JP2699047B2 - Method for producing propylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a propylene-based 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 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 and JP-A-58-63310). 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, JP-A-63-1997
03, JP-A-63-264609, JP-A-1-1263
06, JP-A-1-3111106, 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
-11409, 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. Further, the step of decalcifying the catalyst, which is required for the conventional titanium trichloride catalyst having low activity, is omitted, and the production process can be simplified and streamlined.

[0003]

The propylene-based polymer produced with the above solid catalyst exhibits high stereoregularity, high crystallinity and high rigidity, and has heat resistance, transparency, scratch resistance, and chemical resistance. It is widely used in injection molding, hollow 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. In addition, the propylene-based polymer has the advantage that the higher the stereoregularity and the higher the crystallinity, the smaller the amount of additives such as filler and the like, and the thinner and lighter the molding resin can be. Until now, a means for producing a propylene-based polymer having higher stereoregularity and crystallinity has been desired. An object of the present invention is to provide a stereoregularity,
An object of the present invention is to provide a method for producing a propylene polymer having excellent crystallinity, rigidity and heat resistance.

[0004]

The object of the present invention is to provide magnesium, titanium, titanium halide and silicon halide.
After preparing a solid catalyst exhibiting substantially catalytic activity containing a halogen selected from the group consisting of an electron-donating compound as an essential component, it is further subjected to electron donation in the absence of titanium tetrachloride.
Treated at least once with a reactive compound and then with titanium tetrachloride
Olefin polymerization catalyst composition obtained by treating at least twice
The problem can be solved by a method for producing a propylene-based polymer , characterized in that a propylene polymer is used.

Hereinafter, the present invention will be described specifically. Olefin polymerization catalyst component The 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 includes the following known magnesium compounds, titanium compounds, halogen-containing compounds, and electron donors. It is prepared using an acidic compound. Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide; alkoxymagnesiums such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium; magnesium laurate And carboxylate salts such as magnesium stearate and magnesium acetate; and alkyl magnesium salts such as dimethyl magnesium, diethyl magnesium and butyl ethyl magnesium. These various magnesium compounds can be used alone or in combination of two or more. Preferably, magnesium halide or alkoxymagnesium is used, or magnesium halide is formed during catalyst formation. Particularly preferably, the halogen is chlorine.

[0006] Examples of titanium compounds include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrabutoxytitanium, Examples thereof include alkoxytitanium such as enoxytitanium; and alkoxytitanium halides such as ethoxytitanium chloride, butoxytitanium chloride, phenoxytitanium chloride, dibutoxytitanium dichloride and tributoxytitanium chloride. These various titanium compounds can be used alone or in combination of two or more. Preferred are tetravalent titanium compounds containing halogenation, and particularly preferred is titanium tetrachloride.

[0007] Halogen-containing compounds, halogen fluorine, chlorine, bromine or iodine, preferably also a titanium halide such as <br/> titanium tetrachloride, titanium tetrabromide is chlorine,
The silicon tetrachloride, halogenated silicon, such as silicon tetrabromide
Is used.

The electron donating compound generally includes an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound and the like. Examples of the oxygen-containing compound include alcohols, ethers, esters, acid halides, and acid anhydrides. 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 and 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 ethoxy benzoate, ethyl ethoxy benzoate, 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 and phthalic chloride. And acid anhydrides such as maleic anhydride and phthalic anhydride. In addition, these electron donating compounds are
The seeds can be used alone or in combination of two or more. Preferred are esters, and particularly preferred are phthalic esters.

The use amount of each of the above components is arbitrary as long as the effect is recognized in the present invention, but the following ranges are generally preferred. The amount of the titanium compound used is 0.000 in molar ratio with respect to the amount of the magnesium compound used.
It is good to be in the range of 1 to 1000, preferably 0.01 to 1
00 is within the range. If necessary, a halogen compound is used, but if used, the amount used is such that the titanium compound and the magnesium compound contain a halogen,
Regardless of whether or not it is contained, the molar ratio is preferably in the range of 0.01 to 1000, more preferably 0.1 to 100, based on the amount of magnesium used. The amount of the electron donating compound used is preferably in the range of 0.001 to 10 in terms of molar ratio with respect to the amount of the magnesium compound, and more preferably in the range of 0.01 to 5.

The method for preparing the solid catalyst used in the present invention comprises the steps of temporarily or stepwise contacting or reacting a magnesium compound, a titanium compound, an electron-donating compound and, if necessary, an auxiliary such as a halogen-containing compound. A conventionally known method for preparing a solid catalyst obtained by the reaction can be used. Specific examples of known methods include the following preparation methods. (1) A method of contacting a magnesium halide with an electron-donating compound and a titanium compound as required. (2) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a tetraalkoxytitanium and a specific polymer-silicon compound. (3) A method in which a magnesium compound is dissolved with tetraalkoxytitanium and an electron-donating compound, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halide compound. (4) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron-donating compound, and a titanium halide compound are brought into contact therewith. (5) Grignards represented by organomagnesium compounds
A metal reagent is allowed to react with a reducing agent, a halogenating agent, or the like, and then the electron donating compound is brought into contact with a titanium compound. (6) A method in which a halogenating agent and / or a titanium compound is brought into contact with an alkoxymagnesium compound in the presence or absence of an electron donating compound. (7) A method of dissolving a magnesium compound with tetraalkoxytitanium, treating with a polymer-silicon compound, and then treating 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, and the like.

The solid catalyst prepared by the above method is used at least once with the above electron donating compound and at least twice with titanium tetrachloride.
By performing the above treatment, the olefin weight obtained in the present invention is obtained.
A combined catalyst component is prepared. These components of the solid catalyst component
The first method is to treat the child in the absence of titanium tetrachloride.
Treatment with the donor compound at least once, and then successively
The treatment is performed twice or more with titanium oxide. 1 treatment with titanium tetrachloride
The high performance obtained by the present invention cannot be obtained.
No. The electron donating compound was used during the preparation of the solid catalyst.
It may be the same as or different from the above. Electron donating
Compounds can be used alone or in combination of two or more.
It can also be used in combination. First treatment is tetrachloride
If it is titanium, the first treatment is with an electron donating compound.
Even in processing, a substantial amount of titanium tetrachloride coexists there
In such a case, the high performance obtained by the present invention cannot be obtained.

The catalyst for olefin polymerization prepared by the above method is used for the polymerization of propylene in combination with an organoaluminum compound and a stereoregularity improver as described below. It is possible to polymerize. Usually, 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 pre-polymerization is usually performed in the coexistence of an organic aluminum compound and an electron donating compound used in the polymerization described later. The prepolymerization can be generally carried out in an inert hydrocarbon solvent, but can also be carried out in a liquid monomer or a gas phase monomer. As the monomers used in the prepolymerization, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1
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. In addition, these monomers can be used not only in one kind but also in two or more kinds stepwise or as a mixture. In addition, hydrogen can also be used as a molecular weight regulator at the time of prepolymerization.

Propylene Polymerization The olefin polymerization catalyst component can polymerize a propylene polymer in the presence of an organoaluminum compound and a stereoregularity improver. The organoaluminum compound used in the present invention is typically a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum; dimethylaluminum hydride, diethylaluminum hydride Alkyl aluminum hydrides such as dibutyl aluminum hydride; alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and 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. These organoaluminum compounds may be used alone or in combination of two or more. Preferably, it is a trialkylaluminum. Representative stereoregularity improvers used in the present invention include aromatic carboxylic acid ester compounds, Si-O-
Examples thereof include a silicon compound having a C or Si-NC bond, an acetal compound, a germanium compound having a Ge-OC bond, and a nitrogen or oxygen heterocyclic compound having an alkyl substituent.

Specific examples of these compounds include aromatic carboxylic 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 and tetraethoxysilane; benzophenonedimethoxyacetal, benzophenonediethoxyacetal, acetophenonedimethoxyacetal, acetophenonediethoxydi Acetal compounds such as ethoxyacetal; germanium compounds such as diphenyldimethoxygermane and phenyltriethoxygermane;
Heterocyclic compounds such as 6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpyran can be exemplified. These stereoregularity improvers can be used alone or in combination of two or more. Preferred are silicon compounds and acetal compounds, and particularly preferred are silicon compounds having a Si-OC bond.

The polymerization method in the production method of the present invention is not particularly limited, and a known method can be used. The method can be applied to a gas phase polymerization method in addition to a liquid phase polymerization method such as slurry polymerization or bulk polymerization. Further, the present invention can be applied not only to batch polymerization but also to continuous polymerization and batch polymerization. As a polymerization solvent in the case of slurry polymerization, a singly or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane and toluene is used. Furthermore, the polymerization method in the production method of the present invention can be used for multistage polymerization of two or more polymerization reactors. The polymerization temperature is about −50 to 200 ° C., preferably 20 to 150 ° C.
° C and the polymerization pressure is from atmospheric pressure to 100 kg / cm ^2.
G, preferably 3 to 50 Kg / cm ² G. Also,
At the time of polymerization, the molecular weight can be adjusted by adding an appropriate amount of hydrogen. Homopolymerization of propylene in the production method of the present invention, the general formula R-CH = CH ₂ (the R is a hydrocarbon residue of hydrogen atoms or a C 1-20, a branched group or) expressed in Copolymerized with α-olefins. 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. Further, styrene derivatives such as styrene and α-methylstyrene, butenes such as butadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, and allyltrialkylsilanes are exemplified. In addition, these monomers are not only one kind but also two kinds.
More than one kind can be mixed and used. 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 form a multistage by combining homopolymerization and copolymerization. Further, the propylene-based polymer obtained in the present invention can further improve the crystallinity and high-speed moldability by adding a known nucleating agent. In addition, rubber components are blended for the purpose of improving impact resistance, and antioxidants, antistatic agents, flame retardants, anti-blotting agents, slip agents, lubricants, anti-fog agents, dyes commonly used in polypropylene, Pigments, oils, waxes and the like can be blended in any blending ratio.

[0016]

The present invention will be described below in detail with reference to examples. The evaluation of the physical properties of the polypropylene in the examples is based on the following measuring methods. (1) MFR: Melt flow rate is JIS-K675
8 (230 ° C.). (2) Stereoregularity: Isotacticity was evaluated in mm (%) by ¹³ C-NMR. mm (%) is the fraction in 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 (T _mp ), crystallization temperature (T _cp ): Measured by a differential scanning calorimeter (DSC). (4) Flexural modulus: 100 parts by weight of polypropylene, butylated hydroxytoluene (BHT) 0.1.
1 part by weight of tetrakis [methylene-3- (3 ′, 5′-
Di-tertbutyl-4′-hydroxyphenyl) propionate] Methane (0.1 part by weight) and calcium stearate (0.1 part by weight) were blended, and granulation and injection molding were performed to prepare an ASTM type test piece. . The flexural modulus is A
It was measured by STMD-747-61T.

Example 1 Preparation of olefin polymerization catalyst component Preparation of solid catalyst Under a nitrogen atmosphere, 47.6 g of anhydrous magnesium chloride (50
0 mmol), 250 ml of decane and 234 ml (1.5 mol) of 2-ethylhexyl alcohol at 130 ° C.
After performing a heating reaction for 2 hours to obtain a homogeneous solution, 11.1 g (75 mmol) of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour, and phthalic anhydride was added to the homogeneous solution. Dissolved. After cooling the obtained homogeneous solution to room temperature, the whole amount was dropped into 2.01 (18 mol) of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the dropping, the temperature of the mixed solution was raised to 1 over 4 hours.
The temperature was raised to 10 ° C, and when the temperature reached 110 ° C, 26.8 ml (125 mmol) of diisobutyl phthalate was added, and the mixture was stirred and reacted at 110 ° C for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and then, 2.01 (18 mol) of titanium tetrachloride was suspended in the reaction product.
The reaction was performed at 10 ° C. for 2 hours. After completion of the reaction, a solid portion was collected again by filtration under hot conditions, and washed with decane 2.01 at 110 ° C. seven times and with hexane 2.01 at room temperature three times. When the titanium content in the obtained solid catalyst was measured,
7% by weight. Treatment with electron donating compound and titanium tetrachloride 40 g of the solid catalyst obtained above was suspended in 600 ml of toluene, and 11.9 g of diisobutyl phthalate was added at 25 ° C.
(43 mmol) for 1 hour. After completion of the reaction, 110 added titanium tetrachloride 200 ml (1.8 mol)
The temperature was raised to ° C. and the reaction was performed for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration, and then 200 ml (1.8 mol) of titanium tetrachloride was suspended in the reaction product.
The reaction was carried out at 2 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration, and decomposed at 110 ° C with 1.01 decane.
Wash three times with 1.01 hexane at room temperature. The titanium content in the obtained solid catalyst component was measured.
It was 23% by weight. Under propylene polymerization nitrogen atmosphere,
200 mg of the solid catalyst component prepared in the above manner, 11.4 g (100 mmol) of triethylaluminum, 5.64 g (30 mmol) of cyclohexylmethyldimethoxysilane prepared in an autoclave equipped with a stirrer having an internal volume of 601.
And then hydrogen was charged so as to be 18 kg of propylene and 0.13 mol% with respect to propylene.
And the polymerization was carried out for 1 hour. One hour later, unreacted propylene was removed to terminate the polymerization. as a result,
4460 g of polypropylene were obtained. Polymerization activity is 2
2.3 kg / g-olefin polymerization catalyst component, [mm] of the produced polypropylene is 98.1%, and MFR is 8.7.
g / 10 min, T _mp 163.7 ° C., T _cp 109.0
° C., the flexural modulus was 18,400 kg / cm ² .

Comparative Example 1 Propylene polymerization was carried out in the same manner and under the same conditions as in Example 1 except that the solid catalyst prepared in Example 1 was used as it was without treatment during propylene polymerization. As a result, 4800 g of polypropylene was obtained. The polymerization activity was 24.0 kg / g-olefin polymerization catalyst component, and the produced polypropylene had a [mm] of 97.5.
%, MFR is 15.8 g / 10 min, _Tmp is 161.5
° C., T _cp is 108.0 ° C., the flexural modulus, 17000K
g / cm ² .

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

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

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

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

[0023]

[Table 1]

Example 8 Preparation of solid catalyst 50.0 g (440 mmol) of diethoxymagnesium
l), 15.3 g of di-n-butyl phthalate (55 mmol
1) was stirred under reflux in 250 ml of methylene chloride under a nitrogen atmosphere for 1 hour. The resulting suspension was treated with titanium tetrachloride 2.0
1 (18 mol), heated to 110 ° C., and reacted for 2 hours. After completion of the reaction, the precipitated solid was reacted with 2.01 (18 mol) of titanium tetrachloride at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was washed three times with n-decane 2.01 at 110 ° C., and washed with n-hexane 2.01 at room temperature until no chloride ion was detected. Drying under reduced pressure at 40 ° C. gave the desired solid catalyst component. The titanium content in the obtained solid catalyst component was measured and found to be 2.31% by weight. Preparation of olefin polymerization catalyst 40 g of the solid catalyst obtained above was suspended in 600 ml of toluene, and 9.6 g of diethyl phthalate (43 m
mol)) for 1 hour. After completion of the reaction, 200 ml (1.8 mol) of titanium tetrachloride was added, and the temperature was raised to 110 ° C.
The reaction was continued for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and then titanium tetrachloride 200
ml (1.8 mol) were suspended and reacted at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration, and washed with 110 ° C decane 1.01 seven times and with room temperature hexane 1.01 three times. When the titanium content in the obtained solid catalyst component was measured, it was 2.10% by weight.
Met. Polymerization of Propylene Propylene polymerization was performed in the same manner and under the same 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.

Comparative Example 6 Propylene polymerization was carried out in the same manner and under the same 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 in the same manner and under the same conditions as in Example 8, except that diisopropyldimethoxysilane and dicyclopentyldimethoxysilane were used in the same amount in place of cyclohexylmethyldimethoxysilane during the polymerization of propylene. Was. The results of the polymerization evaluation are summarized in Table 2.

Comparative Examples 7-8 Propylene polymerization was carried out in the same manner and under the same conditions as in Comparative Example 6, except that diisopropyldimethoxysilane and dicyclopentyldimethoxysilane were used in place of cyclohexylmethyldimethoxysilane during the polymerization of propylene. Was. The results of the polymerization evaluation are summarized in Table 2.

[0028]

[Table 2]

Comparative Example 9 The solid catalyst prepared in Example 1 was not treated,
Propylene polymerization was carried out in the same manner and under the same conditions as in Example 1, except that the following treatment was performed to prepare an olefin polymerization catalyst. Treatment twice with titanium tetrachloride, with electron donating compound
Single treatment 40 g of the solid catalyst obtained in Example 1 was dissolved in toluene 60
0 ml, and titanium tetrachloride 200 ml (1.8 m
ol) was added and the temperature was raised to 110 ° C., and the reaction was performed for 2 hours.
After completion of the reaction, a solid portion was collected by hot filtration, and thereafter,
200 ml (1.8 mol) of titanium tetrachloride was added to the reaction product.
Was suspended and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 25 ° C, and diisobutyl phthalate 11.9 g was obtained.
(43 mmol) was added and reacted at 25 ° C. for 1 hour. After completion of the reaction, the temperature was raised to 110 ° C., and a solid portion was collected by hot filtration, and washed seven times with 1.0 liter of decane at 110 ° C. and three times with 1.0 liter of hexane at room temperature. The titanium content of the obtained catalyst component was measured and found to be 2.67% by weight. Propylene polymerization The obtained olefin polymerization catalyst was treated in the same manner as in Example 1,
When propylene polymerization was carried out under the conditions, 4360 g of polypropylene was obtained. The polymerization activity is 21.8 kg /
g-olefin polymerization catalyst component, [mm] of the produced polypropylene was 97.6%, MFR was 9.8 g / 10 min,
Tmp was 162.3 ° C., Tcp was 108.5 ° C., and the flexural modulus was 17,400 kg / cm ² . Comparative Example 10 The solid catalyst prepared in Example 1 was not treated,
Propylene polymerization was carried out in the same manner and under the same conditions as in Example 1, except that the following treatment was performed to prepare an olefin polymerization catalyst. Single treatment with electron donating compound, with titanium tetrachloride
Single treatment 40 g of the solid catalyst obtained in Example 1 was dissolved in toluene 60
0 ml and diisobutyl phthalate 1 at 25 ° C.
It was made to react with 1.9 g (43 mmol) for 1 hour. After the completion of the reaction, 400 ml (3.6 mol) of titanium tetrachloride was added, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and decane
Washed 7 times with 1 and 3 times with 1.01 of hexane at room temperature. When the titanium content in the obtained catalyst component was measured,
2.41% by weight. Propylene polymerization The obtained olefin polymerization catalyst was treated in the same manner as in Example 1,
When propylene polymerization was performed under the conditions, 3960 g of polypropylene was obtained. The polymerization activity was 19.8 kg /
g-olefin polymerization catalyst component, [mm] of the produced polypropylene was 97.9%, MFR was 9.0 g / 10 min,
Tmp was 162.7 ° C., Tcp was 108.6 ° C., and the flexural modulus was 17,800 kg / cm ² . Comparative Example 11 The solid catalyst prepared in Example 1 was not treated,
Propylene polymerization was carried out in the same manner and under the same conditions as in Example 1, except that the following treatment was performed to prepare an olefin polymerization catalyst. Simultaneous treatment with an electron donating compound and titanium tetrachloride 40 g of the solid catalyst obtained in Example 1 was dissolved in toluene 60
0 ml and diisobutyl phthalate 1 at 25 ° C.
1.9 g (43 mmol) and titanium tetrachloride 200 m
1 (1.8 mol) was added, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and washed seven times with decane 1.01 at 110 ° C. three times and with hexane 1.01 at room temperature three times. The titanium content in the obtained catalyst component was measured and found to be 2.47% by weight. Propylene polymerization The obtained olefin polymerization catalyst was treated in the same manner as in Example 1,
When propylene polymerization was carried out under the conditions, 3720 g of polypropylene was obtained. The polymerization activity is 18.6 kg /
g-olefin polymerization catalyst component, [mm] of the produced polypropylene was 97.7%, MFR was 9.5 g / 10 min,
Tmp was 162.5 ° C., Tcp was 108.6 ° C., and the flexural modulus was 17,500 kg / cm ² . Comparative Example 12 The solid catalyst prepared in Example 1 was not treated,
Propylene polymerization was carried out in the same manner and under the same conditions as in Example 1, except that the following treatment was performed to prepare an olefin polymerization catalyst. Simultaneous treatment with electron donating compound and titanium tetrachloride
Thereafter, titanium tetrachloride was treated once.
0 ml and diisobutyl phthalate 1 at 25 ° C.
1.9 g (43 mmol) and titanium tetrachloride 200 m
1 (1.8 mol) was added, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and then 200 ml of titanium tetrachloride was added to the reaction product.
(1.8 mol) was suspended and reacted at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration, and washed with 110 ° C decane 1.01 seven times and with room temperature hexane 1.01 three times. When the titanium content in the obtained catalyst component was measured, it was 2.30% by weight. Propylene polymerization The obtained olefin polymerization catalyst was treated in the same manner as in Example 1,
When propylene polymerization was performed under the conditions, 3860 g of polypropylene was obtained. The polymerization activity was 19.3 kg /
g-olefin polymerization catalyst component, [mm] of the produced polypropylene was 97.7%, MFR was 9.7 g / 10 min,
Tmp was 162.5 ° C., Tcp was 108.6 ° C., and the flexural modulus was 17,600 kg / cm ² .

[Table 3] Comparative Example 13 (Example 1 of JP-A-63-3007) (a) [Preparation of solid catalyst component (A)] A metal magnet was placed in a 2-liter autoclave equipped with a stirrer.
12 g ( 0.49 mol) of calcium powder was added, and
0.6 g of urine, 334.3 g of 2-ethylhexanol
(2.6 mol) and titanium tetrabutoxide 16
8.0 g (0.49 mol), ethyl benzoate 14.8
g 80.099 mol), and 1 liter of decane.
After heating, the temperature was raised to 90 ° C to eliminate the generated hydrogen gas.
The mixture was stirred for 1 hour under a nitrogen blanket. Continue at 140 ° C
And react for 1 hour.
Was obtained (Mg-Ti solution). Inner volume 50
0.04 Mg equivalent of Mg-Ti solution in 0 ml flask
After adding 8 mol and rapidly cooling to -20 ° C, i-butylaluminum
14.9 g of um dichloride diluted to 50% with decane
The solution was added over 2 hours. After adding everything, the room
The slurry containing the white solid product
I got it. A slurry containing the white solid product thus obtained
After the temperature was raised to 60 ° C., 1.8 g of ethyl benzoate was obtained.
(0.012 mol) was added. Then cool to 45 ° C
Then, 47 ml of titanium tetrachloride was added to 1,2-dichloroethane 4
The whole amount of the solution diluted with 7 ml was added and reacted for 4 hours.
Thereafter, stirring was further performed at 70 ° C. for 1 hour. Filter the product
The solid part was collected by performing
47 ml is suspended in 47 ml of 1,2-dichloroethane
Then, the mixture was stirred at 70 ° C. for 1 hour. Add hexane to the product
Sufficiently until no liberated titanium compound is detected
A washing operation was performed. Thus the solid suspended in hexane
A slurry of the catalyst component (A) was obtained. Remove supernatant and remove nitrogen
It was dried under elementary atmosphere and subjected to elemental analysis.
It was 30% by weight. (B) Propylene polymerization (2 liters of autocure
However, in the additional test, polypropylene
In order to measure the power factor, a 60 l auto
Reave). 60l stainless steel electromagnetic stirring type auto
The inside of the clave is sufficiently replaced with nitrogen, and as a catalyst component (B)
87.5 mmol of triethylaluminum, catalyst component
9.39 mmol of ethyl benzoate as (C) and
The solid catalyst component (A) obtained in the above (a) was 0.1% in terms of Ti.
89 mmol were added sequentially. Autoclave internal pressure
Adjust to 0.1 kg / cm ² G and add hydrogen to 0.2 kg / c
After adding m ² G, press in 15.0 kg of liquid propylene.
Was. Stirring was started and the internal temperature of the autoclave was reduced to 6
The temperature was raised to 5 ° C, and propylene was polymerized at the same temperature for 1.5 hours.
I let you. After completion of the polymerization reaction, stop stirring and simultaneously
Release the reactive propylene, 5880 g of polypropylene
was gotten. The polymerization activity was 40.8 kg / g-olefin
The polymerization catalyst component, [mm] of the produced polypropylene is
96.2%, MFR is 5.7 g / 10 min, Tmp is 15
9.7 ° C., Tcp 106.8 ° C., flexural modulus 160
It was 00 kg / cm ² . In the preparation step (a) , the white solid product obtained at an intermediate stage before adding and reacting ethyl benzoate and then titanium tetrachloride was added.
Propylene polymerization was carried out under the same polymerization conditions.
No propylene was substantially produced. Comparative Example 14 (Example 1 of JP-A-64-105) (a) [Preparation of solid catalyst component (A)] In a 2- liter autoclave equipped with a stirrer, a metal magnet was placed.
12 g (0.49 mol) of calcium powder was added, and
0.6 g of urine, 334.3 g of 2-ethylhexanol
(2.6 mol) and titanium tetrabutoxide 16
8.0 g (0.49 mol), ethyl benzoate 14.8
g 80.099 mol), and 1 liter of decane.
After heating, the temperature was raised to 90 ° C to eliminate the generated hydrogen gas.
The mixture was stirred for 1 hour under a nitrogen blanket. Continue at 140 ° C
And react for 1 hour.
Was obtained (Mg-Ti solution). Inner volume 50
0.04 Mg equivalent of Mg-Ti solution in 0 ml flask
After adding 8 mol and rapidly cooling to -20 ° C, i-butylaluminum
14.9 g of um dichloride diluted to 50% with decane
The solution was added over 2 hours. After adding everything, the room
The slurry containing the white solid product
I got it. A slurry containing the white solid product thus obtained
After the temperature is raised to 60 ° C, sorbitan distearate
Was added at 500 ppm. Then ethyl benzoate 1.8
g (0.012 mol), titanium tetrachloride 47
solution diluted with 47 ml of 1,2-dichloroethane
Was added and the mixture was reacted for 4 hours. At this time, the solid product
No collection was seen. Stir at 70 ° C for 1 hour
Was. The solids are collected by filtration of the product and
47 ml of titanium tetrachloride in 1,2-dichloroethane
The suspension was suspended in 47 ml and stirred at 70 ° C. for 1 hour. To the product
Titanium compounds released by addition of hexane no longer detected
Washing operation was performed until the cleaning operation was completed. Thus, hexane
To obtain a slurry of suspended solid catalyst component (A) to. Supernatant
The solution was removed, dried under a nitrogen atmosphere, and subjected to elemental analysis.
On the other hand, Ti was 6.11% by weight. (B) Propylene polymerization (2 liters of autocure
However, in the additional test, polypropylene
In order to measure the power factor, a 60 l auto
Reave). 2l stainless steel electromagnetic stirring type autoclave
The inside of the slave is sufficiently replaced with nitrogen, and the catalyst component (B) is used as a catalyst.
87.5 mmol of triethylaluminum, catalyst component
9.39 mmol of ethyl benzoate as (C) and
The solid catalyst component (A) obtained in the above (a) was 0.1% in terms of Ti.
98 mmol were added sequentially. Autoclave internal pressure
Adjust to 0.1 kg / cm ² G and add hydrogen to 0.2 kg / c
After adding m ² G, press in 15.0 kg of liquid propylene.
Was. Stirring was started and the internal temperature of the autoclave was reduced to 6
The temperature was raised to 5 ° C, and propylene was polymerized at the same temperature for 1.5 hours.
I let you. After completion of the polymerization reaction, stop stirring and simultaneously
Release the reaction propylene, 6660 g of polypropylene
was gotten. The polymerization activity was 42.8 kg / g-olefin.
The polymerization catalyst component, [mm] of the produced polypropylene is
96.8%, MFR is 5.0 g / 10 min, Tmp is 16
0.4 ° C., Tcp 107.5 ° C., flexural modulus 166
It was 00 kg / cm ² . In the preparation step (a) , the white solid product obtained at an intermediate stage before adding and reacting ethyl benzoate and then titanium tetrachloride was added.
Propylene polymerization was carried out under the same polymerization conditions.
No propylene was substantially produced. Comparative Example 15 (Example 1 of JP-A-3-263408) <Preparation of a solid catalyst component> A capacity of 50 which was sufficiently substituted with nitrogen gas and provided with a stirrer.
10 g of diethoxymagnesium in a 0 ml round bottom flask
And 60 ml of toluene and put in suspension, and then
60 ml of TiCl ₄ was added to this suspension, and the temperature was raised to 70 ° C.
After adding 2.0 ml of butanol, the temperature was further raised to 90 ° C.
Warm and add 2.0 ml of phthalic dichloride. That
Thereafter, the temperature was raised to 115 ° C., and the reaction was performed while stirring for 2 hours.
Was. After the completion of the reaction, 200 ml for the obtained solid substance
Wash twice under reflux with toluene and add toluene
And 60 ml of TiCl ₄ and 115 ml
Repeated 3 times an operation of in reacting with stirring for 2 hours
I returned. Thereafter, the reaction product was treated with n-heptane 2 at 40 ° C.
Washed 10 times with 00 ml. The solid thus obtained is
When the titanium content in the body catalyst component was measured,
7% by weight. <Polymerization> (In the above publication, a 2 l autoclave was used.
However, the additional test measures the flexural modulus of polypropylene.
Therefore, a 60-liter autoclave was used as in the example.
ing). A stirrer with an internal volume of 60 l that has been sufficiently replaced with nitrogen gas
6.0 g of triethyl aluminum in an autoclave with
2.1 g of 1,8-epoxy paramenthane and the solid
90 mg of the catalyst component were charged. Then, the hydrogen gas 54
l, 42 l of liquefied propylene, and charged at 70 ° C. for 30 minutes
Was polymerized. After polymerization, the obtained polypropylene
Was dried under reduced pressure at 80 ° C. 7160g of polypropylene
I got Polymerization activity is 151 kg / g-olefin polymerization
The catalyst component and the resulting polypropylene had a [mm] of 96.
7%, MFR 16.5 g / 10 min, Tmp 160.
9 ° C., Tcp 107.6 ° C., flexural modulus 16400
kg / cm ² . In addition, the above-mentioned <control of solid catalyst component>
The same weight applies to the solid product obtained in the intermediate process
Propylene polymerization was carried out under mixed conditions.
There were few.

According to the present invention, a propylene-based polymer having extremely high stereoregularity and rigidity can be produced at low cost, which is industrially valuable.

[Brief description of the drawings]

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

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa No. 2 in Oita, Oita City, Oita Prefecture Showa Denko KK Oita Research Laboratories 64-64 (JP, A) JP-A-3-263408 (JP, A)

Claims (1)

(57) [Claims] 1. Magnesium, titanium, halogenated titanium
Substantially selected from the group consisting of halogens and silicon halides, and a catalytic activity essentially comprising an electron donating compound.
An olefin polymerization catalyst obtained by preparing a solid catalyst having a catalytic property , firstly treating it with an electron-donating compound at least once in the absence of titanium tetrachloride, and then treating it at least twice with titanium tetrachloride A method for producing a propylene-based polymer, comprising using a component.