JP2001048927A - 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 production of the polypropylene suitable for molding methods such as a sheet- molding method, a blow molding method and an injection molding method in the presence of the MgCl2-carrying type catalyst, and to provide a method for polymerizing the propylene. SOLUTION: This catalyst for polymerizing propylene comprises the following components (A) and (B). The component (A): a solid catalyst obtained by the mutual contact of the following components (A1) and (A2). The component (A1): a solid component containing titanium, magnesium and a halogen as essential components and used for the polymerization catalyst. The component (A2): 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). The component (B): an organic aluminum compound component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymerization catalyst and a polymerization method capable of obtaining a polypropylene 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, and for that purpose, a wide molecular weight distribution is required. Also in injection molding, it is necessary to have a high melt tension in order to improve the appearance of molding.

[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, the stereoregularity is inferior, 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]

SUMMARY OF THE INVENTION The present invention provides a catalyst for propylene polymerization comprising the following components (A) and (B).

Component (A): A solid catalyst obtained by contacting the following components (A1) and (A2) Component (A1): A solid component for polymerization containing titanium, magnesium and halogen as essential components A2): Organic compound represented by the following general formula 1

[0013]

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.).

Component (B): a process for polymerizing propylene, characterized by polymerizing propylene or a copolymerizable monomer with propylene in the presence of the organoaluminum compound component and the propylene polymerization catalyst. is there.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a combination of a specific component (A) and a specific component (B). Here, the term “combined” does not mean that the components are only those shown, that is, only the component (A) and the component (B), and does not impair the effects of the present invention. It does not exclude that other components coexist.

(A) Solid Catalyst Component The solid catalyst component (A) of the present invention is a contact product of a specific solid component (component (A1)) and a specific organic compound (component (A2)). Such solid catalyst component (A) of the present invention does not exclude the coexistence of other suitable components other than the essential two components. Component (A1) The solid component used in the present invention is a solid component for stereoregular polymerization of propylene, which contains titanium, magnesium and halogen as essential components.

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 desired compound. And that these elements may be present as being bonded to each other.

The magnesium compound used as the 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. Magnesium dihalides Among them, dialkoxy magnesium, and the like of ^{_{Mg (OR 16) 2 - p}} X p ( where, R
¹⁶ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents a 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.

Also, 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.

Also, 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.

Component (A2) An organic compound represented by the following general formula 1 is used. General formula 1

[0031]

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.

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 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 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 prepared, and the solid product is brought into contact with the organic compound represented by the above general formula 1 (a two-stage method). However, in the process of preparing a solid product containing titanium, magnesium and halogen as essential components, it is also possible to employ a method of producing the component (A) at a stroke by means of the presence of this organic compound (ie, a one-step method). . 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 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 preferable.

The amount of the titanium compound used is 0.0001 in terms of 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.

The amount of the organic compound used as the component (A2) is 0.04 in molar ratio to the titanium component constituting the component (A).
It is in the range of 1 to 1000.

When the vinylsilane compound is used, the amount of the vinylsilane compound to be used is m with respect to the titanium component constituting the component (A).
The ol ratio is preferably in the range of 0.001 to 1000, and more preferably 0.01 to 100.

The amount of the aluminum and boron compounds used 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 the components of the component (A) with other components such as an electron donor, if necessary, for example, by the following production method.

(A) A method of contacting a magnesium halide, a titanium-containing compound, an organic compound represented by the general formula 1, an electron donor, and a silicon compound as required.

(Ii) Alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, a titanium halide-containing compound, an organic compound represented by the general formula 1, an electron donor and a silicon compound are brought into contact with the compound, if necessary. Method.

(C) A solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer-silicon compound is added to an organic compound represented by the general formula 1, a titanium halide compound and / or a silicon halide compound. Washing the reaction product contacted with an inert organic solvent and then contacting with a silicon compound. As the polymer-silicon compound, a compound represented by the following formula is suitable.

[0055]

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 represented by the general formula 1 is added to a solid component precipitated by a halogenating agent or a titanium halide compound. The organic compound and the sulfonic acid ester compound, if necessary, simultaneously or 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, an organic compound represented by the general formula 1 and, if necessary, a sulfonic acid ester compound are simultaneously contacted, or they are separately contacted.

(F) A halogenating agent and / or a titanium compound, a silicon compound and an organic compound represented by the general formula 1 and, if necessary, a sulfonic acid ester compound are added to the alkoxymagnesium compound in the presence or absence of an electron donor. A method of contacting simultaneously below or separately contacting each other.

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 a component 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 prepolymerization 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 above-mentioned 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 determined by the amount of the component (A1)
It is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g per 1 g of the solid component.

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.

[0066] 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 of the organoaluminum compound component (B) to the titanium component in the solid catalyst component (A) is generally Al / Ti = 1 to 1000 mol / mol, preferably Al / Ti = 1 to 1000 mol / mol. Ti = 10-500mol
/ Mol ratio.

<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

[0074]

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 Co., Ltd. Measurement 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] Using an SJ type (in-line screw type) injection molding machine,
Spiral flow measurement was performed 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)] 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, 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 for producing the component (A).

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
5 g of the solid component synthesized above was introduced, and 1.0 ml of 1,1′-binaphthyl-dimethoxy ether and 1.7 g of triethylaluminum were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride.

[Polymerization Polymerization] In a 1.5-liter stainless steel autoclave having a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane and the component (A) produced above were added. 15m
g, 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 / c.
Propylene was polymerized under the conditions of m ² G, polymerization temperature = 75 ° C., and 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% Pellet obtained Was used to perform spiral flow measurement. Activity during polymerization, attack derivation rate, MF of polymer
R, MT, and spiral flow values are shown in Table 1 below for both the following examples and comparative examples.

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.

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 0.4 mol
And reacted at 80 ° C. for 6 hours. After completion of the reaction, n
-It was sufficiently washed with heptane to obtain a solid component for producing the component (A).

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
5 g of the solid component synthesized above was introduced, and 1.0 ml of 1,1′-binaphthyl-dimethoxy ether was added at 30 ° C. for 2 minutes.
Contact for an hour. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride.

[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 and the component (A) produced above were added. 15m
g, 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 / c.
Propylene was polymerized under the conditions of m ² G, polymerization temperature = 75 ° C., and 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., and then 3.3 ml of cellosolve acetate was introduced.
Allowed to react for 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.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
5 g of the solid component synthesized above was introduced, and 1.0 ml of 1,1′-binaphthyl-dimethoxy ether and 1.7 g of triethylaluminum were contacted at 30 ° C. for 2 hours.
After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride.

[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 and the component (A) produced above were added. 15m
g, 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 / c.
Propylene was polymerized under the conditions of m ² G, polymerization temperature = 75 ° C., and polymerization time = 2 hours.

Comparative Example-1 In [Production of Component (A)], as Component (A2),
Using 0.5 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and further 300 ml of hydrogen
The same experiment as in Example 1 was carried out except that was successively introduced.

Comparative Example 2 In [Production of component (A)], component (A2)
_{(Cyclo-C 6 H 11)} 2 Si (O-CH 3) 2 0.7
The same experiment as in Example 1 was performed, except that 300 ml of hydrogen was successively introduced using 300 ml of hydrogen.

Comparative Example 3 Example 1 was repeated except that 100 ml of hydrogen was introduced without using component (A2) in [Production of component (A)].
The same experiment was performed.

[0094]

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 molding, sheet molding, injection molding and the like.

[0095]

[Table 1]

[Brief description of the drawings]

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

Continued on the front page F-term (reference) 4J028 AA01A AB01A AC02A AC04A AC05A AC06A AC07A AC09A AC10A AC14A AC15A AC17A BA01A BA01B BA02A BB00A BB01A BB01B BC01A BC05A BC09A BC15A BC15B BC16 BC19 BC17 BC17 BC19 BC17 BC17 BC16 BC CA52A CB23A CB25A CB27A CB30A CB35A CB43A CB44A CB45A CB52A CB53A CB56A CB58A CB63A CB64A CB66A CB68A CB74A CB92A CB95A DA01 DA02 DA03 DA04 DA05 DA06 EA01 EB04 EC01 EC02 EC03 GA12 4J100 AA02Q AA03P AA04Q AA07Q AA09Q AA15Q AA16Q AA17Q AA19Q AB02Q AB08Q AB16Q AR16Q AR17Q AR18Q AR22Q AS01Q AS02Q AS03Q CA01 CA04 FA02 FA09

Claims (4)

[Claims] A propylene polymerization catalyst comprising the following components (A) and (B): Component (A):
Solid catalyst obtained by contacting the following components (A1) and (A2) Component (A1): A solid component for polymerization containing titanium, magnesium and halogen as essential components Component (A2): The following general formula 1 An organic compound represented by the general formula 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.). Component (B): Organoaluminum compound component 2. The propylene polymerization catalyst according to claim 1, wherein the component (A1) solid component for polymerization contains an electron donor selected from a phthalic acid diester compound, a cellosolve acetate compound and a phthalic acid dihalide compound. 3. A method for polymerizing propylene, comprising polymerizing propylene or a copolymerizable monomer with propylene in the presence of the catalyst for propylene polymerization according to claim 1 or 2. 4. The method according to claim 3, wherein the copolymerizable monomer is an α-olefin.