JP2988227B2 - Method for producing olefin polymer and catalyst for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an olefin polymer which can form two homopolypropylenes in a specific region in the same polymer by disordering the arrangement of monomer units in isotactic polypropylene. Catalyst,
And a method for producing an olefin polymer using the polymerization catalyst. More specifically, the present invention relates to a method for producing an olefin polymer which is excellent in rigidity and stretchability and can be suitably used for films, fibers, hollow molding, extrusion molding and the like, and to an olefin polymerization catalyst used for producing the polymer.

[0002]

2. Description of the Related Art Polypropylene is an excellent synthetic resin having high rigidity and high mechanical strength.
Since the mechanical properties are greatly improved and the transparency is also significantly improved, it is widely used for applications such as stretched films, stretched tapes, flat yarns, split fibers, and bands.

[0003] Polypropylene includes a homopolymer composed of a homopolymer of propylene and a random copolymer in which a small amount of α-olefin is copolymerized. Since the rigidity of the homopolymer is superior, it is not suitable for applications requiring rigidity. Usually, a homopolymer is used after being stretched. However, when a homopolymer having a high stereoregularity is used, the rigidity is improved but the workability is reduced. As a method for improving the processability of a homopolymer, there has been proposed a method using a composition in which two types of polypropylene homopolymers having different stereoregularities are mixed (Japanese Patent Laid-Open No. 23607/1986).
However, in this proposal, although the processability is slightly improved, a very low regularity homopolymer having an isotactic pentad fraction of 0.50 to 0.92 in the insoluble portion due to boiling heptane is 90 to 10% by weight. %, The rigidity and heat resistance of the polypropylene are sacrificed, and the inherent characteristics of the homopolymer cannot be exhibited.

On the other hand, as a method for improving the stretchability of a homopolymer, a method using a random copolymer (Japanese Patent Laid-Open No.
No. 32512, JP-A-59-135209) have been proposed. However, even if such a method is used, the stretchability is somewhat improved, but the stereoregularity is rapidly deteriorated and the rigidity is reduced only by copolymerizing a small amount of ethylene.

As described above, at present, the rigidity, heat resistance, and the like inherent in high stereoregularity polypropylene are mixed by mixing very low-order polypropylene or by random copolymerization of propylene and α-olefin. Efforts have been made to improve the processability and the like while sacrificing the properties, etc., and to produce a well-balanced resin as a whole. However, polypropylene having both excellent rigidity and processability has not yet been developed.

[0006]

Under such circumstances,
The problem to be solved by the present invention, that is, an object of the present invention is to solve the above-mentioned problems of the prior art by using an olefin polymerization catalyst that provides a polypropylene having a novel composition. In addition, the present invention provides a method for producing a novel olefin polymer having excellent rigidity and excellent processability, and a catalyst for olefin polymerization used for producing the polymer.

[0007]

The present invention provides (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (B) an organoaluminum compound, and (C) an electron donor (α). ) And at least two kinds of electron donors including an electron donor (β) (provided that the electron donor (α) is used together with the solid catalyst component (A) and the organoaluminum compound (B) for polymerization) The turbulence index mmrr / mmmm of the xylene-insoluble portion at 105 ° C. of polypropylene is 0 ≦ mmrr / mmmm ≦
105 of homopolypropylene obtained by using the electron donor (β) for polymerization together with the solid catalyst component (A) and the organoaluminum compound (B).
Turbidity index of xylene insoluble part is 0.0068 <mmrr
/Mmmm≦0.0320), wherein the olefin is homopolymerized or copolymerized using an olefin polymerization catalyst comprising: (A) magnesium, titanium, halogen and electron. A solid catalyst component containing a donor as an essential component; (B) an organoaluminum compound; (C) at least two or more electron donors including an electron donor (α) and an electron donor (β); Of homopolypropylene obtained by using the polymer (α) together with the solid catalyst component (A) and the organoaluminum compound (B) for polymerization.
The turbulence index mmrr / mmmm of the xylene insoluble part at 5 ° C is 0.
≦ mmrr / mmmm ≦ 0.0068 and a turbulence index of a xylene-insoluble portion at 105 ° C. of homopolypropylene obtained by using the electron donor (β) for polymerization together with the solid catalyst component (A) and the organoaluminum compound (B). Satisfies 0.0068 <mmrr / mmmm ≦ 0.0320).

Hereinafter, the present invention will be described specifically.

(A) Solid catalyst component (A) The solid catalyst component (A) of the present invention containing magnesium, titanium, halogen and an electron donor as essential components is:
What is generally called a titanium-magnesium composite catalyst can be used, and can be obtained by contacting a magnesium compound, a titanium compound and an electron donor as described below.

In the present invention, the titanium compound used for the synthesis of the solid catalyst component (A) is, for example, a compound represented by the general formula Ti (O
R ¹ ) _a X _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number 0 ≦ a ≦ 4)
And a titanium compound represented by the following formula:
Specifically, titanium tetrachloride compounds such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide Trihalogenated alkoxy titanium compounds such as, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride,
Dihalogenated dialkoxytitanium compounds such as diethoxytitanium dibromide, trimethoxytitanium chloride,
Monohalogenated trialkoxytitanium compounds such as triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride and triethoxytitanium bromide, and tetraalkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium and tetraphenoxytitanium Can be mentioned. These titanium compounds may be used alone or in combination of two or more. Furthermore,
These titanium compounds may be used after being diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, the magnesium compound used in the synthesis of the solid catalyst component (A) may be a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond and having a reducing ability, or a magnesium compound having no reducing ability. Compounds can be used. Specific examples of magnesium compounds having a reducing ability include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, dihexyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, butyl ethoxy magnesium, butyl magnesium Hydride and the like. These reducing magnesium compounds,
It may be used in the form of a complex compound with an organic aluminum compound. On the other hand, specific examples of magnesium compounds having no reducing ability include magnesium dichloride, magnesium dibromide, magnesium dihalide compounds such as magnesium diiodide, methoxymagnesium chloride, ethoxymagnesium chloride, butoxymagnesium chloride, isopropoxymagnesium chloride, Alkoxy magnesium halide compounds such as phenoxy magnesium chloride, diethoxy magnesium, dibutoxy magnesium, diisopropoxy magnesium, dialkoxy magnesium compounds such as diphenoxy magnesium, magnesium laurate,
Examples thereof include magnesium carboxylate such as magnesium stearate. These magnesium compounds having no reducing ability may be those synthesized in advance or from a magnesium compound having reducing ability at the time of preparing the solid catalyst component by a known method.

In the present invention, the electron donor used in the synthesis of the solid catalyst component (A) includes alcohols, phenols, ketones, aldehydes, carboxylic acids, and the like.
Oxygen-containing electron donors such as esters, ethers, acid amides, and acid anhydrides of organic or inorganic acids, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Can be. Of these electron donors, esters and ethers of organic acids or inorganic acids are preferably used.

As the esters of organic acids, preferably used are mono- and polyvalent carboxylic esters, such as aliphatic carboxylic esters, olefin carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic acids. Esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, ethyl benzoate, butyl benzoate, toluyl Methyl acrylate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate , Methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate, and the like.

[0014] As preferably esters of inorganic acids of the general formula _{^{R 2 n Si (OR 3)}} 4- n (R 2 is C 1 -C
-20 hydrocarbon groups or hydrogen atoms, R ³ has 1 carbon atom
20 is a hydrocarbon group, and n is 0 ≦ n <4). Specific examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tbutyltrimethoxysilane, and isopropyltrimethoxysilane. Silane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, ditbutyl Dimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, t
Butylmethyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyltbutyldimethoxysilane , Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyltbutyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, vinylmeth Rudimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, tbutyltriethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, Dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-tbutyldiethoxysilane, butylmethyldiethoxysilane, Butylethyldiethoxysilane, t-butylmethyldiethoxysilane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane, dode Methyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropoxy Examples thereof include silane, vinyltributoxysilane, phenyltributoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane, and methyltriaryloxysilane.

Further, as the ethers, preferred are dialkyl ethers and general formulas (R ^{4 to} R ⁷ are linear or branched alkyl, alicyclic, aryl, alkylaryl, arylalkyl groups having 1 to 20 carbon atoms, and R ⁴ or R ⁵ may be hydrogen). Diether compounds as represented can be mentioned. Specific examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, 2, 2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-
Diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-
2-cyclohexyl-1,3-dimethoxypropane, 2
-Isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,
3-dimethoxypropane and the like can be mentioned.

Of these electron donors, ester compounds are particularly preferably used.

As a method for producing such a solid catalyst component, for example, Japanese Patent Publication No. 52-39431 and Japanese Patent Publication No. 5
JP-A-2-36786, JP-A-54-94590, JP-A-55-36203, JP-A-56-41
No. 206, JP-A-57-63310, JP-A-57-59916, JP-A-58-83006, JP-A-61-218606, JP-A-1-31
The method disclosed in Japanese Patent Application Laid-Open No. 9508/1991 and Japanese Patent Application Laid-Open No. 3-706 and the like can be mentioned. These methods include:

(1) A method comprising reacting a liquid magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a precipitating agent, and then treating with a titanium compound or a titanium compound and an electron donor. (2) A method of treating a solid magnesium compound or a complex compound comprising a solid magnesium compound and an electron donor with a titanium compound or a titanium compound and an electron donor. (3) A method in which a liquid magnesium compound and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex. (4) A method in which the reaction product obtained in (1), (2) or (3) is further treated with a titanium compound or an electron donor and a titanium compound. (5) Si-O a solid product obtained by the presence alkoxy titanium compound in the organic silicon compound is reduced with an organomagnesium compound such as Grignard reagent with a bond, an ester compound, a method of treating an ether compound and with TiCl _4. (6) A method in which a contact product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol is contacted with an electron donor and a titanium compound after or without treatment with a halogenating agent. (7) A method in which a magnesium compound such as a magnesium salt of an organic acid or an alkoxy magnesium is contacted with an electron donor and a titanium compound after or without treatment with a halogenating agent. (8) The compound obtained in (1) to (7) is halogen,
A method of treating with either a halogen compound or an aromatic hydrocarbon. Among the methods for synthesizing these solid catalysts, the methods described in (1) to (5) are preferably used, and the method described in (5) is particularly preferably used.

Further, such a solid catalyst component (A) comprises:
Although it can be used alone, it is also possible to impregnate and use a porous substance such as an inorganic oxide or an organic polymer. Such porous inorganic oxides include SiO 2
₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , SiO
₂ -Al ₂ O ₃ composite oxide, MgO-Al ₂ O ₃ composite oxide, MgO-SiO ₂ -Al ₂ O ₃ composite oxide and the like, and the porous organic polymer, polystyrene,
Styrene-divinylbenzene copolymer, styrene-n,
n'-alkylene dimethacrylamide copolymer, styrene-ethylene glycol dimethyl methacrylate copolymer, polyacrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethacryl Methyl acrylate, methyl methacrylate-divinylbenzene copolymer, polyethylene glycol methyl dimethacrylate, polyacrylonitrile,
Acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methyl acrylate copolymer, polystyrene such as polypropylene, polyacrylic Examples thereof include acid ester-based, polyacrylonitrile-based, polyvinyl chloride-based, and polyolefin-based polymers. Of these porous materials, SiO
₂ , Al ₂ O ₃ and styrene-divinylbenzene copolymer are preferably used.

(B) Organoaluminum Compound (B) The organoaluminum compound used as the component (B) of the present invention has at least one Al-carbon bond in the molecule. Typical examples are shown below by a general formula. ^{_{R 8 m AlY 3-m R}} 9 R 10 Al-O-AlR 11 R 12 (R 8 ~R 12 is 1-8 hydrocarbon group with a carbon number, Y represents halogen, hydrogen or alkoxy group, m Is 2 ≦ m ≦
Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and triethylaluminum. Examples thereof include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

Of these organoaluminum compounds,
Trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, and an alkylalumoxane are preferred, and triethylaluminum, triisobutylaluminum, a mixture of a triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are particularly preferred.

(C) Electron Donor (C) As the electron donor catalyst component (C) of the present invention, at least two or more kinds of electron donors including an electron donor (α) and an electron donor (β) are used. The electron donor (α) and the electron donor (β) used satisfy the following conditions.
That is, the homopolypropylene obtained by using the electron donor (α) for the polymerization together with the solid catalyst component (A) and the organoaluminum compound (B) has a turbulence index mmrr / mmmm of a xylene-insoluble portion at 105 ° C. of 0 ≦ mmrr / mm.
mm ≦ 0.0068, preferably 0.0004 ≦ mmr
r / mmmm ≦ 0.0068, more preferably 0.0
004 ≦ mmrr / mmmm ≦ 0.0060 and disturbance of the xylene-insoluble portion at 105 ° C. of the homopolypropylene obtained by using the electron donor (β) for polymerization together with the solid catalyst component (A) and the organoaluminum compound (B). Index is 0.0068 <mmrr / mmmm ≦ 0.032
0, preferably 0.0068 <mmrr / mmmm ≦
0.0200, more preferably 0.0072 ≦ mmr
An electron donor (α) and an electron donor (β) such that r / mmmm ≦ 0.0140 are used. In addition, 105 degreeC xylene insoluble part in this invention is Macromolecules, 21 , 314-31 by Kakugo et al.
9 (1988), a polypropylene polymer was dissolved in xylene at 135 ° C., then charged with sea sand, cooled to 20 ° C., and when heated again, was not extracted at 105 ° C. Part extracted at 105-135 ° C. In addition, the turbulence index of the present invention is as follows: Z
Macromolecule by amberli et al.
s, 13 , 687-689 (1975), and based on EX-270 ( ¹³ C-
By NMR, a polymer solution of o-dichlorobenzene containing 10 wt% of C ₆ D ₆ (polymer concentration 150 mg / 3
ml) was measured at 135 ° C. and 270 MHz.
mm (a peak appears around 21.78 ppm based on TMS) mmrr (TMS based 2
(A peak appears around 1.01 ppm).

In the present invention, as the electron donor used for preparing the electron donor catalyst component (C), the electron donor used for preparing the solid catalyst component (A) can be used. Preferably, each of the bodies (α) and (β) is selected from the following organosilicon compounds.

As such an organosilicon compound,
General formula R^Two _nSi (OR^Three )_4-n(R ^Two Has 1 to 20 carbon atoms
A hydrocarbon group or a hydrogen atom, R^Three Has 1 to 20 carbon atoms
A hydrocarbon group, wherein n is 0 ≦ n <4)
Such organosilicon compounds can be mentioned. Concrete example
As tetramethoxysilane, tetraethoxysila
, Tetrabutoxysilane, tetraphenoxysilane,
Methyltrimethoxysilane, ethyltrimethoxysila
Butyltrimethoxysilane, isobutyltrimethoxy
Sisilane, t-butyltrimethoxysilane, isopropyl
Trimethoxysilane, cyclohexyltrimethoxysila
, Phenyltrimethoxysilane, vinyltrimethoxy
Silane, dimethyldimethoxysilane, diethyldimethoxy
Sisilane, dipropyldimethoxysilane, propylmethyl
Rudimethoxysilane, diisopropyldimethoxysila
Dibutyldimethoxysilane, diisobutyldimethoxy
Sisilane, di-butyldimethoxysilane, butylmethyl
Dimethoxysilane, butylethyldimethoxysilane, t
Butylmethyldimethoxysilane, isobutylisopropyl
Rudimethoxysilane, t-butylisopropyldimethoxy
Silane, hexylmethyldimethoxysilane, hexyl
Tyldimethoxysilane, dodecylmethyldimethoxysila
, Dicyclopentyldimethoxysilane, cyclopent
Methyldimethoxysilane, cyclopentylethyldim
Toxysilane, cyclopentyl isopropyl dimethoxy
Silane, cyclopentyl isobutyl dimethoxysilane,
Cyclopentyl t-butyl dimethoxysilane, dicyclo
Xyldimethoxysilane, cyclohexylmethyldimet
Xysilane, cyclohexylethyldimethoxysilane,
Cyclohexylisopropyldimethoxysilane, cyclo
Hexyl isobutyl dimethoxysilane, cyclohexyl
t-butyldimethoxysilane, cyclohexylcyclopen
Tyldimethoxysilane, cyclohexylphenyl dimethoate
Xysilane, diphenyldimethoxysilane, phenylmeth
Tyldimethoxysilane, phenylisopropyldimethoxy
Sisilane, phenylisobutyldimethoxysilane,
N-tert-butyldimethoxysilane, phenylcyclopent
Rudimethoxysilane, vinylmethyldimethoxysilane,
Methyltriethoxysilane, ethyltriethoxysila
Butyltriethoxysilane, isobutyltriethoxy
Sisilane, t-butyltriethoxysilane, isopropyl
Triethoxysilane, cyclohexyltriethoxysila
, Phenyltriethoxysilane, vinyltriethoxy
Silane, dimethyldiethoxysilane, diethyldiethoxy
Sisilane, dipropyldiethoxysilane, propylmethyl
Rudiethoxysilane, diisopropyldiethoxysila
, Dibutyldiethoxysilane, diisobutyldiethoxy
Sisilane, di-butyldiethoxysilane, butylmethyl
Diethoxysilane, butylethyldiethoxysilane, t
Butylmethyldiethoxysilane, hexylmethyldiethyl
Xysilane, hexylethyldiethoxysilane, dodeci
Methyldiethoxysilane, dicyclopentyldiethoxy
Sisilane, dicyclohexyldiethoxysilane, cyclo
Hexylmethyldiethoxysilane, cyclohexylethyl
Ludiethoxysilane, diphenyldiethoxysilane,
Phenylmethyldiethoxysilane, vinylmethyldiethoxy
Sisilane, ethyltriisopropoxysilane, vinyl
Butoxysilane, phenyltri-t-butoxysilane, 2
-Norbornanetrimethoxysilane, 2-norbornane
Triethoxysilane, 2-norbornanemethyldimethoxy
Sisilane, trimethylphenoxysilane, methyltria
Riloxysilane and the like can be mentioned.

Among the organosilicon compounds as described above, examples of the electron donor (α) include those represented by the general formula R ¹³ R ¹⁴ Si
An organosilicon compound represented by (OR ¹⁵ ) ₂ is preferably used. In the formula, R ¹³ is a hydrocarbon group having 3 to 20 carbon atoms in which the carbon adjacent to Si is secondary or tertiary, and specifically, isopropyl, sec-butyl, t-butyl, t- Branched alkyl groups such as -amyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cycloalkenyl groups such as cyclopentenyl group; and aryl groups such as phenyl group and tolyl group. In the formula, R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group,
Linear alkyl group such as pentyl group, isopropyl group, s
ec-butyl group, t-butyl group, t-amyl group, etc., branched alkyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, phenyl group, tolyl group etc. And an aryl group. Further, in the formula, R ¹⁵ has 1 to 20 carbon atoms.
, And preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the organosilicon compound used as such an electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane,
Di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, isobutylisopropyldimethoxysilane,
t-butylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyltbutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane , Cyclohexyl tbutyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane,
Phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl tbutyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, ditbutyldiethoxysilane, tbutylmethyldiethoxysilane, Examples thereof include dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

Among the organosilicon compounds as described above, examples of the electron donor (β) include those represented by the general formula R ¹⁶ R ¹⁷
An organosilicon compound represented by Si (OR ¹⁸ ) ₂ is preferably used. In the formula, R ¹⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group is particularly preferable.
In the formula, R ¹⁷ is a hydrocarbon group having 1 to 5 carbon atoms, and a hydrocarbon group having 1 carbon atom is particularly preferable. Further, in the formula, R ¹⁸
Is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the organosilicon compound used as the electron donor (β) include dimethyldimethoxysilane, ethylmethyldimethoxysilane, propylmethyldimethoxysilane, butylmethyldimethoxysilane, pentylmethyldimethoxysilane, hexylmethyl Examples thereof include dimethoxysilane, heptylmethyldimethoxysilane, octylmethyldimethoxysilane, dodecylmethyldimethoxysilane, and the like.

(D) Olefin polymerization method The method for supplying each catalyst component to the polymerization tank is as follows except that the catalyst components are supplied in an inert gas such as nitrogen, argon or butane or in an olefin such as propylene without moisture. Is
There are no special conditions to restrict.

The polymerization method of the present invention comprises at least two or more electron donors including the solid catalyst component (A), the organoaluminum compound (B), the electron donor (α) and the electron donor (β). The polymerization of olefin is carried out in the presence of a catalyst, wherein (A), (B) and a single (α)
Mmrr / mmmm of the homopolypropylene obtained by polymerization in the presence of a catalyst comprising 0 ≦ mmrr / mmmm ≦
0.0068, and the mmrr / mmmm of the homopolypropylene obtained by polymerization in the presence of the catalyst comprising (A), (B) and (β) alone is 0.0068 <mm.
There is no particular limitation except that the polymerization is performed under the condition that rr / mmmm ≦ 0.0320.

In the polymerization method of the present invention, the olefin is polymerized in the presence of the above-mentioned catalyst, but the prepolymerization described below may be performed before the polymerization (main polymerization) is performed. The prepolymerization is performed by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), and is preferably performed in a slurry state. Examples of the solvent used for slurrying include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, in forming the slurry, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization is based on 1 mole of titanium atom in the solid catalyst component.
Although it can be selected from a wide range such as 0.5 to 700 mol, 0.8 to 500 mol is preferable, and 1 to 200 mol is particularly preferable.

The amount of the olefin to be prepolymerized is
0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 20 g per gram of the solid catalyst component.
0 g.

The slurry concentration at the time of performing the prepolymerization is from 1 to
500 g-solid catalyst component / l-solvent is preferred, especially 3 g
~ 300 g-solid catalyst component / l-solvent is preferred. The prepolymerization temperature is preferably from -20 to 100 ° C, particularly from 0 to 8 ° C.
0 ° C. is preferred. The partial pressure of the olefin in the gas phase portion in the prepolymerization is preferably 0.01~20kg / cm ^2, especially 0.1 to 10 / cm ² is preferred, the pressure in the prepolymerization, in liquid at a temperature This is not the case for certain olefins. Further, the prepolymerization time is not particularly limited, but is usually preferably from 2 minutes to 15 hours.

In carrying out the prepolymerization, the solid catalyst component, the organoaluminum compound, and the olefin may be supplied by contacting the solid catalyst component with the organoaluminum compound and then supplying the olefin. Any method of supplying the organoaluminum compound after the olefin has been brought into contact may be used. As a method for supplying the olefin, either a method of sequentially supplying the olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of initially supplying a predetermined amount of the olefin at all is used. good. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the obtained polymer.

Further, when the solid catalyst component is preliminarily polymerized with a small amount of olefin in the presence of the organoaluminum compound, an electron donor may be used, if necessary. The electron donor used is part or all of the above-mentioned electron donor catalyst component (C). The amount used is 0.0 to 1 mol of titanium atoms contained in the solid catalyst component.
1 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, and 0.003 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.003 to 5 mol, based on the organoaluminum compound. Preferably it is 0.01 to 2 mol.

The method of supplying the electron donor at the time of the prepolymerization is not particularly limited, and it may be supplied separately from the organoaluminum compound or may be supplied in contact with the organic aluminum compound in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below.

After or as described above, the olefin comprising the solid catalyst component (A), the organoaluminum compound (B) and the electron donor catalyst component (C) is obtained without or with prepolymerization. The main polymerization of olefin is carried out in the presence of a polymerization catalyst of

The olefin that can be used in the main polymerization is
It has 3 or more carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1, 3-
Methyl-butene-1,3-methyl-pentene-1,4-
Methyl-pentene-1, octene-1, decene-1, dodecene-1, cyclohexene and the like. Among these olefins, it is preferable to perform homopolymerization using propylene or butene-1, or to perform copolymerization using a mixed olefin containing propylene or butene-1 as a main component. In the copolymerization according to the present invention, two or more kinds of olefins selected from ethylene and the above-mentioned olefins may be used in combination. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. Then, heteroblock copolymerization in which polymerization is carried out in two or more stages can be easily performed.

A solid catalyst component, an organoaluminum compound,
And the electron donor catalyst component comprising at least two or more electron donors may be supplied individually,
It may be supplied in contact with a person in advance. As the electron donor catalyst component (C), the electron donor (α) and the electron donor (β) may be used at the time of prepolymerization. Sometimes the other component may be used, or both components may be used for the first time during the main polymerization.

The amount of the organoaluminum compound used in the main polymerization is from 1 to 1 per mol of titanium atom in the solid catalyst component.
Although it can be selected from a wide range such as 1000 mol, a range of 5 to 600 mol is particularly preferable.

The total amount of the electron donor catalyst component (C) used in the main polymerization is 0.1 to 2000 mol, preferably 0.3 to 2000 mol, per 1 mol of titanium atom contained in the solid catalyst component. 1000 mol, particularly preferably 0.5 to 8
00 mol, and 0.1 mol based on the organoaluminum compound.
The amount is from 001 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 1 mol.

The main polymerization can be carried out over a temperature range of -30 to 300 ° C, preferably at 20 to 180 ° C. The polymerization pressure is not particularly limited, but is generally from normal pressure to 100 kg /
A pressure of about ² cm ² , preferably about ² to 50 kg / cm ² is employed. As a polymerization system, any of a batch system and a continuous system can be used. In addition, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, bulk polymerization using a liquid olefin as a medium at the polymerization temperature, or gas phase polymerization is also possible.

At the time of the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

[0045]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not particularly limited by the following Examples. In the examples, methods for evaluating various physical properties of the polymer are as follows.

(1) Xylene-soluble portion at 20 ° C. (hereinafter CXS)
After dissolving 1 g of the polymer powder in 200 ml of boiling xylene, the solution was gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and left at 20 ° C. for 3 hours. Is filtered off. Xylene is evaporated from the filtrate and dried under reduced pressure at 60 ° C. to recover a polymer soluble in xylene at 20 ° C.

(2) Boiling heptane-insoluble part (hereinafter abbreviated as II): 3 g of the polymerized powder is extracted with 100 ml of heptane for 6 hours using a Soxhlet extractor.
After evaporating heptane from the extract, the polymer is dried under reduced pressure at 60 ° C. to recover a polymer soluble in boiling heptane.

(3) Intrinsic viscosity (hereinafter abbreviated as [η]): Measured at 135 ° C. in a tetralin solvent. (4) Bulk density (hereinafter abbreviated as BD): ASTM D-18
65. (5) Disturbance index mmrr / m of xylene insoluble part at 105 ° C
mmm: According to the method described in the specification of the present invention.

Example 1 (a) Synthesis of organomagnesium compound 10 equipped with a stirrer, reflux condenser, dropping funnel and thermometer
After the 00 ml flask was replaced with argon, 32.0 g of milled magnesium for Grignard was charged. 120 g of butyl chloride and dibutyl ether 5 were added to the dropping funnel.
Of the magnesium in the flask.
The reaction was started by dropping ml. After the start of the reaction, the dropwise addition was continued at 50 ° C. for 4 hours.
The reaction was continued for hours. Thereafter, the reaction solution is cooled to room temperature,
The solid was filtered off. The butylmagnesium chloride in the sampled reaction solution is hydrolyzed with 1 N sulfuric acid,
When the concentration was determined by back titration with a normal aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2.1 mol / l.

(B) Synthesis of solid product After a 500 ml flask equipped with a stirrer and a dropping funnel was purged with argon, 290 ml of hexane, 7.7 g (23 mmol) of tetrabutoxytitanium and 75.0 g (360 mmol) of tetraethoxysilane were used. Mmol) to obtain a homogeneous solution. Next, 181 ml of the organomagnesium compound solution synthesized in (a) was gradually dropped from the dropping funnel over 3.5 hours while maintaining the temperature in the flask at 5 ° C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, then subjected to solid-liquid separation at room temperature, and washed three times with 300 ml of hexane and three times with 300 ml of toluene.
1 was added.

A portion of the solid product slurry was sampled and subjected to composition analysis. The solid product contained 2.1% by weight of titanium atoms, 36.2% by weight of ethoxy groups and 3.8% of butoxy groups. % By weight. The slurry concentration was 0.125 g / ml.

(C) Synthesis of ester-treated solid 125 ml of the supernatant of the slurry was withdrawn, and 45.8 ml (171 mmol) of diisobutyl phthalate was added.
The reaction was performed at 95 ° C. for 30 minutes. After the reaction, the mixture was separated into solid and liquid, and washed twice with 287 ml of toluene.

(D) Synthesis of solid catalyst component (activation treatment) After the washing in the above (c), toluene.
5 ml, 2.9 ml (11 mmol) of diisobutyl phthalate, 6.3 ml (37 mmol) of butyl ether, and 99 ml (0.90 mol) of titanium tetrachloride were added, and 1
The reaction was performed at 00 ° C. for 3 hours. After the completion of the reaction, the mixture was subjected to solid-liquid separation at the same temperature, and then washed twice with 287 ml of toluene at the same temperature. Then, 74.5 ml of toluene, 6.3 ml (37 mmol) of butyl ether, and 50 ml (0.45 mol) of titanium tetrachloride were added, and the mixture was reacted at 100 ° C. for 1 hour. After the completion of the reaction, the mixture was subjected to solid-liquid separation at the same temperature, washed four times with 287 ml of toluene at the same temperature, washed three times with 287 ml of hexane, and dried under reduced pressure to obtain 46 g of a solid catalyst component.

In the solid catalyst component, 2.2 titanium atoms were contained.
% By weight, 10.7% by weight of a phthalate, 0.7% by weight of an ethoxy group, and 0.3% by weight of a butoxy group.

(E) Polymerization of Propylene A 3-liter stirred stainless steel autoclave was purged with argon, and 2.6 mmol of triethylaluminum and 0.065 of cyclohexylethyldimethoxysilane were added.
Mmol, n-propylmethyldimethoxysilane 0.06
5 mmol and 8.7 m of the solid catalyst component synthesized in (d)
g, and hydrogen equivalent to a partial pressure of 0.33 kg / cm ² was added. Next, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C., and polymerization was carried out at 80 ° C. for 1 hour. After completion of the polymerization, unreacted monomers were purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 2 hours,
254 g of polypropylene powder were obtained.

Therefore, the yield of polypropylene per gram of the solid catalyst component (hereinafter abbreviated as PP / Cat) is
/ Cat = 29,200 (g / g). The ratio of the component soluble in xylene at 20 ° C. in the total polymer yield was CXS = 1.6 (wt%), and the ratio of the component insoluble in boiling heptane in the total polymer yield was II = 99.1 (wt). wt
%), The intrinsic viscosity of the polymer [η] = 1.77, the bulk density of the polymer BD = 0.41 (g / ml), and 105 ° C.
The xylene-insoluble portion was 78.5 (wt%), and the turbulence index of the xylene-insoluble portion at 105 ° C. was mmrr / mmmm = 0.006.
0. Table 1 shows the polymerization conditions and the polymerization results.

Example 2 (a) Polymerization of propylene The same procedure as in Example 1 was carried out except that n-butylmethyldimethoxysilane was used instead of n-propylmethyldimethoxysilane in the polymerization of propylene in Example 1 (e). Polymerization of propylene was carried out by the method. Table 1 shows the polymerization conditions and the polymerization results.

Example 3 (a) Polymerization of propylene The same procedure as in Example 1 was carried out except that n-hexylmethyldimethoxysilane was used instead of n-propylmethyldimethoxysilane in the polymerization of propylene in Example 1 (e). Polymerization of propylene was carried out by the method. Table 1 shows the polymerization conditions and the polymerization results.

Example 4 (a) Polymerization of Propylene In the polymerization of propylene in Example 1 (e), a method was used in the same manner as in Example 1 except that dicyclopentyldimethoxysilane was used instead of cyclohexylethyldimethoxysilane. Polymerization of propylene was performed. Table 1 shows the polymerization conditions and the polymerization results.

Comparative Examples 1 to 5 (a) Polymerization of propylene In the polymerization of propylene in Example 1 (e), instead of the two silane compounds, cyclohexylethyldimethoxysilane, dicyclopentyldimethoxysilane, n-propylmethyldimethoxysilane, Propylene was polymerized in the same manner as in Example 1 except that n-butylmethyldimethoxysilane and n-hexylmethyldimethoxysilane were each used alone in an amount of 0.130 mmol. Table 1 shows the polymerization conditions and the polymerization results.

Comparative Examples 6 to 7 (a) Polymerization of Propylene In the polymerization of propylene in Example 1 (e), cyclohexylethyldimethoxysilane and n-propylmethyldimethoxysilane were each used alone in place of two silane compounds in 0.1. Polymerization of propylene was carried out in the same manner as in Example 1 except that 065 mmol was used. Table 1 shows the polymerization conditions and the polymerization results.

Comparative Example 8 (a) Polymerization of Propylene In the polymerization of propylene in Example 1 (e), except that 0.26 mmol of n-propylmethyldimethoxysilane was used alone instead of the two silane compounds. Example 1
Polymerization of propylene was carried out in the same manner as described above. Table 1 shows the polymerization conditions and the polymerization results.

Example 5 (a) Polymerization of Propylene In the polymerization of propylene in Example 1 (e), 0.026 mmol of cyclohexylethyldimethoxysilane was added.
Propylene was polymerized in the same manner as in Example 1 except that 0.065 mmol of n-propylmethyldimethoxysilane was used. Table 1 shows the polymerization conditions and the polymerization results.

Example 6 (a) Polymerization of Propylene In the polymerization of propylene of Example 1 (e), cyclohexylethyldimethoxysilane was added in an amount of 0.014 mmol,
Propylene was polymerized in the same manner as in Example 1 except that 0.035 mmol of n-propylmethyldimethoxysilane and 1.4 mmol of triethylaluminum were used. Table 1 shows the polymerization conditions and the polymerization results.

[Table 1]

[0066]

EFFECTS OF THE INVENTION By using an olefin polymerization catalyst that provides a polypropylene of a novel composition, a novel steric polypropylene having excellent stiffness, heat resistance, and excellent processability, which is inherent in high stereoregularity polypropylene, is well balanced. Provided are a method for producing an olefin polymer and a catalyst for olefin polymerization used for producing the polymer.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-7703 (JP, A) JP-A-2-170803 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (4)

(57) [Claims] 1. A solid catalyst component containing (A) magnesium, titanium, a halogen and an electron donor as essential components, (B) an organoaluminum compound, (C) an electron donor (α) and an electron donor (β). At least two or more types of electron donors (provided that the electron donor (α) is used together with the solid catalyst component (A) and the organoaluminum compound (B) for polymerization at 105 ° C. in xylene-insoluble part of homopolypropylene). Turbulence index mmr
r / mmmm is 0 ≦ mmrr / mmmm ≦ 0.0068
And the electron donor (β) is converted to the solid catalyst component (A)
And homoorganic compound (B) used in the polymerization with homopolypropylene obtained at 105 ° C. have a turbulence index of xylene-insoluble portion of 0.0068 <mmrr / mmmm ≦
(0.0320). 2. A process for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin using an olefin polymerization catalyst comprising: 2. An electron donor (α) having the general formula R ¹³ R ¹⁴ Si
(OR ^Fifteen ) _Two (Where R ¹³ Indicates that the carbon adjacent to Si is secondary
Or a tertiary hydrocarbon group having 3 to 20 carbon atoms.
R ¹⁴ Is a hydrocarbon group having 1 to 20 carbon atoms; ^Fifteen Is
It is a hydrocarbon group having 1 to 20 carbon atoms. Organic)
A silicon compound wherein the electron donor (β) has the general formula R ¹⁶ R
¹⁷ Si (OR ¹⁸ ) _Two (Where R ¹⁶ Is a straight chain having 1 to 20 carbon atoms
A chain alkyl group; ¹⁷ Is a hydrocarbon group having 1 carbon atom
Yes, R ¹⁸ Is a hydrocarbon group having 1 to 20 carbon atoms. )so
Claims characterized by being an organosilicon compound represented by
Item 10. The method for producing an olefin polymer according to Item 1. 3. A solid catalyst component containing (A) magnesium, titanium, a halogen and an electron donor as essential components, (B) an organoaluminum compound, (C) an electron donor (α) and an electron donor (β). At least two or more types of electron donors (provided that the electron donor (α) is used together with the solid catalyst component (A) and the organoaluminum compound (B) for polymerization at 105 ° C. in xylene-insoluble part of homopolypropylene). Turbulence index mmr
r / mmmm is 0 ≦ mmrr / mmmm ≦ 0.0068
And the electron donor (β) is converted to the solid catalyst component (A)
And homoorganic compound (B) used in the polymerization with homopolypropylene obtained at 105 ° C. have a turbulence index of xylene-insoluble portion of 0.0068 <mmrr / mmmm ≦
0.0320) for the polymerization of olefins. 4. An electron donor (α) having the general formula R ¹³ R ¹⁴ Si
(OR ^Fifteen ) _Two (Where R ¹³ Indicates that the carbon adjacent to Si is secondary
Or a tertiary hydrocarbon group having 3 to 20 carbon atoms.
R ¹⁴ Is a hydrocarbon group having 1 to 20 carbon atoms; ^Fifteen Is
It is a hydrocarbon group having 1 to 20 carbon atoms. Organic)
A silicon compound wherein the electron donor (β) has the general formula R ¹⁶ R
¹⁷ Si (OR ¹⁸ ) _Two (Where R ¹⁶ Is a straight chain having 1 to 20 carbon atoms
A chain alkyl group; ¹⁷ Is a hydrocarbon group having 1 carbon atom
Yes, R ¹⁸ Is a hydrocarbon group having 1 to 20 carbon atoms. )so
Claims characterized by being an organosilicon compound represented by
Item 4. An olefin polymerization catalyst according to Item 3.