JP6176914B2 - Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

  The present invention provides a method for producing a solid catalyst component capable of suppressing an exothermic reaction at the initial stage of polymerization and obtaining a polymer having excellent particle properties in a high yield while maintaining a high degree of stereoregularity, The present invention relates to a method for producing a catalyst and a method for producing a polymer of olefins.

  Conventionally, in the polymerization of olefins, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many olefin polymerization methods have been proposed in which propylene is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound, and an organosilicon compound. For example, Prior Art Document 1 (Japanese Patent Laid-Open No. 1-6006) discloses a solid catalyst component containing an electron donor of a diester compound such as a magnesium compound, a titanium compound and a phthalic acid diester, an organoaluminum compound, and Si- A method of polymerizing olefins having 3 or more carbon atoms using a catalyst comprising a combination with an organosilicon compound having an O—C bond is disclosed.

  Prior Art Document 2 (JP 63-92614 A) discloses a solid catalyst component for α-olefin polymerization obtained by coexisting calcium chloride in dialkoxymagnesium, titanium tetrachloride and aromatic dicarboxylic acid diester. It is disclosed that such catalysts can significantly improve catalyst activity while maintaining other performances such as stereoregularity high.

  Furthermore, Prior Art Document 3 (Japanese Patent Application Laid-Open No. 2010-248437) discloses a solid catalyst component for α-olefin polymerization (A1) characterized by containing magnesium, titanium, halogen, calcium and an electron donating compound as essential components. ), And the solid catalyst component (A1) is contact-treated with a silicon compound (A2) having an alkenyl group, an organosilicon compound (A3), and an organoaluminum compound (A4). The catalyst component for use is disclosed, and it is described that such a catalyst can significantly improve the catalytic activity while maintaining other performance such as stereoregularity high.

Japanese Patent Laid-Open No. 1-6006 JP-A-63-92614 JP 2010-248437 A

  However, α-olefin polymerization solid catalyst components and olefin polymerization catalysts synthesized in this way generally exhibit high polymerization activity, but the exothermic reaction in the initial stage of polymerization is intense, and the polymerization activity rapidly increases with time. It is a solid catalyst having a high so-called initial activity that decreases, and such a solid catalyst having a high initial activity is likely to cause a collapse of the solid catalyst particles due to heat generation during the polymerization reaction, and a large amount of fine powder polymer is generated or generated. Problems occur such as the fine powder polymer melting and forming aggregates. This problem may cause a process failure such as preventing the continuation of the uniform polymerization reaction and causing blockage of the piping during the transfer of the polymer, and the operation of the process may have to be stopped. In addition, since the polymerization activity does not last for a long time, when producing a copolymer such as impact copolymer by multi-stage polymerization, there is a problem that only a small amount of the polymer rubber component can be contained in the polymerization after the second stage. Was. Therefore, in the olefin polymerization process, there has been a demand for an olefin polymerization catalyst that does not cause the above problems, that is, an olefin polymerization catalyst that exhibits high activity and at the same time has suppressed initial activity.

  Therefore, the object of the present invention is to produce a solid catalyst component capable of obtaining a polymer with high initial activity, high polymerization activity, and high bulk specific gravity while maintaining high stereoregularity. It is providing the method, the manufacturing method of a catalyst, and the manufacturing method of an olefin polymer.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, a periodic table having a molar ratio of a solid component containing magnesium, titanium, halogen, and an electron-donating compound to a titanium atom in the solid component is 2 to 22. A solid catalyst component obtained by a method in which a halogen compound of Group 2 element is mixed and contacted in a dry state and a catalyst using the same are found to exhibit high activity and simultaneously suppress initial activity. The invention has been completed.

  That is, the present invention provides a solid component containing magnesium, titanium, halogen and an electron-donating compound and a halogen compound of a Group 2 element of the periodic table having a molar ratio of 2 to 22 with respect to the titanium atom in the solid component in a dry state. And a method for producing a solid catalyst component for olefin polymerization, characterized by being mixed and contacted with each other.

The present invention also provides a solid catalyst component (A) for olefin polymerization obtained by the above method, the following general formula (1);
R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3) (B And an external electron donating compound (C) are brought into contact with each other.

  The present invention also provides a method for producing an olefin polymer, wherein the olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst obtained by the above method.

  The catalyst for olefin polymerization according to the present invention can obtain a polymer having high polymerization activity and high bulk specific gravity in high yield while maintaining high stereoregularity, although initial activity is suppressed. .

  As a solid component (hereinafter also simply referred to as “component (A1)”) used in the method for producing a solid catalyst component for olefin polymerization of the present invention (hereinafter also simply referred to as “solid catalyst component (A)”). Any solid component containing magnesium, titanium, halogen and an internal electron donating compound is not particularly limited. For example, a solid component obtained by co-grinding a magnesium halide and a titanium compound, halogenated in decane After reacting magnesium and 2-ethylhexyl alcohol to obtain a homogeneous solution, the magnesium compound is turbid in a solid component obtained by adding an electron donating compound and a titanium compound, and an inert organic solvent, and an electron donating compound and Solid components obtained by adding and reacting titanium compounds, or metallocene complexes together with aluminoxane compounds Such as a solid component obtained by supporting on a carrier and the like. Component (A1) is preferably in the form of dried particles.

  The production methods of these solid components are exemplified in, for example, JP-A-48-16986, JP-A-56-811, JP-A-59-142206, and JP-A-6-25350. Yes. Among the solid components as described above, a solid component obtained by turbidity of a magnesium compound in an inert organic solvent and addition and reaction of an electron donating compound and a titanium compound has a high bulk specific gravity and a small amount of fine powder components. It is preferable at the point from which an olefin polymer is obtained with a sufficient yield.

  Examples of the magnesium compound (hereinafter also simply referred to as “component (a)”) include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. . Preferred are dihalogenated magnesium, dialkoxymagnesium and halogenated alkoxymagnesium.

The titanium compound (hereinafter, also simply referred to as “component (b)”) has the general formula (3);
Ti (OR ⁴ ) _n X _4-n (3)
(Wherein R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4). Specifically, tetraalkoxy titanium such as tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetra n-butoxy titanium and tetraisobutoxy titanium; titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide Methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, Alkoxy titanium halides such as triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride, etc. And the like. These titanium compounds can be used alone or in combination of two or more. The titanium compound is preferably tetraalkoxytitanium or titanium tetrahalide, and particularly preferably tetraethoxytitanium, tetran-butoxytitanium, or titanium tetrachloride.

  When the magnesium compound and the titanium compound do not contain a halogen, a halogen compound may be used. Examples of the halogen include fluorine, chlorine, bromine and iodine atoms. Among them, chlorine, bromine and iodine are preferable, and chlorine and iodine are particularly preferable. Examples of the halogen compound include tetravalent halogen-containing silicon compounds. More specifically, tetrachlorosilane (silicon tetrachloride), silane tetrahalides such as tetrabromosilane, methoxytrichlorosilane, ethoxytrichlorosilane, propoxytrichlorosilane, n-butoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, Examples include alkoxy group-containing halogenated silanes such as dipropoxydichlorosilane, di-n-butoxydichlorosilane, trimethoxychlorosilane, triethoxychlorosilane, tripropoxychlorosilane, and tri-n-butoxychlorosilane.

  The electron donating compound (hereinafter, also simply referred to as “component (c)”) is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, Examples include acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds or Si—N—C bonds.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyle ether, diphenyl ether, 9, Ethers such as 9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Monomers such as ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, phenyl cyclohexylbenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate Rubonic acid esters, malonic acid diesters, alkyl-substituted malonic acid diesters, halogen-substituted malonic acid diesters, halogenated alkyl-substituted maleic acid diesters, alkylidene malonic acid diesters, adipic acid diesters, phthalic acid diesters, alkyl-substituted phthalic acid diesters, halogen-substituted Dicarboxylic acid diesters such as phthalic acid diesters, halogenated alkyl-substituted phthalic acid diesters, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid chlorides such as phthalic dichloride, terephthalic acid dichloride, acetaldehyde, propion Aldehydes such as aldehyde, octylaldehyde, benzaldehyde, methylamine, ethylamine, tributylamine, piperidine Amines such as aniline and pyridine, amides such as olefinic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane , Organosilicon compounds containing Si—O—C bonds such as phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamino) dialkoxysilane, alkyl Aminosilane compounds containing Si—N—C bonds such as (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, cycloalkylaminotrialkoxysilane, etc. It is exemplified. These electron donating compounds can be used alone or in combination of two or more. Among the electron donating compounds, dicarboxylic acid diesters are preferable, and aliphatic dicarboxylic acid diesters such as malonic acid diesters and alkyl-substituted malonic acid diesters, and aromatic carboxylic acid diesters such as phthalic acid diesters are particularly preferable.

  Examples of halogen compounds of Group 2 elements of the periodic table (hereinafter also simply referred to as “component (A2)”) include, for example, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide. Strontium chloride, strontium bromide, strontium iodide, barium chloride, barium bromide, barium iodide and the like. Magnesium chloride, calcium chloride and strontium chloride are preferred. The halogen compounds of Group 2 elements of the periodic table can be used alone or in combination of two or more. Component (A2) is preferably an anhydride.

  The component (A2) can be used in the form of particles. As long as the effect of the present invention is recognized, the particle property is arbitrary, and the shape can be either spherical or irregular. It can also be used in the state of primary particles, and those primary particles aggregated to form secondary particles, and secondary particles further aggregated to form tertiary particles can also be used. The particle diameter of the component (A2) is arbitrary as long as the effects of the present invention are not impaired, and preferably the ratio of the average particle diameter of the component (A2) to the solid component (A1) (A2 / A1) Is 1.5 or less, more preferably 0.3 to 1.5, and particularly preferably 0.5 to 1.5.

  In the method for producing a solid catalyst component of the present invention, first, the titanium content in the solid component (A1) is specified, and then the molar ratio of the solid component (A1) to the titanium atom in the solid component (A1) is 2 to 2. 22 halogen compounds (A2) of Group 2 elements of the periodic table are mixed and contacted in a dry state. The dry state means in the absence of a solvent. By mixing and contacting the component (A1) and the component (A2), a polymer having high polymerization activity and high bulk specific gravity can be obtained while maintaining high stereoregularity while suppressing initial activity. It can be obtained efficiently. In addition, when the above contact mixing is performed in the presence of a solvent such as heptane, titanium or an electron donating compound may be eluted from the solid component (A1) and desorbed. On the other hand, since the mixing contact is performed in a dry manner in the absence of a solvent, it is possible to prevent elution and desorption of titanium and electron donating compounds from the solid component (A1). In addition, the contact mixing is performed in an inert gas atmosphere such as nitrogen or argon, in a state where moisture is removed, so that the solid component (A1) contacts and reacts with moisture or oxygen in the atmosphere. It is preferable at the point which does not change in quality. In addition, as a method of specifying the titanium content in the solid component (A1), a method of separating the solid-liquid in the solid component (A1) and performing elemental analysis in the solid component, or a method described in JIS 8311-1997 Examples thereof include a redox titration method.

  The usage-amount of a halogen compound (A2) is 2-22 mol with respect to 1 mol of titanium atoms in a solid component (A1). If the number of moles of the halogen compound (A2) is too small, the initial activity cannot be suppressed. In addition, as a method for specifying the component (A2) content in the solid catalyst component (A), a sample is dissolved with a sulfuric acid solution, then nitric acid and an internal standard solution are added, and inductive coupling is performed using the obtained solution. Examples thereof include a method for quantitative measurement using a plasma emission spectroscopic analyzer (ICP).

  The contact mixing may be performed using a container rotation type mixing device such as a V-type mixer, a stirring type mixing device such as a tank or reactor equipped with a stirrer, and a mixing and grinding device such as a vibration mill or a ball mill. Among these, it is preferable to use a container rotation type mixing device in that particle breakage of the component (A1) or the component (A2) can be prevented.

  The temperature and time during the contact mixing are not particularly limited, but are usually in the range of 0 to 150 ° C., preferably 0 to 120 ° C., 1 minute to 10 hours, preferably 5 minutes to 5 hours. In the contact mixing, it is also one of preferable modes to perform a so-called heat treatment in which treatment is performed at a temperature of room temperature or higher. The temperature during the heat treatment is in the range of 50 to 150 ° C, preferably 80 to 100 ° C. The heat treatment time is 1 minute to 5 hours, preferably 5 minutes to 3 hours. When the solid catalyst component (A) obtained by performing such heat treatment is used for the polymerization of olefins, excessive heat generation at the initial stage of the polymerization can be suppressed, and as a result, a polymer having a small amount of fine powder and a high bulk specific gravity. Can be obtained in high yield.

  When the catalyst containing the solid catalyst component (A) obtained by the above method is used for the polymerization of olefins, the titanium active sites in the solid catalyst component are not poisoned and the dispersibility of the solid catalyst component Will improve. As a result, the activity at the initial stage of polymerization is suppressed, local heat generation during polymerization of olefins, that is, a rapid temperature increase at the initial stage of polymerization, can be suppressed, and the polymerization activity and stereoregularity per Ti in the solid catalyst component are enhanced. While maintaining the above, a polymer having excellent particle properties and high bulk specific gravity can be obtained.

The production method of the catalyst for olefin polymerization of the present invention comprises a solid catalyst component (A) obtained by the above method, the following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3) (B ) And the external electron donating compound (C).

  Examples of the organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, ethylaluminum sesquichloride, and ethylaluminum hydride, and one or more of them can be used. Triethylaluminum and triisobutylaluminum are preferable.

  The external electron donating compound (C) is the same as the internal electron donating compound that can be used for the preparation of the solid catalyst component. Among them, 9,9-bis (methoxymethyl) fluorene, Ethers such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, esters such as methyl benzoate and ethyl benzoate, and organosilicon compounds are preferred.

As said organosilicon compound, following General formula (2);
R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ³ represents 1 to 1 carbon atoms. 4 represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different, and q is an integer of 0 or 1 to 3). Used.

  Examples of the organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenyl (alkyl) alkoxysilane, vinylsilane, allylsilane, cycloalkylalkoxysilane, cycloalkyl (alkyl) alkoxysilane, (alkylamino) alkoxysilane, and alkyl. (Alkylamino) alkoxysilane, alkyl (dialkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, (polycyclic amino) alkoxysilane, (alkylamino) alkylsilane, (dialkylamino) alkylsilane, cycloalkyl (alkyl) Amino) alkylsilane, (polycyclic amino) alkylsilane, and the like. Among them, di-n-propyldimethoxysilane, diisopropyldimethoxy Silane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxy Silane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxy Silane, cyclohexylcyclopentyldiethoxysilane, 3-methyl Rucyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl (cyclopentyl) dimethoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) ) Dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (Perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, bis (methylamino) di-t-butylsilane, bis (d Arylamino) dicyclopentyl silane and bis (ethylamino) butyldiisopropylsilane are preferably used, organosilicon compound (C) may be used in combination one kind or two or more kinds.

  In the method for producing an olefin polymer of the present invention, olefins are polymerized or copolymerized in the presence of an olefin polymerization catalyst obtained by the above method. The olefins used for the polymerization are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and these olefins may be used alone or in combination of two or more. it can. Ethylene, propylene and 1-butene are preferably used, and ethylene and propylene are particularly preferable.

  In the polymerization method of olefins of the present invention, when propylene is polymerized, copolymerization with other olefins can also be performed. Examples of olefins used for copolymerization include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like, and these olefins may be used alone or in combination of two or more. it can. In particular, ethylene and 1-butene are preferably used.

  The amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. However, the component (B) is usually in the solid catalyst component (A) for olefin polymerization. 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atom. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of component (B).

  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) for olefin polymerization is further added. It is desirable to contact. The polymerization of the olefin in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid.

  For the polymerization of olefins in the present invention, conventional methods such as those used for the polymerization of 1-olefins having 2 to 10 carbon atoms can be used. As the polymerization system, a gas or liquid is used in the presence of an organic solvent. Examples include slurry polymerization in which a monomer is supplied and polymerization is performed, bulk polymerization in which polymerization is performed in the presence of a liquid monomer such as liquefied propylene, and gas phase polymerization in which polymerization is performed in the presence of a gaseous monomer. Can also carry out a polymerization reaction, and gas phase polymerization is particularly preferably used. Further, for example, the method described in Japanese Patent No. 2578408, the continuous gas phase polymerization method described in Japanese Patent No. 4392064, Japanese Patent Application Laid-Open No. 2009-292964, and the polymerization method described in Japanese Patent No. 2766523 are also applied. Is possible. The above polymerization reaction can be carried out batchwise or continuously. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Examples of the reactor suitably used in the olefin polymerization method in the present invention include a reactor such as an autoclave with a stirrer and a fluidized tank, and a granular or powdery polymer is accommodated in this reactor as a stationary phase. Then, use a stirrer or a fluidized bed to give movement.

  The molecular weight of the propylene polymer can be adjusted and set over a wide range by adding a regulator commonly used in the polymerization technology, for example, hydrogen. Further, when copolymerization of propylene and other comonomers is carried out, the incorporation of the comonomers into the polymer chain can be adjusted by appropriately adding an alkanol having 1 to 8 carbon atoms, particularly isopropanol. In order to remove the heat of polymerization, a liquid easily volatile hydrocarbon such as propane or butane may be supplied and vaporized in the polymerization zone.

  The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, particularly preferably 50 to 90 ° C. The polymerization pressure is normal pressure to 10 MPa, preferably normal pressure to 5 MPa, particularly preferably 1 to 4 MPa. When copolymerization of propylene and other comonomer is performed, the partial pressure of propylene and comonomer is adjusted to be 1:99 to 99: 1. Preferably, the partial pressure of propylene and comonomer is 50:50 to 99: 1.

  Further, in the present invention, when the olefin is polymerized using the catalyst containing the solid catalyst component (A) for polymerizing olefins, the component (B) and the component (C) (also referred to as main polymerization), the catalyst activity and the stereoregulation are determined. In order to further improve the properties and particle properties of the resulting polymer, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary. Preferably, the component (B) is first charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefins are introduced. After contacting the solid catalyst component (A) for polymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.

  When olefins are polymerized in the presence of an olefin polymerization catalyst formed according to the present invention, a polymer having low initial activity and excellent particle properties is obtained as compared with the case where a conventional catalyst is used. It can be obtained with good yield while maintaining a high degree of regularity.

(Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples, but these are exemplifications and do not limit the present invention.

Example 1
[Preparation of solid component (A1)]
A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium, 100 ml of toluene, and 17.5 mmol (6.0 ml) of di-n-butyl phthalate to obtain a turbid liquid. Formed. Next, a mixed solution of 60 ml of titanium tetrachloride and 40 ml of toluene was added to the turbid liquid kept at a liquid temperature of 5 ° C. Then, after maintaining this temperature for 1 hour, it heated up to 110 degreeC and made it react, stirring at 110 degreeC for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 100 ° C. Thereafter, 100 ml of normal temperature toluene and 20 ml of titanium tetrachloride were newly added, the temperature was raised to 100 ° C., and the reaction was carried out with stirring for 15 minutes. After completion of the reaction, the supernatant was removed. The above operation was further repeated twice, followed by washing 8 times with 150 ml of n-heptane at 40 ° C., removing the supernatant, and drying to obtain a particulate solid component (A1). In addition, the titanium content rate in this solid component (A1) was 2.1 weight%, and the magnesium content rate was 18.9 weight%.

<Preparation of solid catalyst component (AA1)>
9 g of particulate solid component (A1) and 1 g of particulate calcium chloride anhydride (component (A2)) were introduced into a V-type mixer (Transparent Micro V-Mixer, manufactured by Tsutsui Rika Kikai Co., Ltd.) under a nitrogen atmosphere. Then, in a dry state in a nitrogen atmosphere, the mixture was rotated and mixed at 23 rpm for 5 minutes at 30 rpm to obtain a solid catalyst component (AA1). That is, the weight ratio ((A1) :( A2)) of the component (A1) and the component (A2) during the rotary mixing was 9: 1. At this time, the molar ratio of calcium chloride anhydride (component (A2)) to titanium derived from component (A1) was 2.3. Further, the ratio of the average particle diameter (component (A2) / component (A1)) was 0.8.

<Formation of polymerization catalyst and propylene polymerization>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, triethylaluminum (1.32 mmol), cyclohexylmethyldimethoxysilane (0.13 mmol) and the solid catalyst component (AA1) as titanium atoms were added in an amount of 0.0026. A millimolar charge was formed to form a polymerization catalyst. Thereafter, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated, and polymerized at 70 ° C. for 1 hour. With respect to the obtained polymer, catalytic activity, maximum propylene reaction rate, BD (bulk density), melt flow rate (MI, g-PP / 10 min), and xylene-soluble component amount at 23 ° C. (XS) , Wt%). The results are shown in Table 1.

[Titanium content]
The titanium content in the solid component or the solid catalyst component was measured according to the method (redox titration) described in JIS 8311-1997 “Titanium determination method in titanium ore”.

[Content of group 2 atom in the periodic table]
The content of Group 2 atom in the periodic table in the solid catalyst component was measured by the following method. Dissolve the sample with sulfuric acid solution, then add nitric acid, allow to cool, and then use the solution obtained by adding yttrium standard solution as internal standard element to the solution. The content of Group 2 atom of the periodic table was measured by the product, model number SPS-3100).

The catalytic activity was calculated by the following two methods.
(1) The catalyst activity (E) indicating the amount (D) g of polymer produced per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.
Catalytic activity (E) = product polymer (D) kg / (weight of solid catalyst component g × 1 hour)
(2) The polymerization activity (F) per millimole of titanium contained in the solid catalyst component was calculated by the following equation.
Catalyst activity (F) (kg-PP / mmol-Ti) = product polymer (D) g / Ti (mmol) in solid catalyst component

<Method for measuring xylene-soluble components>
4.0 g of the polymer was charged into 200 ml of para-xylene, and the polymer was dissolved over 2 hours under the boiling point of xylene (138 ° C.). Thereafter, the mixture was cooled to 23 ° C., and the insoluble component and the dissolved component were separated by filtration. The solvent of the dissolved component was distilled off and dried by heating. The resulting polymer was converted into a xylene-soluble component, and the relative value (XS,% by weight) relative to the produced polymer (F) was shown.

<Measurement of propylene reaction rate>
700 mL of heptane, 2.11 mmol of triethylaluminum, and 0.21 mmol of cyclohexylmethyldimethoxysilane (CMDMSi) were charged into an autoclave with a stirrer having an internal volume of 1.5 liter that was completely replaced with propylene gas. After 5 minutes at 20 ° C., 100 ml of hydrogen gas was added and the temperature was raised to 80 ° C. The propylene pressure was adjusted to 0.6 MPa, and 0.0084 mmol of the solid catalyst component (AA) dispersed in mineral oil was added as titanium atoms, and slurry polymerization was performed for 30 minutes. The propylene reaction rate during the polymerization was measured sequentially by using a mass flow meter and the propylene absorption rate (liter / minute). The propylene reaction rate was estimated to be equal to the propylene absorption rate, and the propylene reaction rate was determined by the following equation.
Propylene reaction rate ^(kg-C 3 / g- catalyst · hour)
= Propylene absorption rate (liter / minute) x 60 (minute / hour) /22.4 (liter / mol) x 42 (g / mol) / solid catalyst component (g) / 1000 (kg / g)
Further, the maximum value G (kg-C ³ / g-catalyst · time) recorded in the reaction rate measurement divided by the catalyst activity E (kg-PP / g-catalyst) of the solid catalyst component (G / E ratio), which was used as an index for judging the intensity of the reaction in the early stage of polymerization.

(Example 2)
<Preparation of solid catalyst component (AA2)>
A solid catalyst component (AA2) was prepared in the same manner as in Example 1 except that magnesium chloride anhydride was used instead of calcium chloride anhydride. At this time, the molar ratio of magnesium chloride anhydride to titanium in the solid catalyst component (AA2) was 2.7. The ratio of the average particle diameter (component (A2) / component (A1)) was 0.5.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA2) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Example 3)
<Preparation of solid catalyst component (AA3)>
Instead of 9 g of the solid component (A1), 8.5 g of the solid component (A1) was used, and in the same manner as in Example 1 except that 1.5 g of strontium chloride anhydride was used instead of 1.0 g of calcium chloride anhydride. A solid catalyst component (AA3) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) was 8.5: 1.5, and strontium chloride anhydrous with respect to titanium in the solid catalyst component (AA3) The molar ratio of the product was 2.5. The ratio of the average particle diameter (component (A2) / component (A1)) was 1.0.
<Formation of polymerization catalyst and propylene polymerization>
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA3) was used. The results are shown in Table 1.

Example 4
<Preparation of solid catalyst component (AA4)>
In place of 9 g of the solid component (A1), 7 g of the solid component (A1), and in place of 1 g of calcium chloride anhydride of the component (A2), 3 g of calcium chloride anhydride was used. A solid catalyst component (AA4) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) is 7: 3, and the molar ratio of calcium chloride anhydride to titanium in the solid catalyst component (AA4) is It was 8.8. Further, the ratio of the average particle diameter (component (A2) / component (A1)) was 0.8.
<Formation of polymerization catalyst and propylene polymerization>
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA4) was used. The results are shown in Table 1.

(Example 5)
<Preparation of solid catalyst component (AA5)>
Instead of 9 g of the solid component (A1), 7 g of the solid component (A1) was used, and instead of 1 g of calcium chloride anhydride of the component (A2), 3 g of magnesium chloride anhydride was used. A solid catalyst component (AA5) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) is 7: 3, and the molar ratio of magnesium chloride anhydride to titanium in the solid catalyst component (AA5) is 10.3. The ratio of the average particle diameter (component (A2) / component (A1)) was 0.5.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA5) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Example 6)
<Preparation of solid catalyst component (AA6)>
In place of 9 g of the solid component (A1), 5 g of the solid component (A1), and 5 g of calcium chloride anhydride instead of 1 g of calcium chloride anhydride of the component (A2), as in Example 1, A solid catalyst component (AA6) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) is 5: 5, and the molar ratio of calcium chloride anhydride to titanium in the solid catalyst component (AA6) is 20.5. Further, the ratio of the average particle diameter (component (A2) / component (A1)) was 0.8.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1, except that the solid catalyst component (AA6) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Example 7)
[Preparation of solid component (A1-1)]
32 g of ground magnesium for Grignard was charged into a 1000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Next, a mixed liquid of 120 g of butyl chloride and 500 ml of dibutyl ether was dropped into the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and solid content was removed by filtration to obtain a magnesium compound solution. Next, a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 240 ml of hexane, 5.4 g of tetrabutoxytitanium and 61.4 g of tetraethoxysilane to obtain a homogeneous solution. The magnesium compound solution (150 ml) was added dropwise at 5 ° C. over 4 hours to react, and then stirred at room temperature for 1 hour. Next, the reaction solution was filtered at room temperature to remove the liquid portion, and then the remaining solid was washed 8 times with 240 ml of hexane and dried under reduced pressure to obtain a solid product. Next, 8.6 g of the solid product was charged into a 100-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and further 48 ml of toluene and 5.8 ml of diisobutyl phthalate were added. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, the liquid part was removed by filtration, and the remaining solid was washed 8 times with 85 ml of toluene. After completion of the washing, 21 ml of toluene, 0.48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride were added to the flask and reacted at 100 ° C. for 8 hours. After completion of the reaction, solid-liquid separation is performed at 100 ° C., the solid content is washed twice with 48 ml of toluene, then the above treatment with the mixture of diisobutyl phthalate and titanium tetrachloride is performed again under the same conditions, and washed with 48 ml of hexane eight times. , Filtered and dried to obtain a powdered solid component (A1-1). The titanium content in the solid component was measured and found to be 1.9% by weight.

[Preparation of solid catalyst component (AA7)]
A solid catalyst component (AA7) was prepared in the same manner as in Example 1 except that the solid component (A1-1) was used instead of the component (A1). At this time, the molar ratio of calcium chloride anhydride to titanium derived from the component (A1-1) was 2.5. The ratio of the average particle diameter (component (A2) / component (A1)) was 1.5.
[Formation of polymerization catalyst and propylene polymerization]
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA7) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Comparative Example 1)
<Preparation of solid catalyst component (AA8)>
In place of 9 g of the solid component (A1), 10 g of the solid component (A1), and 0 g of calcium chloride anhydride instead of 1 g of calcium chloride anhydride of the component (A2), as in Example 1, A solid catalyst component (AA8) was prepared. That is, in Comparative Example 1, the addition of the component (A2) is omitted, and the molar ratio of the component (A2) to titanium derived from the component (A1) is set to zero.
[Formation of polymerization catalyst and propylene polymerization]
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA8) was used. The results are shown in Table 1.

(Comparative Example 2)
<Preparation of solid catalyst component (AA9)>
A solid catalyst component (AA9) was prepared in the same manner as in Example 1 except that 1 g of potassium chloride anhydride was used instead of 1 g of calcium chloride anhydride. At this time, the molar ratio of the component (A2) to titanium derived from the solid component (A1) was 3.4.
[Formation of polymerization catalyst and propylene polymerization]
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA9) was used. The results are shown in Table 1.

(Comparative Example 3)
<Preparation of solid catalyst component (AA10)>
In place of 9 g of the solid component (A1), 6 g of the solid component (A1), and 4 g of vanadium chloride anhydride instead of 1 g of calcium chloride anhydride of the component (A2), as in Example 1, A solid catalyst component (AA10) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) is 6: 4, and the molar ratio of vanadium chloride anhydride to titanium in the solid catalyst component (AA10) is It was 9.7.
[Formation of polymerization catalyst and propylene polymerization]
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA10) was used. The results are shown in Table 1.

(Comparative Example 4)
<Preparation of solid catalyst component (AA11)>
Example 1 except that 9.4 g of the solid component (A1) was used instead of 9 g of the solid component (A1), and 0.6 g of calcium chloride anhydride was used instead of 1 g of calcium chloride anhydride of the component (A2). Similarly, a solid catalyst component (AA11) was prepared. At this time, the weight ratio of component (A1) to component (A2) ((A1) :( A2)) is 9.4: 0.6, and calcium chloride anhydride with respect to titanium in the solid catalyst component (AA11). The molar ratio of was 1.3.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA11) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Comparative Example 5)
<Preparation of solid catalyst component (AA12)>
A liter of stainless steel ball with a diameter of 25.4 mm is filled in a 1 liter stainless steel grinding pot, and 18 g of magnesium chloride anhydride and 2.0 g of calcium chloride anhydride are added under a nitrogen atmosphere to obtain an amplitude. Co-grinding was performed for 24 hours under the conditions of 3 mm and 1400 rpm. Next, 120 ml of heptane, 15 g of co-pulverized product, and 106 ml of tetrabutoxytitanium were added to a 500-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and reacted at 90 ° C. with stirring for 2 hours. . After the reaction, the uniform solution was cooled to 40 ° C., 24 ml of methylhydrogenpolysiloxane was added, and a precipitation reaction was performed for 5 hours. The precipitated solid product was thoroughly washed with heptane. Next, 40 g of precipitated solid product and 200 ml of heptane were introduced into a 500 ml round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer, and further 12 ml of silicon tetrachloride was added, The reaction was carried out for 3 hours. The solid product was washed thoroughly with heptane. Subsequently, 400 ml of heptane and 1.0 ml of phthalic acid dichloride were added to the obtained solid product. After reacting at 90 ° C. for 1 hour, the solid product was thoroughly washed with heptane, and then 200 ml of heptane and 15 ml of titanium tetrachloride were added to the obtained solid product. After reacting at 95 ° C. for 3 hours, the solid product Was thoroughly washed with heptane. After adding 200 ml of heptane and 4.0 ml of silicon tetrachloride to the solid product and reacting at 90 ° C. for 1 hour, the solid product is thoroughly washed with heptane, filtered and dried to obtain a powdery solid catalyst component It was. The titanium content in the solid catalyst component was measured and found to be 1.4 wt%, the calcium chloride content was 12.5 wt%, and the calcium chloride relative to the titanium content in the obtained solid catalyst component The molar ratio of anhydride was 3.8.
<Formation of polymerization catalyst and propylene polymerization>
In place of the solid catalyst component (AA1), the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (AA12) was used. The results are shown in Table 1.

(Comparative Example 6)
<Preparation of solid catalyst component (AA13)>
A liter of stainless steel balls with a diameter of 25.4 mm was filled in a 1 liter stainless steel grinding pot, and 10 g of diethoxymagnesium and 10 g of calcium chloride anhydride were added in a nitrogen atmosphere, and the amplitude was 3 mm and the rotation Co-pulverization was performed for 5 hours under the condition of several 1400 rpm. Next, 50 ml of toluene and 9 g of the co-ground product were put into a 500 ml round bottom flask sufficiently substituted with nitrogen gas and equipped with a stirrer, and stirred at room temperature for 5 minutes. Thereafter, 50 ml of titanium tetrachloride was added, the temperature was raised to 90 ° C., 1.9 g of di-n-butyl phthalate was added, the temperature was further raised to 115 ° C., and the mixture was reacted for 2 hours with stirring. The obtained solid product was separated by filtration, washed with 100 ml of toluene at 90 ° C., added with 40 ml of titanium tetrachloride and 60 ml of toluene, and reacted at 115 ° C. with stirring for 2 hours. After completion of the reaction, the mixture was cooled to 40 ° C., washed with heptane, filtered and dried to obtain a powdered solid catalyst component. The solid catalyst component had a titanium content of 1.2 wt% and a calcium chloride content of 45.9 wt%. The molar amount of calcium chloride anhydride relative to the titanium content of the obtained solid catalyst component was The ratio was 16.5.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA13) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

(Comparative Example 7)
<Preparation of solid catalyst component (AA14)>
20 g of the solid catalyst component (AA4) obtained in Example 4 was charged into a 500 ml round bottom flask which was sufficiently substituted with nitrogen gas and equipped with a stirrer. Next, a mixed solution of 40 ml of titanium tetrachloride and 160 ml of toluene was added at room temperature. Then, it heated up to 100 degreeC and made it react, stirring at 100 degreeC for 1 hour. After completion of the reaction, the supernatant was removed, and the resulting solid product was washed 4 times with 150 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (AA14). In addition, the titanium content in the obtained solid catalyst component (AA14) is 1.3% by weight, the calcium chloride anhydride content is 29.8% by weight, and is based on the titanium content derived from the component (A1). The molar ratio of calcium chloride anhydride was 9.9.
<Formation of polymerization catalyst and propylene polymerization>
A catalyst for polymerization and propylene polymerization were performed in the same manner as in Example 1 except that the solid catalyst component (AA14) was used instead of the solid catalyst component (AA1). The results are shown in Table 1.

  From the results of Table 1, the solid catalyst component of the present invention has a high polymerization activity per mole of titanium contained in the solid catalyst component and a small G / E ratio value indicating the intensity of the reaction at the initial stage of polymerization. From this, it is a catalyst in which the reaction at the initial stage of polymerization is suppressed, and a polymer having excellent stereoregularity and bulk specific gravity can be obtained while maintaining high polymerization activity per mole of titanium contained in the solid catalyst component. I understand.

  The catalyst for olefin polymerization of the present invention is a catalyst that maintains high catalytic activity in propylene polymerization and suppresses the initial reaction (G / E ratio) relative to the polymerization activity, and has a particle shape and stereoregularity. Excellent polypropylene can be obtained.

Claims (7)

A solid component containing magnesium, titanium, halogen and an electron donating compound and a halogen compound of a Group 2 element of the periodic table having a molar ratio of 2.3 to 20.5 with respect to the titanium atom in the solid component are mixed in a dry state. A method for producing a solid catalyst component for olefin polymerization, which is characterized by contacting.   The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the halogen compound of the Group 2 element of the periodic table is a chloride.   3. The production method according to claim 1, wherein mixing and contact are performed in an inert gas atmosphere. Solid catalyst component (A) for olefin polymerization obtained by the method according to any one of claims 1 to 3,
The following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3) (B ) And an external electron donating compound (C) are brought into contact with each other. The external electron donating compound (C) is represented by the following general formula (2); R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ³ represents 1 to 1 carbon atoms. 4 represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, and may be the same or different, q is an integer of 0 or 1 to 3). It is a compound, The manufacturing method of the catalyst for olefin polymerization of Claim 4 characterized by the above-mentioned.   6. A process for producing an olefin polymer, wherein the olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst obtained by the method according to claim 4 or 5.   The method for producing an olefin polymer according to claim 6, wherein the olefin is propylene.