JPH02206604A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain in high yield the title polymer of high stereoregularity free from odor and discoloration by polymerization of an olefin using a catalytic system comprising metallocene containing cyclopentadienyl ring and a solid containing Ti, Mg and halogen as the essential components. CONSTITUTION:The objective polymer can be obtained by polymerization of an olefin using a catalytic system comprising (A) a solid component containing as the essential components Ti, Mg and halogen and (B) metallocene containing cyclopentadienyl ring, at least one compound selected from those of formulas I [(C5R) is cyclopentadienyl group, etc.; R<1> is H, 1-20C hydrocarbon, etc.: R<2> is 1-4C alkylene, dialkylsilicon, etc,: R<3> is 1-20C hydrocarbon; R4 is 1-20C hydrocarbon or halogen; M is group IV A, VA or VIA transition metal element; t is 0 or 1; p is 1, 2 or 3; q is 4 or 5], II (R<5> is 1-20C alkylidene) and III(Q is methyl or Cl: R<6> is 1-18C hydrocarbon), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Field of Application The present invention relates to a method for producing an olefin polymer. More specifically, the present invention makes it possible to produce highly stereoregular polymers in good yield when applied to the polymerization of olefins, especially α-olefins having 3 or more carbon atoms, by using a specific catalyst system. It is possible.

(2) Prior Art Conventionally proposed olefin polymerization catalysts consisting of a solid catalyst component containing magnesium, titanium, and halogen as essential components and organoaluminum generally have extremely high polymerization activity, but the stereoregularity of the product polymer In the case of α-olefins whose properties are sensitive, it is necessary to use various electron donors during the preparation of the solid catalyst and during the polymerization.

For example, among these, the earliest developed
Some use aromatic monocarboxylic acid esters as electron donors (for example, JP-A-54-132494 and JP-A-54-4294). Aromatic monocarboxylic acid esters are generally used to improve the stereoregularity of the resulting polymer both during the preparation of the solid catalyst and during the polymerization. For this reason, it imparts a characteristic ester odor to the produced polymer and causes coloration, and cannot be said to have industrially satisfactory performance.

Furthermore, catalysts that generally use electron donors during polymerization are
The problem is that the polymerization rate decreases due to the reaction between the organic aluminum and the electron donor.

Therefore, it is desired to develop a catalyst system that can solve the above problems and produce a highly stereoregular polymer in high yield without using an electron donor during the preparation of a solid catalyst or during polymerization. From this point of view, the present inventors have already discovered a method for producing polyolefins with high stereoregularity without using an electron donor during the preparation of a solid catalyst or during polymerization (Japanese Patent Laid-Open No. 83 -48204). However, its stereoregularity (isotafticity) is 90
%, which is not necessarily sufficient performance.

In general, industrial olefin polymerization catalysts such as magnesium chloride-supported titanium catalysts support a large amount of titanium in order to increase the olefin polymerization activity per catalyst, and a plurality of polymerization active species exist.

That is, since monodispersed titanium species and clustered titanium species are supported on the solid catalyst, the polymerization active species is not a single species. For clustered titanium species, Ma
kroIIol, Chati, 189.1531
(198g), it is generally difficult to provide a high degree of stereospecificity, and in order to provide a solid catalyst with a higher degree of stereospecificity, titanium species such as this It is considered desirable to reduce the That is, it is desirable to reduce the amount of titanium supported on the solid catalyst.

(3) Problems to be Solved by the Invention The purpose of the present invention is to produce olefin polymers with high stereoregularity without using any electron donors, such as aromatic carboxylic acid esters, during the preparation of solid catalysts or during polymerization. The object of the present invention is to provide a polymerization method that can obtain high yields. According to the method of the present invention, no electron donor is required at all during the preparation of the solid catalyst and during the polymerization, so there are no problems with odor and coloration imparted to the produced polymer.

(4) Means for Solving the Problems The above objects are achieved by polymerizing olefins using a catalyst system consisting of the following components (A) and (B).

That is, component (A) is a solid component containing titanium, magnesium, and halogen as essential components.

The magnesium compound used as the magnesium source used in the present invention is not particularly limited, and is used for the stereoregular polymerization of normal α-olefins and the preparation of highly active catalysts for the production of ethylene alone or copolymers such as linear polyethylene. Examples include those used as raw materials.

Examples of such magnesium compounds include magnesium halide, dialkylmagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like.

These various magnesium compounds can be used alone or in combination of two or more. Among these, lower alkoxymagnesiums such as magnesium chloride, dimethoxymagnesium, and jetoxymagnesium are preferred.

The titanium compound serving as the titanium source is TiCρ4゜TiBr
Titanium tetrahalides such as TiI4; Ti (OCH3)C13, Ti (OC2H
5) CD3゜T i (0-n C4H9) CD a
, T t (OC2H5) B ra; trihalogenated alkoxy titanium such as Tl(OCH)Cg
Ti(OC2H5)20g2゜32 2' Ti(0-n C4Hg)2 C112,Ti(OC3
H7) Dihalogenated alkoxy titanium such as 2CN2:
TI(OCH)Cjl! , Ti (OC2H5)3C1
゜TI(0-nC4H9)3Cj2. TI (OCH3)
Monohalogenated trialkoxytitanium such as 3Br; T
i (OCR) 'ri (OC2H5)4゜3
4' Ti (OC3H7)4. Ti (0-nC4H9)
Examples include tetraalkoxytitanium such as No. 4.

These may be used alone or in combination of two or more. Among these, it is preferable to use high halogen-containing compounds, especially T iCI! It is preferable to use 4.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but it may also be supplied from known halogenating agents such as aluminum halides, silicon halides, and phosphorous halides. You can also do it.

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

The amounts of each of the above components to be used are arbitrary, but are generally preferably within the following ranges.

The amount of the titanium compound to be used is preferably in the range of 0.0001 to 1000 in molar ratio to the amount of the magnesium compound used, and preferably in the range of 0.01 to 1O.

When using such compounds as halogen sources,
Regardless of whether the titanium compound and/or magnesium compound contains halogen or not, the amount used is 0.0 molar ratio to the amount of magnesium used. O1
It is preferably within the range of ~.1000, more preferably 0.
It is within the range of 1 to 100.

The solid component for preparing component (A) is prepared using the above-mentioned magnesium source, titanium source, and halogen source, for example, by the following manufacturing method.

■ A method of bringing a magnesium halide into contact with a titanium-containing compound, ■ A method of bringing an alkoxymagnesium compound into contact with a titanium compound and/or a halogenating agent and then contacting a titanium compound, ■ An organomagnesium compound represented by Grignard reagent A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and a titanium compound is brought into contact with a solid component precipitated by a titanium halide or a halogenating agent. , ■ A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide and a titanium halide, ■ A method in which titanium halogen is added to the solid component obtained by contacting magnesium halide with a titanium tetraalkoxide and a polymeric silicon compound. (2) A method in which a solid component obtained by reacting metallic magnesium with an organic halide is brought into contact with a titanium compound.

Regarding the amount of titanium supported on the solid component (A), 1.
It is preferably 5% by weight or less, particularly preferably 1.0% by weight.
It is as follows.

Component (B) is a metallocene consisting of a cyclopentadienyl ring, and has the following general formula (1), [II) or [■]: (CR1) R2MR3R' 5 q p t $-p ''] R2
(CR') MR5(II) t 5q2 [wherein (CR') is a cyclopentadienyl group q or a substituted cyclopentadienyl group.

R1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R1 may be the same or different,
Two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group may form a ring having 4 to 6 carbon atoms together with R1 to which they are bonded. R2 is a group that connects two (CR1) groups, and is selected from an alkylene group having 1 to q4 carbon atoms, a dialkylgermanium group, a dialkylsilicon group, an alkylphosphine group, and an alkylamine group. R3 is a hydrocarbon group having 1 to 20 carbon atoms, R4 is a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and R5 is an alkylidene group having 1 to 20 carbon atoms. M is IVA, VA, in the periodic table.
It is a transition metal element of Group VIA. t is 0 or 1, p is 1, 2 or 3, and q is 4 or 5. However, when p is 1, t is 0, and when t is 1, q is 4.
p is 2, and when t is 0, q is 5. Q is a methyl group or a chlorine atom, and R8 is a hydrocarbon group having 1 to 1B carbon atoms. However, when Q is a methyl group, R8 is a methyl group. ] or 28! That's all.

In the cyclopentadienyl compound represented by the general formula (13, (n) and CIII), it is a substituted cyclopentadienyl group. R1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, alkenyl group, aryl group, alkylaryl group, or arylalkyl group, and R1 may be the same or different. Often, two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group may form a ring having 4 to 6 carbon atoms together with R1 to which they are bonded. R is a group that connects two (C5R9),
It is selected from an alkylene group having 1 to 4 carbon atoms, a dialkylgermanium group, a dialkyl silicone group, an alkylphosphine group, and an alkylamine group. R3 is an alkyl group, an alkenyl group, an aryl group, an alkylaryl group,
A hydrocarbon group having 1 to 20 carbon atoms such as an arylalkyl group, and R4 is a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, or a halogen. R5 is an alkylidene group having 1 to 20 carbon atoms. M
are IVA and VA on the periodic table.

It is a transition metal element of Group VIA. t is 0 or 1, p is 1.2 or 3, and q is 4 or 5.

However, when p is 1, t is 0, when t is 1, q is 4, p
is 2, and when t is 0, q is 5. Q is a methyl group or a chlorine atom, and R6 is a hydrocarbon group having 1 to 18 carbon atoms such as an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, or an arylalkyl group. However, when Q is a methyl group, R8 is a methyl group.

Specific examples of the hydrocarbon groups in R1, R8, R4 and R6 include methyl, ethyl, propyl, butyl,
Isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, hexadecyl, 2-
Examples include ethylhexyl and phenyl.

Specific examples of the alkylene group in R2 include methylene, ethylene, propylene, and the like. Examples of the halogen atom in R4 include chlorine, bromine, and iodine, with chlorine being preferred. Above R5
Specific examples of the alkylidene group in are methylidene, ethylidene, propylidene, and the like.

Specific examples of the transition metal element M include titanium,
Zirconium, vanadium, hafnium, etc. can be mentioned, and among them, titanium is preferable.

Specific examples of the cyclopentagenyl compounds represented by general formulas (1), (If) and CIII) include the following compounds (Cp-cyclopentagenyl,
Ind-indenyl, Me-methyl, Et■ethyl, p
h-phenyl).

Bis(cyclopentadienyl)dimethyltitanium
Cp2TiMe2 Bis(methylcyclopentadienyl) Dimethyltitanium (Me Cp)2T i Me2 Bis(pentamethylcyclopentagenyl) dimethyltitanium ((Me) Cp) 2 TiMe2 Bis(cyclopentadienyl) Methyl coo titanium Cp 2 T iM e Cj! Bis(cyclopentadienyl)dimethylzirconium
Cp 2 Z r M e 2bis(indenyl)dimethyltitanium (Ind) 2TiMe2 bis(indenyl)dimethylzirconium (Ind)
ZrMe2 Ethylenebis(tetrahydroindenyl)dimethylzirconiumEt(HInd)2ZrMe2 (μmchloro)(μmmethylene)bis(cyclopentagenyl)(dimethylaluminum)titanium (blank below) (μmmethylene)(μmmethyl)bis(cyclo pentagenyl) (dimethylaluminum) titanium methylphosphine dicyclopentajenyl diphenyl titanium (μm methylene) (μm methyl) bis(methylcyclopentagenyl) (dimethylaluminum) titanium methylene dicyclopentagenyl dimethyl titanium bis(methyl cyclopentadienyl) diphenyl titanium (M e Cp) 2 T i Ph 2 dimethylsilyl dicyclopentadienyl diphenyl titanium These cyclopentadienyl compounds can be used alone or in combination of two or more. It is possible.

The use of the cyclopentagenyl compound represented by the above general formula CI], (n), (m) is the component (A
) with a molar ratio of 0 to the titanium contained in the solid component.
, 1 to 1000 is preferable.

The operation method for polymerizing olefins using the catalyst system of the present invention is not particularly limited, and known methods such as slurry polymerization, gas phase polymerization, solution polymerization, bulk polymerization, continuous polymerization, and batch polymerization can be used. used. For example, in the case of slurry polymerization, the polymerization solvent is heptane,
Saturated aliphatic or aromatic hydrocarbons such as hexane, pentane, cyclohexane, benzene, toluene, etc. alone or in mixtures, or olefin monomers used in polymerization are used. The polymerization temperature is selected from the range of 20 to 150°C, preferably 0 to 100°C, and the pressure is from atmospheric pressure to
Usually selected from the range of 100 atmospheres.

The first nophine to be polymerized using the catalyst system of the present invention has the general formula R-CH-CH2, where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and has no substituent. It can be expressed as: Specifically, for example,
ethylene, propylene, 1-butene, 1-pentene, 1
-Olefins such as hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. Preference is given to ethylene and propylene, particularly preferably propylene. Moreover, copolymerization can also be carried out using the above-mentioned olefins.

(6) Examples Example 1 Anhydrous magnesium chloride (obtained by heating and drying commercially available anhydrous magnesium chloride in a stream of dry nitrogen at about 500°C for 15 hours) 20 g (0,
21 mol) was placed in a container for a vibrating ball mill (cylindrical stainless steel, filled with porcelain balls having an internal volume of 1 fI and a diameter of 10 mm, approximately 50% by apparent volume).

This was attached to a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz, and pulverization was performed for 16 hours. Obtained pulverized material 5
g in a 200 ml flask and heated at 30°C under nitrogen for 30 minutes.
m1 of T iCfl 4. The resulting reaction product was filtered and the solid product was washed 10 times with 60 ml of dry toluene. After washing, a magnesium chloride-supported titanium catalyst was obtained by drying at 40° C. under reduced pressure. The obtained solid catalyst was found to contain 0.52% by weight of titanium by colorimetric analysis.

K, C1auss et al.'s method (K, C1auss,
H, Be5t1an.

Justus Liebig Ann, Chew,
, 854. 8 (19(i2), ),
Bis(cyclopentadienyl)dichlorotitanium (C
p T 1C1l 2 ) and methyllithium (MeL
i) to produce bis(cyclopentadienyl)dimethyltitanium (Cp 2 TIM e 2 ).
was synthesized and isolated. Synthetically isolated C p T I M
e2 is unstable to heat and light, and in consideration of its ease of use during polymerization, the compound was
．． 25a+ol#! The solution was diluted and stored in the dark at -78°C under a nitrogen gas atmosphere.

Polymerization of propylene A 200 ml glass flask was used as a polymerization vessel. The reaction vessel was previously placed under a nitrogen atmosphere, 200+ag of component (A) prepared above was introduced, and the entire amount of heptane was added as a polymerization solvent [Cp TiMe2 to be added later].
(including the amount of hebutane solution in the calculation) was added so that the amount was 1100 m. After stirring for 5 minutes at a polymerization temperature of 40° C., nitrogen gas was exhausted, propylene gas was introduced, and the mixture was saturated for 20 minutes. The polymerization pressure was a total pressure of 1 at 11. Closed. Then, C
p TIM e 2 in hebutane solution (0.25 m
Polymerization was initiated by adding 8 ml of ol/N). Polymerization was carried out for 1 hour, and the polymerization was stopped by adding a hydrochloric acid-methanol mixed solvent to the polymerization system. The produced polymer was thoroughly washed with methanol and then dried in vacuum. The polymerization activity is .

930g-polypropylene/g-titanium・hour (hereinafter referred to as z
-PP/g-TI-h). No problems such as odor or coloration were observed in the produced polymer.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method. That is, the produced polymer was extracted with boiling hebutane for 6 hours, and the weight percent of the insoluble portion was determined as the isotactic index (+, 1.). The 1.1° of the polymer produced in this example was 97.2%.

Synthesis of Example 2 C p T i M e synthesized in Example 1
2, bis(
Methylcyclopentadienyl) dichlorotitanium ((
MeCp)TiCg2) and MeLi were reacted to synthesize and isolate bis(methylcyclopentadienyl)dimethyltitanium [(MeCp)TiMe2). Further, as in Example 1, considering the chemical properties of (MeCp)TiMe2 and ease of use during polymerization, the compound was diluted in a 0.25 ggol/N solution of heptane and stored in the same manner.

C p T i M e 2 used in Propylene Polymerization Example 1
Hebutane solution (0,25 mol/j!) of (MeCp)TiMe2 in place of 8 ml of hebutane solution (0,25 mol/j!)
25 ■ ol / i) ) Except that 8 ml was used.
Polymerization of propylene was carried out in the same manner as in Example 1.

The polymerization activity was 1340 g-PP/g-TI-h.

No problems such as odor and coloration were observed in the produced polymer.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated in the same manner as in Example 1 by the boiling hebutane extraction method. 1.1. of the polymer produced in this example. was 97.5%.

Comparative Example 1 Polymerization of propylene In place of 8 ml of Cp TiMe2 hebutane solution (0.25 mol/N) as component (B), triethylaluminum hebutane solution (0.25 mol/i
) Polymerization of propylene was carried out in the same manner as in Example 1 except that 8 ml was used. Polymerization activity 4100
g-PP/g-Ti·h.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method in the same manner as in Example 1. 1.1. of the polymer produced in this example. was 38.0%. In this way, when a general organic aluminum such as triethylaluminum is used and no electron donor is used during solid catalyst preparation and polymerization,
1.1. of the produced polymer. It can be seen that this is extremely low.

Comparative Example 2 Anhydrous magnesium chloride (obtained by heating and drying commercially available anhydrous magnesium chloride at about 500°C for 15 hours in a dry nitrogen stream) 20 g
1sol) and titanium tetrachloride 2.3ml (21+amo
1) was placed in a container for a vibrating ball mill (stainless steel cylindrical type, filled with approximately 50% apparent volume of porcelain balls having an internal volume of 1 g and a diameter of 10 m+s). The amplitude of this is 6mm5
It was installed in a vibrating ball mill with a vibration frequency of 3011z, and co-pulverized for 16 hours. 5 g of the obtained co-pulverized material was transferred to 200 m
1 flask and washed 10 times with 60 ml of dry toluene under nitrogen at 60°C. After washing, a solid catalyst was obtained by drying at 40° C. under reduced pressure. The obtained solid catalyst was found to contain 2.95% by weight of titanium by colorimetric analysis.

Component (A) 50+ag prepared in Example 2 during polymerization of propylene
Polymerization of propylene was carried out in the same manner as in Example 1, except that . Polymerization activity is 250gPP/g
-TiΦh.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method in the same manner as in Example 1. 1.1. of the polymer produced in this example. was 89.8%. When the amount of titanium supported during the preparation of the solid catalyst is high as in the case of the prior art, the stereoregularity of the produced polymer is lower than in Example 1 where the titanium content is low.

Comparative Example 3 Anhydrous magnesium chloride (obtained by heating and drying commercially available anhydrous magnesium chloride in a stream of dry nitrogen at about 500°C for 15 hours) 20 g
1g+ol) and ethyl benzoate 2.25z (1.5w
*ol) was placed in a container for a vibrating ball mill (cylindrical stainless steel, filled with porcelain balls having an internal volume of Ill and a diameter of io+++m to approximately 50% apparent volume). Attach this to a vibrating ball mill with an amplitude of 6 fins and a frequency of 30 Hz, and
Co-milling was carried out for I time. 200 g of the obtained co-pulverized material
ml flask and heated at 120°C under nitrogen to 30 ml of T i Cj! 4 was reacted. The resulting reaction product was filtered and the solid product was washed 10 times with 80 ml of dry toluene at 60°C. After washing, a solid catalyst was obtained by drying at 40° C. under reduced pressure. The obtained solid catalyst was determined by colorimetric analysis to contain 1.90 fli% titanium,
Also, by gas chromatography, 4.82% by weight
was found to contain ethyl benzoate.

Polymerization of propylene 50 mg of component (A) prepared in Comparative Example 3 during polymerization.

Cp T i M e 2 in hebutane solution (0,25
Instead of 8 ml of triethylaluminum in hebutane (0,25io1/N
) Polymerization of propylene was carried out in the same manner as in Example 1 except that 8 ml was used. Polymerization activity is 6450s
r-PP/g-Tl-h.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method in the same manner as in Example 1. of the polymer produced in this comparative example! , 1. was 49.8%. Even when an electron donor is used during the preparation of a solid catalyst, the stereoregularity of the resulting polymer is quite insufficient.

Comparative Example 4 50 mg of component (A) prepared in Comparison n3 above during polymerization of propylene
, Cp TLMe2 in hebutane solution (0.25 mol
Hebutane solution of triethylaluminum (0.25 mol/l) as component (B) instead of 8 ml)
8 ml of a hebutane solution of ethyl benzoate (0.25 mo
l/j! ) Polymerization of propylene was carried out in the same manner as in Example 1 except that 2.7 ml was used. Polymerization activity is 4830. -PP/tr -TiΦh.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method in the same manner as in Example 1. ■ of the polymer produced in this comparative example, 1. was 92.1%. It can be seen that the use of an electron donor not only during the preparation of the solid catalyst but also during the polymerization greatly improves the stereoregularity of the resulting polymer. However, the resulting polymer still had an odor based on ethyl benzoate.

Example 3 Component (A) Preparation of magnesium chloride-supported titanium catalyst Using a 2.0 g round bottom flask, the flask was sufficiently replaced with nitrogen, and then 30 g of powdered metallic magnesium was added.
, 1.0 g of iodine and 1,2I of n-butyl chloride were introduced, and the mixture was reacted for 5 hours at the boiling point of n-butyl chloride. After the reaction, the supernatant was removed and the product was
After washing three times with m1 ropetyl chloride, the product was dried at 40° C. under reduced pressure to obtain a powdery solid product.

20 g of the obtained solid product was pulverized at 16:00 using a vibrating ball mill in the same manner as in Example 1. 5 g of the obtained pulverized material was reacted with titanium tetrachloride at 30° C. in the same manner as in Example 1 to obtain a magnesium chloride supported titanium catalyst. The obtained solid catalyst was determined by colorimetric analysis to be 0.51
It was found to contain % titanium by weight.

Polymerization of propylene Propylene polymerization was carried out in the same manner as in Example 1, except that 200 μm of component (A) prepared in Example 5 was used during the polymerization. Polymerization activity is 1460g-PP/t
It was number r-Tl.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling heptane extraction method in the same manner as in Example 1. 1,1 of the polymers produced in this example. was 97.0%.

Example 4 Polymerization of propylene 200 g of component (A) prepared in Example 5 during polymerization.

Cp2 T i M e2 in hebutane solution (0,25i
o1/fl) instead of 8 ml (MeCp)'rtMe2
Polymerization of propylene was carried out in the same manner as in Example 1 except that 8 ml of hebutane solution (0.25 mol/!I) was used. Polymerization activity is 1590. - PP/g
-TI・h.

Stereoregularity of the produced polymer The stereoregularity of the produced polymer was evaluated by the boiling hebutane extraction method in the same manner as in Example 1. 1.1. of the polymer produced in this example. was 9B, 7%.

(7) Effects According to the polymerization method of the present invention, an olefin polymer with high stereoregularity can be obtained in good yield without using any of the various electron donors that were conventionally required during solid catalyst preparation and polymerization. be able to. Since no electron donor, typified by aromatic carboxylic acid esters, is used during the preparation of the solid catalyst or during polymerization, problems with odor and coloration do not occur in the resulting polymer.

[Brief explanation of the drawing]

FIG. 1 is a flowchart relating to a method for preparing a catalyst used in the method for producing an olefin polymer of the present invention.

Claims (1)

[Scope of Claims] 1. A method for polymerizing olefins, which comprises polymerizing using a catalyst system consisting of the following components (A) and (B). Component (A): A solid component containing titanium, magnesium and halogen as essential components. Component (B): Metallocenes consisting of a cyclopentadienyl ring and having the following general formula [I], [II] or [III]
, (C_5R^1_q)_pR^2_tMR^3R^4_
3_-_p[I]R^2_t(C_5R^1_q)_
2MR＾5〔II〕▲There are mathematical formulas, chemical formulas, tables, etc.▼〔
III] [In the formula, (C_5R^1_q) is a cyclopentadienyl group or a substituted cyclopentadienyl group. R^1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R^1 may be the same or different, and represents a cyclopentadienyl group or a substituted cyclopentadienyl group. Two adjacent carbon atoms forming the ring may form a ring having 4 to 6 carbon atoms together with R^1 bonded to each. R^2 is a group that connects two (C_5R^1_q), and is selected from an alkylene group having 1 to 4 carbon atoms, a dialkylgermanium group, a dialkyl silicone group, an alkylphosphine group, and an alkylamine group. R^3 is a hydrocarbon group having 1 to 20 carbon atoms, and R^4
is a hydrocarbon group or halogen atom having 1 to 20 carbon atoms, and R^5 is an alkylidene group having 1 to 20 carbon atoms. M is a transition metal element in groups IVA, VA, and VIA of the periodic table. t is 0 or 1, p is 1, 2 or 3, and q is 4 or 5. However, when p is 1, t is 0, when t is 1, q is 4, p is 2, and when t is 0, q
is 5. Q is a methyl group or a chlorine atom, and R^
6 is a hydrocarbon group having 1 to 18 carbon atoms. However, when Q is a methyl group, R^6 is a methyl group. ]At least one type of compound represented by. 2. The method for polymerizing olefins according to claim 1, characterized in that no electron donating compound is used during the preparation of component (A) and during the olefin polymerization. 3. The method for polymerizing olefins according to claim 1 or 2, wherein the titanium content of component (A) is 1.5% by weight or less.