JP2001048914A - Propylene polymerization catalyst and polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymerization catalyst enabling the production of a polypropylene suitable for various molding methods such as sheet molding, blow molding and injection molding by using an MgCl2-supported catalyst and provide a propylene polymerization method. SOLUTION: The objective propylene polymerization catalyst is composed of the following components A, B and C. The component A is a solid catalyst produced by contacting a component A1 with a component A2 wherein A1 is a solid component for polymerization containing Ti, Mg and a halogen as essential components and A2 is an organic compound expressed by formula I (R2 to R10 are each a substituent), the component B is an organic aluminum compound component and the component C is a silicon compound component expressed by formula II R11R123mSi(OR13)m (R11, R12 and R13 are each a hydrocarbon group; 2<=m<=3).

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 polypropylene having high melt tension and excellent moldability. Therefore, the crystalline polypropylene obtained in the present invention is blow molded, sheet molded,
It can be suitably used for 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 therefore a wide molecular weight distribution is required. Also in injection molding, a high melt tension is required to improve the appearance of the 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 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
Since it is narrower than the iCl ₃ -based catalyst and the melt tension is not sufficiently high, there is a problem that the molding processability is inferior in sheet molding and blow molding, and the molding appearance is poor such as a flow mark in injection molding. there were.

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 to provide a polypropylene suitable for a molding method such as sheet molding, blow molding and injection molding by using a MgCl ₂ supported catalyst. Is what you do.

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]

Means for Solving the Problems The present invention has been made as a result of intensive studies to solve the above-mentioned problems, and comprises the following components (A), (B) and (C). Characteristic catalyst for propylene polymerization, Component (A): a solid catalyst obtained by bringing the following components (A1) and (A2) into contact Component (A1): polymerization containing titanium, magnesium, and halogen as essential components Component for solid component (A2): 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.).

Component (B): Organoaluminum compound component Component (C): Silicon compound component represented by the following general formula 2 General formula 2 R ¹¹ R ¹² _3-m Si (OR ¹³ ) _m (where R ¹¹ is a hydrocarbon group containing or not containing a hetero atom, R ¹² is a hydrocarbon group the same as or different from R ¹¹ , R ¹³ is a hydrocarbon group, and m is 2 ≦ m ≦ 3.) And a method for polymerizing propylene, comprising polymerizing propylene or propylene and another copolymerizable monomer in the presence of the above-mentioned propylene polymerization catalyst.

[0014]

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 The solid catalyst (A) of the present invention comprises a specific solid component (component (A)
1)) and a specific organic compound (component (A2)). Such a solid catalyst (A) of the present invention does not exclude the coexistence of other suitable components other than the above essential two components.

Component (A1) The solid component used in the present invention is a solid component for stereoregular polymerization of propylene containing 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.
Among them, Mg (OR ¹⁶ ) _{2 −pX p} (wherein magnesium dihalide, dialkoxy magnesium, etc.)
R ¹⁶ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents 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.

The halogen is usually supplied from the above-mentioned magnesium and / or titanium halides, but may be other halogen sources, for example aluminum halides such as AlCl ₃ or silicon halides such as SiCl _4. Halides, phosphorus halides such as PCl ₃ , PCl ₅ , tungsten halides such as WCl ₆ , Mo
It can be supplied from a known halogenating agent such as a halide of molybdenum such as Cl ₅ .

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, such as organic acid polyvalent esters such as 1,2-dicarboxylic acid-di-n-hexyl and diethyl 1,1-cyclobutane-dicarboxylate, (f) ethyl silicate and silicic acid Butyl, 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

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 produced, and the solid product is brought into contact with an organic compound represented by the above general formula (a two-stage method). 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 (in other words, a one-step method) by making the organic compound already exist. 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 ether compound used as the component (A2) is in the range of 0.01 to 1000 in molar ratio with respect to the titanium component constituting the component (A).

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 component (A1) with the component (A2) and optionally 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, an organic compound represented by the general formula 1, and, if necessary, an electron donor or a silicon compound.

(B) Alumina or magnesia is treated with a phosphorus halide compound, and then contacted with a magnesium halide, a titanium halide-containing compound, an organic compound represented by the general formula 1, an electron donor, a silicon compound and the like, if necessary. How to let.

(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 simultaneously contacting the silicon compound with the electron donor or separately contacting the silicon compound and the electron donor.

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

[0056]

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 with 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 with a halogenating agent or a titanium halogen 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) The alkoxymagnesium compound is simultaneously contacted with a halogenating agent and / or a titanium compound, an organic compound represented by the general formula 1, and, if necessary, a silicon compound in the presence or absence of an electron donor. Or contacting each 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 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 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.

[0067] 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 and 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.

Component (C) Silicon compound component A silicon compound component represented by the following general formula:¹¹ R¹² _3-mSi (OR¹³)_m (Where R¹¹Is a hydrocarbon containing or not containing a hetero atom
And R is¹²Is R¹¹Same or different hydrocarbon group as
It is. Also R¹³Is a hydrocarbon group and m is 2 ≦ m ≦ 3
You. The following compounds can be specifically mentioned. (Ter
t-C_FourH₉) Si (CH_Three) (OCH_Three)_Two, (Ter
t-C_FourH₉) Si (C_TwoH_Five) (OCH_Three)_Two, (Tert
-C_FourH₉) Si (n-C_ThreeH₇) (OCH_Three)_Two, (Ter
t-C_FourH₉) Si (iso-C)_ThreeH₇) (OCH_Three)_Two,
(Tert-C_FourH₉) (OCH_Three) Si (n-C_FourH₉)
(OCH_Three)_Two, (Tert-C_FourH₉) Si (iso-C)
_ThreeH₉)_Two, (Tert-C_FourH₉) Si (sec-C
_FourH₉) (OCH_Three)_Two, (Tert-C_FourH₉) Si (te
rt-C_FourH₉) (OCH_Three)_Two, (Tert-C_FourH₉) S
i (n-C_FiveH₁₁) (OCH_Three)_Two, (Tert-C
_FourH₉) Si (cyclo-C)_FiveH₉) (OCH_Three)_Two, (T
ert-C_FourH₉) Si (n-C₆H₁₃) (OCH_Three)_Two,
(Tert-C_FourH₉) Si (cyclo-C)₆H₁₁)
(OCH_Three)_Two, (Tert-C_FourH₉) Si (On-C
_ThreeH₇) (OCH_Three)_Two, (Tert-C_FourH₉) Si (O-
iso-C_ThreeH₇) (OCH_Three)_Two, (Tert-C_FourH₉)
Si (On-C_FourH₉) (OCH_Three)_Two, (Tert-C
_FourH₉) Si (O-iso-C_FourH₉) (OCH_Three)_Two, (T
ert-C_FourH₉) Si (O-sec-C_FourH₉) (OCH
_Three)_Two, (Tert-C_FourH₉) Si (O-tert-C_Four
H₉) (OCH_Three)_Two, (Tert-C_FourH₉) Si (O-
n-C_FiveH₁₁) (OCH_Three)_Two, (Tert-C_FourH₉) S
i (O-cyclo-C_FiveH₉) (OCH_Three)_Two, (Ter
t-C_FourH₉) Si (On-C₆H₁₃) (OCH_Three)_Two,
(Tert-C_FourH₉) Si (O-cyclo-C)
₆H₁₁) (OCH_Three)_Two, (Iso-C_ThreeH₇)_TwoSi (OC
H_Three)_Two, (Iso-C_FourH_FiveH₁₁)_TwoSi (OCH_Three)_Two,
(Cyclo-C_FiveH₉)_TwoSi (OCH_Three)_Two, (Cyc
lo-C₆H₁₁) Si (CH_Three) (OCH_Three)_Two, (Cy
clo-C₆H₉)_TwoSi (OCH_Three)_Two, (Sec-C_FourH
₉)_TwoSi (OCH_Three)_Two, (Neo-C₁₁) Si (C
_TwoH _Five) (OCH_Three)_Two, (Cyclo-C₆H₁₁) Si
(N-C_FourH₉) (OCH_Three)_Two, (Cyclo-C
₆H₁₁) Si (cyclo-C)_FiveH₉) (OCH_Three)_Two,
(C_TwoH_Five)_ThreeCSi (CH_Three) (OCH_Three)_Two, (C_TwoH_Five)
_ThreeCSi (C_TwoH_Five) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi
(N-C_ThreeH₇) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (i
so-C_ThreeH₇) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (n
-C_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (iso
-C_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (sec
-C_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (ter
t-C_FourH₉) (OCH_Three) _Two, (C_TwoH_Five)_ThreeCSi (n-
C_FiveH₁₁) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (cycl
o-C_FiveH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (n-
C₆H₁₃) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (cycl
o-C₆H₁₁) (OCH_Three)_Two, H (CH_Three)_TwoC (CH_Three)
_TwoCSi (CH_Three) (OCH_Three)_Two, H (CH_Three)_TwoC (CH
_Three)_TwoCSi (C_TwoH_Five) (OCH_Three)_Two, H (CH_Three)_TwoC
(CH_Three)_TwoCSi (n-C_ThreeH₇) (OCH_Three)_Two, H (C
H_Three)_TwoC (CH_Three)_TwoCSi (iso-C_ThreeH₇) (OCH
_Three)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (n-C_FourH₉)
(OCH_Three)_Two, (CH_Three)_Two(C _TwoH_Five) CSi (CH_Three)
(OCH_Three)_Two, (Tert-C_FourH₉) Si (OC
_TwoH_Five) (OCH_Three)_Two(CH_Three)_Two(C_TwoH_Five) CSi (OC
_TwoH_Five) (OCH_Three)_Two, (CH _Three) (C_TwoH_Five)_TwoCSi (O
C_TwoH_Five) (OCH_Three)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCS
i (OC_TwoH_Five) (OCH_Three)_Two, (Norbornyl) Si
(CH_Three) (OCH_Three)_Two, (Norbornyl) Si (OC_Two
H_Five) (OCH_Three)_Two, (Adamantyl) Si (OC
_TwoH_Five) (OCH_Three)_Two, (Adamantyl) Si (CH_Three)
(OCH_Three)_TwoSilicon compound component and component of component (C)
The proportion of the organoaluminum compound component (B) is Si
/Al=0.01 to 10 mol / mol is generally used.
Preferably, Si / Al = 0.05 to 1.0 mol / mol.
Used in proportions.

<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, and the method exemplified below is employed. be able to.

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

[0076]

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
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, 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 thoroughly washed with toluene.
Then 100 ml of TiCl ₄ and toluene 1
Then, the reaction mixture was 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 contacted with 1.0 ml of 1-1 ′ binaphthyl dimethoxy ether at 30 ° C. for 2 hours. After the contact is completed, it is sufficiently washed with n-heptane,
A component (A) mainly composed of magnesium chloride was obtained.

[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, 125 mg of triethylaluminum as the component (B), and (C) as (tert-C ₄ H ₉₎
0.72 mg of (CH ₃ ) Si (OCH ₃ ) ₂ and 15 mg of the component (A) prepared above, and then 150 mg of hydrogen
ml, and the temperature was increased and the polymerization pressure was increased to 5 kg / cm.
Propylene was polymerized under the conditions of ² G, a polymerization temperature of 75 ° C., and a polymerization time of 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.

The activity during the polymerization, the attack derivation ratio, the MFR, MT, and spiral flow value of the polymer are shown in Table 1 in the following Examples and Comparative Examples.

Comparative Example-1 In [Production of Component (A)], component (A2)
The same experiment as in Example 1 was performed except that 36 mg of 2-isopropyl-2-isopentyl-dimethoxy-propane was used, and 300 ml of hydrogen was sequentially introduced in [propylene polymerization].

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, the resultant was washed with n-heptane. Then, phthalic acid chloride 0.025 was added to 25 ml of n-heptane.
24 mol was mixed, introduced into the flask at 70 ° 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 80 ° C.
Allowed to react for 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 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, 125 mg of triethylaluminum as component (B), and (C) as (tert-C ₄ H ₉₎
0.72 mg of (CH ₃ ) Si (OCH ₃ ) ₂ and 15 mg of the component (A) prepared above, and then 150 mg of hydrogen
ml, and the temperature was increased and the polymerization pressure was increased to 5 kg / cm.
Propylene was polymerized under the conditions of ² G, a polymerization temperature of 75 ° C., and a polymerization time of 2 hours.

Comparative Example-2 In [Production of component (A)], component (A2)
Using 36 mg of 2-isopropyl-2-isopentyl-dimethoxypropane, [polymerization of propylene]
Example 2 except that 300 ml of hydrogen was successively introduced in
The same experiment was performed.

Comparative Example 3 In [Production of Component (A)], component (A2)
0.5 ml of (c-Hex) ₂ Si (O—CH ₃ ) ₂ was used.
The same experiment as in Example 2 was performed except that 0 ml was introduced.

Comparative Example 4 An experiment was conducted in the same manner as in Example 2 except that the component (A2) was not used, the component (C) was not used, and 100 ml of hydrogen was introduced.

[0097]

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

[0098]

[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 AC04A AC05A AC06A AC07A AC09A AC14A AC15A AC17A AC19A BA00A BA01A BA02B BB00A BB01B BC05A BC14B BC15B BC16B BC24B BC27B BC13ACAB CAA CAB CAA CAB CAA EB02 EB04 EB11 EB21 EC01 EC02 FA01 FA02 FA04 FA06 FA07 4J100 AA02Q AA03P AA04Q AA07Q AA15Q AA16Q AA19Q AB01Q AS00R CA01 CA04 CA05 FA09

Claims (4)

[Claims] 1. A propylene polymerization catalyst comprising the following components (A), (B) and (C). Component (A): Solid catalyst obtained by contacting the following component (A1) with component (A2) Component (A1): Solid component for polymerization containing titanium, magnesium, and halogen as essential components Component (A2): Organic compound represented by the following general formula 1 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): an organoaluminum compound component Component (C): a silicon compound component represented by the following general formula 2: General formula 2 R ¹¹ R ¹² _3-m Si (OR ¹³ ) _m (where R ¹¹ is A hydrocarbon group containing or not containing a hetero atom, R ¹² is the same or different hydrocarbon group as R ¹¹ , R ¹³ is a hydrocarbon group, and m is 2 ≦ m ≦ 3.) 2. The propylene polymerization catalyst according to claim 1, wherein the component (A1) solid component for polymerization contains 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 another copolymerizable monomer in the presence of the catalyst for propylene polymerization according to claim 1 or 2. 4. The method according to claim 3, wherein the other copolymerizable monomer is an α-olefin.