JP2013213074A - METHOD FOR PRODUCING SOLID CATALYST COMPONENT FOR α-OLEFIN POLYMERIZATION, AND THE SOLID CATALYST COMPONENT - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a solid catalyst component (a) for α-olefin polymerization by which the particle diameter distribution and the average particle diameter of the solid catalyst can be controlled while keeping the high productivity, high catalytic activity and high stereoregularity, and to provide a solid catalyst component (A) capable of suppressing the formation of causative particles of short pass.SOLUTION: A method for producing a solid catalyst component (a) by bringing a magnesium compound (a1) into contact with an alkoxy titanium compound (a2), an organosilicon compound (a3), an alkoxysilicon compound (a4), an electron donor (a5), a hydroxy-containing compound (a6) and a halogen compound (a7) in an inert hydrocarbon solvent to react them includes regulating the molar ratio [(a5)/(a1)] of the component (a5) to the component (a1) to >0 and ≤0.1. The solid catalyst component (A) and the like are also provided.

Description

  The present invention relates to a process for producing a solid catalyst component (a) for α-olefin polymerization in which the average particle diameter is controlled and the solid catalyst component (A), and more specifically, the average particle diameter while maintaining a narrow particle size distribution. Is a method for producing an α-olefin polymerization solid catalyst component (a), which is arbitrarily controlled, and a polymerization activity and stereospecificity comprising a solid catalyst component (a), a vinylsilane compound, an organic Al compound and an electron donating compound. The present invention relates to an excellent solid catalyst component (A).

  Typical methods for producing polypropylene include slurry polymerization, bulk (bulk) polymerization, gas phase polymerization, and the like. In order to improve the impact resistance of polypropylene and the like, it is known to add an α-olefin copolymer to a polypropylene homopolymer. As a general method, a so-called block copolymerization is performed in which polymerization is performed (first polymerization step), and then propylene and an α-olefin other than propylene are copolymerized (second polymerization step).

In performing block copolymerization, it is advantageous to further reduce the production cost by using a method in which each component is continuously produced in different polymerization tanks as compared with a batch type (batch type). That is, in order to produce two different components (a homopolymer of propylene and a copolymer of propylene and an α-olefin other than propylene), it is said that it is preferably produced by a continuous process of two tanks, A continuous reactor having a bulk polymerization tank as a first polymerization reactor and a gas phase polymerization tank as a second polymerization reactor has become a standard production process worldwide.
In the production of olefin polymers, development of a polymerization catalyst having high polymerization performance and operability is desired particularly in a continuous reactor. In addition, in order to obtain excellent products, many studies on the improvement of polymerization catalysts and processes have been made all over the world. As a catalyst having high polymerization activity and high stereospecificity, for example, the method disclosed in Patent Document 1 has been improved.
However, there were problems regarding the quality and operability of the product obtained in the continuous reactor.

In addition, the block copolymer obtained by the two-tank continuous process generally tends to be inferior in impact resistance or the like as compared with that obtained in a batch type. This is presumed to be the following mechanism.
That is, since a residence time distribution exists in a simple two-tank continuous process, many unreacted polymers and catalyst components are transferred from the first reactor to the second reactor without passing through a predetermined residence time. The phenomenon of transport (short path) is seen. When short-passed particles are sent to the second reactor, the composition of the resulting block copolymer forms a heterogeneous state. Many of these short-passed components are thought to form a highly viscous copolymer, which tends to form fish eyes when the polymer is molded, and stress is concentrated in this area. It is often the starting point for destruction. Therefore, it causes a decrease in the quality of the block copolymer.

  Therefore, in order to improve the product quality of polypropylene, it is desirable to suppress a short path in the first reactor. Devices that suppress short paths have been studied, and studies are being made to prevent short paths using a classifier or the like. Patent Document 2 discloses a method in which a plurality of polymerization tanks are connected in series in the first polymerization step, but such a method is a multi-tank process in which a large number of reactors are installed. It is not economical from the aspect of.

In addition, a method of installing a classifier during transfer from the first reactor to the second reactor has been proposed. For example, Patent Document 3 discloses a method of concentrating and classifying polypropylene particles and removing short-passed particles. Furthermore, in Patent Document 4, there is a method in which the polymer slurry of the first reactor is withdrawn while stirring, and this is counter-currently washed to obtain a slurry with a small component of small particle size and supplied to the second reactor. .
However, such a simple classification system has some effects but has not yet been solved.
Therefore, a classification system using a cyclone method so as to obtain the maximum efficiency of classification is also proposed in Patent Document 5 and the like.
However, even with a classification system using a cyclone system, separation of particles having a small particle diameter of less than 75 μm is insufficient, and there is a disadvantage that productivity is remarkably lowered when the recycling rate is increased in order to increase classification efficiency.

The above is an example of a device proposal based on the idea of avoiding short path causative particles as much as possible. Recently, studies have been conducted to suppress the generation of causative particles of short paths. ing. As a solid catalyst for olefin polymerization, one having a narrow particle size distribution is considered desirable.
There has been proposed a method using a classification system comprising a precipitation liquid classifier after using a magnesium compound-supporting highly active catalyst having a narrow particle size distribution. For example, in Patent Document 6, when the particle size distribution of the solid catalyst component is approximated by the Rosin-Rammler distribution, the n-term indicating the particle size distribution is n ≧ 5, and the sedimentation fluid classifier is used. Thus, it is possible to improve the short path by transferring the slurry containing a large amount of large particles to the second reactor and returning the slurry containing a large amount of small particles to the first reactor. However, when the average particle size of the catalyst is excessively small, there is a problem that the catalyst stays in the first reactor for a long time. In addition, when an excessively large average particle size is used, particles extracted from the large first reactor stay in the lower part of the classifier, and polymerization proceeds locally to form a polymerized lump. It had problems such as clogging in a fluidized flash tank.

In a continuous process in which the first reactor is a bulk polymerization tank and the second reactor is a gas phase polymerization tank, the polymer slurry in the propylene liquid of the first reactor is continuously withdrawn and put into the second reactor. Some of them are equipped with a high-pressure degassing facility for vaporizing liquefied propylene during transfer and transferring gaseous propylene and a polymer to the second reactor. This is called a fluidized flash tank, and has a dispersion plate in the lower part of the tank and forms a fluidized bed by gas flow or a fluidized bed by gas flow and mechanical stirring. Therefore, even if the particle size distribution is narrow, if the polymer extracted from the first reactor is excessively large, the fluidity in the tank is lowered, and a polymerized mass is formed by a local polymerization reaction, resulting in poor extraction. In some cases, the operation of the plant must be stopped, which is disadvantageous in terms of cost. In addition, if the polymer extracted from the first reactor is too small, the entrainment in the fluid flash tank may cause clogging of the filter in the recycle line, or may cause sheeting by adhering to the tank. As a result, operation becomes difficult and the plant is stopped. Therefore, it is necessary to operate with reduced productivity. Moreover, when operating in a plant using a some catalyst, since an operating condition must be changed with the particle size of a polymer, an operating load becomes large.
From the above, there has been a strong demand for a stable production method of a solid catalyst that has a narrow particle size distribution and can control the average particle size of the solid catalyst to an appropriate value without impairing the polymerization performance.

In order to control the particle diameter of the polymer, a method of controlling the average particle diameter of the solid catalyst is effective. The following three methods for producing an olefin polymerization catalyst are known (by Edward P. Moore, Jr., Polypropylene Handbook).
1. 1. Physical route 2. Physical + chemical route Chemical route The chemical route is general, and the formation method, halogenation method, and internal donor species of the magnesium chloride used as a carrier are different for each company, and they are characterized.
In general, as a method for producing an olefin polymerization catalyst, magnesium chloride is added with alcohol such as ethanol, heated and mixed, dissolved, and then formed into a solution-like adduct, through a nozzle, a coolant or Many methods are used to spray the cooling gas. In these methods, a method of controlling the particle diameter by using two reactors and controlling the flow rate from the nozzle and the shear rate on the coolant / gas side has been proposed (see, for example, Patent Document 6). ).
These methods require a plurality of reactors, and a solid / liquid separator is often used, resulting in expensive equipment. Therefore, among chemical routes, magnesium chloride and alkoxymagnesium compounds are dissolved, and these catalyst support precursors are made of halides such as titanium tetrachloride to form magnesium chloride, and the active compound of the titanium compound that becomes the active site. The method of carrying out the loading in one reactor is advantageous in terms of the construction cost of the plant. However, when using the method in which the formation of magnesium chloride and the titanium compound are performed simultaneously, the rate of formation of dissolved magnesium chloride is remarkably fast, and it is difficult to control the particle size in a region where the stirring power is low. The stirring speed during the chemical reaction must be increased greatly. Further, when the shear rate is low, aggregates of the solid catalyst are likely to be generated, and the polymerization performance is lowered and the operability in the polymerization plant is remarkably lowered. Therefore, an invention of a technique that changes only the average particle diameter of the catalyst without impairing the polymerization performance is desired.

As a catalyst for polypropylene having a narrow particle size distribution, a method is disclosed in which an alkoxymagnesium compound, a titanium compound, a silicon compound, and an electron donor are contact-reacted and then slurried with a titanium halide compound (for example, patents). References 7 and 8).
In Patent Document 1, a liquid reaction product obtained by contacting magnesium alkoxide, titanium alkoxide, silicon alkoxide with an electron donor such as a carboxylic acid ester is subjected to contact treatment with a halogen-containing titanium compound. , A method for obtaining a solid catalyst component, and a catalyst for olefin polymerization obtained by bringing the obtained solid catalyst component into contact with an organic Al compound and an electron donor are disclosed.
However, although these methods have improved the catalyst having high polymerization activity and high stereospecificity, the controllability of the average particle diameter of the solid catalyst component has not been improved. In addition, as far as the inventors know, in terms of a method for producing a polymerization catalyst having a high productivity while maintaining a narrow particle size distribution, it is not yet sufficient, and further development of a technique for improving the polymerization catalyst is desired. ing.

Japanese Patent No. 3533734 Japanese Patent Publication No.49-12589 JP 55-116716 A JP 51-106533 A JP-A-7-286004 U.S. Pat. No. 4,399,054 Japanese Patent Laid-Open No. 10-265520 Japanese Patent No. 3354026

  In view of the above-mentioned problems of the prior art, the object of the present invention is to control the particle size distribution and the average particle size of the solid catalyst while maintaining high productivity, high catalytic activity, and high stereospecificity. The object of the present invention is to provide a method for producing a solid catalyst component (a) for olefin polymerization and a solid catalyst component (A) capable of suppressing the generation of short path causative particles.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention produced a magnesium compound (a1) represented by a specific formula under an inert hydrocarbon solvent when producing the solid catalyst component (a). In addition to the alkoxytitanium compound (a2), the organosilicon compound (a3), the alkoxysilicon compound (a4) and the electric donor (a6), the hydroxy group-containing compound (a5) is greater than 0 with respect to the magnesium compound (a1). After forming a liquid reaction product (a *) at a molar ratio of 0.1 mol / mol or less, the halogen compound (a7) is contacted and slurried, whereby the solid catalyst component (a ), A solid catalyst component (a) that can freely control only the average particle diameter can be obtained while maintaining high performance, and further desired by using this method. Ensure that Hitoshitsubu diameter of the catalyst is obtained, based on these findings, it completed the present invention, led.
The above findings are obtained from the following technical idea and mechanism of the present invention.
That is, in addition to the magnesium compound (a1), the alkoxytitanium compound (a2), the organosilicon compound (a3), the alkoxysilicon compound (a4), and the electric donor (a6) represented by the specific formula, the hydroxy group-containing compound (a5 ) Can be dispersed in a liquid or an inert solvent by contacting them in an inert solvent, and the dispersed material, ie, the reaction product (a *), is directly added to the hydroxy-containing compound (a5). In particular, an alcohol or the like is generated by reaction of some hydroxy-containing compounds with an alkoxymagnesium compound to form an emulsion. In this case, the hydroxy-containing compound has a great influence on the change in the emulsion size of the liquid or dispersed alkoxymagnesium compound. In the region where the amount of the hydroxy-containing compound is small, the emulsion size is large, and in the region where the amount of addition is large, the emulsion size is small. By halogenating this solution or dispersion using a halide (a7) such as titanium tetrachloride, the particle size of the solid catalyst component is increased in the region where the addition amount of the hydroxy-containing compound is small, and the addition amount is reduced. In many regions, the particle diameter of the solid catalyst component is small. Therefore, it has become possible to produce a solid catalyst component and a catalyst carrier having a controlled average particle diameter without greatly changing the number of stirring.

That is, according to the first invention of the present invention, in the method of producing the solid catalyst component (a) by contacting and reacting the components (a1) to (a7) shown below in an inert hydrocarbon solvent. There,
Provided is a method for producing a solid catalyst component, wherein the molar ratio [(a5) / (a1)] of the component (a5) to the component (a1) is greater than 0 and 0.1 or less.
Component (a1): Magnesium compound represented by the following general formula General formula: Mg (OR ¹ ) _n (OR ² ) _2-n
(Wherein R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, R ¹ and R ² may be the same or different, and n represents 0 ≦ n ≦ 2)
Component (a2): Alkoxytitanium compound represented by the following general formula: General formula: Ti (OR ³ ) _4-m X _m
(In the formula, R ³ represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen, and m represents 0 ≦ m <4.)
Component (a3): the general organic silicon compound represented by the formula _{^{formula: Q p SiX K (OR 4}} ) 4-p-k
(Wherein Q and R ⁴ represent an alkyl group, an aryl group or an aralkyl group which may be the same or different from each other, X represents a halogen, and p and k are 0 <p, 0 ≦ k, 0 < (The number p + k <4 is shown.)
Component (a4): Alkoxy silicon compound represented by the following general formula: General formula: Si (OR ⁵ ) ₄
(In the formula, R ⁵ represents an alkyl group, an aryl group, or an aralkyl group.)
Component (a5): hydroxyl group-containing compound represented by the following general formula: General formula: R ⁶ OH
(In the formula, R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a silicon-containing group.)
Component (a6): an electron donating compound comprising a phthalic acid derivative and / or a compound having at least two ether bonds (a7): a halogen compound represented by the following general formula: MX ₄
(In the formula, M represents an arbitrary element, and X represents halogen.)

According to the second invention of the present invention, the solid catalyst component (a) obtained from the production method according to the first invention is brought into contact with the following components (b1) to (b3). A featured solid catalyst component (A) is provided.
Component (b1): Vinylsilane compound and / or allylsilane compound Component (b2): Alkoxysilicon compound represented by the following general formula (1) General formula (1): R ⁸ R ⁹ _a Si (OR ¹⁰ ) _b
(Wherein R ⁸ represents a linear, branched or cyclic hydrocarbon group, R ⁹ represents a hydrocarbon group which is the same as or different from R ⁸ , R ¹⁰ represents a hydrocarbon group, a And b are 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3.)
Component (b3): Organoaluminum compound

  According to a third aspect of the present invention, there is provided the solid catalyst component (A) characterized in that in the second aspect, the solid catalyst component (A) is prepolymerized.

According to the production method of the solid catalyst component (a) for α-olefin polymerization of the present invention, the average particle size of the solid catalyst is maintained while maintaining high productivity, high catalytic activity, high stereospecificity and narrow particle size distribution. In the range of 6 to 12 μm, the solid catalyst component (a) that can be freely controlled can be obtained.
Moreover, the solid catalyst component (A) for α-olefin polymerization of the present invention is a solid catalyst component having an average particle size arbitrarily controlled while maintaining a narrow particle size distribution and excellent in polymerization activity and stereospecificity.
For this reason, the α-olefin polymerization catalyst including the α-olefin polymerization solid catalyst component (A) and the solid catalyst component (A) of the present invention has a very high catalytic activity. The production cost of the block copolymer can be reduced, and the stereoregularity of the resulting propylene polymer or block copolymer is high.

It is a flowchart figure for understanding the technical content of this invention regarding a Ziegler type catalyst. It is the schematic showing the manufacturing process of the polypropylene used by the Example and the comparative example.

  Hereinafter, the present invention will be described specifically and in detail with respect to the solid catalyst component (a), the production method of the solid catalyst component (a), the solid catalyst component (A), the catalyst, and the like.

1. Solid catalyst component for α-olefin polymerization (a)
In the production method of the solid catalyst component (a) of the present invention, the obtained solid catalyst component (a) for α-olefin polymerization is brought into contact with the components (a1) to (a7) shown below in an inert hydrocarbon solvent. It is a solid catalyst component (a) obtained by making it react. In particular, the following magnesium compound (a1), alkoxytitanium compound (a2), organosilicon compound (a3), alkoxysilicon compound (a4), hydroxy group-containing compound (a5) and electricity donor (a6) are preferably contacted. The solid catalyst component (a) is obtained by forming a liquid reaction product (a *) and then contacting the halogen compound (a7) for reaction.

(1-1) Magnesium compound (a1)
In the production method of the solid catalyst component (a) for α-olefin polymerization of the present invention, the magnesium compound (a1) used is represented by the following general formula.
General formula: Mg (OR ¹ ) _n (OR ² ) _2-n
(Wherein R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, R ¹ and R ² may be the same or different, and n represents 0 ≦ n ≦ 2)

Examples of the magnesium compound (a1) include Mg (OCH ₃ ) ₂ , Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₆ H ₅ ) ₂ , Mg (OCH ₂ C ₆ H ₅ ) ₂ , Mg (OC ₂ H ₅ ) Dialkoxymagnesium such as (OC ₆ H ₅ ), diaryloxymagnesium, alkyloxyaryloxymagnesium and the like. These compounds can be used alone or in combination.

(1-2) Alkoxytitanium compound (a2)
In the production method of the solid catalyst component (a) for α-olefin polymerization of the present invention, the alkoxytitanium compound (a2) used is represented by the following general formula.
General formula: Ti (OR ³ ) _4-m X _m
(In the formula, R ³ represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen, and m represents 0 ≦ m <4.)

Examples of the alkoxytitanium compound (a2) include alkoxytitanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (OC ₂ H _{5). ) 3 Cl, Ti (O-} n-C 4 H 9) 3 Cl, and a halogen-containing alkoxy titanium such as _{Ti (O-n-C 4} H 9) 2 Cl 2. These compounds can be used alone or in combination.

(1-3) Organosilicon compound (a3)
In the method for producing the solid catalyst component (a) for α-olefin polymerization of the present invention, the organosilicon compound (a3) used is represented by the following general formula.
The general ^{_{formula: Q p SiX K (OR 4}} ) 4-p-k
(Wherein Q and R ⁴ represent an alkyl group, an aryl group or an aralkyl group which may be the same or different from each other, X represents a halogen, and p and k are 0 <p, 0 ≦ k, 0 < (The number p + k <4 is shown.)

Examples of the organosilicon compound (a3) include CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ Si (On-C ₄ H ₉ ) ₃ , CH ₃ Si (OC _{6 H 5) 3, C 2} H 5 Si (OCH 3) 3, C 2 H 5 Si (OC 2 H 5) 3, C 2 H 5 Si (O-n-C 4 H 9) 3, C 2 H ₅ Si (OC ₆ H ₅ ) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H ₅ Si (OC ₂ H ₅ ) ₃ , C ₆ H ₅ Si (On-C ₄ H ₉ ) _{3 , C 6 H 5 Si (OC} 6 H 5) 3, (CH 3) 2 Si (OCH 3) 2, (CH 3) 2 Si (OC 2 H 5) 2, (CH 3) 2 Si (O-n _{-C 4 H 9) 2, (} CH 3) 2 Si (OC 6 H 5) 2, (C 2 H 5) 2 Si (OC _{3) 2, (C 2 H} 5) 2 Si (OC 2 H 5) 2, (C 2 H 5) 2 Si (O-n-C 4 H 9) 2, (C 2 H 5) 2 Si (OC _{6 H 5) 2, (C} 6 H 5) 2 Si (OCH 3) 2, (C 6 H 5) 2 Si (OC 2 H 5) 2, (C 6 H 5) 2 Si (O-n-C _{4 H 9) 2, (C} 6 H 5) 2 Si (OC 6 H 5) 2 alkyl group such as an aryl group-containing alkoxysilane or aryloxy _{silanes, CH 3 SiCl (OCH 3)} 2, CH 3 SiCl (OC ₂ H ₅ ) ₂ , CH ₃ SiCl (On-C ₄ H ₉ ) ₂ , CH ₃ SiCl (OC ₆ H ₅ ) ₂ , C ₆ H ₅ SiCl (OCH ₃ ) ₂ , C ₆ H ₅ SiCl (OC _{2 H 5) 2, C 6} H 5 SiCl (O-n-C 4 _{9) 2, C 6 H 5} SiCl (OC 6 H 5) can be exemplified alkoxysilane or aryloxy silanes containing an alkyl group or an aryl group and a halogen such as _2. These compounds can be used alone or in combination.

(1-4) Alkoxysilicon compound (a4)
In the method for producing a solid catalyst component (a) for α-olefin polymerization of the present invention, the alkoxysilicon compound (a4) used is represented by the following general formula.
General formula: Si ^(OR _{5) 4} or _{^{Si (OR 5), 4-}} s X s
(In the formula, R ⁵ represents an alkyl group, an aryl group, or an aralkyl group. X represents a halogen, and s represents a number of 0 ≦ s <4.)

Examples of the alkoxysilicon compound (a4) include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (On-C ₄ H ₉ ) ₄ , and Si (OC ₆ H ₅ ) ₄ . Halogen-containing alkoxysilanes and halogen-containing aryloxys such as alkoxysilanes, aryloxysilanes, Si (OC ₂ H ₅ ) ₃ Cl, Si (On-C ₄ H ₉ ) ₃ Cl, Si (OC ₆ H ₅ ) ₃ Cl Mention may be made of silane. These compounds can be used alone or in combination.

(1-5) Hydroxyl group-containing compound (a5)
In the method for producing the solid catalyst component (a) for α-olefin polymerization of the present invention, the hydroxyl group-containing compound (a5) used is represented by the following general formula.
General formula: R ⁶ OH
(In the formula, R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a silicon-containing group.)

  The hydroxyl group-containing compound (a5) can be used regardless of alcoholic hydroxy group or phenolic hydroxy group, and includes methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, cyclohexane. Mention may be made of alcohols such as hexanol and benzyl alcohol, silanols such as trimethylsilanol and triphenylsilanol, and phenols such as phenol, cresol, xylenol and butylphenol. These compounds can be used alone or in combination.

(1-6) Electron donating compound (a6)
In the production method of the solid catalyst component (a) for α-olefin polymerization of the present invention, the electron donor compound (a6) used is composed of a phthalic acid derivative and / or a compound having at least two ether bonds.
Examples of the phthalic acid derivative include phthalic acid, phthalic acid ester, phthalic anhydride, phthalic acid halide, phthalic acid amide, and the like. Moreover, aliphatic and aromatic alcohol can be used as alcohol which is a component of a phthalate ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group can be used. In addition, an alcohol having an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used. In addition, fluorine, chlorine, bromine, iodine, or the like can be used as the halogen which is a constituent element of phthalic acid halide. Furthermore, aliphatic and aromatic amines can be used as the amine that is a constituent of phthalic amide. Among these amines, ammonia, aliphatic amines typified by ethylamine and dibutylamine, amines having aromatic free radicals typified by aniline and benzylamine, and the like can be used.
Moreover, as a phthalic acid derivative, it can have arbitrary number of arbitrary substituents in the arbitrary positions of an aromatic ring. Examples of substituents include aliphatic radicals, aromatic radicals, aliphatic alkoxy groups, aromatic alkoxy groups, aliphatic amino groups, aromatic amino groups, halogens and the like. it can. These phthalic acid derivatives can be used in combination of a plurality of compounds. Moreover, you may have a different functional group in the same molecule. Among these, preferred are phthalic acid ester compounds typified by diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, phthalic halide compounds typified by phthaloyl dichloride, and phthalic anhydride. Representative phthalic anhydrides.

As the compound having at least two ether bonds, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. In general, it is desirable to use a compound represented by the following general formula.
_{^{R 3 O-C (R 2}} ) 2 -C (R 1) 2 -C (R 2) 2 -OR 3
(R ¹ and R ² in the above formula represent any free radical selected from the group consisting of hydrogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group. R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon. Represents a group.)

R ¹ in the above general formula represents an arbitrary radical selected from the group consisting of hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. The hydrocarbon group that can be used as R ¹ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ¹ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group. It is desirable to use. Two R ^{1 's} may combine to form one or more rings. In this case, a cyclopolyene structure containing 2 or 3 unsaturated bonds in the ring structure can be taken. Further, it may be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And alicyclic hydrocarbon groups, and aromatic hydrocarbon groups typified by phenyl groups.

R ² in the above general formula represents an arbitrary radical selected from the group consisting of hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ² can be selected from the examples of R ¹ . Preferably it is hydrogen.
R ³ in the above general formula represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, R ³ can be selected from the examples when R ¹ is a hydrocarbon group. Preferably, it is a C1-C6 hydrocarbon group, and more preferably an alkyl group. Most preferred is a methyl group.
Furthermore, when R ^{1 to} R ³ are heteroatom-containing hydrocarbon groups, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon. Regardless of whether R ^{1 to} R ³ are hydrocarbon groups or heteroatom-containing hydrocarbon groups, they may optionally contain halogen. When R ^{1 to} R ³ contain a heteroatom and / or halogen, the skeleton structure is preferably selected from the examples in the case of a hydrocarbon group. Further, the eight substituents of R ^{1 to} R ³ may be the same as or different from each other.

  Preferred examples of the compound having at least two ether bonds used in the present invention include 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2,2-diisobutyl. -1,3-diethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3- Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3- Dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, , 9-bis (methoxymethyl) fluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (Methoxymethyl) -1,2,3,4-tetrahydrofluorene, 1,1-bis (1′-butoxyethyl) cyclopentadiene, 1,1-bis (α-methoxybenzyl) indene, 1,1-bis ( Phenoxymethyl) -3,6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornadinene, and the like. These compounds having at least two ether bonds can be used alone or in combination of a plurality of compounds.

  Furthermore, alkoxysilanes can also be mentioned as compounds having at least two ether bonds. Tetramethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, t-butyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyl Dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, ethyltriethoxysilane, propyltri Ethoxysilane, isopropyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane Cyclohexyl triethoxysilane, diethyl diethoxy silane, dipropyl silane, diisopropyl diethoxysilane, diphenyl diethoxy silane, t- butyl methyl diethoxy silane, and a cyclohexyl methyl diethoxy silane.

  Of these electron donors (a6), esters and alkoxysilanes are preferably used, and esters are more preferable. Among the esters, carboxylic acid esters are more preferably used, particularly preferably phthalate esters, and most preferably diethyl phthalate.

(1-7) Liquid reaction product (a *)
In the method for producing the solid catalyst component (a) of the present invention, the obtained solid catalyst component (a) is preferably an inert hydrocarbon solvent, preferably the above magnesium compound (a1), alkoxytitanium compound (a2), organic After contacting the silicon compound (a3), the alkoxysilicon compound (a4), the hydroxy group-containing compound (a5) and the electric donor (a6) to form a liquid reaction product (a *), the following halogen compound It is a solid catalyst component (a) obtained by contacting (a7) and reacting.

Magnesium compound (a1), alkoxytitanium compound (a2), organosilicon compound (a3), alkoxysilicon compound (a4), hydroxy-containing compound (a5) and electron donation when obtaining a liquid reaction product (a *) There is no restriction | limiting in particular in the reaction sequence with a body (a6).
Further, during the reaction, an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene, xylene can be present, and it is preferable to use toluene for the production.
The reaction temperature is 60 to 250 ° C., preferably 100 to 180 ° C., and the reaction time is about 0.5 to 4 hours.

When the amounts of the above (a1) to (a6) are expressed in molar ratios, usually (a1) :( a2) :( a3) :( a4) :( a5) :( a6) = 1: 0.05 It is carried out in the range of ˜4: 0.05 to 5: 0 to 2: 0 to 5: 0.01 to 2, but in the production method of the solid catalyst component (a) of the present invention, (a1) :( a5) is preferably in the range of 1: 0 to 0.5, more preferably (a1) :( a5) is greater than 1: 0 and less than or equal to 0.5, and more preferably (a1): (A5) is greater than 1: 0 and less than or equal to 0.1, particularly preferably (a5) / (a1) is 0.01 to 0.08, most preferably (a5) / (a1) is 0. It is desirable that it is 0.01-0.05.
That is, in the present invention, in particular, the hydroxy group-containing compound (a5) is added to the magnesium compound (a1) at a molar ratio of greater than 0 to 0.1 mol / mol or less, and a liquid reaction product (a * ).

The particle size is controlled by bringing the liquid reaction product (a *) into contact with the halogen compound (a7) shown below, preferably a halogen-containing titanium compound (a7), followed by treatment at elevated temperature. A solid catalyst component (a) can be obtained. Under the present circumstances, although the density | concentration of the magnesium compound (a1) in an inert solvent can take arbitrary values, it can implement in the range of 0.01-100 mol / L, Preferably it is 0.5-1 mol / L.
The inventors of the present invention added the hydroxy group-containing compound (a5) to the magnesium compound (a1) at a molar ratio of greater than 0 and 0.1 mol / mol or less to obtain a liquid reaction product (a *). After the formation of, the halogen compound (a7) is brought into contact and slurried so that the solid catalyst component (a) can be freely controlled only for the average particle diameter while maintaining high performance of the solid catalyst component (a). This mechanism is not necessarily clear, but is considered as follows.
In other words, the mechanism by which the particle size-controlled solid catalyst component can be obtained is that the hydroxy-containing compound produces an alcohol or the like directly or by reaction of a part of the hydroxy-containing compound with an alkoxymagnesium compound. Form. In this case, the hydroxy-containing compound has a great influence on the change in the emulsion size of the liquid or dispersed alkoxymagnesium compound. The present inventors consider that the particle size of the solid catalyst component is large in the region where the amount of the hydroxy-containing compound is small, and that the particle size of the solid catalyst component is small in the region where the amount of addition is large.

(1-8) Halogen compound (a7)
In the method for producing a solid catalyst component (a) for α-olefin polymerization of the present invention, the halogen compound (a7) used is represented by the following general formula.
General formula: MX ₄
(In the formula, M represents an arbitrary element, and X represents halogen.)

Examples of the halogen compound _{(a7), TiCl 4, TiBr} 4, titanium tetrahalides such as TiI _4, and SiCl _4, silicon tetrahalide such as SiBr _4, SiI ₄ can also be used. Regardless of the transition metal or typical metal, M in the general formula can be any element as long as the effect of the present invention is not impaired. _Further, it is possible to use _{Ti (O-n-C 4} H 9) Cl 3, halogen-containing alkoxy titanium such as _{Ti (OC 6 H 5) Cl} 3, also a halogen-containing aryloxy titanium. Furthermore, alkyl halide compounds represented by Grignard reagents can also be used. Among these, a chlorine-containing titanium compound is preferable, and titanium tetrahalide is particularly preferable.

  In the contact between the liquid reaction product (a *) and the halogen compound (a7), when the temperature rises, solids are likely to precipitate and coarse particles increase. Therefore, the contact is usually at a low temperature, specifically, It is performed at a temperature of 20 ° C. or lower. In addition, Preferably, it is -80-10 degreeC, More preferably, it is performed in the range of -50-0 degreeC. Furthermore, the number of contact with the halogen compound (a7) can be performed singly or a plurality of times. When the reaction product obtained by the single contact is contacted a plurality of times, the electron donor (a6) is singly used. It is also possible to make contact with the halogen compound after contact with the electron donor and after washing, or contact with the electron donor (a6) at the same time.

  In the present invention, after the halogen compound (a7) component is contacted, the temperature is raised to 50 ° C. at 2.0 ° C./min or less, preferably 1.0 ° C./min or less, Furthermore, the solid catalyst component (a) is obtained by processing at a temperature exceeding 110 ° C. The temperature increase is not necessarily performed uniformly, and a step in which the temperature becomes constant during the process may be provided. By reducing the temperature increase rate in this way, it is possible to obtain a polymerization catalyst component having excellent particle properties and a narrow particle size distribution in terms of bulk density, particle size distribution, and fine powder amount.

The maximum temperature is higher than 110 ° C. However, if the temperature is too high, an undesirable result such as a decrease in activity is caused. Therefore, the treatment is usually performed at a temperature higher than 110 ° C and lower than 170 ° C. Is normal. The time required for one treatment at a temperature exceeding 110 ° C. is not limited, but is usually 0.5 to 12 hours. In the case where the halogen compound (a7) is treated a plurality of times, the rate of temperature increase is arbitrary in the second and subsequent treatments.
After performing the above-mentioned treatment, it can be washed with an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene, xylene, etc. to obtain a slurry of a solid catalyst component with a controlled average particle size. .

In order to obtain a solid catalyst component (a) having high performance as an olefin polymerization catalyst, preferred combinations are as follows. The amount used and contact conditions are as described above.
(A1): Mg (OR) ₂ (R: alkyl group or aryl group)
(A2): Ti (OR) ₄ (R: alkyl group)
(A3): RSi (OR) ₃ (R: aryl group and / or alkyl group)
(A4): Si (OR) ₄ (R: alkyl group)
(A5): ROH (R: aryl group and / or alkyl group)
(A6): Phthalic acid diester (a7): TiCl ₄

2. α-Olefin Polymerization Solid Catalyst Component (A)
By the method for producing a solid catalyst component (a) of the present invention, the obtained solid catalyst component (a) can be directly supplied to a reactor to obtain an olefin polymer. However, in order to obtain further excellent polymerization performance, the solid catalyst component (a) and the vinylsilane compound and / or allylsilane compound (b1), alkoxysilicon compound (b2), organic Al compound (b3) and / or It is preferable to newly form the solid catalyst component (A) by contacting with the olefin.

(2-1) Vinylsilane compound and / or allylsilane compound (b1)
The vinylsilane compound (b1a) and / or allylsilane compound (b1b) used in the present invention will be described.
As the vinylsilane compound (b1a), compounds disclosed in JP-A-2-34707 and JP-A-2003-292522 can be used. Moreover, as an allylsilane compound (b1b), the compound disclosed by Unexamined-Japanese-Patent No. 2006-169283 can be used.
These vinylsilane compounds and allylsilane compounds have a structure in which at least one hydrogen atom of monosilane (SiH ₄ ) is substituted with a vinyl group or an allyl group, and a part or all of the remaining hydrogen atoms are replaced with other free radicals. And can be represented by the following general formulas (1) and (1 ′).
[CH ₂ = CH-] _m SiX _n R ⁷ _j (OR ⁸ ) _k (1)
[CH ₂ = CH—CH ₂ —] _m SiX _n R ⁷ _j (OR ⁸ ) _k (1 ′)
(In the general formulas (1) and (1 ′), X represents halogen, R ⁷ represents hydrogen or a hydrocarbon group, R ⁸ represents hydrogen, a hydrocarbon group, or an organosilicon group. 1 ≦ m, 0 ≦ n ≦ 3, 0 ≦ j ≦ 3, 0 ≦ k ≦ 2, p + n + j + k = 4)

In the general formulas (1) and (1 ′), m represents the number of vinyl groups or allyl groups, and takes a value of 1 or more and 4 or less. More preferably, the value of m is desirably 1 or 2, particularly preferably 2. In the general formulas (1) and (1 ′), X represents a halogen, and examples thereof include fluorine, chlorine, bromine and iodine. When there are a plurality, they may be the same or different from each other. Of these, chlorine is particularly preferred. n represents the number of halogens and takes a value of 0 or more and 3 or less. More preferably, the value of n is preferably 0 or more and 2 or less, particularly preferably 0.
In the general formulas (1) and (1 ′), R ⁷ represents hydrogen or a hydrocarbon group, preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, more preferably hydrogen or a carbon atom having 1 to 12 carbon atoms. An arbitrary radical selected from a hydrogen group is represented. Preferable examples of R ⁷ include hydrogen, an alkyl group typified by a methyl group and a butyl group, a cycloalkyl group typified by a cyclohexyl group, and an aryl group typified by a phenyl group. Particularly preferred examples of R ⁷ include hydrogen, methyl group, ethyl group, phenyl group, and the like. J represents the number of R ⁷ and takes a value of 0 or more and 3 or less. More preferably, the value of j is preferably 1 or more and 3 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. When j is 2 or more, a plurality of R ⁷ may be the same as or different from each other.
R ⁷ may be an allyl group in (1) or a vinyl group in (1 ′).

In the general formulas (1) and (1 ′), R ⁸ represents hydrogen, a hydrocarbon group, or an organosilicon group. When R ⁸ is a hydrocarbon group, it can be selected from the same group of compounds as R ⁷ . When R ⁸ is an organosilicon group, it is preferably an organosilicon group having a hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of the organosilicon group that can be used as R ⁸ include alkyl group-containing silicon groups typified by trimethylsilyl groups, aryl group-containing silicon groups typified by dimethylphenylsilyl groups, and dimethylvinylsilyl groups. Vinyl group-containing silicon groups, and silicon groups formed by combining them such as propylphenylvinylsilyl groups. k represents the number of R ⁸ and takes a value of 0 or more and 2 or less. In the case of a compound having a value of k corresponding to 3, such as vinyltriethoxysilane, the performance as the vinylsilane compound (b1a) in the present invention is not exhibited, and the organosilicon compound having an alkoxy group in the present invention (b2) This is not preferable because it exhibits the performance as described above. This is considered to be the same as structurally similar to t-butyltriethoxysilane (as will be described later, this t-butyltriethoxysilane is an organosilicon compound having an alkoxy group (b2) in the present invention). It is valid). More preferably, the value of k is desirably 0 or more and 1 or less, particularly preferably 0. When the value of k is 2, two R ⁸ may be the same or different from each other. Regardless of the value of k, R ⁷ and R ⁸ may be the same or different.

These vinylsilane compounds (b1a) can be used not only alone but also in combination with a plurality of compounds. Examples of preferred compounds include CH ₂ ═CH—SiMe ₃ , [CH ₂ ═CH—] ₂ SiMe ₂ , CH ₂ ═CH—Si (Cl) Me ₂ , CH ₂ ═CH—Si (Cl) ₂ Me, _{CH 2 = CH-SiCl 3,} [CH 2 = CH-] 2 Si (Cl) Me, [CH 2 = CH-] 2 SiCl 2, CH 2 = CH-Si (Ph) Me 2, CH 2 = CH- _{Si (Ph) 2 Me, CH} 2 = CH-SiPh 3, [CH 2 = CH-] 2 Si (Ph) Me, [CH 2 = CH-] 2 SiPh 2, CH 2 = CH-Si (H) Me _{2, CH 2 = CH-Si} (H) 2 Me, CH 2 = CH-SiH 3, [CH 2 = CH-] 2 Si (H) Me, [CH 2 = CH-] 2 SiH 2, CH 2 = _{CH-SiEt 3, CH 2 =} CH-Si _{Bu 3, CH 2 = CH-} Si (Ph) (H) Me, CH 2 = CH-Si (Cl) (H) Me, CH 2 = CH-Si (Me) 2 (OMe), CH 2 = CH- Si (Me) ₂ (OSiMe ₃ ), CH ₂ ═CH—Si (Me) ₂ —O—Si (Me) ₂ —CH═CH ₂ , and the like can be given. Here, Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl.
Among _{them, CH 2 = CH-SiMe 3} , [CH 2 = CH-] 2 SiMe 2, and most _preferably from CH 2 = CH-SiMe _3.

  Similarly, the allylsilane compounds (b1b) can be used not only alone but also in combination with a plurality of compounds. Examples of preferred compounds include allyltrimethylsilane, allyltriethylsilane, allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltribromosilane, diallyldimethylsilane, diallyldiethylsilane, List diallyldivinylsilane, diallylmethylvinylsilane, diallylmethylchlorosilane, diallyldichlorosilane, diallyldibromosilane, triallylmethylsilane, triallylethylsilane, triallylvinylsilane, triallylchlorosilane, triallylbromosilane, tetraallylsilane, etc. Can do. Among these, allyltrimethylsilane is preferable.

  The vinylsilane compound (b1a) and the allylsilane compound (b1b) may be used alone or in combination. It is particularly preferable to use the vinylsilane compound (b1a) alone.

(2-2) Alkoxysilicon compound (b2)
The alkoxysilicon compound (b2) used in the present invention is a compound represented by the following general formula (1).
General formula (1): R ⁸ R ⁹ _a Si (OR ¹⁰ ) _b
(In the general formula (1), R ⁸ represents a linear, branched or cyclic hydrocarbon group, R ⁹ represents the same or different hydrocarbon group as R ^8, and R ¹⁰ represents a hydrocarbon group. A and b are 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3.)

The hydrocarbon group that can be used as R ⁸ is generally one having 1 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁸ include a branched aliphatic hydrocarbon group typified by a t-butyl group and an i-propyl group, and a cyclopentyl group (c—C ₅ H ₉ —). And a cycloaliphatic hydrocarbon group typified by a cyclohexyl group (c-C ₆ H ₁₁ ), an aromatic hydrocarbon group typified by a phenyl group, and the like. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group as R ^8. It is desirable.

In the general formula (1) of the alkoxysilicon compound (b2), R ⁹ represents a hydrocarbon group. The hydrocarbon group that can be used as R ⁹ is generally one having 1 to 20 carbon atoms, preferably one having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁹ include a linear aliphatic hydrocarbon group typified by a methyl group and an n-propyl group, an i-propyl group, and a t-butyl group. A branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group typified by a cyclopentyl group or a cyclohexyl group, an aromatic hydrocarbon group typified by a phenyl group, and the like. More preferably, it is desirable to use a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group as R ⁹ , and in particular, a methyl group, an ethyl group, an n-propyl group N-butyl group, i-butyl group, i-pentyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like are desirable. When the value of a in the organosilicon compound (b2) general formula (1) is 2 or more, a plurality of R ⁸ and R ⁹ may be the same or different.

In the general formula (1) of the alkoxysilicon compound (b2), R ¹⁰ represents a hydrocarbon group. The hydrocarbon group that can be used as R ¹⁰ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹⁰ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ¹⁰ may be the same or different.

Preferred examples of the alkoxysilicon compound (b2) used in the present invention include t-Bu (Me) Si (OMe) ₂ , t-Bu (Et) Si (OMe) ₂ , t-Bu (n-Pr) Si. _{(OMe) 2, (t-} Bu) (i-Bu) Si (OMe) 2, (t-Bu) 2 Si (OMe) 2, (c-Hex) (Me) Si (OMe) 2, (c- _{Hex) (Et) Si (OMe} ) 2, (c-Pen) 2 Si (OMe) 2, (c-Hex) (i-Bu) Si (OMe) 2, t-Bu (Me) Si (OEt) 2 _{, t-Bu (Et) Si} (OEt) 2, t-Bu (n-Pr) Si (OEt) 2, (t-Bu) (i-Bu) Si (OEt) 2, (t-Bu) 2 Si _{(OEt) 2, (c-} Hex) (Me) Si (OEt) 2, (c-Hex) _Et) Si _{(OEt) 2,} may be mentioned (c-Pen) 2 Si ( OEt) 2, and (c-Hex) (i- Bu) Si (OEt) 2. Here, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Ph = phenyl, c-Hex = cyclohexyl, c-Pen = cyclopentyl.
These organosilicon compounds can be used not only alone but also in combination with a plurality of compounds.

(2-3) Organoaluminum compound (b3)
As the organoaluminum compound (b3) used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula (5).
R ⁹ _c AlX _d (OR ¹⁰ ) _e (5)
[In General Formula (5), R ⁹ represents a hydrocarbon group. X represents halogen or hydrogen. R ¹⁰ represents a hydrocarbon group or a bridging group by Al. c ≧ 1, 0 ≦ d ≦ 2, 0 ≦ e ≦ 2, and c + d + e = 3. )

In the general formula (5), R ⁹ is a hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms. desirable. Specific examples of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In the general formula (5), X is halogen or hydrogen. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In the general formula (5), R ¹⁰ is a hydrocarbon group or a bridging group by Al. When R ¹⁰ is a hydrocarbon group, R ¹⁰ can be selected from the same group as exemplified for the hydrocarbon group of R ⁹ . Moreover, it is also possible to use alumoxane compounds represented by methylalumoxane as the organoaluminum compound (b3), in which case R ¹⁰ represents a cross-linking group of Al.

Examples of compounds that can be used as the organoaluminum compound (b3) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalumoxane, and the like. Can be mentioned. Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (b3), not only a single compound but also a plurality of compounds can be used in combination.

(2-4) Preparation of solid catalyst component (A) In the present invention, the solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) ) To obtain the solid catalyst component (A).
You may make an arbitrary component contact by arbitrary methods in the range which does not impair the effect of this invention. As the contact condition of each component, it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. In general, the following conditions are preferred.

  The contact temperature is about -50 to 200 ° C, preferably -10 to 100 ° C, more preferably 0 to 70 ° C, and particularly preferably 10 to 60 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent. Preferably, it is desirable to use a method of contacting with stirring in the presence of an inert solvent.

The amount ratio of each component constituting the solid catalyst component (A) in the present invention may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range. . The amount of the vinylsilane compound and / or allylsilane compound (b1) used is a molar ratio with respect to the titanium component constituting the solid catalyst component (a), preferably in the range of 0.001 to 1,000, particularly preferably 0. The range of .01 to 100 is desirable.
Further, the amount used in the case of using the alkoxysilicon compound (b2) is a molar ratio with respect to the titanium component constituting the solid catalyst component (a), preferably in the range of 0.01 to 1,000, particularly preferably. The range of 0.1-100 is desirable.
Further, the amount of the organoaluminum compound (b3) used is an atomic ratio of aluminum to the titanium component constituting the solid catalyst component (a) (number of moles of aluminum atom / number of moles of titanium atom), preferably 0.1 to It is within the range of 100, and particularly preferably within the range of 1-50.

  Regarding the contact procedure of the solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3), any procedure can be used. Specific examples include the following procedure (i) to procedure (iii).

Procedure (i): Method in which the solid catalyst component (a) is contacted with the vinylsilane compound and / or the allylsilane compound (b1), then the alkoxysilicon compound (b2) is contacted, and the organoaluminum compound (b3) is further contacted. Procedure (ii): Method (iii) of contacting the solid catalyst component (a) with the vinylsilane compound and / or the allylsilane compound (b1) and the alkoxysilicon compound (b2), and then contacting the organoaluminum compound (b3). : Method to contact all compounds simultaneously

  Further, any of the vinyl silane compound and / or the allyl silane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) can be brought into contact with the solid catalyst component (a) a plurality of times. In this case, the compounds used a plurality of times may be the same or different.

  In the preparation of the solid catalyst component (A), washing with an inert solvent can optionally be performed in the middle and / or finally. Examples of preferable solvent species include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

The solid catalyst component (A) in the present invention may be prepolymerized before being used in the main polymerization. Prior to the polymerization process, a small amount of polymer is generated around the catalyst in advance, so that the catalyst becomes more uniform and the generation amount of fine powder can be suppressed. As the monomer in the prepolymerization, compounds disclosed in JP-A No. 2004-124090 can be used.
Specific examples of the compound include olefins represented by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, and the like, styrene, α-methylstyrene, allylbenzene, and chlorostyrene. Styrene-like compounds typified by, etc., and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1 , 9-decadiene, divinylbenzenes, and the like, and the like. Of these, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzenes, and the like are particularly preferable.

In the case of using a prepolymerized solid catalyst component (A), the prepolymerization can be performed by an arbitrary procedure in the preparation procedure of the solid catalyst component (A).
For example, after prepolymerizing the solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) can be contacted. Moreover, after making a solid catalyst component (a), a vinylsilane compound and / or an allylsilane compound (b1), an alkoxysilicon compound (b2), and an organoaluminum compound (b3) contact, prepolymerization can also be performed.
In addition to the above, when the solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) are contacted, prepolymerization may be performed simultaneously. . In particular, preferably, after bringing the solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) into contact, prepolymerization is performed as is, or The solid catalyst component (a), the vinylsilane compound and / or the allylsilane compound (b1), the alkoxysilicon compound (b2), and the organoaluminum compound (b3) may be contacted and then washed with an inert solvent and then prepolymerized. Can be mentioned.

In the prepolymerization, the reaction conditions between the solid catalyst component (A) or the solid catalyst component (a) and the monomer can be any conditions as long as the effects of the present invention are not impaired. In general, the following range is preferable.
On the basis of the solid catalyst component (A) or the solid catalyst component (a) per gram, the prepolymerization amount is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to A range of 10 g is desirable.
Moreover, the reaction temperature at the time of prepolymerization is -150-150 degreeC, Preferably it is 0-100 degreeC. And it is desirable to make the reaction temperature at the time of preliminary polymerization lower than the polymerization temperature at the time of main polymerization. In general, the reaction is preferably carried out with stirring, and an inert solvent such as hexane or heptane can also be present. The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization.

3. Optional Components of α-Olefin Polymerization Catalyst Other optional components in the main polymerization will be described. In the present invention, it is an essential requirement to use the solid catalyst component (A) as a catalyst. However, the organoaluminum compound (B) and the organosilicon compound (C) described below are within the range not impairing the effects of the present invention. , And an optional component such as a compound (D) having at least two ether bonds can be used.

(3-1) Organoaluminum compound (B)
In the catalyst of the present invention, as the organoaluminum compound (B) used as an optional component, compounds disclosed in JP-A-2004-124090 can be used. Preferably, it can be selected from the same group as exemplified in the organoaluminum compound (b3) used in preparing the solid catalyst component (A). At this time, the organoaluminum compound (B) and the organoaluminum compound (b3) may be the same or different. The organoaluminum compound (B) can be used alone or in combination with a plurality of compounds.

(3-2) Organosilicon compound (C)
In the catalyst of the present invention, as the organosilicon compound (C) used as an optional component, compounds disclosed in JP-A No. 2004-124090 can be used. It is preferable to use a compound represented by the following general formula (6).
R ¹¹ R ¹² _f Si (OR ¹³ ) _g (6)
[In General Formula (6), R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ¹² represents an arbitrary radical selected from the group consisting of hydrogen, halogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. R ¹³ represents a hydrocarbon group. 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3. ]

In General Formula (6), R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. The hydrocarbon group that can be used as R ¹¹ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹¹ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ¹¹ , and in particular, i-propyl group, i-butyl group, t-butyl group, texyl group, cyclopentyl group, It is desirable to use a cyclohexyl group or the like.
When R ¹¹ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^11, it is desirable to select from the example of R ¹¹ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In General Formula (6), R ¹² represents hydrogen, halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. Examples of the halogen that can be used as R ¹² include fluorine, chlorine, bromine, iodine, and the like. When R ¹² is a hydrocarbon group, it generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹² include a linear aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And an aliphatic hydrocarbon group typified by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. Among these, it is desirable to use methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and the like. When R ¹² is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples in the case where R ¹¹ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable. When the value of f is 2, two R ¹² may be the same or different. Regardless of the value of f, R ¹² and R ¹¹ may be the same or different.

In the general formula (6), R ¹³ represents a hydrocarbon group. The hydrocarbon group that can be used as R ¹³ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹³ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ¹³ may be the same or different.

Preferable examples of the organosilicon compound (B) having an alkoxy group used in the present invention include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et _{) Si (OMe) 2, t} -Bu (n-Pr) Si (OMe) 2, c-Hex (Me) Si (OMe) 2, c-Hex (Et) Si (OMe) 2, c-Pen 2 Si _{(OMe) 2, i-Pr} 2 Si (OMe) 2, i-Bu 2 Si (OMe) 2, i-Pr (i-Bu) Si (OMe) 2, n-Pr (Me) Si (OMe) 2 , T-BuSi (OEt) ₃ , (Et ₂ N) ₂ Si (OMe) ₂ , Et ₂ N—Si (OEt) ₃ ,

And so on.
At this time, the alkoxysilicon compound (b2) represented by the general formula (1) and the organosilicon compound (C) used as an optional component may be the same or different. As the organosilicon compound (C), not only a single compound but also a plurality of compounds can be used in combination.

(3-3) Compound (D) having at least two ether bonds
As the compound (D) having at least two ether bonds used as an optional component in the catalyst of the present invention, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. . Preferably, the electron donor compound (a6) used in the solid catalyst component (a) can be selected from the same group as exemplified in the compound having at least two ether bonds. At this time, the compound having at least two ether bonds used in preparing the solid catalyst component (a) and the compound (D) having at least two ether bonds used as optional components of the catalyst are the same. May be different. As the compound (D) having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.

(3-4) Other optional components Unless the effects of the present invention are impaired, components other than the organoaluminum compound (B), the organosilicon compound (C), and the compound (D) having at least two ether bonds are added. It can be used as an optional component of the catalyst.
For example, as disclosed in Japanese Patent Application Laid-Open No. 2004-124090, the use of a compound (E) having a C (═O) N bond in the molecule suppresses generation of an amorphous component such as CXS. be able to. In this case, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone, etc. can be mentioned as preferred examples. An organometallic compound having a metal atom other than Al, such as diethyl zinc, can also be used.

Although the usage-amount of the arbitrary component in the catalyst of this invention may be arbitrary in the range which does not impair the effect of this invention, generally the inside of the following range is preferable.
The amount used when the organoaluminum compound (B) is used is preferably a molar ratio to the titanium component constituting the solid catalyst component (A) (number of moles of organoaluminum compound (B) / number of moles of titanium atoms), preferably 1. It is in the range of ˜1,000, and particularly preferably in the range of 10 to 500.
Further, the amount used when the organosilicon compound (C) is used is preferably a molar ratio to the titanium component constituting the solid catalyst component (A) (number of moles of organosilicon compound (C) / number of moles of titanium atoms). Is in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.
Further, when the compound (D) having at least two ether bonds is used, the amount used is the molar ratio to the titanium component constituting the solid catalyst component (A) (the number of moles of the compound (D) having at least two ether bonds). / Mol number of titanium atoms), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 1000.

4). Polymerization Any olefin having a carbon-carbon double bond can be used as the olefin used in the polymerization. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, etc. Examples include 12 α-olefins, olefins such as vinylcyclohexane and styrene, internal olefins such as 2-butene, 2-pentene, cyclopentene and cyclohexene, and silicon-containing olefins such as vinylsilane and allylsilane. These may be used alone, or after polymerization alone, a block copolymer may be produced by carrying out copolymerization as a mixture of monomers arbitrarily selected continuously. Of these olefins, α-olefins are particularly preferably used.

When an α-olefin having 3 or more carbon atoms is used among the α-olefins, a polymer rich in stereoregularity can be obtained. In particular, in the case of propylene homopolymerization using propylene and copolymerization of propylene with other α-olefins, extremely high isotacticity can be obtained. The reaction conditions are usually 1-100 atm, preferably 1-40 atm, and usually 40-120 ° C, preferably 50-90 ° C.
Moreover, as a molecular weight adjustment method of a production | generation polymer, well-known molecular weight regulators, such as hydrogen and diethyl zinc, can be added suitably.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to these Examples. The measuring method of each physical property value in the present invention is shown below.
(1) Measurement of catalyst particle size:
The particle size distribution was measured by a wet method using a laser diffraction particle size distribution measuring device (LMS-350) manufactured by Seishin Corporation. The sample was made into a suspension with an appropriate concentration using heptane as a dispersion medium. In the obtained particle size distribution, the average particle size was determined to be a particle size that was 50 wt% integrated on a volume basis.
(2) MFR:
Evaluation was performed under the conditions of 230 ° C. and 21.18 N based on JIS K6921 using a melt indexer manufactured by Takara.
(3) Polymer bulk density:
The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
(4) Polymer average particle size The particle size distribution of the powder sample was measured by a sieving method according to JIS Z8801. In the obtained particle size distribution, an average particle size was defined as a particle size that was 50 wt% integrated on a weight basis. Moreover, the uniformity coefficient (Uc = D60 / D10) and the curvature coefficient (Uc ′ = (D30) ² / (D60 × D10) were calculated using the obtained values of D10 to D90.
(5) CXS:
The sample (about 5 g) was completely dissolved once in 140 ° C. p-xylene (300 ml). Thereafter, the mixture was cooled to 23 ° C., and a polymer was precipitated at 23 ° C. for 12 hours. After the precipitated polymer was filtered off, p-xylene was evaporated from the filtrate. The polymer remaining after evaporation of p-xylene was dried under reduced pressure at 100 ° C. for 2 hours. The polymer after drying was weighed, and the value of CXS was obtained as the weight% with respect to the sample.

(6) Density:
Using the extruded strand obtained at the time of MFR measurement, the density gradient tube method was used in accordance with JIS K7112 D method.
(7) Ti content:
The sample was accurately weighed, hydrolyzed, and measured using a colorimetric method. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.
(8) Silicon compound content:
The sample was accurately weighed and decomposed with alcohol. The silicon compound concentration in the obtained alcohol solution was determined by comparing with a standard sample using gas chromatography. The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in the alcohol and the weight of the sample. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.
(9) Solvent:
The solvent was dehydrated with Molecular Sieves MS-4A and then bubbled with purified nitrogen to degas air.

[Example 1]
(1) Preparation of reaction product (a *) (contact of components (a1) to (a6))
In a 1.6 m ³ vertical stainless steel autoclave having a heat-exchangeable bellows-type baffle plate and an anchor-type stirring blade inside, and a heat insulating material provided outside the tank, Mg (OEt) ₂ : 45.0 kg And then slurried with 270.0 kg of toluene, and then charged with 86.0 kg of Ti (OBu) _4, heated to 140 ° C. with stirring at 85 rpm, reacted for 3 hours, and then stirred. The temperature was lowered to 130 ° C.
Next, a mixed solution of Me-Si (OPh) ₃ : 90.0 kg and toluene: 100 kg was dropped at a constant rate over 1 h from the upper part of the stainless steel reactor, and then the aging was performed for 2 h while maintaining the internal temperature at 130 ° C. The process was performed and the reaction solution was obtained.
Next, the temperature of the reaction solution was lowered to 25 ° C., and a mixed solution of tetraethoxysilane: 5.0 kg and toluene: 100 kg was added dropwise from the upper part of the reactor at an equal rate over 1 h, and reacted at 25 ° C. for 1 h.
Next, a mixed solution of PhOH: 0.37 kg and toluene: 10 kg was added at an equal rate from the top of the reactor, and the reaction was allowed to proceed for 1 h while maintaining at 25 ° C.
Next, a mixed solution of diethyl phthalate: 9.5 kg and toluene: 20 kg was dropped from the upper part of the reactor at an equal speed, and the concentration of Mg (OEt) _{2 in} toluene in the system was adjusted to 0.62 mol / L. Additional toluene was added to obtain a liquid reaction product (a *).

(2) Preparation of solid catalyst component (a) The obtained liquid reaction product (a *) was cooled to −10 ° C. at a stirring speed of 135 rpm and held for 0.5 h. ₄ : 320 kg was added dropwise over 2 hours. At this time, cooling was performed using a serpentine heat exchanger so that the temperature of the reactor was maintained at −10 to −5 ° C., and a solid reaction product was obtained from the liquid reaction product.
Next, the obtained reaction product was heated to 15 ° C. at 30 ° C./1 h, stirred for 1 h at 15 ° C., then heated to 50 ° C. over 1 h, held at 50 ° C. for 1 h, The temperature was raised to 120 ° C. over 1 h, and the mixture was stirred at 120 ° C. for 1 h. Next, heating and stirring were stopped, and the supernatant was removed at 100 ° C., and then washed with toluene so that the washing rate was 1/50 to obtain a solid slurry.
Further, TiCl ₄ : 400 kg was added to the obtained solid slurry at room temperature from the top of the reactor at a stirring rate of 135 rpm (TiCl ₄ treatment second time). The slurry was heated to 120 ° C. over 1 h and reacted at that temperature for 1 h.
Next, stop heating and stirring, remove the supernatant at 100 ° C., wash with toluene so that the washing rate becomes 1/100, and further add solvent with heptane so that the residual liquid rate becomes 1/200. And 45.0 kg of the solid catalyst component (a) was obtained. At this time, the average particle diameter of the obtained solid catalyst component (a) was 10.8 μm, and fine powder and coarse particles were not observed. The uniformity coefficient Uc = 1.5 and the curvature coefficient Uc ′ = 1.1 and a narrow particle size distribution were obtained.

(3) Production of prepolymerized catalyst component 10 kg of the solid catalyst component (a) obtained in Example 1 (2) was placed in a 3 m3 vertical stainless steel autoclave equipped with a stirring blade, a thermometer and a cooling jacket. Then, normal hexane was added to dilute to a solid component concentration of 5.0 (g / l).
While stirring the resulting slurry at 120 rpm, trimethylvinylsilane: 1.35 kg, t-butylmethyldiethoxysilane: 1.7 kg, and TEA: 4.75 kg were added from the top of the reactor at 15 ° C.
Then, after the addition was completed, the mixture was kept at 15 ° C. for 1 hour with continued stirring, further heated to 30 ° C., and stirred at the same temperature for 2 hours.
Next, the temperature is lowered again to 15 ° C., and 150.0 kg of propylene gas is applied to the gas phase part of the reactor for 10 hours so that the prepolymerized polymer becomes 15 kg-PP / kg-catalyst while maintaining the same temperature. The prepolymerization was performed by feeding at a constant speed. After the feed was completed, the stirring was stopped and the supernatant liquid was removed, followed by washing with normal hexane to obtain a prepolymerized catalyst slurry.
The remaining liquid ratio was 1/12. The obtained slurry of the prepolymerized catalyst had 14.6 kg of propylene polymer per 1 kg of the solid catalyst component. The content of metal Ti in the catalyst was 1.3 wt%, and the content of t-butyl methyldiethoxysilane was 7.5 wt%. The average particle diameter of the prepolymerized catalyst was 19.4 μm, and neither fine powder nor coarse particles were observed.

(4) Production of propylene polymer As shown in FIG. 2, between the liquid phase polymerization tank 1 with an internal volume of 1.7 m ^{3 and} a stirring type gas phase polymerization tank 7 with a 1.9 m ³ , a double tube Propylene polymer was continuously produced by a process incorporating a degassing system comprising a heat exchanger 3 and a fluidized flash tank 4.
In the liquid phase polymerization tank 1, liquefied propylene, hydrogen, TEA, and t-butyl ethyldimethoxysilane (TBEDMS) were continuously fed. In addition, liquefied propylene was fed at 170 kg / hr, and hydrogen was continuously fed as TEA, TBEDMS, and a molecular weight regulator. Each feed amount was adjusted to 40 molppm, 2 molppm, and 4 molppm with respect to propylene to be fed. The total pressure at this time was 3.1 MPa.
Further, the prepolymerized catalyst obtained in Example 1 (3) was fed as a solid component so as to be 0.5 g / hr. Moreover, the polymerization tank 1 was cooled so that the polymerization temperature became 70 ° C. The slurry polymerized in this polymerization tank was supplied to the fluidized flash tank 4 through the double tube heat exchanger 3 using the slurry pump 2 so as to be about 30 kg / h as polypropylene particles. The average residence time of the polypropylene particles in the liquid phase polymerization tank 1 was 1.0 h.
The polypropylene particles had an average particle diameter Dp50 of 290 μm and an average activity of 62,000 g-PP / g-cat. , MFR was 5 g / 10 min, and CXS was 1.1 wt%. The catalytic activity is defined as the polypropylene yield (g) per gram of the solid component contained in the solid catalyst component.
The polymer particles fed to the fluidized flash tank 4 through the double tube heat exchanger 3 are maintained at 70 ° C. while feeding propylene gas heated from the lower part in the fluidized flash tank 4. did. The solid polypropylene particles obtained here were sent to the gas phase polymerization tank 7 to carry out copolymerization of propylene-ethylene continuously. In order to enhance the mixing effect, a gas mixture of propylene, ethylene and hydrogen was circulated by the gas blower 10 in the gas phase polymerization tank 7 provided with an auxiliary stirring blade. Propylene and ethylene were controlled so that the pressure in the gas phase polymerization tank 7 was 1.7 MPa and the molar fraction of propylene was 55 mol%. Moreover, hydrogen was fed so that it might become 1.5 mol% with respect to propylene, ethylene, and the sum total. Moreover, ethanol was used as an activity inhibitor. The feed amount of ethanol was set to 0.5 (m.r.) with respect to Al atoms in TEA supplied accompanying the polymer particles supplied to the gas phase polymerization tank 7. While maintaining the polymerization temperature at 70 ° C., the extraction rate of the polymer from the gas phase polymerization tank 7 was adjusted to about 35 kg.
The average residence time in the gas phase polymerization tank 7 was 1.0 h. When the polymerization staying particles extracted from the gas phase polymerization tank 7 were analyzed, the average activity was 72,300 g-PP / g-cat. The MFR was 5 g / 10 min, the EPR content was 16.6% by weight, the average particle size Dp50 was 310 μm, and no fine powder or coarse particles were observed. Furthermore, the adhesion to the inside of the polymerization tank and each circulation system and the fluidity of the polymer in the fluidized flash tank 4 were good, and there was no entrainment or sheeting, and the operation was possible.

[Example 2]
In Example 1 (1), it implemented like Example 1 (1)-(4) except having added 1.1 kg of PhOH. In the same operation as in Example 1 (2), the average particle diameter of the obtained solid catalyst component (a) was 9.7 μm, and no fine powder or coarse particles were observed. The uniformity coefficient Uc = 1.6, the curvature coefficient Uc ′ = 1.1, and a narrow particle size distribution were obtained.
The average particle diameter after the prepolymerization was 18.8 μm, and the solid catalyst contained 1.4 wt% Ti and 8.0 wt% t-Bu, Me-Si (OEt) ₂ .
Further, in the polymerization operation, the average activity in the second reactor (gas phase polymerization tank) is 75,500 g-PP / g-cat. The MFR was 5.3 g / 10 min, the EPR content was 15.6 wt%, the average particle size Dp50 was 290 μm, and no fine powder or coarse particles were observed. I was able to drive without entrainment or seating.

[Example 3]
In Example 1 (1), it implemented like Example 1 (1)-(4) except having added the quantity of PhOH to 3.7 kg. In the same operation as in Example 1 (2), the average particle diameter of the obtained solid catalyst component (a) was 6.2 μm, and fine powder and coarse particles were not observed. The uniformity coefficient Uc = 1.4, the curvature coefficient Uc ′ = 1.2, and a narrow particle size distribution was obtained.
In the polymerization operation, the average activity in the second reactor (gas phase polymerization tank) was 72,400 g-PP / g-cat. Met. Under the present circumstances, the average particle diameter Dp50 of the obtained polypropylene particle | grains is 200 micrometers, the fine powder and the coarse particle were not seen, but it was able to drive | operate without a problem.

[Example 4]
In Example 1 (1), it implemented like Example 1 (1)-(4) except having added 0.12 kg of methanol instead of PhOH. The average particle size of the obtained solid catalyst component (a) was 10.7 μm in the same manner as in Example 1 (2), and no fine powder or coarse particles were observed.
Also in the polymerization operation, the average activity is 75,000 g-PP / g-cat. No fine powder or coarse particles were observed, and the drivability was good.

[Example 5]
In Example 4, it implemented like Example 4 except having added methanol: 0.38kg. The obtained solid catalyst component (a) had an average particle size of 9.5 μm, and no fine powder or coarse particles were observed.
Also in the polymerization operation, the average activity was 78,200 g-PP / g-cat. No fine powder or coarse particles were observed, and the drivability was good.

[Example 6]
In Example 4, it implemented like Example 4 except the addition amount of methanol having been 1.26 kg. The average particle diameter of the obtained solid catalyst component (a) was 6.5 μm, and fine powder and coarse particles were not observed.
Also in the polymerization operation, the average activity is 70,600 g-PP / g-cat. No fine powder or coarse particles were observed, and the drivability was good.

[Comparative Example 1]
In Example 1 (1), it implemented like Example 1 (1)-(4) except not using PhOH. The average particle size of the obtained solid catalyst component (a) was 15.2 μm by the same operation as in Example 1 (2).
In the polymerization operation, the average activity in the second reactor (gas phase polymerization tank) was 67,600 g-PP / g-cat. The average particle diameter D50 was 550 μm. At this time, poor fluidity in the fluid flash tank was confirmed, and local heat generation was observed. In addition, the product extracted from the second reactor was confirmed to be a polymerized lump or a polymer lump crushed.

[Comparative Example 2]
In Example 1 (1), it implemented like Example 1 (1)-(4) except the addition amount of PhOH having been 5.55 kg. In the same manner as in Example 1 (2), the average particle diameter of the obtained solid catalyst component (a) was 4.0 μm.
In the polymerization operation, the average activity in the second reactor (gas phase polymerization tank) was 70,300 g-PP / g-cat. The average particle diameter D50 was 110 μm. At this time, entrainment occurred in the fluidized flash tank, and productivity had to be reduced. In addition, sheeting at the top of the cyclone in the circulatory system was observed.

[Comparative Example 3]
In Example 4, it implemented like Example 4 except the addition amount of methanol having been 1.89 kg. The average particle diameter of the obtained solid catalyst component (a) was 4.1 μm.
In the polymerization operation, the average activity in the second reactor (gas phase polymerization tank) was 70,000 g-PP / g-cat. The average particle diameter D50 was 100 μm. At this time, entrainment occurred in the fluidized flash tank, and productivity had to be reduced. In addition, sheeting at the top of the cyclone in the circulatory system was observed.

  The results of Examples and Comparative Examples are summarized in Table 1.

  If the solid catalyst component (a) obtained from the method for producing a solid catalyst component of the present invention is used, an olefin polymerization catalyst (A) having an appropriate average particle size without impairing the particle size distribution, polymerization activity and stereospecificity (A ) Is obtained. When the particle size-controlled olefin polymerization catalyst thus obtained is used, a stable operation can be performed in a polymerization facility having a fluidized flash tank.

1. 1. Liquid phase polymerization tank 2. Slurry pump Double tube heat exchanger4. Fluid flush tank 5. Heat exchanger 6. 6. Gas blower 7. Gas phase polymerization tank Cyclone 9. Circulating gas cooler10. Gas blower

Claims (3)

A method for producing a solid catalyst component (a) by contacting and reacting the following components (a1) to (a7) in an inert hydrocarbon solvent,
A method for producing a solid catalyst component, wherein the molar ratio [(a5) / (a1)] of the component (a5) to the component (a1) is greater than 0 and 0.1 or less.
Component (a1): Magnesium compound represented by the following general formula General formula: Mg (OR ¹ ) _n (OR ² ) _2-n
(Wherein R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, R ¹ and R ² may be the same or different, and n represents 0 ≦ n ≦ 2)
Component (a2): Alkoxytitanium compound represented by the following general formula: General formula: Ti (OR ³ ) _4-m X _m
(In the formula, R ³ represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen, and m represents 0 ≦ m <4.)
Component (a3): the general organic silicon compound represented by the formula _{^{formula: Q p SiX K (OR 4}} ) 4-p-k
(Wherein Q and R ⁴ represent an alkyl group, an aryl group or an aralkyl group which may be the same or different from each other, X represents a halogen, and p and k are 0 <p, 0 ≦ k, 0 < (The number p + k <4 is shown.)
Component (a4): Alkoxy silicon compound represented by the following general formula: General formula: Si (OR ⁵ ) ₄
(In the formula, R ⁵ represents an alkyl group, an aryl group, or an aralkyl group.)
Component (a5): hydroxyl group-containing compound represented by the following general formula: General formula: R ⁶ OH
(In the formula, R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a silicon-containing group.)
Component (a6): an electron donating compound comprising a phthalic acid derivative and / or a compound having at least two ether bonds (a7): a halogen compound represented by the following general formula: MX ₄
(In the formula, M represents an arbitrary element, and X represents halogen.) A solid catalyst component (A) obtained by contacting the solid catalyst component (a) obtained from the production method according to claim 1 with the following components (b1) to (b3).
Component (b1): Vinylsilane compound and / or allylsilane compound Component (b2): Alkoxysilicon compound represented by the following general formula (1) General formula (1): R ⁸ R ⁹ _a Si (OR ¹⁰ ) _b
(Wherein R ⁸ represents a linear, branched or cyclic hydrocarbon group, R ⁹ represents a hydrocarbon group which is the same as or different from R ⁸ , R ¹⁰ represents a hydrocarbon group, a And b are 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3.)
Component (b3): Organoaluminum compound   The solid catalyst component (A) according to claim 2, wherein the solid catalyst component (A) is prepolymerized.

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