JP6926789B2 - Method for producing crystalline propylene polymer - Google Patents

Description

The present invention relates to a method for producing a crystalline propylene polymer. Specifically, in a method for producing a crystalline propylene polymer using a fluidized bed reactor, propylene is produced by using an organic silicon compound as a catalyst component in a specific polymerization catalyst. It relates to a polymerization method which facilitates control of the crystallinity of the above.

The propylene polymer has good mechanical properties such as rigidity and heat resistance, can be manufactured at a relatively low cost, and has excellent resource reusability and environmental protection, so it is widely applied as an important industrial material. ing.
The high rigidity, which is a characteristic of propylene polymers, is further improved by increasing the crystallinity, but depending on the application, it is necessary to control the crystallinity to a certain level. For example, in a BOPP film (biaxially stretched film) used as a food packaging material, the productivity of the stretching process of BOPP, that is, the molding speed, is better when the crystallinity of the propylene polymer used is low, and at the time of stretching. Problems such as film rupture can be prevented. Therefore, it is important to have a technology that can easily control the crystallinity according to the purpose.

Conventionally, as a method for controlling the crystallinity of a propylene polymer, a method of copolymerizing propylene with a small amount of ethylene has been known, but in this method, in order to control the crystallinity and lower the melting point at the same time, , There is a problem that the heat resistance, which is a major feature of the propylene polymer, is lowered. In addition, only a small amount of the amorphous component using the xylene-soluble component (hereinafter, also referred to as “CXS”) as an index is present.
Further, a method of controlling the crystallinity by reducing the stereoregularity of the propylene homopolymer to some extent is also known, but this method is necessary for controlling the crystallinity of the propylene polymer and at the same time for antistatic performance. It is excellent in that CXS can also be increased. However, when this method is used, the amount of Lewis base used as a donor component in the solid catalyst for polymerization is reduced, or a foreign substance such as an aluminum compound is co-supported, and the particles of the solid catalyst component are used. There are drawbacks such as a decrease in strength and an increase in the amount of fine powder polymer that causes operational troubles during the production of the propylene polymer.
In recent years, as described below, as a method for controlling the crystallinity of a propylene polymer, a method of supplying a specific organosilicon compound as a crystallinity adjusting agent to a polymerization reaction system is also known (Patent Document 1). There is.

By the way, in the production of propylene polymers, fluidized bed reactors (vertical vapor phase reactors) are attracting attention because they produce crystalline propylene polymers with less investment funds and lower energy than conventional reactors. ing.

Therefore, as a desirable method for producing a crystalline propylene polymer, a method for producing a crystalline propylene polymer using a fluidized bed reactor and controlling the crystallinity at that time is required.

Patent Document 2 is mentioned as a conventional method for controlling crystallinity in the production of a polymer by a fluidized bed reactor. The present invention is a fluidized bed reactor for producing LLDPE having different crystallinity by changing the ratio of alkylaluminum / electron donor used for polymerization. Cannot be applied.

As a method for controlling the crystallinity of the propylene polymer, as described above in paragraph 0003, a method of supplying a specific organosilicon compound as a crystallinity adjusting agent to the polymerization reaction system is known (Patent Document 1). However, when this method is applied to the vapor phase polymerization process using a fluidized bed reactor, resin lumps are formed in the reactor and there is a problem in operational stability.
Using a specific organosilicon compound as a crystallinity modifier, the crystallinity of the crystalline propylene polymer is controlled to a desired region, with high productivity, especially under conditions of very low crystallinity formation. Patent Document 3 has been proposed as a method for producing a crystalline propylene polymer. However, in this production method, the crystallinity of the obtained crystalline propylene polymer varies depending on the process fluctuations such as production amount, temperature and pressure, and the fluctuations in the amount of impurities contained in the raw materials such as propylene and organoaluminum compounds. May present problems.
Patent Document 4 has also been proposed as a method for controlling the crystallinity of a propylene polymer, and the present invention is to adjust the supply amount of a crystallinity adjusting agent for a specific organic silicon compound to be supplied to a reactor. Discloses that a propylene polymer having a desired crystallinity is produced. However, although there is an exemplary description in this document of a fluidized bed reactor, a horizontal reactor having a stirrer rotating about the horizontal axis, and the like, a specific embodiment is a horizontal reaction having a stirrer rotating about the horizontal axis. It uses a vessel, and nothing is described about its specific application to a fluidized bed reactor and its catalytic conditions. Then, when the present inventor carried out the invention of this document in a fluidized bed reactor, it was found that a resin mass was generated in the reactor and operational stability became a problem. Therefore, the fluidized bed reactor is commercially available. There was a problem that could not be implemented.

Under these circumstances, there is a demand for a method for easily and accurately controlling the crystalline propylene polymer to the required crystallinity, and in particular, a method for producing a propylene polymer using a fluidized bed reactor is utilized. At that time, there is a demand for a method for easily adjusting (controlling) the degree of crystallinity.

Japanese Unexamined Patent Publication No. 10-007727 Japanese Patent Application Laid-Open No. 2013-536301 JP-A-2009-024074 Japanese Unexamined Patent Publication No. 2014-024979

The present invention has been made in view of the above-mentioned background technology and its problems, and the subject of the present invention is to utilize a method for producing a propylene polymer using a fluidized bed reactor, in which case the production efficiency is improved. , To provide a method capable of adjusting (controlling) the crystallinity of a propylene polymer.

In order to solve the above-mentioned problems of the present invention, the present inventor utilizes a method for producing a propylene polymer using a fluidized bed reactor, and at that time, adjusts (controls) the crystallinity of the propylene polymer with high production efficiency. ) In search of a possible method, when utilizing the method for producing a propylene polymer using a fluidized bed reactor, examination of each polymerization condition in the polymerization of the propylene polymer by the fluidized bed reactor, examination of the composition of the polymerization catalyst, and examination of the composition of the polymerization catalyst We scrutinized each condition in the supply of the organic silicon compound as a crystallinity adjuster, and further refined the method of supplying liquefied propylene as a raw material.
As a result, the above-mentioned problems of the present invention can be solved by newly setting the polymerization conditions in the fluidized bed reactor, the supply conditions of the organosilicon compound, the composition of the polymerization catalyst, the supply specifications of the liquefied propylene, and the like. Recognized this, and came to create the present invention.

That is, the present invention utilizes a method for producing a propylene polymer using a fluidized bed reactor (vertical gas phase reactor), and at that time, the crystallinity of the propylene polymer can be adjusted (controlled) with high production efficiency. It is a method of setting specifications in a fluidized bed reactor, a method of supplying a liquefied propylene monomer as a raw material (which enables a stable polymerization reaction), and a setting of a polymerization catalyst containing an organic silicon compound as a crystallinity adjuster. This is a method for producing a crystalline propylene polymer, which is mainly characterized by the above.

More specifically, the present invention is a method for producing a crystalline propylene polymer by continuously polymerizing vapor phase propylene in the presence of a propylene polymerization catalyst in a fluidized bed reactor.
(I) In a fluidized bed reactor,
(I) Supply the raw material propylene monomer to the fluidized bed reactor,
(Ii) Part or all of the raw material propylene monomer is directly supplied to the fluidized bed reactor as a supplementary propylene monomer.
(Iii) The supplementary propylene monomer contains liquefied propylene and contains.
(Iv) A crystalline propylene polymer is produced from a fluidized bed reactor.
(V) The supply amount of the supplementary propylene monomer shall be 10 to 100% by weight with respect to the production amount of the crystalline propylene polymer.
(II) The catalyst for propylene polymerization contains a solid catalyst component (A) containing the following component (A1), an organoaluminum compound (B), and an organosilicon compound (C) represented by the following general formula (1). This is a method for producing a crystalline propylene polymer, which is characterized by the above. Then, the following settings are made as the polymerization catalyst.
Component (A1): Solid component containing titanium, magnesium, halogen, and a phthalic acid derivative and / or an ether compound having at least two ether bonds as an essential component Organosilicon compound (C): R ¹ R ² _a Si (OR) ³ ) _b ... (1)
(In the formula, R ¹ is a branched or cyclic hydrocarbon group having a secondary or tertiary carbon atom at the β-position of Si, and R ² is the same or different hydrocarbon group as ^{R 1.} R ³ represents a hydrocarbon group, and 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3).

The present invention has such an invention as a basic invention, and as an accompanying embodiment invention (each invention of a dependent claim) with respect to this basic invention (the invention of the independent claim of claim 1), The supply propylene is specified (claim 2), the solid catalyst component (A) is specified in more detail (claim 3), the supply of the organic silicon compound (C) is specified (claim 4), and the degree of crystallization is determined. Each invention is specified (Claim 5) and is a method for producing a propylene polymer for a food packaging film (Claim 6).

Thus, the present invention utilizes a method for producing a propylene polymer using a fluidized bed reactor, and at that time, a method capable of adjusting (controlling) the crystallinity of the propylene polymer with high production efficiency. The main features are the setting of specifications in the vessel, the method of supplying the liquefied propylene monomer of the raw material, and the setting of the polymerization catalyst containing the organic silicon compound of the crystallinity adjuster (control of crystallinity by an external donor), and the configuration described in paragraph 0013. The requirement (specific matter of the invention) is a new and exceptionally significant structure, and cannot be found in any document in the prior art.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been generally described. Therefore, the overall configuration of the present invention can be summarized as follows [1]. ] To [6].
Here, the method for producing a unique crystalline propylene polymer in [1] is configured as the basic invention [1], and each of the following inventions [2] adds ancillary requirements to the basic invention, or is the same. The embodiment is shown, and the inventions [1] to [6] are collectively referred to as the present invention.

[1] A method for producing a crystalline propylene polymer by continuously polymerizing vapor-phase propylene in the presence of a propylene polymerization catalyst in a fluidized bed reactor.
(I) In a fluidized bed reactor,
(I) Supply the raw material propylene monomer to the fluidized bed reactor,
(Ii) Part or all of the raw material propylene monomer is directly supplied to the fluidized bed reactor as a supplementary propylene monomer.
(Iii) The supplementary propylene monomer contains liquefied propylene and contains.
(Iv) A crystalline propylene polymer is produced from a fluidized bed reactor.
(V) The supply amount of the supplementary propylene monomer shall be 10 to 100% by weight with respect to the production amount of the crystalline propylene polymer.
(II) The catalyst for propylene polymerization contains a solid catalyst component (A) containing the following component (A1), an organoaluminum compound (B), and an organosilicon compound (C) represented by the following general formula (1). A method for producing a crystalline propylene polymer.
Component (A1): Solid component (A1) containing titanium, magnesium, halogen, and a phthalic acid derivative and / or an ether compound having at least two ether bonds as an essential component.
Organosilicon compound (C): R ¹ R ² _a Si (OR ³ ) _b ... (1)
(In the formula, R ¹ is a branched or cyclic hydrocarbon group having a secondary or tertiary carbon atom at the β-position of Si, and R ² is the same or different hydrocarbon group as ^{R 1.} R ³ represents a hydrocarbon group, and 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3).
[2] The propylene from the raw material propylene supply pipe is gasified propylene, and the amount of supplied propylene monomer is the sum of the amount of propylene from the raw material propylene supply pipe and the amount of supply propylene from the propylene supply pipe. The method for producing a crystalline propylene polymer according to [1], wherein the total amount is the amount of propylene consumed in the polymerization and corresponds to the amount of the propylene polymer produced.

[3] The crystalline propylene polymer according to [1], wherein the solid catalyst component (A) is formed by contact-treating the following components (A1), (A2), (A3) and (A4). Manufacturing method.
Component (A1): Solid component containing titanium, magnesium, halogen, and a phthalic acid derivative and / or an ether compound having at least two ether bonds as an essential component (A2): Vinylsilane compound and / or allylsilane compound component (A3) ): Organosilicon compound represented by the following general formula (2) R ¹¹ R ¹² _f Si (OR ¹³ ) _g ... (2)
(In the formula, R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ¹² represents any free group selected from the group consisting of hydrogen, halogen, hydrocarbon groups and heteroatom-containing hydrocarbon groups. Represented. R ¹³ represents a hydrocarbon group. 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3)
Ingredient (A4): Organoaluminium compound

[4] The method for producing a crystalline propylene polymer according to any one of [1] to [3], which comprises a step of adjusting the supply amount of the organosilicon compound (C).
[5] The method for producing a crystalline propylene polymer according to any one of [1] to [4], wherein the crystallinity is represented by a xylene-soluble component (CXS).
[6] A method for producing a propylene polymer for a food packaging film, which comprises using the method for producing a crystalline propylene polymer according to any one of [1] to [5].

The present invention utilizes a method for producing a propylene polymer using a fluidized bed reactor, and at that time, a method capable of adjusting (controlling) the crystallinity of the propylene polymer with high production efficiency, and the use of a fluidized bed reactor. This makes it possible to produce a crystalline propylene polymer with a small amount of investment and low energy as compared with a conventional reactor.
Specifically, in the method for producing a crystalline propylene polymer of the present invention, in the use of an organosilicon compound as a crystallinity adjuster, even if a silicon compound is supplied to a fluidized bed reactor, a resin mass is formed in the reactor. Can be suppressed, the silicon compound can be used as a crystallinity modifier, and the crystallinity of the propylene polymer can be efficiently controlled. Then, by directly feeding the liquefied propylene to the reactor, a stable polymerization reaction (stable operation) can be performed.

It is a structural schematic diagram of the fluidized bed reactor which showed one of the Embodiments of this invention. It is a master curve showing the relationship between the production rate and the crystallinity (CXS amount), which shows one of the embodiments of the present invention. It is a master curve which shows one of the embodiments of the present invention and reveals the relationship between the supply amount of the crystallinity adjuster (organosilicon compound (C)) and the crystallinity (CXS amount).

1. 1. Basic Configuration of the Present Invention The present invention utilizes a method for producing a propylene polymer using a fluidized bed reactor, and at that time, a method capable of adjusting (controlling) the crystallinity of the propylene polymer with high production efficiency and flowing. The main features are the setting of specifications in the bed reactor, the method of supplying the raw material propylene monomer, and the setting of the polymerization catalyst containing the organic silicon compound of the crystallinity adjuster (control of crystallinity by an external donor), which is described in paragraph 0017. The configuration in [1] is the basic configuration of the present invention. The crystallinity is specifically represented by the amount and density of CXS (xylene-soluble component of the polymer) component.
In the following, in the method for producing a crystalline propylene polymer of the present invention, the catalyst for polymerization, the production process and conditions, the use of the crystalline propylene polymer, the crystalline propylene polymer and the like will be described in detail below. Explain to.

2. Polymerization catalyst (1) Basic configuration The present invention is used as a polymerization catalyst for a crystalline propylene polymer, and as a basic configuration, as described in paragraph 0017 [1], a solid containing the following component (A1). A method for producing a crystalline propylene polymer, which comprises a catalyst component (A), an organoaluminum compound (B), and an organosilicon compound (C) represented by the following general formula (1).
Component (A1): Solid component (A1) containing titanium, magnesium, halogen, and an ether compound having a phthalic acid derivative and / or at least two ether bonds as an essential component (wherein, titanium, magnesium, and halogen are used here. At least one of the ether compounds which is an essential component and has at least two ether bonds with the phthalic acid derivative may be contained as an essential component.)
Organosilicon compound (C): R ¹ R ² _a Si (OR ³ ) _b ... (1)
(In the formula, R ¹ is a branched or cyclic hydrocarbon group having a secondary or tertiary carbon atom at the β-position of Si, and R ² is the same or different hydrocarbon group as ^{R 1.} R ³ represents a hydrocarbon group, and 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3).

(2) Detailed Provisions of Solid Catalyst Component (A) The solid catalyst component (A) is defined in detail as described in [3] of paragraph 0018 (embodiment), and the solid catalyst component (A) is described below. The components (A1), (A2), (A3) and (A4) of the above are contact-treated. In addition, (A1) is an essential component, and (A2) to (A4) are optional components.
(A1) A solid component containing titanium, magnesium, a halogen, a phthalic acid derivative, or a compound having at least two ether bonds as an essential component.
(A2) Vinylsilane compound and / or allylsilane compound,
(A3) Organosilicon compound represented by the following general formula (2) R ¹¹ R ¹² _f Si (OR ¹³ ) _g ... (2)
(In the formula, R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ¹² represents any free group selected from the group consisting of hydrogen, halogen, hydrocarbon groups and heteroatom-containing hydrocarbon groups. Represented. R ¹³ represents a hydrocarbon group. 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3)
(A4) Organoaluminium compound,

(3) Solid component (A1)
In the present invention, the solid component (A1) is an essential component of titanium (A1a), magnesium (A1b), halogen (A1c), and a phthalic acid derivative (A1d) and / or an ether compound (A1e) having at least two ether bonds. Contains as. Here, "contained as an essential component" means that any component may be contained in any form in addition to the listed components as long as the effects of the present invention are not impaired. For example, an electron donor (A1f) may be contained as an optional component.

(3-1) Titanium (A1a)
Any titanium compound can be used as the titanium source. As a typical example, a compound disclosed in JP-A-3-234707 can be mentioned.
Regarding the valence of titanium, titanium compounds having arbitrary valences of tetravalent, trivalent, divalent and 0 valent can be used, but tetravalent and trivalent titanium compounds are preferable, and tetravalent is more preferable. It is desirable to use the titanium compound of.

Specific examples of the tetravalent titanium compound include titanium halide compounds represented by titanium tetrachloride, alkoxy titanium compounds represented by tetrabutoxytitanium, and tetrabutoxytitanium dimer (BuO) ₃ Ti-O-Ti ( OBu) _{Condensed compounds of alkoxytitanium having a TIOTi bond typified by 3} , organic metal titanium compounds typified by dicyclopentadienyl titanium dichloride, and the like can be mentioned. Of these, titanium tetrachloride and tetrabutoxytitanium are particularly preferable.
Moreover, as a specific example of a trivalent titanium compound, a halogenated titanium compound represented by titanium trichloride can be mentioned. As the titanium trichloride, a compound produced by any known method such as a hydrogen-reduced type, a metallic aluminum-reduced type, a metallic titanium-reduced type, and an organoaluminum-reduced type can be used.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds. Further, a mixture of the above titanium compounds, a compound in which the average composition formula is a mixture thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), a phthalate ester, etc. Mixtures with other compounds (for example, compounds such as Ph (CO ₂ BU) ₂ and TiCl ₄ ) can be used.

(3-2) Magnesium (A1b)
Any magnesium compound can be used as the magnesium source. As a typical example, a compound disclosed in JP-A-3-234707 can be mentioned.
Generally, magnesium halide compounds typified by magnesium chloride, alkoxymagnesium compounds typified by diethoxymagnesium, metallic magnesium, oxymagnesium compounds typified by magnesium oxide, and magnesium hydroxide are typified. Hydroxymagnesium compounds, Grinard compounds typified by butylmagnesium chloride, organic metal magnesium compounds typified by butylethylmagnesium, inorganic acids typified by magnesium carbonate and magnesium stearate, and magnesium salt compounds of organic acids. , And a compound in which the average composition formula is a mixture thereof (for example, Mg (OEt) _m Cl _2-m ; a compound such as 0 <m <2) can be used. Of these, magnesium halide compounds, alkoxymagnesium compounds, Grignard compounds and the like are preferable.

When particularly large catalyst particles are produced, it is preferable to use dialkoxymagnesium whose catalyst particle size can be easily controlled. The dialkoxymagnesium may be obtained by reacting metallic magnesium with a halogen or an alcohol in the presence of a halogen-containing metal compound in the catalyst production step, as well as using one produced in advance.
Further, in the present invention, the suitable dialkoxymagnesium as the component (A1b) is in the form of granules or powder, and the shape thereof may be amorphous or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the operability of handling the produced polymer powder during the polymerization operation is improved.

The above-mentioned spherical dialkoxymagnesium does not necessarily have to be a true spherical shape, and an elliptical shape or a potato-shaped one can also be used. Specifically, the shape of the particles is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3 or less, preferably 1 to 2, and more preferably 1 to 1.5. ..
Further, as the dialkoxymagnesium, one having an average particle size of 1 to 200 μm can be used. It is preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution with less fine powder and coarse powder. Specifically, the amount of particles having a size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the amount of particles having a size of 100 μm or more is 10% or less, preferably 5% or less. Further, the particle size distribution is represented by ln (D90 / D10) (where D90 is the particle size at 90% of the integrated particle size and D10 is the particle size at 10% of the integrated particle size), which is 3 or less. It is preferably 2 or less.
Methods for producing spherical dialkoxymagnesium as described above include, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A. It is exemplified in Japanese Patent Publication No. 8-73388.

(3-3) Halogen (A1c)
As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferable.
Halogen is generally supplied from the above titanium compounds and / or magnesium compounds, but can also be supplied from other compounds. Typical examples include silicon halide compounds typified by silicon tetrachloride, aluminum halogenated compounds typified by aluminum chloride, and organic halogenated compounds typified by 1,2-dichloroethane and benzyl chloride. Halogenated borane compounds typified by trichloroborane, halogenated phosphorus compounds typified by phosphorus pentoxide, halogenated tungsten compounds typified by tungsten hexachloride, and halogenated molybdenum compounds typified by molybdenum pentoxide And so on. These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is particularly preferable.

(3-4) Phthalic acid derivative (A1d)
As the phthalic acid derivative (A1d), phthalic acid, phthalate ester, phthalic acid anhydride, phthalic acid halide, phthalic acid amide and the like can be used.
Aliphatic and aromatic alcohols can be used as the alcohol which is a component of the phthalate ester. Among these alcohols, an alcohol composed of an aliphatic free group having 1 to 20 carbon atoms such as an ethyl group, a butyl group, an isobutyl group, a heptyl group, an octyl group and a dodecyl group is preferable. More preferably, an alcohol composed of an aliphatic free group having 2 to 12 carbon atoms is desirable. Further, an alcohol composed of an alicyclic radical such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group can also be used.
Further, as the halogen which is a component of the phthalic acid halide, fluorine, chlorine, bromine, iodine and the like can be used. Of these, chlorine is the most preferable.
Further, as the amine which is a component of the phthalic acid amide, an aliphatic amine and an aromatic amine can be used. Among these amines, aliphatic amines typified by ammonia, ethylamine and dibutylamine, amines having an aromatic free group typified by aniline and benzylamine in the molecule, and the like can be exemplified as preferable compounds.

As a phthalic acid derivative, any number of substituents can be provided at any location on the aromatic ring. Examples of the substituent include an aliphatic free group, an aromatic free group, an aliphatic alkoxy group, an aromatic alkoxy group, an aliphatic amino group, an aromatic amino group, a halogen and the like. can.
These phthalic acid derivatives can be used alone or in combination with a plurality of compounds. Moreover, it may have different functional groups in the same molecule. Of these, preferred are phthalate compounds typified by diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, phthalate halide compounds typified by phthaloyl dichloride, and phthalic anhydride. Typical examples are phthalic anhydrides.

(3-5) Compound having at least two ether bonds (A1e)
As the compound (A1e) having at least two ether bonds used in the present invention, the 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 (3).
R ⁶ OC (R ⁵ ) ₂ C (R ⁴ ) ₂ C (R ⁵ ) ₂ OR ⁶ ... (3)
(In the general formula (3), R ⁴ and R ⁵ represent any free radical selected from hydrogen, hydrocarbon groups or heteroatom-containing hydrocarbon groups. R ⁶ is a hydrocarbon group or heteroatom-containing hydrocarbon. Represents a radical.)

The ^{hydrocarbon group that can be used as R 4} 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 ⁴ include a linear aliphatic hydrocarbon group represented by an n-propyl group, and a branched group represented by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group represented by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group represented by a phenyl group. More preferably, the R ^4, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group, especially, i- propyl, i- butyl, i- pentyl group, a cyclopentyl group, a cyclohexyl group , Etc. are desirable.
The two R ⁴ may form one or more rings bonded to. At this time, a cyclopolyene-based structure containing two or three unsaturated bonds in the ring structure can also be adopted. Further, it may be condensed with another cyclic structure. Regardless of whether it is a monocyclic type, a double ring type, or with or without condensation, it may have one or more hydrocarbon groups 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 a linear aliphatic hydrocarbon group represented by an n-propyl group, a branched aliphatic hydrocarbon group represented by an i-propyl group and a t-butyl group, a cyclopentyl group and a cyclohexyl group. Examples thereof include an alicyclic hydrocarbon group typified by, an aromatic hydrocarbon group typified by a phenyl group, and the like.

In the general formula (3), R ⁵ can be specifically selected from the examples of ^{R 4.} Hydrogen is preferred.
Further, in the general formula (3), R ⁶ can be specifically selected from an example in the case where ^{R 4 is a hydrocarbon group.} It is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group. Most preferably it is a methyl group.
Further, when R ^{4 to} R ⁶ are heteroatom-containing hydrocarbon groups, it is desirable that the heteroatom be selected from nitrogen, oxygen, sulfur, phosphorus, or silicon. Further ^{, regardless of whether R 4 to} R ⁶ are hydrocarbon groups or heteroatom-containing hydrocarbon groups, halogens may be optionally contained. When R ^{4 to} R ⁶ contain heteroatoms and / or halogens, the skeletal structure thereof is preferably selected from the examples of hydrocarbon groups. Further, R may be the same or different.

Preferred examples of the compound (A1e) having at least two ether bonds used in the present invention are 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 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, 9,9-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) inden, 1,1-bis (phenoxymethyl) -3,6-dicyclohexylinden, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (Methoxymethyl) -2,5-novornadinene and the like can be mentioned.
Among them, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl Particularly preferred are -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane and 9,9-bis (methoxymethyl) fluorene.
These compounds having at least two ether bonds (A1e) can be used alone or in combination of a plurality of compounds.

(3-6) Electron donor (A1f)
The solid component (A1) may contain an electron donor (A1f) as an optional component. As a typical example of the electron donor (A1f), a compound disclosed in JP-A-2004-124090 can be mentioned. Generally, organic acids and inorganic acids and their derivatives (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds and the like are used. It is desirable to use it.

Examples of the organic acid compound that can be used as an electron donor include aromatic carboxylic acid compounds typified by benzoic acid and one or two substituents at the 2-position such as 2-n-butyl-malonic acid. A large number of aliphatic compounds typified by succinic acid having one or two substituents at the 2-position or one or more substituents at the 2- and 3-positions, such as malonic acid and 2-n-butyl-succinic acid. Examples thereof include valent carboxylic acid compounds, aliphatic carboxylic acid compounds typified by propionic acid, aromatic and aliphatic sulfonic acid compounds typified by benzene sulfonic acid and methane sulfonic acid. These carboxylic acid compounds and sulfonic acid compounds may have any number of unsaturated bonds at any place in the molecule, such as maleic acid, regardless of whether they are aromatic or aliphatic.

Examples of the organic acid derivative compound that can be used as an electron donor include the above-mentioned organic acid esters, acid anhydrides, acid halides, and amides.
Aliphatic and aromatic alcohols can be used as the alcohol which is a component of the ester. Among these alcohols, an alcohol composed of an aliphatic free group having 1 to 20 carbon atoms such as an ethyl group, a butyl group, an isobutyl group, a heptyl group, an octyl group and a dodecyl group is preferable. More preferably, an alcohol composed of an aliphatic free group having 2 to 12 carbon atoms is desirable. Further, an alcohol composed of an alicyclic radical such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group can also be used.

As the halogen which is a component of the acid halide, fluorine, chlorine, bromine, iodine and the like can be used. Of these, chlorine is the most preferable. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different.
Aliphatic and aromatic amines can be used as the amine which is a component of the amide. Among these amines, aliphatic amines typified by ammonia, ethylamine and dibutylamine, amines having an aromatic free group typified by aniline and benzylamine in the molecule, and the like can be exemplified as preferable compounds.

Examples of the inorganic acid compound that can be used as an electron donor include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. It is desirable to use an ester as the derivative compound of these inorganic acids. Specific examples include tetraethoxysilane (ethyl silicate) and tetrabutoxysilane (butyl silicate).

Examples of the ether compound that can be used as the electron donor include aliphatic ether compounds typified by dibutyl ether and aromatic ether compounds typified by diphenyl ether.

Ketone compounds that can be used as electron donors include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2,2,4,6,6-pentamethyl-3, Examples thereof include polyvalent ketone compounds typified by 5-heptandione.

Examples of the aldehyde compound that can be used as an electron donor include aliphatic aldehyde compounds typified by propionaldehyde and aromatic aldehyde compounds typified by benzaldehyde.

Alcohol compounds that can be used as electron donors include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenols, phenol derivative compounds typified by cresol, glycerin and 1,1'-bi. Examples of aliphatic or aromatic polyhydric alcohol compounds represented by -2-naphthol can be exemplified.

Amine compounds that can be used as electron donors include aliphatic amine compounds typified by diethylamine, nitrogen-containing alicyclic compounds typified by 2,2,6,6-tetramethyl-piperidin, and aniline. Aromatic amine compounds typified by, nitrogen atom-containing aromatic compounds typified by pyridine, polyvalent amine compounds typified by 1,3-bis (dimethylamino) -2,2-dimethylpropane, etc. It can be exemplified.

Further, as a compound that can be used as an electron donor, a compound containing the above-mentioned plurality of functional groups in the same molecule can also be used. Examples of such compounds are 2-benzoyl-benzoic acid, which are ester compounds having an alcoholic group in the molecule represented by ethyl acetate- (2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate. Ketoester compounds typified by ethyl, ketoether compounds typified by (1-t-butyl-2-methoxyethyl) methylketone, represented by N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Amino ether compounds, halogeno ether compounds typified by epoxy chloropropane, and the like can be mentioned.

These electron donors can be used alone or in combination with a plurality of compounds. Of these, preferred are malonate ester compounds having one or two substituents at the 2-position, such as diethyl 2-n-butyl-malonate, such as diethyl 2-n-butyl-succinate. These include succinic acid ester compounds having one or two substituents at the 2-position or one or more substituents at the 2-position and the 3-position, respectively.

(3-7) Amount of Each Component in (A1) Used The amount ratio of the amount of each component used in the solid component (A1) in the present invention is arbitrary as long as the effect of the present invention is not impaired. However, in general, the following range is preferable.
The amount of the titanium compounds (A1a) used is a molar ratio (number of moles of the titanium compound / number of moles of the magnesium compound) to the amount of the magnesium compounds (A1b) used, and is preferably 0.0001 to 1. It is in the range of 000, and particularly preferably in the range of 0.01 to 10. When a compound (A1c) that is a halogen source is used in addition to the magnesium compound and the titanium compound, the amount used is regardless of whether each of the magnesium compound and the titanium compound contains halogen or not. The molar ratio (the number of moles of the halogen source compound / the number of moles of the magnesium compound) is preferably in the range of 0.01 to 1,000, particularly preferably 0, with respect to the amount of the magnesium compounds used. It is preferably in the range of 1 to 100.

When the phthalic acid derivative (A1d) and / or the compound having at least two ether bonds (A1e) is used when preparing the solid component (A1), the amount used is molar with respect to the amount of the magnesium compound used. The ratio (the number of moles of the phthalic acid derivative and / or the compound having at least two ether bonds / the number of moles of the magnesium compound) is preferably in the range of 0.001 to 10, and particularly preferably 0.01 to 5. Within the range is desirable.

When the electron donor (A1f) is used as an optional component when preparing the solid component (A1), the amount used is the molar ratio (number of moles of electron donor / magnesium compound) to the amount of the magnesium compound used. The number of moles) is preferably in the range of 0.001 to 10, and particularly preferably in the range of 0.01 to 5.

(3-8) Contact Method of Each Component The solid component (A1) in the present invention is obtained by contacting each of the above-mentioned constituent components in the above-mentioned quantitative ratio. As the contact conditions for each component, although it is necessary that oxygen is not present, any conditions can be used as long as the effects of the present invention are not impaired. Generally, the following conditions are preferable.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill or a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

When preparing the solid component (A1), washing with an inert solvent may be performed at the middle and / or at the end. Preferred 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.

Any method can be used as the method for preparing the solid component (A1) in the present invention. Specifically, the following method can be exemplified. The present invention is not limited by the following examples.

(I) A method in which a halogen-containing titanium compound represented by titanium tetrachloride is brought into contact with an alkoxy group-containing magnesium compound represented by diethoxymagnesium. If necessary, an optional component such as an electron donor or a silicon halide compound may be contacted. At this time, the optional components may be brought into contact with the halogen-containing titanium compounds at the same time, or may be brought into contact with each other separately.

(Ii) A method in which titanium-containing compounds are brought into contact with halogen-containing magnesium compounds typified by magnesium chloride.
If necessary, an optional component such as an electron donor or a silicon halide compound may be contacted. At this time, the optional components may be brought into contact with the titanium-containing compounds at the same time, or may be brought into contact with each other separately.

(Iii) Halogen-containing magnesium compounds typified by magnesium chloride are dissolved using alcohol compounds, epoxy compounds, phosphate ester compounds and the like, and halogen-containing titanium compounds typified by titanium tetrachloride. How to contact with.
Particles may be formed by spray-drying or dropping the particles into a poor solvent such as a cooled hydrocarbon solvent before contacting the titanium compounds containing halogen. Further, if necessary, an optional component such as an electron donor or a silicon halide compound may be brought into contact with the donor. At this time, the optional components may be brought into contact with the halogen-containing titanium compounds at the same time, or may be brought into contact with each other separately.

(Iv) Titanium tetrachloride is added to a solid component obtained by contacting a halogen-containing magnesium compound represented by magnesium chloride, an alkoxy group-containing titanium compound represented by tetrabutoxytitanium, and a specific polymer silicon compound component. A method of contacting a halogen-containing titanium compound represented by the above and / or a halogen-containing silicon compound represented by silicon tetrachloride.
As the polymer silicon compound, a compound represented by the following general formula (4) is suitable.
[-Si (H) (R) -O-] q ... (4)
(Here, R is a hydrocarbon group having about 1 to 10 carbon atoms, and q indicates the degree of polymerization such that the viscosity of this polymer silicon compound is about 1 to 100 centi-stokes.) Specific compound. Examples of the above include methylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and the like. Further, if necessary, an arbitrary component such as an electron donor may be brought into contact with the material. At this time, the optional components may be brought into contact with the halogen-containing titanium compounds and / or the halogen-containing silicon compounds at the same time, or may be brought into contact with each other separately.

(V) After contacting an alkoxy group-containing magnesium compound represented by diethoxymagnesium with an alkoxy group-containing titanium compound represented by tetrabutoxytitanium, a halogenating agent or a halogen represented by titanium tetrachloride is contained. A method of contacting with titanium compounds.
If necessary, an arbitrary component such as an electron donor may be brought into contact with the material. At this time, the optional components may be contacted at the same time as the halogenating agent or the titanium compounds containing halogen, or may be contacted separately.

(Vi) A method in which metallic magnesium is brought into contact with alcohol and, if necessary, iodine-containing compounds typified by iodine, and then brought into contact with halogen-containing titanium compounds typified by titanium tetrachloride.
If necessary, an optional component such as an electron donor or a silicon halide compound may be contacted. At this time, the optional components may be brought into contact with the halogen-containing titanium compounds at the same time, or may be brought into contact with each other separately.

(Vii) A method for contacting an organic magnesium compound such as a Grignard reagent typified by butylmagnesium chloride with a titanium-containing compound.
As the titanium-containing compounds, alkoxy group-containing titanium compounds typified by tetrabutoxytitanium, halogen-containing titanium compounds typified by titanium tetrachloride, and the like can be used. If necessary, an electron donor, an alkoxy group-containing silicon compound typified by tetraethoxysilane, and an arbitrary component such as a silicon halide compound may be brought into contact with each other. At this time, the optional components may be brought into contact with the titanium-containing compound at the same time, or may be brought into contact with each other separately.

Among the preparation methods exemplified above, the methods described in (i) and (v) above are particularly preferable. By using these methods, a catalyst having a large particle size suitable for the vapor phase polymerization process can be prepared.
In each of the above methods, the essential components, a phthalic acid derivative and / or an ether compound having at least two ether bonds, are also appropriately contacted.

(4) Vinylsilane compound and / or allylsilane compound (A2)
The vinylsilane compound (A2a) and / or the allylsilane compound (A2b) used in the present invention will be described.
As the vinylsilane compound (A2a), a compound disclosed in JP-A-2003-292522 can be used. Further, as the allylsilane compound (A2b), the compound disclosed in JP-A-2006-169283 can be used. These vinylsilane compounds and allylsilane compounds are monosilanes (compounds having a structure in which at least one of SiH is replaced with a vinyl group or an allyl group and some or all of the remaining hydrogen atoms are replaced with other free radicals). , Can be expressed by the following general formulas (5) and (5').
[CH ₂ = CH-] _m SiX _n R ⁷ _j (OR ⁸ ) _k … (5)
[CH ₂ = CH-CH _2- ] _m SiX _n R ⁷ _j (OR ⁸ ) _k ... (5')
(In the general formulas (5) and (5'), X represents a halogen. R ⁷ represents a hydrogen or a hydrocarbon group. R ⁸ represents a hydrogen, a hydrocarbon group or an organic silicon group. 1 ≦ m ≦ 4,0 ≦ n ≦ 3,0 ≦ j ≦ 3,0 ≦ k ≦ 2, m + n + j + k = 4)

In the general formulas (5) and (5'), 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 preferably 1 or 2, and particularly preferably 2.
Further, in the general formulas (5) and (5'), X represents a halogen, and fluorine, chlorine, bromine, iodine and the like can be exemplified. When there are a plurality of them, they may be the same or different from each other. Of these, chlorine is particularly preferable. 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 0 or more and 2 or less, and particularly preferably 0.
Further, in the general formulas (5) and (5'), R ⁷ represents a hydrogen or a hydrocarbon group, preferably a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. Represents any free group selected from the hydrocarbon groups of. Examples of preferable R ⁷ include hydrogen, an alkyl group typified by a methyl group and a butyl group, a cycloalkyl group typified by a cyclohexyl group, an aryl group typified by a phenyl group, and the like. Particularly preferable R ⁷ includes a methyl group, an ethyl group, a phenyl group and the like.
j represents the number of ^{R 7,} it takes a value of 0 to 3. 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 Rs may be the same or different from each other.
Further, R ⁷ may be an allyl group in the general formula (5) or a vinyl group in the general formula (5').

In the general formulas (5) and (5'), R ⁸ represents a hydrogen, hydrocarbon group or organosilicon group. When R ⁸ is a hydrocarbon group, it can be selected from the same hydrocarbon groups 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 organic silicon group that can be used as R ⁸ include an alkyl group-containing silicon group represented by a trimethylsilyl group, an aryl group-containing silicon group represented by a dimethylphenylsilyl group, and a dimethylvinylsilyl group. Examples thereof include a vinyl group-containing silicon group and a silicon group formed by combining them such as a propylphenylvinylsilyl group.
k represents the number of ^{R 8,} take 0 to 2 values. On the other hand, in the case of a compound such as vinyltriethoxysilane in which the value of k corresponds to 3, the performance as the vinylsilane compound (A2a) in the present invention is not exhibited, and the organosilicon compound having an alkoxy group in the present invention ( It is not preferable because it exhibits the performance as C). It is considered that this is because it behaves in the same manner as t-butyltriethoxysilane which is structurally close to each other (as described later, this t-butyltriethoxysilane is used as the organosilicon compound (C) having an alkoxy group in the present invention. It is valid). More preferably, the value of k is preferably 0 or more and 1 or less, and particularly preferably 0. If the value of k is 2, two R ⁸ may be different and be identical to one another. Further, regardless of the value of k, R ⁷ and R ⁸ may be the same or different.

These vinylsilane compounds (A2a) 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-SiBu 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 mentioned. Among these, CH ₂ = CH-SiMe ₃ and [CH ₂ = CH-] ₂ SiMe ₂ are more preferable, and [CH ₂ = CH-] ₂ SiMe ₂ is most preferable.

Similarly, the allylsilane compounds (A2b) 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, Examples thereof include diallyldivinylsilane, diallylmethylvinylsilane, diallylmethylchlorosilane, diallyldichlorosilane, diallyldibromosilane, triallylmethylsilane, triallylethylsilane, triallylvinylsilane, triallylchlorosilane, triallylbromosilane, and tetraallylsilane. can. Among these, diallyldimethylsilane is preferable.

The vinylsilane compound (A2a) and the allylsilane compound (A2b) may be used alone or in combination of both. Particularly preferably, it is desirable to use the vinylsilane compound (A2a) alone.

(5) Organosilicon compound (A3)
The organosilicon compound (A3) used in the present invention is an organosilicon compound represented by the following general formula (2), which has a function of controlling crystallinity by an external donor.
R ¹¹ R ¹² _f Si (OR ¹³ ) _g ... (2)
(In the formula, R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ¹² represents any free group selected from the group consisting of hydrogen, halogen, hydrocarbon groups and heteroatom-containing hydrocarbon groups. Represented. R ¹³ represents a hydrocarbon group. 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3)

In the general formula (2), the ^{hydrocarbon group that can be used as R 11} generally has 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ¹¹ include a branched aliphatic hydrocarbon group typified by an i-butyl group and a 2,2-dimethyl-propyl group, and a cyclopentyl-methyl group (c-). Alicyclic hydrocarbon groups typified by C ₅ H _9- CH _2- ) and cyclohexyl-methyl groups (c-C ₆ H _11- CH _2- ), aromatic hydrocarbon groups typified by benzyl groups, etc. Can be mentioned. More preferably, the R ^11, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group, especially, i- butyl group, 2,2-dimethyl - propyl, 2-methyl - butyl , Cyclopentyl-methyl group, cyclohexyl-methyl group and the like are desirable.

In the general formula (2), the ^{hydrocarbon group that can be used as R 12} 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 ¹² include a linear aliphatic hydrocarbon group represented by a methyl group and an n-propyl group, an i-propyl group, an i-butyl group, and t-. Examples thereof include a branched aliphatic hydrocarbon group represented by a butyl group, an alicyclic hydrocarbon group represented by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group represented by a phenyl group. More preferably, the R ^12, a linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, or, it is desirable to use an alicyclic hydrocarbon group, especially, a methyl group, an ethyl group, n- propyl It is desirable to use a group, n-butyl group, i-butyl group, i-pentyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like. When the value of f is 2, a plurality of R ^12s may be the same or different.

In the general formula (2), 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 include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branched aliphatic hydrocarbon group represented by an i-propyl group and a t-butyl group, and the like. Can be mentioned. Of these, a methyl group and an ethyl group are most preferable. When the value of g is 2 or more, a plurality of R ^13s may be the same or different.

As a preferable example of the organosilicon compound (A3) used in the present invention,
(I-Bu) ₂ Si (OMe) ₂ , (i-Pr) (i-Bu) Si (OMe) ₂ , (i-Pen) (i-Bu) Si (OMe) ₂ , (i-Bu) ( Me) Si (OMe) ₂ , (i-Bu) (Et) Si (OMe) ₂ , (i-Bu) (n-Pr) Si (OMe) ₂ , (i-Bu) (n-Bu) Si ( OMe) ₂ , t-BuCH ₂ (Me) Si (OMe) ₂ , t-BuCH ₂ (Et) Si (OMe) ₂ , t-BuCH ₂ (n-Pr) Si (OMe) ₂ , (t-BuCH ₂₎ ) (I-Bu) Si (OMe) ₂ , (t-BuCH ₂ ) ₂ Si (OMe) ₂ , (c-HexCH ₂ ) (Me) Si (OMe) ₂ , (c-HexCH ₂ ) (Et) Si (OMe) ₂ , (c-PenCH ₂ ) ₂ Si (OMe) ₂ , (c-HexCH ₂ ) (i-Bu) Si (OMe) _{2, and the} like can be mentioned.
These organosilicon compounds can be used not only alone but also in combination with a plurality of compounds.

(6) Organoaluminium compound (A4)
As the organoaluminum compound (A4) used in the present invention, a compound disclosed in JP-A-2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula (6).
R ⁹ _c AlX _d (OR ¹⁰ ) _e ... (6)
(In the general formula (6), R ⁹ represents a hydrocarbon group. X represents a halogen or hydrogen. R ¹⁰ represents a hydrocarbon group or a bridging group by Al. C ≧ 1, 0 ≦ d ≦ 2, 0 ≦ e ≦ 2, c + d + e = 3)

In the general formula (6), R ⁹ is a hydrocarbon group, preferably one having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group and the like. Of these, a methyl group, an ethyl group and an isobutyl group are most preferable.
Further, in the general formula (6), X is halogen or hydrogen. Examples of the halogen that can be used as X include fluorine, chlorine, bromine, and iodine. Of these, chlorine is particularly preferable.
Further, in the general formula (6), R ¹⁰ is a hydrocarbon group or a cross-linking group by Al. When R ¹⁰ is a hydrocarbon group, ^{R 10} can be selected from the same group as in the example of the hydrocarbon group of ^{R 9.} Further, as the organoaluminum compound (A4), almoxane compounds typified by methylarmoxane can also be used, in which case R ^l0 represents a crosslinked group by Al.

Examples of compounds that can be used as the organic aluminum compound (A4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, and methylalmoxane. Can be mentioned. Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (A4), not only a single compound can be used, but also a plurality of compounds can be used in combination.

(7) Method for preparing solid catalyst component (A) The solid catalyst component (A) in the present invention is (A1) a solid component, (A2) a vinylsilane compound, and / or an allylsilane compound, and (A3) the following general formula (2). ), Organosilicon compounds,
R ¹¹ R ¹² _f Si (OR ¹³ ) _g ... (2)
(In the formula, R ¹¹ is a hydrocarbon group or a heteroatom-containing hydrocarbon group, and R ¹² represents any free group selected from the group consisting of hydrogen, halogen, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ¹³ represents a hydrocarbon group. 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3) and (A4) an organic aluminum compound are brought into contact with each other. At this time, arbitrary components may be brought into contact with each other by any method as long as the effects of the present invention are not impaired. As the contact conditions for each component of the solid catalyst component (A), although it is necessary that oxygen is not present, any condition can be used as long as the effects of the present invention are not impaired. Generally, the following conditions are preferable.

The contact temperature is about −50 ° C. to 200 ° C., preferably −10 ° C. to 100 ° C., more preferably 0 ° C. to 70 ° C., and particularly preferably 10 ° C. to 60 ° C.
Further, as the contact method, a mechanical method using a rotary ball mill, a vibration mill, or the like, a method of contacting by stirring in the presence of an inert diluent, and the like can be exemplified. Preferably, it is desirable to use a method of contacting by stirring in the presence of the Inactive Diluent.

The amount ratio of the amount of each component used to constitute the solid catalyst component (A) in the present invention may be arbitrary as long as the effect of the present invention is not impaired, but generally, the following range is used. preferable.
The amount of the vinylsilane compound and / or the allylsilane compound (A2) used is the molar ratio of the titanium component constituting the solid component (A1) (the number of moles of the vinylsilane compound and / or the allylsilane compound (A2) / the number of moles of titanium atoms). It is preferably in the range of 0.001 to 1,000, and particularly preferably in the range of 0.01 to 100.
When the organic silicon compound (A3) represented by the general formula (2) is used, the amount used is the molar ratio to the titanium component constituting the solid component (A1) (the organic silicon compound represented by the general formula (2)). The number of moles of (A3) / the number of moles of titanium atoms) is preferably in the range of 0.01 to 1,000, and particularly preferably in the range of 0.1 to 100.

Further, it is preferable to adjust the content of the organosilicon compound (A3) represented by the general formula (2) in the solid catalyst component (A) to a certain range. If the amount of (A3) supported is too high, the density of the obtained crystalline propylene polymer is too high or the CXS is too low, which is not preferable. On the contrary, if the amount of (A3) supported is too low, the density is too low or the CXS is too high, which is not preferable. The relationship between the amount used and the amount supported in (A3) differs depending on the method for adjusting the solid component (A1) and the solid catalyst component (A). It can be a preferable carrying amount.
The preferred range of the content of the organosilicon compound (A3) represented by the general formula (2) in the solid catalyst component (A) is 2 to 10 wt%, more preferably 3 to 10 wt%, still more preferably 3 to 8 wt%. %, Most preferably 4-7 wt%.

Further, the amount of the organic aluminum compound (A4) used is the atomic ratio of aluminum to the titanium component constituting the solid component (A1) (number of moles of aluminum atom / number of moles of titanium atom), preferably 0.1 to 100. It is preferably in the range of 1 to 50, particularly preferably in the range of 1 to 50.

For the contact procedure of (A1) solid component, (A2) vinylsilane compound and / or allylsilane compound, (A3) organosilicon compound represented by the general formula (2), and (A4) organoaluminum compound, any procedure can be performed. Can be used. Specific examples include the following procedures (i) to (iii).

Procedure (i): (A1) The solid component is contacted with (A2) a vinylsilane compound and / or an allylsilane compound, and then (A3) an organosilicon compound represented by the general formula (2) is contacted, and further (A4). A method of contacting organoaluminum compounds.
Procedure (ii): (A1) a solid component is contacted with (A2) a vinylsilane compound and / or an allylsilane compound, (A3) an organosilicon compound represented by the general formula (2), and then (A4) an organoaluminum compound. How to make contact.
Procedure (iii): A method of contacting all compounds at the same time.

Further, with respect to (A1) a solid component, a plurality of (A2) vinylsilane compound and / or allylsilane compound, (A3) organosilicon compound represented by the general formula (2), and (A4) organoaluminum compound are all present. Can be contacted several times. At this time, the compounds used a plurality of times may be the same or different from each other.
Further, when preparing the solid catalyst component (A), washing may be carried out with an inert solvent in the middle and / or at the end. Preferred 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.

(8) Essential components other than the solid catalyst component (A) In the present invention, it is essential to use the solid catalyst component (A) and the organoaluminum compound (B) and the organosilicon compound (C), which will be described later, as the catalyst. It is a requirement. Further, any component such as compound (D) having at least two ether bonds can be used as long as the effect of the present invention is not impaired.

(8-1) Organoaluminium compound (B)
As the organoaluminum compound (B) used as an essential component in the catalyst of the present invention, a compound disclosed in JP-A-2004-124090 can be used. Preferably, it can be selected from the same group as the examples in the organoaluminum compound (A4) used in preparing the solid catalyst component (A). At this time, the organoaluminum compound (B) and the organoaluminum compound (A4) may be the same or different.
As the organoaluminum compound (B), not only a single compound can be used, but also a plurality of compounds can be used in combination.

(8-2) Organosilicon compound (C)
As the organosilicon compound (C) used as an essential component in the catalyst of the present invention, a compound disclosed in JP-A-2004-124090 can be used and is represented by the following general formula (1). Use a compound.
R ¹ R ² _a Si (OR ³ ) _b ... (1)
(In the general formula (1), R ¹ is a branched or cyclic hydrocarbon group having a secondary or tertiary carbon atom at the β-position of Si, and R ² is a hydrocarbon that is the same as or different from ^{R 1.} It is a group, and R ³ represents a hydrocarbon group, and 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3.

The ^{hydrocarbon group that can be used as R 1} 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 ¹ include a branched aliphatic hydrocarbon group represented by an i-propyl group and a t-butyl group, and an alicyclic group represented by a cyclopentyl group and a cyclohexyl group. Examples thereof include an aromatic hydrocarbon group represented by a formula hydrocarbon group and a phenyl group. More preferably, a ^{branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group is used as R 1} , and in particular, an i-propyl group, an i-butyl group, a t-butyl group, a texyl group, a cyclopentyl group, and the like. It is desirable to use a cyclohexyl group, etc.

In the general formula (1), R ² is R ¹ the same or different hydrocarbon radicals, to the R ¹ may be selected from the hydrocarbon group described above, select another straight hydrocarbon group But it's okay.
R ² is a hydrocarbon group, generally 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 include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, and a branched aliphatic group represented by an i-propyl group and a t-butyl group. Examples thereof include an alicyclic hydrocarbon group represented by a hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group represented by a phenyl group. Among them, it is desirable to use a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group and the like. Of these, a methyl group and an ethyl group are most preferable.
In the general formula (1), when the value of a is 2, R ² existing in plural may be the same or different.

In the general formula (1), R ³ represents a hydrocarbon group. The ^{hydrocarbon group that can be used as R 3} 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 include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branched aliphatic hydrocarbon group represented by an i-propyl group and a t-butyl group, and the like. Can be mentioned. Of these, a methyl group and an ethyl group are most preferable. If the value of b is 2 or more, R ³ existing in plural numbers may be the same or different.

Preferred examples of the organosilicon compound (C) having an alkoxy group used in the present invention are t-Bu (Me) Si (OME) ₂ , t-Bu (Me) Si (OEt) ₂ , and 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 ,

などを挙げることができる。
この際、一般式（２）で表わされる任意成分の有機ケイ素化合物（Ａ３）と一般式（１）で表され必須成分として用いられる有機ケイ素化合物（Ｃ）とが同一であっても異なっても良い。
有機ケイ素化合物（Ｃ）は、単独の化合物を用いるだけでなく、複数の化合物を併用することもできる。

And so on.
At this time, whether the organosilicon compound (A3) having an arbitrary component represented by the general formula (2) and the organosilicon compound (C) represented by the general formula (1) as an essential component are the same or different. good.
As the organosilicon compound (C), not only a single compound can be used, but also a plurality of compounds can be used in combination.

(8-3) Compound having at least two ether bonds (optional component)
In the catalyst of the present invention, as the compound having at least two ether bonds used as an optional component, the compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. Preferably, it can be selected from the same group as in the example of the compound (A1e) having at least two ether bonds used in the solid catalyst component (A). At this time, the compound (A1e) having at least two ether bonds used when preparing the solid catalyst component (A) and the compound having at least two ether bonds used as an optional component of the catalyst are the same. May be different.
As the compound having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.

(8-4) Other compounds (optional components)
As long as the effect of the present invention is not impaired, a component other than the above compound having at least two ether bonds can be used as an optional component of the catalyst. For example, as disclosed in Japanese Patent Application Laid-Open No. 2004-124090, the formation of an amorphous component such as CXS can be suppressed by using a compound having a C (= O) N bond in the molecule. can. In this case, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone and the like can be mentioned as preferred examples. Further, an organometallic compound having a metal atom other than Al, such as diethylzinc, can also be used.

(8-5) Amount of component other than the solid catalyst component (A) The amount of the above component used in the catalyst of the present invention may be arbitrary as long as the effect of the present invention is not impaired, but is generally used. , The following range is preferable.
The amount of the organoaluminum compound (B) used is the molar ratio (the number of moles of the organoaluminum compound (B) / the number of moles of titanium atoms) to the titanium component constituting the solid catalyst component (A), preferably 1-1. It is in the range of 000, and particularly preferably in the range of 10 to 500.
The amount of the organosilicon compound (C) used is commensurate with the degree of crystallization, but the molar ratio to the titanium component constituting the solid catalyst component (A) (the number of moles of the organosilicon compound (C) / the number of moles of titanium atoms). ), It is preferably in the range of 0.01 to 10,000, and particularly preferably in the range of 0.5 to 500.
Further, when the compound (D) having at least two ether bonds, which is an optional component, is used, the amount used is a molar ratio to the titanium component constituting the solid catalyst component (A) (a compound having at least two ether bonds (D). ) / The number of moles of titanium atoms), preferably in the range of 0.01 to 10,000, and particularly preferably in the range of 0.5 to 500.

3. 3. Use of Polymerization Catalyst (1) Prepolymerization The solid catalyst component (A) in the present invention may be prepolymerized before being used in the main polymerization. By forming a small amount of polymer around the catalyst in advance prior to the polymerization process, the catalyst becomes more uniform and the amount of fine powder generated can be suppressed.

As the monomer in the prepolymerization, a compound disclosed in JP-A-2004-124090 can be used.
Specific examples of the compound include olefins typified by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, styrene, α-methylstyrene, allylbenzene, chlorostyrene and the like. Styrene-like compounds typified by, and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,9- Examples thereof include diene compounds typified by decadien and divinylbenzene. Among them, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzene and the like are particularly preferable.

When a prepolymerized solid catalyst component (A) is used, the prepolymerization can be carried out by any procedure in the procedure for preparing the solid catalyst component (A). For example, after (A1) the solid component is prepolymerized, (A2) a vinylsilane compound and / or an allylsilane compound, (A3) an organosilicon compound represented by the general formula (1), and (A4) an organoaluminum compound are brought into contact with each other. be able to.
Further, after contacting (A1) a solid component, (A2) a vinylsilane compound and / or an allylsilane compound, (A3) an organosilicon compound represented by the general formula (1), and (A4) an organoaluminum compound, prepolymerization is performed. You can also do it.
In addition to the above, when contacting (A1) a solid component, (A2) a vinylsilane compound, and / or an allylsilane compound, (A3) an organosilicon compound represented by the general formula (1), and (A4) an organoaluminum compound. , Prepolymerization may be performed at the same time.
Particularly preferably, after contacting a compound having (A1) a solid component, (A2) a vinylsilane compound, and / or an allylsilane compound, (A3) an organosilicon compound represented by the general formula (1), and (A4) an organoaluminum. It is desirable to perform prepolymerization.
Further, prepolymerization may be performed when the catalyst is prepared from the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C) represented by the general formula (1).

As the reaction conditions between the solid catalyst component (A) or the solid component (A1) and the above-mentioned monomer, any conditions can be used as long as the effects of the present invention are not impaired. Generally, the following range is preferable.
On the basis of 1 gram of the solid catalyst component (A) or the solid component (A1), the amount of prepolymerization is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, and more preferably 0.5 to 0.5. The range of 10 g is desirable. The reaction temperature during prepolymerization is −150 to 150 ° C., preferably 0 to 100 ° C. Then, it is desirable that the reaction temperature at the time of prepolymerization is lower than the polymerization temperature at the time of main polymerization. The reaction is generally preferably carried out under stirring, at which time an inert solvent such as hexane or heptane can be present.
The prepolymerization may be carried out a plurality of times, and the monomers used at this time may be the same or different. Further, after the prepolymerization, the washing can be performed with an inert solvent such as hexane or heptane.

(2) Production process (2-1) Basic mode The production process of the crystalline propylene polymer is a vapor phase method in which the raw material propylene is polymerized in a vapor phase state, and the mixing mode is a flow bed. be. That is, it is a method for producing a crystalline propylene polymer by continuously polymerizing vapor phase propylene in the presence of a propylene polymerization catalyst in a fluidized bed reactor.
The number of polymerization tanks in the fluidized bed reactor (vertical gas phase reactor) may be one or more. When there are a plurality of polymerization tanks, they may be connected in series or in parallel. Further, when there are a plurality of polymerization tanks, the organosilicon compound (C) as a catalyst component as a crystallinity adjusting agent may be charged into only one polymerization tank or in each polymerization tank. Further, when charging into each polymerization tank, the crystallinity of each polymerization tank may be adjusted. Further, as the polymerization method, a continuous method is used from the viewpoint of productivity.

(2-2) Supply of Raw Material Propylene The raw material propylene monomer is supplied directly to the fluidized bed reactor by supplying the raw material propylene monomer to the fluidized bed reactor and using a part or all of the raw material propylene monomer as a supplementary propylene monomer. The supplied and replenished propylene monomer is characterized by containing liquefied propylene.
The propylene from the raw material propylene supply pipe is gasified propylene, and the amount of supplied propylene monomer is the total of the amount of propylene from the raw material propylene supply pipe and the amount of replenishment propylene from the propylene supply pipe. The total amount is the amount of propylene consumed in the polymerization and corresponds to the amount of propylene polymer produced.

(2-3) Heat removal of polymerization Regarding the heat removal method of gas phase polymerization, not only the sensible heat of gas but also the latent heat of liquefied propylene is supplied by supplying propylene in a substantially liquid state to the polymerization tank. It is done using. The propylene in the liquid state may be fresh liquefied propylene or recycled propylene. Fresh propylene is more preferred. At this time, the liquefied component may contain a comonomer component typified by butene and an inactive hydrocarbon component typified by isobutane in addition to propylene.
The ratio of liquefied propylene due to latent heat in the heat removal of the polymerization is preferably 10% or more, more preferably 20% or more, and particularly preferably 30% or more. When the ratio of the liquefied propylene due to the latent heat is within the above range, resin lumps are not formed, the line is not blocked, and the operation stability is not deteriorated, which is preferable.

(2-4) Supply of Liquefied Propylene A part or all of the raw material propylene monomer is a replenishing propylene monomer, the replenishing propylene monomer contains liquefied propylene, and the method of supplying the liquefied propylene is substantially in a liquid state. Propylene is directly supplied to the bed of the crystalline propylene polymer flow bed in the polymerization tank. According to the present invention, a stable polymerization reaction (stable operation) can be carried out by directly feeding the liquefied propylene to the reactor.
The supply amount of the supplementary propylene monomer is 10 to 100% by weight based on the production amount of the crystalline propylene polymer.
The reason for setting "amount of supplied propylene monomer = amount of raw material propylene from pipe 3 + amount of replenishing propylene from pipe 5", that is, a reason for using a part or all of the raw material propylene monomer as replenishing propylene monomer is for replenishment. This is because propylene efficiently generates heat of vaporization, and the reason why the supplementary propylene monomer is liquefied propylene is that heat of vaporization is efficiently generated. Furthermore, the coexistence of liquefied propylene in the reactor can suppress powder charging due to static electricity, and prevent the conventional aggregation due to charged powder, local heat removal failure that occurs thereafter, and lump formation. can do.
According to such specifications, a fluidized bed reactor can be used to industrially and stably produce a crystalline propylene polymer with high production efficiency while controlling the crystallinity.
In particular, by setting the supply amount of liquefied propylene to 10 to 100% by weight with respect to the production amount of the crystalline propylene polymer, stable and safe polymerization can be performed.

(2-5) Polymerization conditions Polymerization conditions such as temperature and pressure can be arbitrarily set as long as the effects of the present invention are not impaired. Specifically, the polymerization temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 50 ° C. or higher, preferably 100 ° C. or lower, further preferably 95 ° C. or lower, and particularly preferably 90 ° C. or lower. Is. The polymerization pressure is preferably 1.2 MPa or more, more preferably 1.4 MPa or more, particularly preferably 1.6 MPa or more, preferably 4.2 MPa or less, still more preferably 3.8 MPa or less, and particularly preferably 3.5 MPa or less. Is.
The residence time can be arbitrarily set according to the size and composition of the polymerization tank, catalytic activity, and the like. Generally, it is set within the range of 30 minutes to 5 hours. When the residence time is short, the crystallinity tends to be high, and when the residence time is long, the crystallinity tends to be low. Therefore, as illustrated in the master curve of FIG. 3, it is necessary to read the expected crystallinity from the residence time in advance and set the amount of the organosilicon compound (C).

(2-6) Catalytic activity The catalytic activity varies depending on the polymerization conditions such as temperature, pressure and residence time, but it is preferably 10,000 gPP / g catalyst or more. Preferably, the catalytic activity is in the range of 15,000 gPP / g catalyst or more and 500,000 gPP / g catalyst or less, more preferably 20,000 gPP / g catalyst or more and 100,000 gPP / g catalyst or less, most preferably 25. It is in the range of 000 gPP / g catalyst or more and 50,000 gPP / g catalyst or less.
When the catalytic activity is within the above range, there is not a large amount of catalyst residue, and it is not necessary to use a large amount of additives such as a neutralizing agent, which is economical and preferable. Further, it is preferable that the catalyst feed portion is easily locally heat-removed and foreign substances such as lumps are less likely to be formed.

(2-7) Manufacturing Equipment The manufacturing equipment is a fluidized bed reactor, as illustrated in FIG. 1, a polymerization catalyst supply means, a raw material propylene supply means, a supplementary propylene supply means, a polymerization reaction means, and crystalline propylene. It has a polymer discharging means.
The polymerization catalyst supply means, the raw material propylene supply means, the replenishment propylene supply means, the supply means of other optional components, and the like can supply each material to the polymerization tank by using a known method. The polymerization catalyst may be supplied as a powder to the polymerization tank as it is, or may be diluted with an inert solvent such as hexane or mineral oil before being supplied.
As a means for discharging the crystalline propylene polymer, a known method can be used to discharge the crystalline propylene polymer from the polymerization tank. There is a method of extracting while adjusting the discharge amount with a control valve, and a method of extracting to the discharge tank in batch and adjusting the discharge amount by the number of times of extraction.

(2-8) Supply of Organosilicon Compound In the production method of the present invention, the step of measuring the crystallinity of the crystalline propylene polymer and the supply amount of the organosilicon compound (C) are determined according to the crystallinity. It is characterized by including a step of adjusting.
The step of measuring the crystallinity can be measured by using a known method. For example, density, CXS, TREF and the like can be used.
Further, the higher the frequency of measurement, the better the accuracy, but from the viewpoint of work efficiency, the lower the frequency, the better. Therefore, as a guide, it is preferable to perform the measurement at intervals before and after the average residence time of the reactor.

The supply amount of the organosilicon compound (C), which is a crystallinity adjuster, is determined by predicting the crystallinity of the crystalline propylene polymer using a master curve of the relationship between the production rate and the crystallinity prepared in advance. Will be done. The relationship master curve is shown in FIG.
Further, the crystallinity of the discharged crystalline propylene polymer is measured, and adjustment is made according to the crystallinity. The crystallinity of the organosilicon compound (C) increases almost in proportion to the supply, but the relationship between the supply amount of the organosilicon compound (C) and the increase in crystallinity is created in advance and the supply amount is created. By determining, faster and more accurate control becomes possible. The master curve is shown in FIG. Based on FIG. 3, the supply amount of the crystallization degree adjusting agent (organosilicon compound (C)) is determined in proportion to the crystallization degree (indicated by the CXS axis on the vertical axis in FIG. 3).
In the present specification, the "crystallinity" means the ratio of crystals contained in the crystalline propylene polymer, and can be evaluated by, for example, the density measured by a known method, CXS, TREF, or the like. It shall be possible.

4. Crystalline Propylene Polymer The crystalline propylene polymer obtained by the present invention has a controlled crystallinity, is excellent in moldability and quality, and has a low manufacturing cost.
Further, the crystalline propylene polymer obtained by the present invention can be used as it is as a product, or may be further subjected to rubber polymerization or the like and used as a product as an impact copolymer.

The crystalline propylene polymer obtained by the present invention is a homopolymer of propylene (i) and a random copolymer (ii) of propylene and other monomers. Each polymer will be described in detail.
(I) Polypolymer of propylene When the crystalline propylene polymer in the present invention is a propylene homopolymer, the melt flow rate (test conditions: 230 ° C., load 2.16 kgf) (MFR) is 0.01 g / 10 The amount is preferably 1,000 g / 10 minutes or less, more preferably 0.1 g / 10 minutes or more and 500 g / 10 minutes or less, and further preferably 0.5 g / 10 minutes or more and 100 g / 10 minutes or less. ..
The CXS is preferably 0.3% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 8% by weight or less, and most preferably 1% by weight or more and 6% by weight or less.
Further, the density is preferably 0.9000 g / ml or more and 0.9100 g / ml or less, more preferably 0.9010 g / ml or more and 0.9090 g / ml or less, and most preferably 0.9020 g / ml or more and 0.9080 g / ml. It is as follows.

Here, CXS is defined as a value measured by the following method. The sample (about 5 g) is completely dissolved once in p-xylene (300 ml) at 140 ° C. The polymer is then cooled to 23 ° C. and the polymer is precipitated at 23 ° C. for 12 hours. After filtering the precipitated polymer, p-xylene is evaporated from the filtrate. The polymer remaining after evaporating p-xylene is dried under reduced pressure at 100 ° C. for 2 hours. The dried polymer is weighed and the CXS value is obtained as% by weight of the sample.
The density can be measured by any method such as specific gravity method, gradient tube method, and X-ray diffraction.

(Ii) Random copolymer When the crystalline propylene polymer in the present invention is a random copolymer of propylene and other monomers, the other monomers are ethylene and / or α-olefin having 4 to 10 carbon atoms. It is desirable to have. More preferably, ethylene and / or 1-butene is preferable, and ethylene is most preferable.
The content of the monomer unit other than propylene in the random copolymer is preferably 10% by weight or less. More preferably 0.01% by weight or more and 3% by weight or less, further preferably 0.05% by weight or more and 2% by weight or less, and particularly preferably 0.1% by weight or more and 1% by weight or less. Moreover, the preferable range of MFR, density and CXS is the same as in the case of the propylene homopolymer.
Here, the content of other monomers can be determined by any analytical method. Specific examples include infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR).

Here, in the present invention, as described above, the monomer other than propylene used in the random copolymer is not particularly limited, and an olefin having 2 to 12 carbon atoms, particularly an α-olefin having 2 to 12 carbon atoms is preferably used. Be done. Specific examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like, and among them, ethylene. , 1-Butene and 4-Methyl-1-pentene are more preferable, and not only one type of these olefins but also two or more types can be used.

In order to adjust the MFR, the concentration of hydrogen, which is a chain transfer agent, in the polymerization tank may be adjusted. Further, in order to adjust the comonomer content, the concentration of the comonomer in the polymerization tank may be adjusted.

In addition, the polymer particles obtained by the present invention exhibit excellent particle properties. Generally, the particle properties of polymer particles are evaluated by polymer bulk density, particle size distribution, particle appearance, and the like.
The polymer particles obtained by the present invention have a polymer bulk density in the range of 0.35 to 0.55 g / ml, preferably in the range of 0.40 to 0.50 g / ml, most preferably 0.43. It is in the range of ~ 0.48 g / ml. The size of the polymer particles can take any value, but the average particle size is preferably in the range of 500 to 3,000 μm, particularly preferably 700 to 2,000 μm. Further, the lower the amount of fine powder, the less fouling in a reactor or the like, which is preferable. The preferred range is 300
The amount of fine powder of μ or less is 5 wt% or less, more preferably 3 wt% or less, particularly preferably 2 wt% or less, and most preferably 1 wt% or less. It goes without saying that 0 wt% is ideal. The amount of fine powder can be measured by any method such as a sieving method, a laser diffraction method, and an image analysis method.

5. Uses of Crystallized Propylene Polymer The crystallized propylene polymer produced using the present invention can be used for any purpose. Examples of the propylene polymer having reduced crystallinity include fields of low crystallinity, such as films, sheets, and fiber yarns. For film applications, any molding method such as biaxial stretching, uniaxial stretching, non-stretching, air-cooled inflation, and water-cooled inflation can be used.
As a more specific application, it can be preferably used for packaging materials such as food packaging films and packaging yarns, and textile materials such as non-woven fabrics for sanitary products.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples, and the present invention is not limited to these Examples. It demonstrates excellence. The method for measuring each physical property value in the present invention is shown below.

(1) Melt flow rate (MFR)
Evaluation was performed using a melt indexer manufactured by Takara Co., Ltd. under the conditions of 230 ° C. and 21.18 N (2.16 kgf) based on JIS K6921.

(2) Density Using the extruded strand obtained at the time of MFR measurement, the density gradient tube method was used for measurement in accordance with the JIS / K7112 / D method.

(3) Ti content The sample was accurately weighed, hydrolyzed, and then measured using the colorimetric method. For the sample after prepolymerization, the content was calculated using the weight excluding the prepolymerized polymer.

[Example 1]
(1) Preparation of solid components An autoclave having a capacity of 10 L equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. To this, at room temperature, 200 g of _{Mg (OEt) 2} and 1 L of _{TiCl 4 were added.} The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Then, the temperature was raised to 110 ° C. and a 3 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene. Further, using purified n-heptane, toluene was replaced with n-heptane to obtain a slurry of the solid component (A1). A part of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (A1) was 2.7 wt%.
Next, an autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (A1) was introduced as the solid component (A1). Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 25 g / L. Here, dimethyl divinyl silane 25 ml, as component (A3) to _{(i-Bu) 2 Si (} OMe) 2 16ml, the n- heptane dilution of _Et 3 Al 40 g added as _Et 3 Al as the component (A2) , 2 hr reaction was carried out at 30 ° C. The reaction product was then used as is for total prepolymerization.

(2) Prepolymerization Using the solid component obtained above, prepolymerization was carried out by the following procedure. Purified n-heptane was introduced into the above slurry to adjust the concentration of the solid component to 20 g / L. After cooling the slurry to 10 ° C., 280 g of propylene was supplied over 4 hr. After the supply of propylene was completed, the reaction was continued for another 30 minutes. The gas phase was then thoroughly replaced with nitrogen and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a solid catalyst component (AI). This solid catalyst component (AI) contained 2.5 g of crystalline propylene polymer per 1 g of solid component. As a result of analysis, the portion of the solid catalyst component (AI) excluding the crystalline propylene polymer contained 1.6 wt% of Ti and 6.2 wt% of (i-Bu) ₂ Si (OMe) _2. It was.

(3) Polymerization of propylene
Polymerization was carried out using a continuous reactor (exemplified in FIG. 1) consisting of a fluidized bed reactor having an inner diameter of 0.33 m and a straight body portion of 3 m. In the fluidized bed reactor (1), the gas extracted from the top of the reactor is circulated, cooled by the heat exchanger (2), and then the gas is diffused from under the reactor floor with a dispersion plate and returned to the reactor to return the fluidized bed. To form. On the other hand, (except liquefied propylene to be introduced directly into the reactor) propylene, H _{2, N 2,} an organic aluminum compound (B), the raw material such as an organic silicon compound (C) is introduced into the fluidized floor of the circulating gas line (3) Will be done. The solid catalyst component (A), from 0.3 m high place than the distribution plate (4), is injected directly into the fluidized bed by N ₂ was purified as a carrier. The liquefied propylene to be directly introduced into the reactor is also introduced from another nozzle (5) having a height of 0.3 meters from the dispersion plate. The polymerization temperature was measured at a height of 0.9 meters above the dispersion plate and controlled to be constant. The produced polymer was batch-extracted into a discharge tank, and the discharge amount was adjusted by the number of times the polymer was extracted.

Temperature 75 ° C. in the reactor, polymerization pressure 3.0 MPa (gauge pressure), the propylene partial pressure 2.4 MPa (absolute pressure) and so as propylene, the _{N 2,} also hydrogen as a molecular weight control agent, hydrogen / propylene The mixture was continuously supplied so as to have a molar ratio of 0.0016. Triethylaluminum was supplied at 5.25 g / hr and (i-Bu) ₂ Si (OMe) ₂ was supplied at 0.40 mmol / hr. Further, the solid catalyst component (AI) was supplied so that the polymer polymerization rate was 13.5 kg / hr. Further, liquefied propylene was supplied directly to the reactor at 8.6 kg / hr. The powder polymerized in the reactor (crystalline propylene polymer component) is produced so that the amount of powder held in the reactor (bed weight) is 35 kg, and nitrogen gas containing water is supplied to stop the reaction. , A crystalline propylene polymer was obtained. The results are shown in Table 1.

[Example 2]
(1) Preparation of solid components An autoclave having a capacity of 10 L equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. To this, at room temperature, 200 g of _{Mg (OEt) 2} and 1 L of _{TiCl 4 were added.} The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Then, the temperature was raised to 110 ° C. and a 3 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and a 2 hr reaction was carried out. The reaction product was thoroughly washed with purified toluene. Further, using purified n-heptane, toluene was replaced with n-heptane to obtain a slurry of the solid component (A1). A part of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (A1) was 2.7 wt%.

Next, an autoclave having a capacity of 20 L equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (A1) was introduced as the solid component (A1). Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 25 g / L. Here, dimethyl divinyl silane 30 ml, 80 g was added as the component (A3) to (t-Bu) MeSi (OMe ) 2 30ml, the n- heptane dilution of _Et 3 Al as _Et 3 Al as the component (A2), The 2 hr reaction was carried out at 40 ° C. The reaction product was then used as is for total prepolymerization.

(2) Prepolymerization Using the solid component obtained above, prepolymerization was carried out by the following procedure. Purified n-heptane was introduced into the above slurry to adjust the concentration of the solid component to 20 g / L. After cooling the slurry to 10 ° C., 280 g of propylene was supplied over 4 hr. After the supply of propylene was completed, the reaction was continued for another 30 minutes. The gas phase was then thoroughly replaced with nitrogen and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was taken out from the autoclave and vacuum dried to obtain a solid catalyst component (A-II). This solid catalyst component (A-II) contained 2.5 g of crystalline propylene polymer per 1 g of the solid component. _{As a result of analysis, 1.0 wt% of Ti and 8.2 wt% of (t-Bu) MeSi (OMe) 2} were contained in the portion of the solid catalyst component (A-II) excluding the crystalline propylene polymer. Was there.

(3) Polymerization of propylene This was carried out using the fluidized bed reactor of Example 1. Temperature 85 ° C. in the reactor, polymerization pressure 3.0 MPa (gauge pressure), the propylene partial pressure 2.2 MPa (absolute pressure) and so as propylene, the _{N 2,} also hydrogen as a molecular weight control agent, hydrogen / propylene The mixture was continuously supplied so as to have a molar ratio of 0.0051. Triethylaluminum was supplied at 5.25 g / hr and (t-Bu) MeSi (OMe) ₂ was supplied at 1.1 mmol / hr. Further, the solid catalyst component (A-II) was supplied so that the polymer polymerization rate was 18.4 kg / hr. Further, liquefied propylene was supplied directly to the reactor at 11.6 kg / hr. The powder polymerized in the reactor (crystalline propylene polymer component) is extracted so that the amount of powder held in the reactor (bed weight) is 60 kg, and nitrogen gas containing water is supplied to stop the reaction. A crystalline propylene polymer was obtained. The results are shown in Table 1.

[Example 3]
The solid catalyst component (A-II) was supplied so that the polymer polymerization rate was 17.8 kg / hr. Further, the procedure was carried out in accordance with Example 2 except that the amount of liquefied propylene directly supplied to the reactor was set to 5.4 kg / hr. The results are shown in Table 1.

[Example 4]
(I-Bu) The procedure was carried out in accordance with Example 1 except that the supply amount of ₂ Si (OMe) _{2 to the reactor was changed to 0.20 mmol.} The results are shown in Table 1.

[Comparative Example 1]
This was carried out in accordance with Example 1 except that the organosilicon compound was not supplied to the reactor and the liquefied propylene was not directly supplied to the reactor. The results are shown in Table 1.

[Comparative Example 2]
This was carried out in accordance with Example 1 except that the organosilicon compound was not supplied to the reactor. The results are shown in Table 1.

[Comparative Example 3]
This was performed using the fluidized bed reactor of Example 1. Temperature 75 ° C. in the reactor, polymerization pressure 3.0 MPa (gauge pressure), the propylene partial pressure 2.4 MPa (absolute pressure) and so as propylene, the _{N 2,} also hydrogen as a molecular weight control agent, hydrogen / propylene The mixture was continuously supplied so as to have a molar ratio of 0.0015. Triethylaluminum was supplied at 5.25 g / hr. Further, the solid catalyst component (AI) was supplied so that the polymer polymerization rate was 14 kg / hr. Extraction was carried out so that the amount of powder held in the reactor (bed weight) was 35 kg. However, the liquefied propylene was not directly supplied to the reactor. In that state, supply of (i-Bu) ₂ Si (OMe) ₂ to the reactor was started at 0.10 mmol / hr. In the second batch of polymer extraction after the start of supply, the polymer was not discharged and the operation was stopped due to lump formation.

[Comparative Example 4]
This was performed using the fluidized bed reactor of Example 1. Temperature 85 ° C. in the reactor, polymerization pressure 3.0 MPa (gauge pressure), the propylene partial pressure 2.2 MPa (absolute pressure) and so as propylene, the _{N 2,} also hydrogen as a molecular weight control agent, hydrogen / propylene The mixture was continuously supplied so as to have a molar ratio of 0.0052. Triethylaluminum was supplied at 5.25 g / hr. Further, the solid catalyst component (A-II) was supplied so that the polymer polymerization rate was 18 kg / hr. Extraction was carried out so that the amount of powder held in the reactor (bed weight) was 60 kg. However, the liquefied propylene was not directly supplied to the reactor. In that state, supply of (t-Bu) MeSi (OMe) ₂ to the reactor was started at 0.10 mmol / hr. In the second batch of polymer extraction after the start of supply, the polymer was not discharged and the operation was stopped due to lump formation.

As is clear from Table 1, the method for producing a crystalline propylene polymer of the present invention (Examples 1 to 4) enables stable operation in a fluidized bed reactor and has a xylene-soluble content (% by weight). It is possible to control the crystallinity of the polymer shown to be constant.
On the other hand, in Comparative Example 1 in which the organosilicon compound (C) was not supplied to the reactor and the liquefied propylene was not directly supplied to the reactor, and Comparative Example 2 in which the organosilicon compound (C) was not used, the crystals of the polymer were crystallized. Sexual deterioration occurred. In Comparative Examples 3 and 4 in which the liquefied propylene was not supplied to the reactor, stable operation was not possible, a resin lump was formed at the same time as the supply of the organosilicon compound, and the powder could not be extracted.
Therefore, the rationality and significance of the constituent elements of the present invention and the usefulness and excellence of the present invention with respect to the prior art have been demonstrated.

The method for producing a crystalline propylene polymer of the present invention makes it possible to produce a crystalline propylene polymer having a controlled crystallinity in a fluidized bed reactor with high production, high efficiency, and low cost. The crystalline propylene polymer thus obtained can be suitably used for film applications such as biaxially stretched films used for food packaging materials and the like.
Therefore, the present invention provides a useful and economical manufacturing technique in the industrial field of crystalline propylene polymers.

1 Fluidized bed reactor 2 Heat exchanger 3 Raw material supply position 4 Catalyst supply position 5 Liquefied prolen supply position

Claims (7)

A method for producing a crystalline propylene polymer by continuously polymerizing vapor phase propylene in the presence of a propylene polymerization catalyst in a fluidized bed reactor.
(I) In a fluidized bed reactor,
(I) Supply the raw material propylene monomer to the fluidized bed reactor,
(Ii) Part or all of the raw material propylene monomer is directly supplied to the fluidized bed reactor as a supplementary propylene monomer.
(Iii) The supplementary propylene monomer contains liquefied propylene and contains.
(Iv) A crystalline propylene polymer is produced from a fluidized bed reactor.
(V) The supply amount of the supplementary propylene monomer shall be 10 to 100% by weight with respect to the production amount of the crystalline propylene polymer.
(II) a propylene polymerization catalyst contains a solid catalyst component comprising the following components (A1) (A), organic aluminum compound (B) and organic silicon compound represented by the following general formula (1) (C) ,
Component (A1): Solid component organosilicon compound (C) containing titanium, magnesium, halogen, and a phthalic acid derivative and / or an ether compound having at least two ether bonds as an essential component: R ¹ R ² _a Si (OR) ³ ) _b ... (1)
(In the formula, R ¹ is a branched or cyclic hydrocarbon group having a secondary or tertiary carbon atom at the β-position of Si, and R ² is the same or different hydrocarbon group as ^{R 1.} R ³ represents a hydrocarbon group, and 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3).
(III) A method for producing a crystalline propylene polymer, wherein the solid catalyst component (A) is supplied to a fluidized bed reactor in the form of powder or diluted with an inert solvent. The propylene from the raw material propylene supply pipe is gasified propylene, and the amount of supplied propylene monomer is the sum of the amount of propylene from the raw material propylene supply pipe and the amount of replenishment propylene from the propylene supply pipe, and the total amount thereof. The method for producing a crystalline propylene polymer according to claim 1, wherein is the amount of propylene consumed in the polymerization and corresponds to the amount of the propylene polymer produced. The crystalline propylene polymer according to claim 1, wherein the solid catalyst component (A) is formed by contact-treating the following components (A1), (A2), (A3) and (A4). Production method.
Component (A1): Solid component containing titanium, magnesium, halogen, and a phthalic acid derivative and / or an ether compound having at least two ether bonds as an essential component (A2): Vinylsilane compound and / or allylsilane compound component (A3) ): Organosilicon compound represented by the following general formula (2) R ¹¹ R ¹² fSi (OR ¹³ ) g ... (2)
(In the formula, R ¹¹ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ¹² represents any free group selected from the group consisting of hydrogen, halogen, hydrocarbon groups and heteroatom-containing hydrocarbon groups. R ¹³ represents a hydrocarbon group, and 0 ≦ f ≦ 2, 1 ≦ g ≦ 3, f + g = 3).
Ingredient (A4): Organoaluminium compound The method for producing a crystalline propylene polymer according to any one of claims 1 to 3, further comprising a step of adjusting the supply amount of the organosilicon compound (C). The method for producing a crystalline propylene polymer according to any one of claims 1 to 4, wherein the crystallinity is represented by a xylene-soluble component (CXS). The crystal according to any one of claims 1 to 5, wherein the solid catalyst component (A) is prepolymerized in the range of 0.001 to 100 g per 1 g of the solid catalyst component. A method for producing a sex propylene polymer. A method for producing a propylene polymer for a food packaging film, which comprises using the method for producing a crystalline propylene polymer according to any one of claims 1 to 6.

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