JPH06136054A - Production of propylene polymer - Google Patents

Abstract

PURPOSE:To obtain a propylene polymer having excellent stereoregularity and rigidity by using an olefin polymerization catalyst component obtained by a specific treatment of a solid catalyst containing magnesium, titanium, halogen and an electron-donative compound as essential components. CONSTITUTION:An olefin polymerization catalyst component is produced by compounding 1mol of a magnesium compound (preferably magnesium chloride) preferably with 0.01-100mol of a titanium compound (preferably titanium tetrachloride), 0.01-100mol of a halogen-containing compound and 0.01-5mol of an electron donative compound (preferably dimethyl phthalate, etc.) and treating the obtained solid catalyst containing magnesium, titanium, halogen and electron- donative compound as essential components once or more with an electron donative compound and twice or more with a halogen-containing compound. The objective polymer is produced by polymerizing propylene using a catalyst obtained by combining the obtained olefin polymerization catalyst component with an organic aluminum compound and a stereroregularity improving agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a propylene polymer. More specifically, it is possible to obtain a propylene-based polymer having extremely high stereoregularity and rigidity.

[0002]

2. Description of the Related Art Up to now, there have been many proposals for a method for producing a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components (JP-A-57-63310, JP-A-58-63). 32604,
JP-A-58-83006, JP-A-59-206408,
JP-A-59-219311, JP-A-60-13060
7, JP-A-61-209207, JP-A-61-2113
09, JP-A-62-72702, JP-A-62-1048.
11, JP-A-62-1705, and JP-A-63-1997.
03, JP-A-63-264609, JP-A-1-1263.
06, JP-A 1-311106, and JP-A 1-31801.
1, JP-A-2-77407, JP-A-2-166104,
JP-A-3-62805, JP-A-3-70710, JP-A-3-163110, JP-A-4-103604, JP-A-4
-1140909, JP-A-4-202505).
These production methods make it possible to obtain a polymer of an α-olefin having 3 or more carbon atoms with high stereoregularity and high activity. Furthermore, the deashing step of the catalyst, which was required in the conventional titanium trichloride-based catalyst with low activity, is omitted, and the manufacturing process can be simplified and rationalized.

[0003]

The propylene-based polymer produced by the above solid catalyst exhibits high stereoregularity, high crystallinity, high rigidity, heat resistance, transparency, scratch resistance, and chemical resistance. It is widely used in injection molding, blow molding, extrusion molding, films, sheets and the like. Also,
By blending with various additives such as a nucleating agent and a filler, these performances can be further enhanced. Incidentally, the propylene-based polymer has an advantage that the higher the stereoregularity and the crystallinity, the more the compounding amount of the filler and the like can be reduced, and the thinner and lighter the molding resin can be. Until now, a means for producing a propylene-based polymer having higher stereoregularity and higher crystallinity has always been desired. The object of the present invention is, compared with the prior art, further stereoregularity,
It is intended to provide a method for producing a propylene-based polymer having excellent crystallinity, rigidity and heat resistance.

[0004]

The above-mentioned object is to prepare a solid catalyst containing magnesium, titanium, halogen, and an electron-donating compound as essential components, and then further prepare an electron-donating compound one or more times, and a halogen-containing compound for two or more times. The problem can be solved by a method for producing a propylene-based polymer using an olefin polymerization catalyst component, which is characterized by treating at least once.

The present invention will be specifically described below. Olefin Polymerization Catalyst Component A solid catalyst composed of magnesium, titanium, halogen, and an electron donating compound used in the preparation of the olefin polymerization catalyst component of the present invention is a known magnesium compound, titanium compound, halogen-containing compound, electron donating compound as described below. It is prepared using a sex compound. Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; alkoxy magnesium such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and diphenoxy magnesium; magnesium laurate. Examples thereof include carboxylates such as magnesium stearate and magnesium acetate; alkyl magnesium such as dimethyl magnesium, diethyl magnesium and butylethyl magnesium. In addition, these various magnesium compounds may be used alone or in combination of two or more. Preferably, magnesium halide, alkoxy magnesium is used, or magnesium halide is formed during catalyst formation. Particularly preferably, the halogen is chlorine.

Titanium compounds include titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide; tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetrabutane. Examples thereof include alkoxytitanium such as enoxytitanium; ethoxytitanium chloride, butoxytitanium chloride, phenoxytitanium chloride, dibutoxytitanium dichloride, and alkoxytitanium halides such as tributoxytitanium chloride. Moreover, these various titanium compounds may be used alone or in combination of two or more. Tetravalent titanium compounds containing halogen are preferred, and titanium tetrachloride is particularly preferred.

Halogen-containing compounds are those in which the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and the specific compounds actually exemplified depend on the catalyst preparation method, but titanium tetrachloride, tetrabromide. Titanium halides such as titanium, silicon tetrachloride, silicon halides such as silicon tetrabromide, phosphorus trichloride, phosphorus halides such as phosphorus pentachloride and the like can be exemplified, but depending on the catalyst preparation method, halogenated hydrocarbon, Halogen molecules or hydrohalic acid may be used.

Examples of the electron-donating compound generally include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds and sulfur-containing compounds. Examples of the oxygen-containing compound include alcohols, ethers, esters, acid halides, acid anhydrides and the like. More specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, 2-ethyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol. , Alcohols such as phenol, cresol, ethylphenol, naphthol; ethers and diethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran, anisole, diphenyl ether; ethyl acetate, chloro Ethyl acetate, Ethyl propionate, Ethyl butyrate, Ethyl acrylate, Ethyl crotonate, Ethyl oleate , Ethyl stearate, phenyl ethyl acetate, methyl benzoate,
Ethyl benzoate, propyl benzoate, butyl benzoate,
Methyl toluate, ethyl toluate, propyl toluate, butyl toluate, methyl ethyl benzoate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, dimethyl phthalate, phthalic acid Diethyl, dipropyl phthalate,
Esters such as di-n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, phthalic acid chloride Examples thereof include acid chlorides; acid anhydrides such as maleic anhydride and phthalic anhydride. In addition, these electron-donating compounds are 1
They may be used alone or in combination of two or more. Esters are preferable, and phthalic acid esters are particularly preferable.

The amount of each of the above components used is arbitrary as long as the effects of the present invention can be recognized, but generally the following ranges are preferred. The amount of the titanium compound used is 0.000 in molar ratio with respect to the amount of the magnesium compound used.
The range of 1-1000 is preferable, and 0.01-1 is preferable.
It is within the range of 00. If necessary, a halogen compound is used, but when used, the amount of the titanium compound and the magnesium compound contains halogen,
Regardless of whether it is not included, the molar ratio with respect to the amount of magnesium used is preferably 0.01 to 1000, and more preferably 0.1 to 100. The amount of the electron-donating compound used is preferably in the range of 0.001 to 10 and preferably in the range of 0.01 to 5 in terms of molar ratio with respect to the amount of the magnesium compound used.

The solid catalyst used in the present invention is prepared by contacting or reacting with a magnesium compound, a titanium compound, an electron-donating compound, and optionally an auxiliary agent such as a halogen-containing compound, temporarily or stepwise. A conventionally known method for preparing a solid catalyst obtained by the above can be used. The following preparation methods are specific examples of known methods. (1) A method in which a magnesium halide is optionally contacted with an electron donating compound and a titanium compound. (2) A method of bringing a titanium halide compound and / or a halogen compound of silicon into contact with a solid component obtained by contacting magnesium halide with tetraalkoxytitanium and a specific polymer-silicon compound. (3) A method in which a magnesium compound is dissolved in tetraalkoxytitanium and an electron donating compound, and the titanium compound is brought into contact with a solid component deposited by a halogenating agent or a titanium halide compound. (4) A method of treating alumina or magnesia with a phosphorus halide compound, and bringing it into contact with a magnesium halide, an electron donating compound and a titanium halide compound. (5) Grigna represented by organomagnesium compounds
Method in which an electron-donating compound and a titanium compound are brought into contact with each other after the reaction of the reagent with a reducing agent or a halogenating agent. (6) A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxymagnesium compound in the presence or absence of an electron-donating compound. (7) A method in which a magnesium compound is dissolved in tetraalkoxytitanium, treated with a polymer-silicon compound, and then treated with a halogen compound of silicon and an organometallic compound. (8) A method of treating a spherical magnesium compound / alcohol complex with an electron donating compound, a titanium halide compound or the like.

The olefin polymerization catalyst component used in the present invention is prepared by treating the solid catalyst prepared by the above method once or more with the above electron donating compound and twice or more with the halogen-containing compound. . The order of these treatments is not particularly limited, but when treated with an electron donating compound, it is preferable to continuously treat with a halogen-containing compound twice or more. When treated once with a halogen-containing compound, it is difficult to obtain the high performance obtained by the present invention. The electron-donating compound may be the same as or different from the one used when preparing the solid catalyst. The electron-donating compounds may be used alone or in combination of two or more. The halogen-containing compound may be the same as or different from the one used when preparing the solid catalyst. The halogen-containing compounds may be used alone or in combination of two or more. The temperature at which the solid catalyst is treated with the electron-donating compound is -30 to 150 ° C, preferably 0 to 100 ° C.
Within the range of. Further, the temperature for treating the solid catalyst with the halogen-containing compound is 0 to 200 ° C., preferably 50 to 1
Within the range of 50 ° C. The amount of the electron-donating compound used is
0.001 to 500 with respect to the titanium atom in the solid catalyst
The molar ratio is preferably in the range of 0.01 to 50 molar times. The amount of the halogen-containing compound used is 0.01 to 10 relative to the titanium atom in the solid catalyst.
It is in the range of 000 mol times, preferably 0.1 to 1
It is in the range of 000 mol times. The treatment of the solid catalyst with the electron-donating compound and the halogen-containing compound can usually be carried out in an inert hydrocarbon medium. Examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene and xylene. Further, these inert hydrocarbon solvents can be used as a solvent for washing the olefin polymerization catalyst after the treatment with the electron-donating compound for the solid catalyst and the halogen-containing compound.

The olefin polymerization catalyst prepared by the above-mentioned method is used for the polymerization of propylene by the combination with an organoaluminum compound and a stereoregularity improver described later. It can be polymerized. Usually, from about 0.01 g to about 1000 g per 1 g of the prepared olefin polymerization catalyst component.
g, the temperature of the prepolymerization is arbitrary, but is -30 to 80 ° C. The prepolymerization is usually carried out in the coexistence of an organoaluminum compound and an electron donating compound used in the polymerization described later. The prepolymerization can generally be carried out in an inert hydrocarbon solvent, but it can also be carried out in a liquid monomer or a gas phase monomer. Examples of monomers used in the prepolymerization include ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and 4,4-dimethyl-1.
Examples include α-olefins such as pentene, vinylcyclopentane and vinylcyclohexane, styrene derivatives such as styrene and α-methylstyrene, dienes such as butadiene and 1,9-decadiene, and allyltrialkylsilanes. Further, these monomers may be used not only in one kind but also in two or more kinds stepwise or as a mixture. In addition, hydrogen may be used as a molecular weight modifier during the prepolymerization.

Propylene Polymerization The above olefin polymerization catalyst component can polymerize a propylene polymer in the coexistence of an organoaluminum compound and a stereoregularity improver. Typical examples of the organoaluminum compound used in the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum; dimethylaluminum hydride and diethylaluminum hydride. , Alkyl aluminum hydrides such as dibutyl aluminum hydride; alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride; alkyl aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide; Aluminoxane, ethyl aluminoxane, aluminoxane such as propyl aluminoxane can be exemplified. Moreover, these organoaluminum compounds may be used alone or in combination of two or more. Preferred is trialkylaluminum. Typical stereoregularity improvers used in the present invention are aromatic carboxylic acid ester compounds, Si-O-
Examples thereof include a silicon compound having a C or Si—N—C bond, an acetal compound, a germanium compound having a Ge—O—C bond, and a nitrogen or oxygen heterocyclic compound having an alkyl substituent.

Specific examples of these compounds include aromatic carboxylic acid esters such as ethyl benzoate, ethyl p-toluate and ethyl p-anisate; phenyltrimethoxysilane, diphenyldimethoxysilane, di-n-propyl. Dimethoxysilane, di-i-propyldimethoxysilane, di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, t-
Silicon compounds such as butyltrimethoxysilane, cyclohexyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane; benzophenone dimethoxyacetate, benzophenone diethoxyacetate, acetophenone dimethoxyacetate, acetophenone diethoxydiene. Acetal compounds such as ethoxy acetal; Germanium compounds such as diphenyldimethoxygermane and phenyltriethoxygermane;
Heterocyclic compounds such as 6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpyran can be exemplified. In addition, these stereoregularity improvers may be used alone or in combination of two or more. A silicon compound and an acetal compound are preferable, and a silicon compound having a Si—O—C bond is particularly preferable.

The polymerization method in the production method of the present invention is not particularly limited, and a known method can be used, and it can be applied to a gas phase polymerization method as well as a liquid phase polymerization method such as slurry polymerization or bulk polymerization. Further, not only batch polymerization but also continuous polymerization and batch polymerization can be applied. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, cyclohexane or toluene is used alone or as a mixture. Furthermore, the polymerization method in the production method of the present invention can be used for multi-stage polymerization of two or more polymerization reactors. The polymerization temperature is about −50 to 200 ° C., preferably 20 to 150.
The polymerization pressure is from atmospheric pressure to 100 Kg / cm ^2.
G, preferably 3 to 50 Kg / cm ² G. Also,
The molecular weight can be adjusted by adding an appropriate amount of hydrogen during the polymerization. In the production method of the present invention, homopolymerization of propylene is represented by the general formula R—CH═CH ₂ (R is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms and may be a branched group). It can also be copolymerized with an α-olefin. Specifically, ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1.
-Pentene, vinylcyclopentane, vinylcyclohexane and the like are exemplified. Further, styrene, styrene derivatives such as α-methylstyrene, dienes such as butadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, and allyltrialkylsilanes are exemplified. Also, these monomers are not limited to one type
It is also possible to mix and use more than one kind. In addition, as described above, the propylene-based polymer of the present invention can be produced by multistage polymerization of two or more polymerization reactors, and can be used for both homopolymerization and copolymerization. It is also possible to combine homopolymerization and copolymerization in multiple stages. Further, the propylene polymer obtained in the present invention can be further improved in crystallinity and high-speed moldability by adding a known nucleating agent. Furthermore, blending rubber components for the purpose of improving impact resistance, antioxidants, antistatic agents, flame retardants, anti-blowing agents, slip agents, lubricants, antifog agents, dyes, which are commonly used in polypropylene. Pigments, oils, waxes and the like can be added in any desired mixing ratio.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples. The physical properties of polypropylene in the examples are evaluated by the following measuring methods. (1) MFR: Melt flow rate is JIS-K675
8 (230 ° C.). (2) Stereoregularity: Isotacticity was evaluated by mm (%) by ¹³ C-NMR. mm (%) is the fraction of triad units in the polypropylene molecular chain. NMR
The method for determining the absorption assignment of the spectrum is Macromolec
ules, 8 , 687 (1975). (3) Melting point ( _Tmp ), crystallization temperature ( _Tcp ): Measured by a differential scanning calorimeter (DSC). (4) Flexural modulus: 100 parts by weight of polypropylene, butyrated hydroxytoluene (BHT) 0.
1 part by weight, tetrakis [methylene-3- (3 ', 5'-
Di-tert-butyl-4′-hydroxyphenyl) propionate] methane (0.1 parts by weight) and calcium stearate (0.1 parts by weight) were blended, granulated and injection-molded to prepare an ASTM type test piece. . Flexural modulus is A
It was measured by STMD-747-61T.

[0017]Example 1 Preparation of olefin polymerization catalyst component Preparation of solid catalyst Under a nitrogen atmosphere, anhydrous magnesium chloride 47.6 g (50
0 mmol), 250 ml decane and 2-ethylhex
234 ml (1.5 mol) of silalcohol at 130 ° C
After heating the mixture for 2 hours to form a uniform solution,
11.1 g (75 mmol) of phthalic anhydride was added
Then, the mixture is stirred and mixed at 130 ° C. for another hour, and then dried.
Phthalic acid was dissolved in the homogeneous solution. Obtained homogeneous solution
Was cooled to room temperature and then kept at -20 ° C.
In 2.0 liters (18 mol) over 1 hour
Defeated After the dropping is completed, the temperature of the mixed solution is kept at 1 for 4 hours.
When the temperature was raised to 10 ° C and reached 110 ° C, phthalic acid was added.
Add 26.8 ml (125 mmol) of diisobutyl.
Then, the mixture was reacted with stirring at 110 ° C. for 2 hours. After the reaction is complete, heat
The solid portion was collected by filtration at room temperature, and then the reaction mixture was filtered.
After suspending 2.0 l (18 mol) of titanium chloride, 1
The reaction was carried out at 10 ° C for 2 hours. After the reaction is complete, heat again.
The solid portion was collected by filtration, and the decane at 110 ° C was added with 2.0 l of decane.
It was washed 7 times and 3 times with 2.0 l of hexane at room temperature. Obtained
The measured titanium content in the solid catalyst was 2.5.
It was 7% by weight. Treatment with electron-donating compounds and halogen-containing compounds 40 g of the solid catalyst obtained above was added to 600 ml of toluene.
Suspend and 11.9 g of diisobutyl phthalate at 25 ° C
It was reacted with (43 mmol) for 1 hour. After the reaction,
Add titanium chloride 200ml (1.8mol) for 2 hours
It was made to react. After the reaction is completed, the solid part is collected by hot filtration.
Then, 200 ml of titanium tetrachloride was added to this reaction product.
After suspending (1.8 mol), let stand for 2 hours at 110 ° C.
I responded. After completion of the reaction, the solid portion is again filtered by hot filtration.
Collect the sample, and decane at 110 ° C 7 times at room temperature
Washed 3 times with 1.0 l of sun. In the obtained solid catalyst component
The titanium content was measured to be 2.23% by weight.
It was. Polymerization of propylene An autoclave with a stirrer and an internal volume of 60 l under a nitrogen atmosphere
200 mg of the solid catalyst component prepared by the above method,
Triethyl aluminum 11.4 g (100 mmo
l), cyclohexylmethyldimethoxysilane 5.64
g (30 mmol), then propylene 18k
g, 0.13 mol% to propylene
Charge hydrogen, raise the temperature to 70 ° C, and polymerize for 1 hour.
It was. After 1 hour, unreacted propylene was removed to complete the polymerization.
Tied up. As a result, 4460 g of polypropylene was obtained.
Was given. Polymerization activity is 22.3 kg / g-olefin polymerization
[Mm] of the catalyst component and the produced polypropylene was 98.
1%, MFR 8.7g / 10min, T_mpIs 163.7
℃, T_cpIs 109.0 ° C, flexural modulus is 18400k
g / cm² Met.

Comparative Example 1 Propylene polymerization was carried out in the same manner and conditions as in Example 1 except that the solid catalyst prepared in Example 1 was used as it was without being treated during propylene polymerization. As a result, 4800 g of polypropylene was obtained. Polymerization activity is 24.0 kg / g-olefin polymerization catalyst component, [mm] of polypropylene produced is 97.5.
%, MFR 15.8 g / 10 minutes, T _mp 161.5
℃, T _cp 108.0 ℃, flexural modulus 17,000k
It was g / cm ² .

Examples 2 to 5 In the propylene polymerization, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, etc. were used instead of cyclohexylmethyldimethoxysilane.
Polymerization of propylene was carried out under the same method and conditions as in Example 1 except that 1 was used. The polymerization evaluation results are summarized in Table 1.

Comparative Examples 2 to 5 During propylene polymerization, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, etc. were used instead of cyclohexylmethyldimethoxysilane.
Propylene polymerization was carried out by the same method and conditions as in Comparative Example 1 except that 1 was used. The polymerization evaluation results are summarized in Table 1.

Example 6 Propylene polymerization was carried out by the same method and conditions as in Example 1 except that 0.26 mol% hydrogen was used in place of 0.13 mol% hydrogen during propylene polymerization. The results of the polymerization evaluation are shown in Table 1.

Example 7 Propylene polymerization was carried out by the same method and conditions as in Example 3, except that 0.26 mol% hydrogen was used instead of 0.13 mol% hydrogen during propylene polymerization. The results of the polymerization evaluation are shown in Table 1.

[0023]

[Table 1]

[0024]Example 8 Preparation of solid catalyst Diethoxymagnesium 50.0 g (440 mmo
1), 15.3 g of di-n-butyl phthalate (55 mmo
l) in 250 ml of methylene chloride under nitrogen atmosphere for 1 hour
The mixture was stirred under reflux for a while. The obtained suspension is treated with titanium tetrachloride 2.0.
1 (18 mol) under pressure, heated up to 110 ° C., and 2:00
Reacted for a while. After the reaction was completed, the precipitated solid was treated with titanium tetrachloride.
Reaction with 2.0 liters (18 mol) for 2 hours at 110 ° C.
It was After completion of the reaction, 3 times with 2.0 l of n-decane at 110 ° C.
After washing, at room temperature, with 2.0 l of n-hexane, chlorine ions
Washed until no longer detected. Dry under reduced pressure at 40 ℃
The target solid catalyst component was obtained. Obtained solid catalyst component
The content of titanium in it was measured and found to be 2.31% by weight.
there were.Preparation of olefin polymerization catalyst 40 g of the solid catalyst obtained above was added to 600 ml of toluene.
Suspension and diethyl phthalate at 25 ℃ 9.6g (43m
(mol) and reacted for 1 hour. After completion of the reaction,
200 ml (1.8 mol) was added and reacted for 2 hours.
It was After the reaction is completed, the solid portion is collected by hot filtration and
After that, 200 ml of titanium tetrachloride (1.8 mo
l) was suspended and then reacted at 110 ° C. for 2 hours. Anti
After completion of the reaction, the solid portion is collected again by hot filtration, and
7 times with 1.0 l of decane at 0 ° C, 1.0 l of hexane at room temperature
It was washed 3 times. Titanium content in the obtained solid catalyst component
When the rate was measured, it was 2.10% by weight. Polymerization of propylene The solid prepared in Example 8 above during propylene polymerization
The same method and conditions as in Example 1 except that a catalyst was used.
Then, propylene polymerization was performed. The polymerization evaluation results are shown in Table 2.
Show.

Comparative Example 6 Propylene polymerization was carried out under the same conditions and conditions as in Example 1, except that the solid catalyst prepared in Example 8 was used during propylene polymerization. The results of the polymerization evaluation are shown in Table 2.

Examples 9 to 10 Propylene polymerization was carried out by the same method and conditions as in Example 8 except that diisopropyldimethoxysilane and dicyclopentyldimethoxysilane were used in equimolar amounts instead of cyclohexylmethyldimethoxysilane during propylene polymerization. It was The polymerization evaluation results are summarized in Table 2.

Comparative Examples 7 to 8 Propylene polymerization was carried out by the same method and conditions as in Comparative Example 6, except that diisopropyldimethoxysilane and dicyclopentyldimethoxysilane were used in equimolar amounts instead of cyclohexylmethyldimethoxysilane during propylene polymerization. It was The polymerization evaluation results are summarized in Table 2.

[0028]

[Table 2]

[0029]

EFFECTS OF THE INVENTION By carrying out the present invention, a propylene polymer having extremely high stereoregularity and rigidity can be produced at low cost and is industrially valuable.

[Brief description of drawings]

FIG. 1 is a flowchart showing a method for producing a propylene-based polymer according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (1)

[Claims] 1. A solid catalyst comprising magnesium, titanium, halogen, and an electron donating compound as essential components is prepared, and then treated with an electron donating compound once or more and with a halogen-containing compound twice or more. A method for producing a propylene-based polymer using the olefin polymerization catalyst component as described above.