of contacting a magnesium halide, a titanium-containing compound and, if necessary, an electron donor.

(B) A method of treating alumina or magnesia with a phosphorus halide compound and contacting it with a magnesium halide, a titanium halide-containing compound and, if necessary, an electron donor.

(C) The reaction product obtained by contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer-silicon compound is not affected. After washing with an active organic solvent, the silicon compound and the electron donor are simultaneously contacted or separately contacted.

As the polymer-silicon compound, a compound represented by the following formula is suitable.

[0049]

Embedded image (Here, R ¹⁸ is a hydrocarbon group having about 1 to 10 carbon atoms, and r is a viscosity of the polymer-silicon compound is 1 to 100.
It shows a degree of polymerization that is about cSt. )In particular,
Methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl Cyclopentasiloxane and the like are preferred.

(D) A magnesium compound is dissolved in a titanium tetraalkoxide and / or an electron donor, and a silicon compound, a titanium compound and, if necessary, an electron Contacting the donors simultaneously, or
The method of contacting each separately.

(E) After reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent and the like,
A method in which an electron donor is brought into contact with this, if necessary, and then a silicon compound, a titanium compound and, if necessary, an electron donor are brought into contact with each other or separately.

(F) A method in which a halogenating agent and / or a titanium compound and a silicon compound are simultaneously contacted with an alkoxymagnesium compound in the presence or absence of an electron donor, or separately.

Among these production methods, (a)
(C), (d) and (f) are preferred. Component (A)
During and / or at the end of its preparation, an inert organic solvent such as an aliphatic or aromatic hydrocarbon solvent (eg, hexane, heptane, toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (eg, chloride n) -Butyl, 1,2-dichloroethylene, carbon tetrachloride chlorobenzene, etc.).

The component (A) used in the present invention can also be used as one having undergone a prepolymerization step comprising contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene. .

Specific examples of olefins used in the preliminary polymerization include those having about 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene,
-Methylbutene-1, 1-pentene, 1-hexene, 4
-Methylpentene-1, 1-octene, 1-decene, 1
-Undecene, 1-eicosene and the like, and specific examples of the diene compound include 1,3-butadiene, isoprene,
1,4-hexadiene, 1,5-hexadiene, 1,3
-Pentadiene, 1,4-pentadiene, 2,4-pentadiene, 2,6-octadiene, cis-2, tra
ns-4-hexadiene, trans-2, trans
-4-hexadiene, 1,3-heptadiene, 1,4-
Heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4, -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,
13-tetradecadiene, p-divinylbenzene, m-
There are divinylbenzene, O-divinylbenzene, dicyclopentadiene and the like.

Further, specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene and the like.

The reaction conditions of the titanium component and the vinyl group-containing compound may be any conditions as long as the effects of the present invention are recognized, but generally the following ranges are preferable. The prepolymerization amount of the vinyl group-containing compound is 0.001 to 100 g, preferably 0.1 to 100 g per 1 g of the solid component (A).
50 g, more preferably in the range of 0.5 to 10 g.

The reaction temperature during the prepolymerization is from -150 to 150
° C, preferably from 0 to 100 ° C. A polymerization temperature that is lower than the “main polymerization”, that is, the polymerization temperature when the α-olefin is polymerized, is preferable. In general, the reaction is preferably carried out with stirring, in which case n-hexane, n-hexane,
An inert solvent such as heptane can also be present.
Prepolymerization can also be performed on a contact product of the component (A1) and the component (A2).

Component (B) Organoaluminum Compound Component The organoaluminum compound component used in the present invention (component
As a specific example of (B)), R¹⁹ _Three−_sAlX_sOr R
²⁰ _Three−_tAl (OR^{twenty one})_t(Where R¹⁹And R ²⁰Is charcoal
A hydrocarbon group or a hydrogen atom having a prime number of 1 to 20,^{twenty one}
Is a hydrocarbon group, X is halogen, s and t
Are 0 ≦ s <3 and 0 <t <3, respectively. )
There is something.

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum; Alkyl aluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; (d) diethylaluminum ethoxide and diethylaluminum Examples thereof include alkylaluminum alkoxides such as phenoxide.

[0061] These (a) to other organometallic compound with an organoaluminum compound (d), for example R ²² ₃ - _u Al (O
R ²³ ) _u (where R ²² and R ²³ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and u is 0 <
u ≦ 3. )) Can also be used in combination.

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 diethyl Combination with aluminum monochloride and the like can be mentioned.

The ratio between the organoaluminum compound component (B) and the titanium component (A) is as follows.
/ Ti = 1 to 1000 mol / mol is common,
Preferably, it is used at a rate of 10 to 500 mol / mol.

Component (C) An organic compound represented by the following general formula 1 is used. General formula 1

[0065]

Embedded image (R ¹ to R ¹⁰ represent carbon, hydrogen, oxygen, halogen, nitrogen,
A substituent having at least one element selected from sulfur, phosphorus, boron and silicon, wherein R ⁷ and R ⁸ and R
⁹ and R ¹⁰ may form a ring together. ).

Specifically, 1,3-butadienyl-1,4
-Dimethyl ether, 1,3-butadienyl-1,4-
Diethyl ether, 1,4-dimethyl-1,3-butadienyl-1,4-dimethyl ether, 1,4-dimethyl-1,3-butadienyl-1,4-diethyl ether,
2,3-dimethyl-1,3-butadienyl-1,4-dimethyl ether, 2,3-dimethyl-1,3-butadienyl-1,4-diethyl ether, 1,2,3,4-tetramethyl-1, 3-butadienyl-1,4-dimethyl ether, 1,2,3,4-tetramethyl-1,3-butadienyl-1,4-diethyl ether, 1,4-diethyl-1,3-butadienyl-1,4- Dimethyl ether, 1,4-diethyl-1,3-butadienyl-1,4
-Diethyl ether, 2,3-diethyl-1,3-butadienyl-1,4-dimethyl ether, 2,3-diethyl-1,3-butadienyl-1,4-diethyl ether, 1,2,3,4-tetraethyl -1,3-butadienyl-1,4-dimethyl ether, 1,2,3,4-tetraethyl-1,3-butadienyl-1,4-diethyl ether, 1,4-diphenyl-1,3-butadienyl-1, 4-dimethyl ether, 1,4-diphenyl-
1,3-butadienyl-1,4-diethyl ether,
2,3-diphenyl-1,3-butadienyl-1,4-
Dimethyl ether, 2,3-diphenyl-1,3-butadienyl-1,4-diethyl ether, 1,2,3,4
-Tetraphenyl-1,3-butadienyl-1,4-dimethyl ether, 1,2,3,4-tetraphenyl-
1,3-butadienyl-1,4-diethyl ether can be mentioned.

R ⁷ and R ⁸ and R ⁹ and R ¹⁰ together form a ring, in particular, as an example of a benzene ring, 1,1 ′
-Binaphthyl-dimethyl ether, 1,1'-binaphthyl-diethyl ether, 2,2'-biphenyl-dimethyl ether, 2,2'-biphenyl-diethyl ether, 3,3 ', 5,5'-tetratert-butyl-
(1,1 ′ biphenyl) -2,2′-dimethyl ether, 3,3 ′, 5,5′-tetratert-butyl-
(1,1'biphenyl) -2,2'-dimethyl ether can be mentioned.

Of these, preferred are 2,2'-biphenyl-dimethyl ether and 2,2'-biphenyl-diethyl ether.

The ratio of the compound represented by the general formula 1 of the component (C) to the organoaluminum compound of the component (B) is 0.1%.
The molar ratio is generally from 01 to 10 mol / mol, preferably from 0.05 to 1.0 mol / mol.

<Polymerization of Propylene> The polymerization method for producing the crystalline polypropylene of the present invention may be any method as long as the target polypropylene of the present invention can be obtained. Can be

Slurry polymerization using a hydrocarbon solvent, liquid-phase solventless polymerization (bulk polymerization) substantially using no solvent, solution polymerization, gas-phase polymerization and the like can be mentioned.

As the polymerization solvent in the case of slurry polymerization,
Saturated aliphatic or aromatic hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, benzene, and toluene are used alone or as a mixture. Examples of the polymerization method employed include a method of performing continuous polymerization, batch polymerization, multistage polymerization, or prepolymerization.

The polymerization temperature is usually about 20 to 200 ° C., preferably 50 to 150 ° C., and the polymerization pressure is from atmospheric pressure to
About 300 kg / cm ² , preferably atmospheric pressure to 100 k
g / cm ^2, at which time hydrogen can be additionally used as a molecular weight regulator.

In the polymerization using the catalyst system of the present invention, in addition to homopolymerization of propylene, copolymerization with a monomer copolymerizable with propylene (eg, ethylene, α-olefin, diene, styrene, etc.) Can also be done. Up to 15% by weight of these copolymerizable monomers in random copolymerization,
In block copolymerization, up to 50% by weight can be used

[0075]

The present invention will be described in more detail with reference to the following examples. The method and apparatus for measuring each physical property value in the present invention are described below.

[MFR] Apparatus: Melt indexer manufactured by Takara Measuring method: JIS-K6758.

[MT] Capillograph 190 ° C. Orifice 2.095 mmφ × 8.1 mm Extrusion speed 10 mm / min. Tensile speed 4 mm / min. [Spiral flow length] Spiral flow measurement was performed using an SJ type (in-line screw type) injection molding machine under the following conditions.

Molding temperature: 240 ° C. Injection pressure: 800 kg / cm ² Injection time: 6 seconds Mold temperature: 40 ° C. Injection rate: 50 g / sec Example-1 [Production of component (A)] A flask sufficiently purged with nitrogen. To
200 ml of dehydrated and deoxygenated n-heptane were introduced, and then 0.4 mol of MgCl ₂ and Ti (On-
0.8 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then methylhydropolysiloxane (of 20 cSt) was added for 48 m.
1 and then reacted for 3 hours. N-
Washed with heptane.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
The solid component synthesized above was converted to 0.24 mo in terms of Mg atom.
1 was introduced. Then, SiCl ₄ was added to 25 ml of n-heptane.
0.4 mol was mixed, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, n
-Washed with heptane. Then, SiCl ₄ 0.4m
was introduced and reacted at 80 ° C. for 6 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A).

[Polymerization of Propylene] In a 1.5-liter stainless steel autoclave equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was used as the above-mentioned component (C). 53 mg of 1'-binaphthyl-dimethoxy ether and 15 mg of the component (A) produced above, 125 mg of triethylaluminum and then 300 ml of hydrogen were introduced, the temperature was raised and the pressure was increased, and the polymerization pressure was 5 kg / cm ² G and the polymerization temperature was 75. ℃,
Propylene was polymerized under the condition of polymerization time = 2 hours. The following additives were blended with the obtained polymer and pelletized by an extruder.

Additive 2,6-di-tert-butylphenol 0.10 wt% RA1010 (manufactured by Ciba-Geigy) 0.05 wt% Calcium stearate 0.10 wt% PTBBA-A1 (manufactured by Shell Chemical) 0.10 wt% Pellets obtained Was used to perform spiral flow measurement. Activity during polymerization, attack derivation rate, MF of polymer
Regarding R, MT, and spiral flow values, the following examples and comparative examples are shown in the following table.

Comparative Example-1 In [Propylene polymerization], 2
The same experiment as in Example 1 was performed, except that 36 mg of -isopropyl-2-isopentyl-1,3-dimethoxypropane was used, and 300 ml of hydrogen was successively introduced.

Example 2 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane were introduced, and then 0.4 mol of MgCl ₂ and Ti (On-
0.8 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then methylhydropolysiloxane (of 20 cSt) was added for 48 m.
1 and then reacted for 3 hours. N-
Washed with heptane.

Then, the flask was sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
The solid component synthesized above was converted to 0.24 mo in terms of Mg atom.
1 was introduced. Then, SiCl ₄ was added to 25 ml of n-heptane.
0.4 mol was mixed, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, n
-Washed with heptane. Then, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane,
The mixture was introduced into the flask at 30 ° C for 30 minutes and reacted at 90 ° C for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then, 0.4 mol of SiCl ₄ was introduced and reacted at 80 ° C. for 6 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component (A).

[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 was used as the above-mentioned component (C). 53 mg of 1'-binaphthyl-dimethoxy ether and 15 mg of the component (A) produced above, 125 mg of triethylaluminum and then 300 ml of hydrogen were introduced, the temperature was raised and the pressure was increased, and the polymerization pressure was 5 kg / cm ² G and the polymerization temperature was 75.
C., propylene was polymerized under the conditions of polymerization time = 2 hours.

Example 3 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 20 g of Mg (OEt) 2 was introduced to form a suspended state. Next, 60 ml of TiCl ₄ was introduced, the temperature was raised from room temperature to 90 ° C., then 3.3 ml of cellosolve acetate was introduced, and the temperature was raised to 100 ° C., and the reaction was carried out for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with toluene. Next, 100 ml of TiCl _{4 and} 100 ml of toluene were introduced and reacted at 110 ° C. for 3 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane.

[Polymerization of Propylene] 500 ml of sufficiently dehydrated and deoxygenated n-heptane was placed in a 1.5-liter stainless steel autoclave equipped with a stirring and temperature control device. 53 mg of 1'-binaphthyl-dimethoxy ether, 15 mg of the component (A) produced above, 125 mg of triethylaluminum, and then 300 ml of hydrogen were introduced, the temperature was raised and the pressure was increased, and the polymerization pressure was 5 kg / cm ² G and the polymerization temperature was 75. ° C,
Propylene was polymerized under the condition of polymerization time = 2 hours.

Comparative Example-2 In [Propylene polymerization], 2
The same experiment as in Example 2 was performed, except that 36 mg of -isopropyl-2-isopentyl-1,3-dimethoxypropane was used, and 300 ml of hydrogen was successively introduced.

Comparative Example 3 In [Polymerization of propylene], as the component (C),
_{(Cyclo-C 6 H 11)} 2 Si (O-CH 3) 2 51m
The same experiment as in Example 2 was performed except that 300 ml of hydrogen was successively introduced using g.

Comparative Example 4 An experiment was conducted in the same manner as in Example 2 except that 100 ml of hydrogen was introduced without using the component (C).

[0091]

According to the present invention, high activity, high stereoregularity,
In addition, polypropylene having a high melt tension can be manufactured. In addition, since it is excellent in molding workability by using this, there is an effect that it can be suitably used for blow, sheet, injection molding and the like.

[0092]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a flow chart for helping the understanding of the present invention.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4J028 AA01A AB01A AC02A AC03A AC04A AC05A AC06A AC09A AC13A AC14A AC15A AC17A AC19A BA00A BA01B BB00A BB01B BC05A BC14B BC15B BC16B BC24B BC27BCA23 CB23C20 CAB CB52A CB53A CB56A CB58A CB62A CB66A CB68A CB92A EA01 EB02 EB03 EB04 EB11 EB21 EC01 EC02 FA01 FA02 FA04 FA06 FA07 GA06 4J100 AA01Q AA02Q AA03P AB01Q AS00Q CA01 CA04 FA02 FA10

Claims (4)

[Claims] 1. A propylene polymerization catalyst comprising the following components (A), (B) and (C). Component (A): Solid component for polymerization containing titanium, magnesium and halogen as essential components Component (B): Organic aluminum compound component Component (C): Organic compound represented by the following general formula 1 General formula 1 1) (R ¹ to R ¹⁰ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and R ⁷ and R ⁸ and R ⁹ and R ^{9 10} may form a ring together.). 2. The catalyst for propylene polymerization according to claim 1, wherein the solid component for polymerization of component (A) comprises an electron donor selected from organic acid ester compounds and organic acid halide compounds. 3. A method for polymerizing propylene, comprising polymerizing propylene or propylene with a copolymerizable monomer in the presence of the catalyst for propylene polymerization according to claim 1 or 2. 4. The method for polymerizing propylene according to claim 3, wherein the copolymerizable monomer is an α-olefin.