JP4879931B2 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

  The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer for producing an α-olefin homopolymer or copolymer.

  In general, an olefin polymer is polymerized by a Ziegler-Natta catalyst composed of a titanium compound and an organoaluminum compound. For example, in the production of polypropylene which is one of olefin polymers, as a solid catalyst component mainly composed of titanium, magnesium, chlorine and an electron donating compound, an organoaluminum compound as a promoter component, and a stereoregularity improver. Isotactic polypropylene has been obtained by using a catalyst containing an organosilicon compound having an alkoxy group, but at present, the catalytic activity during polymerization is improved, the stereoregularity of the olefin polymer is improved, and the olefin polymer is obtained. Improvement of the powder form for stable production is attempted.

For example, for the purpose of improving the morphology such as the particle size and shape of an olefin polymer, JP-A-63-280707 discloses a method for supporting a magnesium compound on an inorganic oxide such as silica, Japanese Laid-Open Patent Publication No. 58-000811 discloses a method in which a magnesium compound is once dissolved in a solvent such as alcohol and then precipitated again.
However, these methods have the disadvantage that the process of supporting, dissolving, and precipitating the magnesium compound is indispensable, so that the process is extremely complicated and the performance stability of the catalyst is lacking. In addition, these methods have a drawback that the catalyst activity during polymerization and the stereoregularity of the olefin polymer are not sufficient.

  Therefore, as a technique for improving these drawbacks, Japanese Patent Application Laid-Open No. 02-413883 discloses a method using a reaction product of metal magnesium, alcohol and a specific amount of halogen as a catalyst support, or Japanese Patent Publication No. 07-025822. In the publication, a method for producing an olefin polymer using a Ziegler-Natta catalyst containing a solid catalyst component obtained by adding an organic acid ester to a reaction product of alkoxymagnesium, a halogenating agent and alkoxytitanium, and further reacting with titanium halide Is disclosed. However, these methods still have insufficient catalyst activity during polymerization and stereoregularity of the olefin polymer.

In JP-A-11-269218, a magnesium compound and a titanium compound are brought into contact with each other at a temperature of 120 ° C. or higher and 150 ° C. or lower in the presence of an electron donating compound, and then in a temperature of 100 ° C. or higher and 150 ° C. or lower. A solid catalyst component for olefin polymerization obtained by washing with an active solvent is disclosed, which is effective for suppressing a decrease in catalyst activity over time during polymerization and improving stereoregularity of an olefin polymer.
However, since the polymerization activity of this catalyst was not always satisfactory, further improvement was required to improve it.

  Accordingly, an object of the present invention is to provide a solid catalyst component for olefin polymerization, an olefin polymerization catalyst, and a method for producing the olefin polymer, which can provide an olefin polymer having high polymerization activity and excellent powder form.

According to the present invention, the following compounds (a) to (c-1) (that is, the compound (a), the compound (b) and the compound (c-1)), or the following compounds (a) to (d) (that is, , Compound (a), compound (b), compound (c-1) and compound (d)) are reacted at a temperature of 120 ° C. or higher and 150 ° C. or lower, washed with an inert solvent, and more than once (for example, The solid catalyst component for olefin polymerization obtained by reacting the halogen-containing titanium compound (a) at a temperature of 120 ° C. or higher and 150 ° C. or lower and washing with an inert solvent is provided.
(A) Halogen-containing titanium compound (b) Alkoxy group-containing magnesium compound (c-1) Halogen-containing silicon compound (d) having a molar ratio of halogen to alkoxy group in the alkoxy group-containing magnesium compound (b) of 0.50 or more ) Electron donating compounds

  By preparing the solid catalyst component in this way, the remaining amount of alkoxy groups can be reduced, and an olefin polymer having high polymerization activity and excellent powder form can be obtained.

According to another aspect of the present invention, the following compounds (a) to (c) (ie, compound (a), compound (b) and compound (c)), or the following compounds (a) to (d) (ie , Molar ratio (RO / Ti) of residual alkoxy group (RO) to titanium loading (Ti) obtained by reacting compound (a), compound (b), compound (c) and compound (d)) A solid catalyst component for olefin polymerization having an A of 0.30 or less is provided.
(A) halogen-containing titanium compound (b) alkoxy group-containing magnesium compound (c) halogen-containing silicon compound (d) electron-donating compound

  By setting the molar ratio (RO / Ti) to 0.30 or less, an olefin polymer having high polymerization activity and excellent powder form can be obtained.

In the compound (c), the molar ratio of the halogen of the compound (c) to the alkoxy group in the compound (b) is preferably 0.50 or more.
By making the molar ratio 0.50 or more, the halogenation reaction of the compound (b) by the compound (c) proceeds effectively, so that the degree of halogenation of the compound (b) is finally improved and by-produced. It is thought that the production | generation of the expected alkoxy titanium compound is suppressed. Thereby, polymerization activity increases.
In some cases, the halogenation reaction of compound (b) by compound (c) proceeds preferentially to the halogenation reaction of compound (b) by compound (a). It is considered that the powder form is excellent because the formation rate is reduced and the refinement of the catalyst is suppressed.

  By such a preparation method, it is considered that the halogenation reaction of the compound (b) by the compounds (a) and (c) is promoted and the alkoxytitanium compound and the like expected to be by-produced are easily extracted from the solid surface. .

  Further, the compound (b) is a compound obtained by reacting metal magnesium, alcohol, and a halogen containing 0.0001 gram atoms or more and / or a halogen-containing compound with respect to 1 mol of the metal magnesium. Is preferred.

If the amount of halogen and / or halogen-containing compound is less than this amount, the particle size of the compound (b) becomes coarse, the degree of halogenation of the compound (b) is suppressed, and the extraction efficiency of alkoxy titanium or the like may be reduced. There is.
By using such a compound (b), the morphology of the olefin polymer can be improved. The compound (b) thus produced is nearly spherical and does not require a classification operation.

  For the preparation of the solid catalyst component of the present invention, an electron donating compound (d) is used as necessary, but the solid catalyst component not using the electron donating compound (d) is particularly an ethylene homopolymer or ethylene. It is suitable as a catalyst for the production of a copolymer, and high polymerization activity can be obtained.

Yet another embodiment of the present invention is an olefin polymerization catalyst comprising the following components [A], [B] or the following components [A], [B], [C].
[A] Solid catalyst component for olefin polymerization [B] Organoaluminum compound [C] Electron-donating compound By configuring the catalyst in this manner, an olefin polymer having high polymerization activity and excellent powder form is obtained. Can do.
In addition, the electron donating compound [C] is included as necessary, and by including this compound, the stereoregularity and / or polymerization activity of the olefin polymer may be improved.

  Yet another embodiment of the present invention is a method for producing an olefin polymer in which an olefin is polymerized using the above olefin polymerization catalyst.

  According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer, in which an olefin polymer having high polymerization activity and excellent powder form can be obtained.

Next, each catalyst component, production method, polymerization method and the like of the present invention will be described. The following are preferred examples and the present invention is not limited thereto.
1. Catalyst component [A] Solid catalyst component for olefin polymerization

(A) Halogen-containing titanium compound As the halogen-containing titanium compound, a compound represented by the following general formula (I) can be preferably used.
TiX ¹ _p (OR ¹ ) _4-p (I)

In the general formula (I), X ¹ represents a halogen atom, among which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ¹ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be linear, branched, or cyclic, and may be sulfur, nitrogen, It may contain heteroatoms such as oxygen, silicon and phosphorus. Among these, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of OR ¹ are present, they may be the same as or different from each other. Specific examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, Examples include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. p shows the integer of 1-4.

  Specific examples of the halogen-containing titanium compound represented by the general formula (I) include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxy titanium trichloride, ethoxy titanium trichloride, propoxy Trihalogenated alkoxytitanium such as titanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dichloride Dihalogenated dialkoxy titanium such as bromide; trimethoxy titanium chloride, triethoxy titanium chloride, triisopropoxy titanium chloride, tri-n-propoxy titanium chloride, tri-n-butoxy titanium chloride, etc. Monohalogenated trialkoxy titanium, and the like. Among these, a high halogen-containing titanium compound, particularly titanium tetrachloride is preferable from the viewpoint of polymerization activity. These halogen-containing titanium compounds may be used alone or in combination of two or more.

(B) Alkoxy group-containing magnesium compound As the alkoxy group-containing magnesium compound, a compound represented by the following general formula (II) can be preferably used.
Mg (OR ² ) _q R ³ _2-q (II)

In the general formula (II), R ² represents a hydrocarbon group, and R ³ represents a hydrocarbon group or a halogen atom. Here, the hydrocarbon group of R ² and R ^3, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and they may be the same or different. Examples of the halogen atom for R ³ include chlorine, bromine, iodine, and fluorine. q shows the integer of 1-2.

Specific examples of the alkoxy group-containing magnesium compound represented by the general formula (II) include dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dihexyloxy magnesium, dioctoxy magnesium, diphenoxy magnesium, di Dialkoxymagnesium and diaryloxymagnesium such as cyclohexyloxymagnesium; alkoxyalkylmagnesium such as ethoxyethylmagnesium, phenoxymethylmagnesium, ethoxyphenylmagnesium, cyclohexyloxyphenylmagnesium, allyloxyalkylmagnesium, alkoxyallylmagnesium and allyloxyallylmagnesium; Butoxymagnesium chloride, cyclohexyloxymagnesium chloride Chloride, phenoxy magnesium chloride, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, etc. alkoxy magnesium halide and allyloxy magnesium halide, such as ethoxy magnesium iodide and the like.
Among these, dialkoxymagnesium can be suitably used from the viewpoint of polymerization activity and stereoregularity, and diethoxymagnesium is particularly preferred.

  In view of the polymerization activity of the catalyst, the powder form of the olefin polymer, and the stereoregularity, the alkoxy group-containing magnesium compound (b) is preferably 0.0001 gram atom with respect to 1 mol of metal magnesium, alcohol, and metal magnesium. It is obtained by reacting a halogen containing the above halogen atoms and / or a halogen-containing compound.

  In this case, the shape of the metallic magnesium is not particularly limited. Therefore, metallic magnesium having an arbitrary particle size, for example, metallic magnesium in the form of granules, ribbons, powders, etc. can be used. Further, the surface state of the metallic magnesium is not particularly limited, but it is preferable that the surface is not formed with a film such as magnesium hydroxide.

  As the alcohol, a lower alcohol having 1 to 6 carbon atoms is preferably used. In particular, ethanol is preferable because a solid product that significantly improves the performance of the catalyst can be obtained. The purity and water content of the alcohol are not particularly limited, but if an alcohol having a high water content is used, magnesium hydroxide is generated on the surface of the magnesium metal, so that an alcohol having a water content of 1% or less, particularly 2,000 ppm or less is used. It is preferable. Furthermore, in order to obtain a better morphology, the smaller the moisture, the better, and generally 200 ppm or less is desirable.

As the halogen, chlorine, bromine or iodine, particularly iodine is preferably used.
The halogen atom of the halogen-containing compound is preferably chlorine, bromine or iodine. Of the halogen-containing compounds, a halogen-containing metal compound is particularly preferable. Specifically, MgCl ₂ , MgI ₂ , Mg (OEt) Cl, Mg (OEt) I, MgBr ₂ , CaCl ₂ , NaCl, KBr and the like can be suitably used as the halogen-containing compound. Among these, MgCl ₂ is particularly preferable. These states, shapes, particle sizes, and the like are not particularly limited, and may be arbitrary, for example, can be used in a solution in an alcohol solvent (for example, ethanol).

  The amount of alcohol used is preferably 2 to 100 mol, particularly preferably 5 to 50 mol, per 1 mol of metal magnesium. If the amount of alcohol used is too large, the yield of the alkoxy group-containing magnesium compound (b) with good morphology may be reduced, and if it is too small, stirring in the reaction vessel may not be performed smoothly. . However, the molar ratio is not limited.

  The amount of halogen used is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 gram atom or more, per mole of magnesium metal. In the case of less than 0.0001 gram atom, there is no great difference from the case where halogen is not used as a reaction initiator, and when the obtained alkoxy group-containing magnesium compound (b) is used as a catalyst support, the catalyst activity and the morphology of the olefin polymer. Etc. may be defective.

  The halogen-containing compound is used in an amount of 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 gram atom, based on 1 mole of metal magnesium. That's it. When the amount is less than 0.0001 gram atom, it is not much different from the case where a halogen-containing compound is not used as a reaction initiator, and when the obtained alkoxy group-containing magnesium compound (b) is used as a catalyst support, The morphology and the like may be poor.

  In the present invention, the halogen and the halogen-containing compound may be used alone or in combination of two or more. A combination of halogen and a halogen-containing compound may also be used. When a halogen and a halogen-containing compound are used in combination, the amount of halogen and the total halogen atom in the halogen-containing compound is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 1 mol of metal magnesium. 0.001 gram atom or more.

  The upper limit of the amount of halogen and / or halogen-containing compound used is not particularly defined, but may be appropriately selected within the range in which the alkoxy group-containing magnesium compound (b) used in the present invention can be obtained. It is preferable to make it less than.

  In the method for producing an olefin polymer of the present invention, the particle size of the alkoxy group-containing magnesium compound (b) can be freely controlled by appropriately selecting the amount of halogen and / or halogen-containing compound used. .

  The production of the alkoxy group-containing magnesium compound (b) is carried out until generation of hydrogen gas is not observed (usually 1 to 30 hours). Specifically, in the case of using iodine as a halogen, after adding solid iodine into metal magnesium and alcohol, a method of reacting by heating, an alcohol solution of iodine was dropped into the metal magnesium and alcohol. Then, it can manufacture by the method of making it react by heating, the method of dripping and reacting the alcohol solution of iodine, heating metal magnesium and an alcohol solution.

  In addition, it is preferable to carry out any method using inert organic solvent (for example, saturated hydrocarbons, such as n-hexane) by inert gas (for example, nitrogen gas, argon gas) atmosphere depending on the case.

  In addition, it is not necessary to add all of the metal magnesium, alcohol and halogen from the beginning, and they may be added separately. A particularly preferred form is a method in which the whole amount of alcohol is added from the beginning and metal magnesium is added in several portions. In such a case, a temporary mass generation of hydrogen gas can be prevented, which is very desirable from the viewpoint of safety. Also, the reaction vessel can be downsized. Furthermore, it becomes possible to prevent entrainment of alcohol and halogen caused by a temporary large amount of hydrogen gas. The number of times of division may be determined in consideration of the scale of the reaction tank, and is not particularly limited. However, considering the complexity of the operation, 5 to 10 times is usually preferable.

  The reaction itself may be either a batch type or a continuous type. Further, as a modified method, an operation in which a small amount of magnesium metal is first charged into the alcohol that has been charged in its entirety from the beginning, the product produced by the reaction is separated and removed in a separate tank, and then a small amount of metal magnesium is charged again. It is also possible to repeat.

Further, from the viewpoint of catalyst activity during polymerization and powder form of the olefin polymer, metal magnesium, alcohol, and halogen and / or halogen-containing compound are reacted at 30 to 60 ° C., more preferably at 40 to 55 ° C. The average particle diameter (D ₅₀ ) of the resulting alkoxy group-containing magnesium compound (b) is 50 μm or less, more preferably 40 μm or less. _Further, it is preferable that _{D 50} is 1μm or more.
The average particle size (D ₅₀ ) is defined as the particle size corresponding to a weight cumulative fraction of 50%. That is, it is shown that the weight sum of the particle group smaller than the particle diameter represented by D ₅₀ is 50% of the total weight of all particles.

By setting the reaction temperature to 30 to 60 ° C., the compound (b) is reduced in particle size while maintaining the spherical and narrow particle size distribution characteristics, the halogenation of the compound (b) proceeds, and the solid catalyst component contains The remaining amount of the alkoxy group can be reduced. When the reaction temperature is higher than this, the particle size reduction does not proceed efficiently, and when the reaction temperature is lower than this, the production rate of the compound (b) is remarkably reduced and the productivity is lowered.
By reducing the average particle size (D ₅₀ ) to 50 μm or less, the halogenation degree of the compound (b) is improved, and the alkoxytitanium compound and the like that are expected to be by-produced are thought to be easily extracted from the solid surface. It is done.

  When the alkoxy group-containing magnesium compound (b) is used for the preparation of the solid catalyst component [A], a dried product may be used, or a product washed with an inert solvent such as heptane after filtration may be used. . In any case, the alkoxy group-containing magnesium compound (b) can be used in the following steps without performing pulverization or classification for aligning the particle size distribution. Further, the alkoxy group-containing magnesium compound (b) is nearly spherical and has a sharp particle size distribution. Furthermore, even if each particle is taken, the variation in sphericity is small.

  Moreover, these alkoxy group containing magnesium compounds (b) may be individual, and may be used in combination of 2 or more types. Furthermore, it may be used by being supported on a support such as silica, alumina or polystyrene, or may be used as a mixture with halogen or the like.

(C) Halogen-containing silicon compound As the halogen-containing silicon compound, a compound represented by the following general formula (III) can be used.
Si (OR ⁴ ) _r X ² _4-r (III)

  By using the halogen-containing silicon compound (c), it may be possible to improve the catalyst activity during polymerization, improve the stereoregularity, and reduce the amount of fine powder contained in the olefin polymer.

In the general formula (III), X ² represents a halogen atom, among which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ⁴ is a hydrocarbon group, which may be a saturated or unsaturated group, may be linear, branched, or cyclic, and may further be sulfur, nitrogen, It may contain heteroatoms such as oxygen, silicon and phosphorus. Among these, a C1-C10 hydrocarbon group, especially an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like are preferable. When a plurality of OR ⁴ are present, they may be the same as or different from each other. Specific examples of R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, Examples include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. r shows the integer of 0-3.

Specific examples of the halogen-containing silicon compound represented by the general formula (III) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, propoxytril. Examples include chlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Of these, silicon tetrachloride is particularly preferred.
By using silicon tetrachloride, it is considered that the rate and reaction rate of the halogenation reaction of compound (b) with silicon tetrachloride can be sufficiently controlled.
These halogen-containing silicon compounds may be used alone or in combination of two or more.

  Moreover, the compound (c) is preferably a halogen-containing silicon compound (c-1) having a halogen molar ratio to the alkoxy group in the compound (b) of 0.50 or more. When such a halogen-containing silicon compound is used, the halogenation of the compound (b) proceeds and the remaining amount of alkoxy groups in the solid catalyst component can be reduced. More preferably, it is a halogen-containing silicon compound having a halogen molar ratio to the alkoxy group in the compound (b) of 0.80 or more.

(D) Electron-donating compound For the preparation of the olefin polymerization catalyst of the present invention, an electron-donating compound (d) is used as necessary. Examples of the electron donating compound (d) include alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, esters of organic acids or inorganic acids, ethers such as monoethers, diethers or polyethers. And oxygen-containing compounds such as ammonia and nitrogen-containing compounds such as ammonia, amines, nitriles and isocyanates. Among these, esters of polyvalent carboxylic acids are preferable, and esters of aromatic polyvalent carboxylic acids are more preferable. Of these, aromatic dicarboxylic acid monoesters and / or diesters are particularly preferred from the standpoint of catalytic activity during polymerization. In addition, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferable.

  Specifically, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6,7, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl of dicarboxylic acids such as 8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl And dialkyl esters such as syl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 3-ethylpentyl, etc. . Among these, phthalic acid diesters are preferable, and linear or branched aliphatic hydrocarbons having 4 or more carbon atoms in the organic group in the ester portion are particularly preferable. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. In addition, these compounds may be used alone or in combination of two or more.

[B] Organoaluminum compound The organoaluminum compound [B] used in the present invention is not particularly limited, but preferably has an alkyl group, a halogen atom, a hydrogen atom, an alkoxy group, an aluminoxane, or a mixture thereof. Can do. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum; dialkyl such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. These organoaluminum compounds may be used alone or in combination of two or more.

[C] Electron-donating compound For the preparation of the olefin polymerization catalyst of the present invention, an electron-donating compound [C] is used as necessary. As such an electron donating compound [C], an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among these, it is particularly preferable to use an organosilicon compound having an alkoxy group.

  Specific examples of the organosilicon compound having an alkoxy group include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxy. Silane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl Butyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butyl (s-butyl) dimethoxy Silane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane, t-butyl (3 3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyl Ethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentyl-t-butyl Dimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, α-naphthyl-1,1,2-trimethylpropyldimethoxysilane, n-tetradecanyl-1,1,2-trimethylpropyldimethyloxysilane, 1,1,2-trimethylpropylmethyldimethoxysilane, 1,1,2-trimethylpropylethyldimethoxysilane, 1,1,2-trimethylpropylisopropyldimethoxy Silane, 1,1,2-trimethylpropylcyclopentyldimethoxysilane, 1,1,2-trimethylpropylcyclohexyldimethoxysilane, 1,1,2-trimethylpropylmyristyldi Toxisilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane Butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, Indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, ethyltriisopropoxysilane Methylcyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, (isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, vinyltriethoxy Silane, vinyltributoxysilane, chlorotriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane, 1,1,2-trimethylpropylisopropoxy Dimethoxysilane, 1,1,2-trimethylpropyl (t-butoxy) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethyl silicate, silicate silicate Le, trimethyl phenoxy silane, methyl tri Lilo silane, vinyltris (beta-methoxyethoxy) silane, vinyl tris acetoxy silane, dimethyl tetraethoxy disiloxane and the like. These organosilicon compounds may be used alone or in combination of two or more.

  Moreover, as such an organosilicon compound, it is obtained by reacting a silicon compound having no Si—O—C bond and an organic compound having an O—C bond in advance or reacting at the time of polymerization of α-olefin. Mention may also be made of compounds. Specific examples include compounds obtained by reacting silicon tetrachloride with alcohol.

  Specific examples of nitrogen-containing compounds include 2,6-substituted piperidines such as 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, and N-methyl2,2,6,6-tetramethylpiperidine. 2,5-substituted azolidines such as 2,5-diisopropylazolidine, N-methyl 2,2,5,5-tetramethylazolidine; N, N, N ′, N′-tetramethylmethylenediamine, N , N, N ′, N′-tetraethylmethylenediamine and the like; substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine, and the like.

  Specific examples of phosphorus-containing compounds include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite and the like. Examples thereof include phosphites.

  Specific examples of the oxygen-containing compound include 2,5-substituted tetrahydrofurans such as 2,2,5,5-tetramethyltetrahydrofuran and 2,2,5,5-tetraethyltetrahydrofuran; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.

2. [A] Preparation Method of Solid Catalyst Component The preparation method of the solid catalyst component [A] is the above halogen-containing titanium compound (a), alkoxy group-containing magnesium compound (b) and halogen-containing silicon compound (c), or as necessary. In response, the electron donating compound (d) is further reacted.
A preferable preparation method is the above-described halogen-containing titanium compound (a), alkoxy group-containing magnesium compound (b) and halogen-containing silicon compound (c), or, if necessary, further an electron-donating compound (d) at 120 ° C. or higher. The reaction is carried out at a temperature of 150 ° C. or lower, washed with an inert solvent, and the halogen-containing titanium compound (a) is further reacted at a temperature of 120 ° C. or higher and 150 ° C. or lower once and washed with an inert solvent. At this time, the compound (c) is a halogen-containing silicon compound (c-1) having a halogen molar ratio to the alkoxy group in the compound (b) of 0.50 or more.
As described above, the compounds (a) to (c) and (a) to (d) are contact-reacted at a specific temperature, and again (one or more times), the halogen-containing titanium compound (a) is contact-reacted at a specific temperature. If done, the polymer activity can be increased.

  Other contact orders are not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon, or each component may be previously contacted after being diluted with an inert solvent such as a hydrocarbon. Examples of the inert solvent include aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane or alicyclic hydrocarbons, aromatic hydrocarbons such as toluene, ethylbenzene, and xylene, and chlorobenzene, tetrachloroethane, and chlorofluorocarbons. And halogenated hydrocarbons such as these or mixtures thereof. Among these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable, and aliphatic hydrocarbons are particularly preferably used.

  The contact order of the compounds (a) to (c) and (a) to (d) is not particularly limited. First, the alkoxy group-containing magnesium compound (b) and the halogen-containing silicon compound (c) are brought into contact with each other. When the halogen-containing titanium compound (a) is contacted, and finally the electron-donating compound (d) is contacted and reacted, and further the halogen-containing titanium compound (a) is contacted, the polymerization activity can be increased. preferable.

  Here, a halogen containing titanium compound (a) is 0.5-100 mol normally with respect to 1 mol of magnesium of an alkoxy group containing magnesium compound (b), Preferably, 1-50 mol is used. When this molar ratio deviates from the above range, the catalyst activity may be insufficient.

  Moreover, an electron-donating compound (d) is 0.01-10 mol normally with respect to 1 mol of magnesium of an alkoxy-group containing magnesium compound (b), Preferably, 0.05-1.0 mol is used. When this molar ratio deviates from the above range, catalyst activity and stereoregularity may be insufficient.

  The halogen-containing silicon compound (c) usually has a molar ratio of halogen to alkoxy groups in the alkoxy group-containing magnesium compound (b) of 0.50 or more, preferably 0.60 to 4.0, more preferably 1. Use an amount of 0.0-2.5. If this amount is less than the above range, the catalyst activity and stereoregularity will not be sufficiently improved, resulting in an increase in the amount of fine powder of the produced polymer and a decrease in bulk density. Never become.

  Furthermore, the contact reaction of the above-mentioned compounds (a) to (c) and (a) to (d) is preferably performed at a temperature range of 120 to 150 ° C., particularly preferably 125 to 140 ° C. after all of these are added. Do. If this contact temperature is outside the above range, the catalyst activity and stereoregularity may not be sufficiently improved. The contact is usually performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. When the solvent is used, the pressure at this time varies depending on the type, contact temperature, and the like, but is usually in the range of normal pressure to 5 MPa, preferably normal pressure to 1 MPa. Further, during the contact operation, stirring is preferably performed in terms of contact uniformity and contact efficiency. These contact conditions are the same for the second and subsequent contact reactions of the halogen-containing titanium compound (a).

  In the contact operation of the halogen-containing titanium compound (a), when a solvent is used, it is usually 5,000 ml or less, preferably 10 to 1,000 ml, per 1 mol of the halogen-containing titanium compound (a). Use solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may deteriorate.

  Furthermore, the washing temperature with an inert solvent after contact / reaction of the halogen-containing titanium compound (a) is 100 to 150 ° C., particularly preferably 120, after the first contact / reaction of the halogen-containing titanium compound (a). Washing with an inert solvent at a temperature of ˜140 ° C. is preferable because the effect of improving the catalytic activity and stereoregularity may be increased. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, chlorobenzene, tetrachloroethane, Halogenated hydrocarbons such as chlorofluorocarbons or mixtures thereof. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used.

  The washing temperature after the contact and reaction of the halogen-containing titanium compound (a) for the second and subsequent times is 100 to 150 ° C., particularly preferably 120 to 140 ° C. from the viewpoint of stereoregularity. Sometimes it is better to wash.

  As the cleaning method, a method such as decantation or filtration is preferable. There are no particular restrictions on the amount of inert solvent used, the washing time, and the number of washings, but usually 100 to 100,000 milliliters, preferably 500 to 50,000 milliliters of solvent is used per mole of magnesium compound. Usually, it is performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. If this ratio deviates from the above range, cleaning may be incomplete.

  The pressure at this time varies depending on the type of solvent, the washing temperature, etc., but is usually from normal pressure to 5 MPa, and preferably from normal pressure to 1 MPa. Further, during the cleaning operation, it is preferable to perform stirring from the viewpoint of cleaning uniformity and cleaning efficiency. In addition, the obtained solid catalyst component can also be preserve | saved in inert solvents, such as a dry state or hydrocarbon.

The solid catalyst component [A] thus obtained preferably has a molar ratio of the remaining alkoxy group to the titanium loading of 0.30 or less.
Further, the molar ratio is more preferably 0.20 or less, and further preferably 0.15 or less.

Moreover, it is preferable that alkoxy group residual amount (RO) is 0.13 mmol / g or less. The reason for this is that when the alkoxy group residual amount exceeds 0.13 mmol / g, the polymerization activity is low, and the catalyst cost is increased and the catalyst residue such as Cl in the powder is increased, which may deteriorate the quality. It is.
Further, the remaining amount of alkoxy groups is more preferably 0.10 mmol / g or less, and further preferably 0.08 mmol / g or less.

Moreover, it is preferable that a titanium load is 1.5 weight% or more. This is because when the titanium loading is less than 1.5% by weight, the activity per catalyst may be low even if the activity per titanium is high (even if RO / Ti is low).
Further, the titanium loading is more preferably 1.8% by weight or more, and further preferably 2.0% by weight or more.

When the solid catalyst component [A] is prepared using the electron donating compound (d), the molar ratio, the remaining alkoxy group, and the titanium loading amount are easily set to the above preferable values.
Furthermore, the remaining amount of alkoxy groups can be controlled by selecting a specific carrier to be used or by controlling the catalyst preparation conditions.
The amount of titanium supported can be controlled by setting the catalyst preparation conditions, particularly the reaction temperature between the compound (a) and each component and the washing temperature after the reaction of the compound (a) to a specific temperature.

3. Production method of olefin polymer The amount of each component used in the olefin polymerization catalyst of the present invention is not particularly limited, but the solid catalyst component [A] is usually converted into titanium atoms per liter of reaction volume. An amount is used that ranges from 0.00005 to 1 millimolar.

  The organoaluminum compound [B] is used in such an amount that the aluminum / titanium atomic ratio is usually in the range of 1 to 1,000, preferably 10 to 500. When this atomic ratio deviates from the above range, the catalytic activity may be insufficient.

  When the electron donating compound [C] is used, [C] / [B] (molar ratio) is usually 0.001 to 5.0, preferably 0.01 to 2.0, more preferably 0. An amount is used that ranges from .05 to 1.0. If this molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when prepolymerization is performed, the amount of the electron donating compound [C] used can be further reduced.

As the olefin used in the present invention, α-olefin represented by the general formula (IV) is preferable.
R ⁵ —CH═CH ₂ (IV)

In the general formula (IV), R ⁵ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group, or a straight chain or branched chain, Alternatively, it may be annular. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane , Butadiene, isoprene, piperylene and the like. These olefins may be used alone or in combination of two or more. Among the olefins, ethylene and propylene are particularly preferable.

  In the polymerization of olefin in the present invention, from the viewpoint of catalyst activity during polymerization, stereoregularity of the olefin polymer, and powder form, the olefin may be preliminarily polymerized and then the main polymerization may be performed as desired. . In this case, the olefin is usually added in the presence of a catalyst obtained by mixing the solid catalyst component [A], the organoaluminum compound [B] and, if necessary, the electron donating compound [C] in a predetermined ratio. Prepolymerization is carried out at a temperature in the range of 100 ° C. at a pressure of from about atmospheric pressure to about 5 MPa, and then the olefin is main-polymerized in the presence of a catalyst and a prepolymerized product.

  There are no particular restrictions on the type of polymerization in this main polymerization, and it can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, etc., and further applicable to both batch polymerization and continuous polymerization. Yes, it can be applied to two-stage polymerization and multi-stage polymerization under different conditions.

  Furthermore, with respect to the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 8 MPa, preferably from 0.2 to 5 MPa, and the polymerization temperature is usually from 0 to 200 ° C., preferably from the viewpoint of polymerization activity. Is appropriately selected within the range of 30 to 100 ° C. The polymerization time depends on the type of olefin as a raw material and the polymerization temperature, but is usually 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.

  The molecular weight of the olefin polymer can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present. In addition, for the catalyst component in the present invention, the solid catalyst component [A], the organoaluminum compound [B], and the electron donating compound [C] are mixed and contacted at a predetermined ratio, and then the olefin is immediately introduced. Polymerization may be performed, or after aging for about 0.2 to 3 hours after contact, olefin may be introduced to perform polymerization. Further, this catalyst component can be supplied suspended in an inert solvent or olefin. In the present invention, the post-treatment after polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after polymerization, a nitrogen gas stream or the like may be passed through the polymer powder derived from the polymerization vessel in order to remove olefins contained therein. Accordingly, pelletization may be performed by an extruder, and in this case, a small amount of water, alcohol, or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the monomer is completely separated from the polymer derived from the polymerization vessel, and then pelletized.

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. Incidentally, the average particle diameter (D ₅₀ ) of the alkoxy group-containing magnesium compound (b), the remaining amount of the alkoxy group of the solid catalyst component, the Ti loading amount, and the bulk density of the polymer powder, the average particle diameter (D ₅₀ ), The amount of coarse powder, intrinsic viscosity [η], and stereoregularity [mmmm] were determined as follows.

(1) Average particle diameter (D ₅₀ ) of the alkoxy group-containing magnesium compound (b): The compound (b) is suspended in a hydrocarbon solvent and measured by a light transmission method. The particle size distribution obtained by this method was plotted on lognormal probability paper, and the 50% particle size was obtained as the average particle size.

(2) Alkoxy group remaining amount: After sufficiently drying the solid catalyst component, this was precisely weighed, sealed in a vial, and sufficiently decalcified using 1.2N hydrochloric acid. Thereafter, insoluble matter was filtered, and the amount of alcohol in the filtrate was quantified by gas chromatography, and the corresponding remaining amount of alkoxy groups was calculated.

(3) Ti supported amount: After sufficiently drying the solid catalyst component, this was precisely weighed and sufficiently decalcified using 3N sulfuric acid. Thereafter, the insoluble matter was filtered, phosphoric acid was added to the filtrate as a masking agent, and the absorbance at 420 nm of the solution developed by adding 3% hydrogen peroxide was measured using FT-IR to determine the Ti concentration. The amount of Ti supported in the solid catalyst component was calculated.

(4) Bulk density: The polymer was measured according to JIS K6721.

(5) Average particle diameter (D ₅₀ ) of polymer, fine powder amount, coarse powder amount: The particle size distribution measured using a sieve was plotted on log-normal probability paper, and the 50% particle size was determined as the average particle size. . Further, the weight fraction with an opening size of 250 μm or less was defined as the amount of fine powder, and the weight fraction with an opening size of 2830 μm or more was defined as the amount of coarse powder.

(6) Intrinsic viscosity [η] of the polymer: The polymer was dissolved in decalin and measured at 135 ° C.

(7) Stereoregularity of polymer [mmmm]: The polymer was dissolved in a 90:10 (volume ratio) mixed solution of 1,2,4-trichlorobenzene and heavy benzene, and ¹³ C-NMR (JEOL Ltd.) ), Product name: LA-500), and quantitative determination was performed using a methyl group signal measured at 130 ° C. by a proton complete decoupling method.

The isotactic pentad fraction [mmmm] is a ¹³ C-NMR spectrum proposed by A. Zambelli et al. In Macromolecules Vol. 6, 925 (1973). The isotactic fraction in the pentad unit in the polypropylene molecular chain obtained from
In addition, the method for determining the assignment of the peak of the ¹³ C-NMR spectrum was in accordance with the assignment proposed in Macromolecules, Vol. 8, page 687 (1975), such as A. Zambelli.

Example 1
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.0057 gram Atomic ratio, reaction temperature: manufactured by reacting at 50 ° C., D ₅₀ : 35 μm) 16 g was added. After heating to 40 ° C. and adding 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) and stirring for 4 hours, 3.4 ml of di-n-butyl phthalate was added. This solution was heated to 65 ° C., and subsequently 77 ml of titanium tetrachloride was dropped, and the mixture was stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Thereafter, 122 milliliters of titanium tetrachloride was added, and the mixture was stirred for 2 hours at an internal temperature of 125 ° C. for 2 hours, and then washed with dehydrated octane at 125 ° C. six times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization A stainless steel autoclave with a stirrer having an internal volume of 1 liter was sufficiently dried, and after nitrogen substitution, 400 ml of heptane dehydrated at room temperature was added. While adding 2.0 mmol of triethylaluminum, 0.25 mmol of dicyclopentyldimethoxysilane and 0.0025 mmol of the solid catalyst component prepared in (1) in terms of Ti atom, 0.1 MPa of hydrogen was added, and then propylene was introduced. The temperature was raised to 80 ° C. and a total pressure of 0.8 MPa, and then polymerization was carried out for 1 hour.
Thereafter, the temperature was lowered and the pressure was released, the contents were taken out, and placed in 2 liters of methanol to deactivate the catalyst. It was filtered off and vacuum dried to obtain a propylene polymer. The evaluation results are shown in Table 1.

Example 2
(1) Preparation of solid catalyst component In Example 1 (1), the solid catalyst component was prepared in the same manner as in Example 1 except that the washing temperature with octane after the second titanium tetrachloride supporting reaction was changed to room temperature. And evaluated. The results are shown in Table 1.

(2) Propylene polymerization In Example 1 (2), 0.5 mmol of cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane, and the solid catalyst component prepared in (1) above was 0.005 mmol in terms of Ti atom. In addition, propylene was polymerized in the same manner as in Example 1 except that 0.05 MPa of hydrogen was used, and the resulting propylene polymer was evaluated. The results are shown in Table 1.

Example 3
(1) Preparation of Solid Catalyst Component In Example 1 (1), diethoxy having an iodine / Mg gram atomic ratio of 0.00019 and an average particle size (D ₅₀ ) of 10 μm produced at a reaction temperature of 50 ° C. A solid catalyst component was prepared and evaluated in the same manner as in Example 1 except that magnesium was used. The results are shown in Table 1.

(2) Propylene polymerization In Example 1 (2), propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used, and the resulting propylene polymer was evaluated. . The results are shown in Table 1.

Example 4
(1) Preparation of Solid Catalyst Component In Example 1 (1), diethoxy having an iodine / Mg gram atomic ratio of 0.019 and an average particle size (D ₅₀ ) of 70 μm produced at a reaction temperature of 78 ° C. A solid catalyst component was prepared and evaluated in the same manner as in Example 1 except that magnesium was used. The results are shown in Table 1.

(2) Propylene Polymerization In Example 1 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 1, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Example 5
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.019 gram Atomic ratio, reaction temperature: manufactured by reacting at 78 ° C., D ₅₀ : 70 μm) 16 g was added. After heating to 40 ° C. and adding 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) and stirring for 4 hours, 47 ml of titanium tetrachloride was added dropwise. The temperature of this solution was raised to 65 ° C., 3.4 ml of di-n-butyl phthalate was added, the temperature was raised to 125 ° C., and subsequently stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Thereafter, 77 ml of titanium tetrachloride was added, the mixture was stirred for 2 hours at an internal temperature of 125 ° C., contact operation was performed, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and stirred at room temperature, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Example 6
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.019 gram Atomic ratio, reaction temperature: manufactured by reacting at 78 ° C., D ₅₀ : 70 μm) 16 g was added. After heating to 40 ° C. and adding 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) and stirring for 4 hours, 3.4 ml of di-n-butyl phthalate was added. This solution was heated to 65 ° C., followed by dropwise addition of 47 ml of titanium tetrachloride, and stirred for 1 hour at an internal temperature of 125 ° C. for contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Thereafter, 77 ml of titanium tetrachloride was added, the mixture was stirred for 2 hours at an internal temperature of 125 ° C., contact operation was performed, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and stirred at room temperature, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Example 7
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.019 gram Atomic ratio, reaction temperature: manufactured by reacting at 78 ° C., D ₅₀ : 70 μm) 16 g was added. After heating to 40 ° C. and adding 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) and stirring for 4 hours, 3.4 ml of di-n-butyl phthalate was added. This solution was heated to 65 ° C., followed by dropwise addition of 47 ml of titanium tetrachloride, and stirred for 1 hour at an internal temperature of 125 ° C. for contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Thereafter, 77 ml of titanium tetrachloride was added, and the mixture was stirred for 1 hour at an internal temperature of 125 ° C., then the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted, and then washed with dehydrated octane at 125 ° C. Was repeated 7 times. Further, again, 77 ml of titanium tetrachloride was added, and a contact operation was performed by stirring for 2 hours at an internal temperature of 125 ° C. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. Further, 100 ml of dehydrated octane was added and stirred at room temperature, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 1
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.019 gram Atomic ratio, reaction temperature: manufactured by reacting at 78 ° C., D ₅₀ : 70 μm) 16 g was added. After heating to 40 ° C. and adding 8.0 ml of silicon tetrachloride (halogen / alkoxy group: 1.0) and stirring for 4 hours, 3.4 ml of di-n-butyl phthalate was added. This solution was heated to 65 ° C., followed by dropwise addition of 47 ml of titanium tetrachloride, and stirred for 1 hour at an internal temperature of 125 ° C. for contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. Further, 100 ml of dehydrated octane was added and stirred at room temperature, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 2
(1) Preparation of solid catalyst component A solid catalyst component was prepared and evaluated in the same manner as in Example 5 except that in Example 5 (1), the treatment step with silicon tetrachloride was omitted. The results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 3
(1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 5 except that 0.8 ml of silicon tetrachloride (halogen / alkoxy group: 0.10) was used in Example 5 (1). And evaluated. The results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 4
(1) Preparation of solid catalyst component After replacing a three-necked flask with an internal volume of 0.5 liter with a stirrer with nitrogen gas, 80 ml of dehydrated octane, diethoxymagnesium (metallic magnesium, ethanol and iodine, Iodine / Mg: 0.019 gram Atomic ratio, reaction temperature: manufactured by reacting at 78 ° C., D ₅₀ : 70 μm) 16 g was added. After heating to 50 ° C. and adding 4.8 ml of silicon tetrachloride (halogen / alkoxy group: 0.60) and stirring for 20 minutes, 2.5 ml of diethyl phthalate was added. This solution was heated to 70 ° C., followed by dropwise addition of 47 ml of titanium tetrachloride, and stirred for 2 hours at an internal temperature of 110 ° C. for contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, the temperature was raised to 90 ° C. with stirring, and the mixture was held for 1 minute. Then, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Thereafter, 77 ml of titanium tetrachloride was added, the mixture was stirred for 2 hours at an internal temperature of 110 ° C., contact operation was performed, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Thereafter, 100 ml of dehydrated octane was added and stirred at room temperature. Stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times to obtain a solid catalyst component. The evaluation results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 5
(1) Preparation of solid catalyst component
In Comparative Example 4 (1), without using the iodine, except that the average particle size was synthesized at a reaction temperature of 78 ° C. (D ₅₀₎ was used carriers diethoxymagnesium was ball 24 hours milling process 540μm are comparative examples In the same manner as in No. 4 , a solid catalyst component was prepared and evaluated. The results are shown in Table 1.

(2) Propylene polymerization In Example 2 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 2, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

Comparative Example 6
(1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 4 except that 2.4 ml of silicon tetrachloride (halogen / alkoxy group: 0.30) was used in Example 4 (1). Prepared and evaluated. The results are shown in Table 1.

(2) Propylene Polymerization In Example 1 (2), except that the solid catalyst component prepared in (1) above was used, propylene was polymerized in the same manner as in Example 1, and the resulting propylene polymer was evaluated. did. The results are shown in Table 1.

  As can be seen from Table 1, it was confirmed that the propylene polymers of the examples had high polymerization activity and were excellent in stereoregularity and powder form.

It is a schematic diagram which shows the manufacturing method of the catalyst for olefin polymerization of this invention, and an olefin polymer.

Claims (12)

The following compounds (a) to (c-1) or the following compounds (a) to (d) are reacted at a temperature of 120 ° C. or higher and 150 ° C. or lower, and an inert solvent at a washing temperature of 100 ° C. or higher and 150 ° C. or lower. A solid catalyst component for olefin polymerization obtained by washing and further reacting at least once with a halogen-containing titanium compound (a) at a temperature of 120 ° C. or more and 150 ° C. or less, and washing with an inert solvent,
After contacting the following compound (b) and the following compound (c-1), contacting the following compound (a),
A solid catalyst component for olefin polymerization in which the molar ratio (RO / Ti) of the remaining amount of alkoxy group (RO) to the amount of titanium supported (Ti) is 0.30 or less.
(A) Halogen-containing titanium compound (b) Metallic magnesium, alcohol, and an alkoxy group obtained by reacting a halogen containing 0.0001 gram atoms or more and / or a halogen-containing compound with respect to 1 mole of the metal magnesium Containing magnesium compound (c-1) Halogen containing silicon compound (d) electron donating compound having a molar ratio of halogen to alkoxy group in the alkoxy group containing magnesium compound (b) of 0.80 or more   The solid catalyst component for olefin polymerization according to claim 1, wherein a washing temperature with an inert solvent after the second and subsequent reactions is 100 ° C or higher and 150 ° C or lower.   The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the halogen and / or the halogen-containing compound contains a halogen atom of 0.0005 gram atom or more and less than 0.06 gram atom with respect to 1 mole of the metal magnesium. .   The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein a reaction temperature of the metal magnesium, alcohol, and halogen and / or halogen-containing compound is 30 to 60 ° C. The average particle diameter of the solid catalyst component according to any one of claims 1 to 4 (D ₅₀₎ is 50μm or less of the compound (b).   The said compound (b) is dialkoxy magnesium, The solid catalyst component for olefin polymerization as described in any one of Claims 1-5. The said compound ( c-1) is a silicon tetrachloride, The solid catalyst component for olefin polymerization as described in any one of Claims 1-6.   The said molar ratio (RO / Ti) is 0.20 or less, The solid catalyst component for olefin polymerization as described in any one of Claims 1-7.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 8, wherein the remaining amount of alkoxy group (RO) is 0.13 mmol / g or less.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 9, wherein the amount of titanium supported is 1.5% by weight or more. An olefin polymerization catalyst comprising the following components [A], [B] or the following components [A], [B], [C].
[A] Solid catalyst component for olefin polymerization according to any one of claims 1 to 10 [B] Organoaluminum compound [C] Electron donating compound   The manufacturing method of the olefin polymer which superposes | polymerizes an olefin using the catalyst for olefin polymerization of Claim 11.

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