JP2007321136A - Method for producing polypropylene-based block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a high-MFR polypropylene-based block copolymer having excellent product quality in high productivity. <P>SOLUTION: The method for producing the polypropylene-based block copolymer of the polymer components(a) and (b) mentioned below in the mass ratio of (10:90) to (84:16) by such a vapor-phase polymerization process as to remove heat of reaction mainly by the heat of vaporization of liquefied propylene is provided, wherein a solid catalytic component(A) obtained by mutual contact treatment of (A1) a solid component essentially containing titanium, magnesium and a halogen, (A2) a vinylsilane compound and (A3) an alkoxy-bearing organosilicon compound and/or a compound having at least two ether linkages is used. The polymer component(a) is 5 mass% or less in comonomer unit content and 50 g/10min or greater in MFR determined at 230°C and 21.18 N, and the polymer component(b) is 20-80 mass% in propylene unit content. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polypropylene block copolymer, and more particularly to a method for producing a high MFR polypropylene block copolymer having excellent product quality with high productivity.

Polypropylene has good mechanical properties such as rigidity and heat resistance, and can be manufactured at a relatively low cost, so that it is applied to a wide range of applications. Polypropylene is widely used not only as a homopolymer but also as a copolymer with a comonomer such as ethylene or butene. Of these, block copolymers are often used for applications that require both rigidity and impact strength. Polypropylene-based block copolymer means a blend of a polymer component mainly composed of propylene and a random copolymer component of propylene and other monomers, generally in order under conditions corresponding to each component. By carrying out the polymerization, it is produced using a technique of blending the respective components in the reactor.
One of the typical uses of propylene-based block copolymers is injection molding applications such as automobile bumpers. In recent years, polypropylene block copolymer MFR has been used to improve the productivity of injection molding processes. It has been desired to increase this. The MFR of the propylene block copolymer is the MFR of the polymer component mainly composed of propylene, the MFR of the random copolymer component of propylene and other monomers, and the random copolymer component unit in the block copolymer. The content is uniquely determined by the three. In order to increase the quality of the block copolymer, particularly the impact strength, it is necessary to keep the MFR of the random copolymer component and the content of the random copolymer component unit within a certain range. In order to increase the MFR of the block copolymer while maintaining it, it is desired to further increase the MFR of the polymer component mainly composed of propylene.

On the other hand, with regard to the polypropylene manufacturing process, technical improvements have been continued from the viewpoint of simplification of the process, reduction of production cost, and improvement of productivity. At the time when polypropylene was industrially produced, the performance of the catalyst was low, and it was necessary to remove the catalyst residue and atactic polymer from the obtained polypropylene, which was mainly a process such as a slurry method using a solvent. It was. Thereafter, as the catalyst performance has progressed significantly, the gas phase polymerization process is now the mainstream. Among various gas phase polymerization processes, the method of removing the heat of polymerization using the latent heat of liquefied propylene is advantageous in that it can have a large heat removal capability with a small facility.
A horizontal reactor having a stirrer rotating around a horizontal axis is known as an olefin gas phase polymerization tank of the type that removes the heat of polymerization using the latent heat of vaporization of liquefied propylene.
Generally, catalyst particles gradually grow into polymer particles by a polymerization reaction. When polymerization is carried out in a horizontal reactor, these particles progress along the axial direction of the reactor while gradually growing due to the two forces of formation of polypropylene by polymerization and mechanical stirring. For this reason, particles having a uniform growth degree, that is, a residence time are aligned with time from the upstream side to the downstream side of the reactor. That is, in the horizontal reactor, the flow pattern is a piston flow type, which has the effect of narrowing the residence time distribution to the same extent as when several complete mixing tanks are arranged in series. This is an excellent feature not found in other polymerization reactors, and a single reactor can easily achieve a degree of solid mixing equivalent to two, three or more reactors. This is economically advantageous.
When producing polypropylene, the method of removing the heat of polymerization using the latent heat of vaporization of liquefied propylene and using a horizontal cylindrical reactor having a stirrer rotating around the horizontal axis is as described above. It has excellent characteristics.
When producing a polypropylene block copolymer, a polymer component (a) mainly composed of propylene is produced in the first polymerization step, and a random copolymer component of propylene and other monomers is produced in the second polymerization step. It is common to produce (b). At this time, if the residence time distribution of the polymer particles leaving the first polymerization step and entering the second polymerization step is wide, fouling occurs in the reactor that performs the second polymerization step, or the surface of the block copolymer that is the product Problems such as a drop in impact strength are likely to occur. This is because the dispersion of the activity of the polymer particles entering the second polymerization step becomes large due to the wide distribution of the residence time, and the random copolymer component is excessively produced in the second polymerization step. This is thought to be due to the increase in particles.
Therefore, when producing a polypropylene-based block copolymer, it is desirable to use a production method having a narrow residence time distribution. From this point of view, a horizontal cylindrical reactor having a stirrer rotating around a horizontal axis is used. It can be said that the method used has a high advantage over other methods.

As described above, the gas phase polymerization process using the latent heat of liquefied propylene has excellent characteristics. However, in the case of producing polypropylene having a high MFR, which has been desired in recent years, it is solved in terms of productivity. Have problems to be solved. When utilizing the latent heat of liquefied propylene, it is a general method to extract gas from the polymerization tank, liquefy it by cooling with a heat exchanger, and return it to the polymerization tank again. The temperature at which the gas liquefies (dew point) depends on the pressure and the composition of the gas. Therefore, when a gas component having a low dew point such as hydrogen or ethylene is mixed with propylene alone, the amount of mixing increases. The dew point decreases. The cooling capacity of the heat exchanger is determined by the equipment. When the same equipment is used, the ability to liquefy gas decreases as the dew point of the gas component decreases, that is, the heat removal ability decreases. On the other hand, when producing polypropylene, it is common to use hydrogen capable of causing a chain transfer reaction as a molecular weight regulator. In order to produce a higher MFR, ie, a lower molecular weight polypropylene, it is necessary to use a higher concentration of hydrogen. Therefore, in the gas phase polymerization process using the latent heat of liquefied propylene, when trying to produce polypropylene having a high MFR, there is a problem that productivity decreases due to the problem of heat removal. When the MFR polypropylene block copolymer is produced, the problem further increases in the first polymerization step.
Therefore, several methods for solving this problem by improving the catalyst have been proposed. For example, a method of using an organoaluminum component and an alumoxane as a cocatalyst (see, for example, Patent Document 1), a method of using an organoaluminum component and an organic zinc component as a cocatalyst (see, for example, Patent Document 2), and halogen-containing. A method of supporting a component on a solid catalyst (for example, see Patent Document 3), a method using an organosilicon compound having an amino group (for example, see Patent Documents 4, 5, and 6), a branched or alicyclic hydrocarbon group And a method using a specific organosilicon compound having both an amino group and an amino group (for example, see Patent Documents 7 and 8).
However, although such a method is satisfactory in terms of the physical properties of the obtained polypropylene, there is still no satisfactory performance in terms of the productivity of high MFR polypropylene. Development is desired.

Japanese Patent Laid-Open No. 7-25927 JP-A-8-66710 JP 2000-7725 A JP-A-8-3215 JP 2004-315742 A JP 2005-48045 A JP-A-8-100019 JP-A-8-157519

  This invention makes it a subject to provide the method of manufacturing the high MFR polypropylene block copolymer provided with the outstanding product quality with high productivity in the condition of this prior art.

  The present inventors have developed an improved solid catalyst component for propylene using a specific vinylsilane compound as one of the constituent components, and as a result of earnestly examining methods for applying it to various polymerization processes, this improved solid catalyst component In combination with a gas phase polymerization process that removes heat mainly using the latent heat of liquefied propylene significantly increases the productivity of propylene-based block copolymers with high MFR. The inventors have found that the manufacturable range can be expanded and have come to make the present invention based on this finding.

That is, according to the first invention of the present invention, the following polymer component (a) and polymer component (b) are obtained by a gas phase polymerization process in which heat of reaction is mainly removed by heat of vaporization of liquefied propylene: A method for producing a polypropylene-based block copolymer containing at a mass ratio of 90 to 84:16,
Solid component (A1) containing titanium, magnesium and halogen as essential components (hereinafter sometimes abbreviated as “solid component (A1)”) and vinylsilane compound (A2) (hereinafter referred to as “component (A2)”) And an organosilicon compound having an alkoxy group and / or a compound (A3) having at least two ether bonds (hereinafter, the former is referred to as “component (A3a)” and the latter is referred to as “component ( A3b) ”, or a solid catalyst component (A) obtained by contact-treating these in general and may be abbreviated as“ component (A3) ”). A manufacturing method is provided.
Polymer component (a): a propylene homopolymer or a random copolymer of propylene and one or more comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, The unit content is 5% by mass or less, and the MFR measured at 230 ° C. and 21.18N is 50 g / 10 min or more. Polymer component (b): Propylene, ethylene and an α-olefin having 4 to 8 carbon atoms. A random copolymer with at least one comonomer selected from the group, wherein the propylene unit content is 20% by mass or more and 80% by mass or less

  According to the second invention of the present invention, in the first invention, the gas phase polymerization process is a two-stage gas phase polymerization process, and the solid catalyst component (A) is used. In one stage, propylene is polymerized alone, or in the second stage, propylene is copolymerized with one or more comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. There is provided a method for producing a polypropylene-based block copolymer, which is a copolymer of ethylene and at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms.

According to the third invention of the present invention, in the first or second invention, the vinyl silane compound (A2) is a compound represented by the following general formula (1). A method for producing a polymer is provided.
[CH ₂ = CH-] _m SiX _n R ¹ _j (OR ² ) _k (1)
(In the formula, X represents halogen, R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, a hydrocarbon group or an organosilicon group, and m ≧ 1, 0 ≦ n ≦ 3, 0 ≦ j ≦ 3, 0 ≦ (k ≦ 2, m + n + j + k = 4)

According to a fourth aspect of the present invention, in any one of the first to third aspects, the organosilicon compound having an alkoxy group is a compound represented by the following general formula (2): A method for producing a polypropylene block copolymer is provided.
R ³ R ⁴ _a Si (OR ⁵ ) _b (2)
(Wherein R ³ is a hydrocarbon group or a heteroatom-containing hydrocarbon group, R ⁴ is any radical selected from the group consisting of hydrogen, halogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group, R ⁵ is Represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3.)

According to the fifth invention of the present invention, in any one of the first to fourth inventions, the compound (A3b) having at least two ether bonds is a compound represented by the following general formula (3). A method for producing a polypropylene-based block copolymer is provided.
_{^{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8 ... (3)
(Wherein R ⁶ and R ⁷ represent any free radical selected from the group consisting of hydrogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group, and R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. )

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, the polymer component (b) has a random copolymer having an MFR in the range of 0.5 to 5.0 g / 10 min. Provided is a method for producing a polypropylene block copolymer, which is a polymer.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the solid catalyst component (A) is prepolymerized, and the method for producing a polypropylene block copolymer Is provided.

  According to an eighth invention of the present invention, in any one of the first to seventh inventions, the production of a polypropylene block copolymer characterized by having a catalytic activity of 30,000 gPP / g catalyst or more. A method is provided.

  According to a ninth aspect of the present invention, in any one of the first to eighth aspects, the vapor phase polymerization process is carried out in a reactor having a stirrer. A method for producing a coalescence is provided.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the gas phase polymerization process is carried out in a horizontal reactor having a stirrer that rotates about a horizontal axis. A process for producing a polypropylene-based block copolymer is provided.

  According to an eleventh aspect of the present invention, there is provided a method for producing a polypropylene-based block copolymer characterized in that in any one of the first to tenth aspects of the invention, no peroxide is used.

  According to the production method of the present invention, a high MFR polypropylene-based block copolymer can be produced with high productivity, and since the catalytic activity is very high, the production cost can be reduced, In addition, since the obtained polypropylene has high stereoregularity, a high-quality product excellent in the balance between rigidity and impact strength can be obtained. The polypropylene block copolymer thus obtained is particularly suitable for applications such as injection molded products represented by automobile parts and household appliance parts.

  In the following, the present invention will be described specifically and in detail with respect to catalysts, production processes and conditions, polypropylene block copolymers, and uses of polypropylene block copolymers.

[I] Catalyst In the present invention, the catalyst for the polypropylene-based block copolymer has (A1) a solid component containing titanium, magnesium, and halogen as essential components, (A2) a vinylsilane compound, and (A3) an alkoxy group. A solid catalyst component (A) obtained by contacting an organosilicon compound (A3a) and / or a compound (A3b) having at least two ether bonds is used. Under the present circumstances, in the range which does not impair the effect of this invention, arbitrary components, such as an organoaluminum compound (B), an organosilicon compound (C), and the compound (D) which has an at least 2 ether bond, can be used. .

1. Solid catalyst component (A)
The solid catalyst component (A) used in the present invention is obtained by contacting the following (A1) to (A3). At this time, other optional components such as the organoaluminum compound (A4) may be contacted by any method as long as the effects of the present invention are not impaired. Each component is described in detail below.

(1) Solid component (A1)
In the present invention, the solid component (A1) contains titanium (A1a), magnesium (A1b), and halogen (A1c) as essential components, and may contain an electron donor (A1d) as an optional component. . Here, “containing as an essential component” indicates that an optional component may be included in any form within the range not impairing the effects of the present invention, in addition to the essential three components. Solid components themselves containing titanium, magnesium, and halogen as essential components are known and will be described in detail below.

(A1a) Titanium Any arbitrary titanium compound can be used as a titanium source. Typical examples include compounds disclosed in JP-A-3-234707. The valence of titanium may be any of tetravalent, trivalent, divalent, and zerovalent, but is preferably tetravalent or trivalent, and more preferably tetravalent.

Specific examples of tetravalent titanium compounds include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, tetrabutoxy titanium dimer (BuO) ₃ Ti—O—Ti ( Examples thereof include condensation compounds of alkoxy titanium having a Ti—O—Ti bond typified by OBu) ₃ and organometallic titanium compounds typified by dicyclopentadienyl titanium dichloride. Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.
Specific examples of the trivalent titanium compound include titanium halide compounds represented by titanium trichloride. As titanium trichloride, a compound produced by any known method such as a hydrogen reduction type, a metal aluminum reduction type, a metal titanium reduction type, or an organoaluminum reduction 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 or a compound whose average composition formula is a mixed formula thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), or a phthalate ester Complexes with other compounds such as Ph (CO ₂ Bu) ₂ .TiCl ₄ and the like can be used.

(A1b) Magnesium Any magnesium compound can be used as the magnesium source. Typical examples include compounds disclosed in JP-A-234707. In general, magnesium halide compounds represented by magnesium chloride, alkoxymagnesium compounds represented by diethoxymagnesium, metal magnesium, oxymagnesium compounds represented by magnesium oxide, and magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds typified by butylmagnesium chloride, organometallic magnesium compounds typified by butylethylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, In addition, a compound in which a mixture thereof or an average composition formula thereof is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used. Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

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

(A1d) Electron Donor The solid component (A1) may contain an electron donor as an optional component. Typical examples of the electron donor (A1d) include compounds disclosed in JP-A No. 2004-124090. In general, 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, etc. It is desirable to use

  Examples of the organic acid compound used as the electron donor include aromatic polycarboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malonic acid. One or two substituents at the 2-position, such as malonic acid or 2-n-butyl-succinic acid having one or two substituents at the 2-position, or one or more substitutions at the 2-position and 3-position, respectively. Aliphatic carboxylic acid compounds typified by succinic acid having a group, aliphatic carboxylic acid compounds typified by propionic acid, aromatic and aliphatic sulfonic acids typified by benzenesulfonic acid and methanesulfonic acid Examples thereof include compounds. These carboxylic acid compounds and sulfonic acid compounds may have an arbitrary number of unsaturated bonds at arbitrary positions in the molecule like maleic acid, regardless of whether they are aromatic or aliphatic.

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

Fluorine, chlorine, bromine, iodine, or the like can be used as the halogen that is a component of the acid halide. Of these, chlorine is most preferred. 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 that is a constituent of the amide. Among these amines, ammonia, aliphatic amines typified by ethylamine and dibutylamine, amines having aromatic free radicals typified by aniline and benzylamine, and the like can be exemplified as preferable compounds. .

  Examples of the inorganic acid compound used as the electron donor include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and the like.

  Examples of ether compounds used as electron donors include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane and 2 -Aliphatic polyvalent ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9- Examples thereof include polyvalent ether compounds having an aromatic free radical in the molecule represented by bis (methoxymethyl) fluorene. Preferred examples of the polyvalent ether compounds can be selected from the examples of the compound (D) having at least two ether bonds in the present specification.

Examples of the ketone compound used as an electron donor include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2,2,4,6,6-pentamethyl-3,5-heptane. Examples thereof include polyvalent ketone compounds represented by dione.
Examples of the aldehyde compound used as the electron donor include aliphatic aldehyde compounds typified by propionaldehyde, aromatic aldehyde compounds typified by benzaldehyde, and the like.

  Examples of alcohol compounds used as electron donors include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenol derivative compounds typified by phenol and cresol, glycerin and 1,1′-bi-2-phenyl. Examples thereof include aliphatic or aromatic polyhydric alcohol compounds represented by naphthol.

  Examples of amine compounds used as electron donors include aliphatic amine compounds typified by diethylamine, nitrogen-containing alicyclic compounds typified by 2,2,6,6-tetramethyl-piperidine, and aniline. Aromatic amine compounds, nitrogen atom-containing aromatic compounds represented by pyridine, polyvalent amine compounds represented by 1,3-bis (dimethylamino) -2,2-dimethylpropane, and the like be able to.

  Moreover, the compound used as an electron donor can also be a compound containing the above-mentioned plural functional groups in the same molecule. Examples of such compounds include ester compounds having an alkoxy group typified by acetic acid- (2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate in the molecule, 2-benzoyl-benzoic acid Ketoester compounds represented by ethyl, ketoether compounds represented by (1-t-butyl-2-methoxyethyl) methylketone, represented by N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine Aminoether compounds, halogenoether compounds typified by epoxy chloropropane, and the like.

  These electron donors can be used not only alone but also in combination with a plurality of compounds. Among these, preferred are dibutyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic ester compounds having one or two substituents at the 2-position, such as butyl-diethyl malonate, one or two substituents at the 2-position, such as 2-n-butyl-diethyl succinate, or 2 Succinic acid ester compounds having one or more substituents at each of the 3-position and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane An aliphatic polyvalent ether represented by 1,3-dimethoxypropane having one or two substituents at the 2-position Compounds include, 9,9-bis (methoxymethyl) polyhydric ether compounds having a radical of aromatic typified fluorene in the molecule, and the like.

The amount ratio of each component constituting the solid component (A1) in the present invention can be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range.
The amount of titanium compounds used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable. When a halogen source compound is used in addition to the magnesium compound and the titanium compound, the amount used is the same as the magnesium compound used regardless of whether the magnesium compound and the titanium compound contain halogen or not. The molar ratio (number of moles of the halogen source compound / number of moles of the magnesium compound) to the amount used is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100. The inside is desirable.
When an electron donor is used as an optional component in preparing the solid component (A1), the amount used is a molar ratio with respect to the amount of magnesium compound used (number of moles of electron donor / number of moles of magnesium compound). ), Preferably in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.

The solid component (A1) in the present invention is obtained by contacting each of the above components constituting the solid component in the above quantitative ratio. As the contact condition of each component, it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

  In preparing the solid component (A1), washing may be performed with an inert solvent in the middle and / or finally. Examples of preferable solvent species include aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as toluene, and halogen-containing hydrocarbons such as 1,2-dichloroethylene and chlorobenzene.

  Any method can be used as a method for preparing the solid component (A1) in the present invention. Specifically, the methods disclosed in the following patents can be exemplified. In addition, this invention is not restrict | limited at all by the following illustration.

(I) A method in which a titanium-containing compound is brought into contact with a magnesium compound containing a halogen typified by magnesium chloride.
You may contact arbitrary components, such as an electron donor and a halogenated silicon compound, as needed. At this time, the optional components may be contacted simultaneously with the titanium-containing compounds or may be contacted separately.

(Ii) Magnesium compounds containing halogen typified by magnesium chloride are dissolved using alcohol compounds, epoxy compounds, phosphate ester compounds, etc., and containing halogen typified by titanium tetrachloride A method of contacting with titanium compounds.
Prior to contact with the halogen-containing titanium compounds, the particles may be formed using a method such as spray drying or dropping to a poor solvent such as a cooled hydrocarbon solvent. Moreover, you may contact arbitrary components, such as an electron donor and a halogenated silicon compound, as needed. In this case, the optional component may be brought into contact with the titanium compound containing halogen, or may be brought into contact separately.

(Iii) A solid component obtained by contacting a magnesium compound containing halogen typified by magnesium chloride with an alkoxy group-containing titanium compound typified by tetrabutoxytitanium and a specific polymer silicon compound, and titanium tetrachloride A method of contacting a titanium compound represented by halogen and / or a silicon compound containing halogen represented by silicon tetrachloride.
As the polymer silicon compounds, those represented by the following general formula (4) are suitable.
[-Si (H) (R) -O-] q (4)
(Here, R represents a hydrocarbon group having 1 to 10 carbon atoms, and q represents a degree of polymerization such that the viscosity of the polymeric silicon compound is 1 to 100 centistokes.)
Specific examples of the compound include methyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and the like. Moreover, you may contact arbitrary components, such as an electron donor, as needed. In this case, the optional component may be contacted simultaneously with the titanium compound containing halogen and / or the silicon compound containing halogen, or may be contacted separately.

(Iv) After contacting an alkoxy group-containing magnesium compound typified by diethoxymagnesium with an alkoxy group-containing titanium compound typified by tetrabutoxytitanium, a halogenating agent or a halogen typified by titanium tetrachloride is contained. Contacting with titanium compounds.
If necessary, an optional component such as an electron donor may be contacted. In this case, the optional component may be contacted simultaneously with the halogenating agent or the halogen-containing titanium compound, or may be contacted separately.

(V) A method of bringing an alkoxy group-containing magnesium compound typified by diethoxymagnesium into contact with a titanium compound containing a halogen typified by titanium tetrachloride.
You may contact arbitrary components, such as an electron donor and a halogenated silicon compound, as needed. In this case, the optional component may be brought into contact with the titanium compound containing halogen, or may be brought into contact separately.

(Vi) A method of bringing metal magnesium into contact with an alcohol and, if necessary, an iodine-containing compound typified by iodine, and then contacting with a halogen-containing titanium compound typified by titanium tetrachloride.
You may contact arbitrary components, such as an electron donor and a halogenated silicon compound, as needed. In this case, the optional component may be brought into contact with the titanium compound containing halogen, or may be brought into contact separately.

(Vii) A method of contacting an organic magnesium compound such as a Grignard reagent typified by butyl magnesium chloride with a titanium-containing compound.
Examples of the titanium-containing compounds include alkoxy group-containing titanium compounds typified by tetrabutoxytitanium and halogen-containing titanium compounds typified by titanium tetrachloride. If necessary, an optional component such as an electron donor, an alkoxy group-containing silicon compound represented by tetraethoxysilane, and a halogenated silicon compound may be contacted. In this case, the optional component may be brought into contact with the titanium-containing compound at the same time or may be brought into contact separately.

(2) Vinylsilane compound (A2)
As the vinylsilane compound (A2) used in the present invention, compounds disclosed in JP-A-2-34707 and JP-A-2003-292522 can be used. These vinylsilane compounds are compounds having a structure in which at least one hydrogen atom of monosilane (SiH ₄ ) is substituted with vinyl groups, and a part or all of the remaining hydrogen atoms are replaced with other free radicals. It can represent with General formula (1).
[CH ₂ = CH-] _m SiX _n R ¹ _j (OR ² ) _k (1)
(In the formula, X represents halogen, R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, a hydrocarbon group or an organosilicon group, and m ≧ 1, 0 ≦ n ≦ 3, 0 ≦ j ≦ 3, 0 ≦ (k ≦ 2, m + n + j + k = 4)

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

In general formula (1), R ² represents hydrogen, a hydrocarbon group, or an organosilicon group. When R ² is a hydrocarbon group, it can be selected from the same group of compounds as R ¹ . When R ² 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 used as R ² 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 ² and takes a value of 0 or more and 2 or less. In the case of a compound having a k value of 3 such as vinyltriethoxysilane, the performance as the vinylsilane compound (A2) in the present invention is not exhibited, and the organosilicon compound (A3c) having an alkoxy group in the present invention is used. This is not preferable because the performance of This is considered to be the same as structurally similar to t-butyltriethoxysilane (as will be described later, this t-butyltriethoxysilane is effective as an organosilicon compound (A3c) having an alkoxy group in the present invention. Is). More preferably, the value of k is desirably 0 or more and 1 or less, and particularly preferably 0. When the value of k is 2, two R ² may be the same as or different from each other. Regardless of the value of k, R ¹ and R ² may be the same or different.

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

(3) (A3) Organosilicon compound (A3a) having an alkoxy group and / or compound (A3b) having at least two ether bonds
(A3a) Organosilicon Compound Having Alkoxy Group As the organosilicon compound (A3a) having an alkoxy group used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula (2).
R ³ R ⁴ _a Si (OR ⁵ ) _b (2)
(Wherein R ³ is a hydrocarbon group or heteroatom-containing hydrocarbon group, R ⁴ is a free radical selected from the group consisting of hydrogen, halogen, hydrocarbon group and heteroatom-containing hydrocarbon group, and R ⁵ is a hydrocarbon group. And 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, and a + b = 3.)

In general formula (2), R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.
The hydrocarbon group used as R ³ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group used as R ³ include a linear aliphatic hydrocarbon group represented by an n-propyl group, a branched aliphatic group represented by an i-propyl group and a t-butyl group. Examples thereof include a hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ³ , and in particular, i-propyl group, i-butyl group, t-butyl group, i-hexyl group, cyclopentyl. It is desirable to use a group, a cyclohexyl group, or the like.
When R ³ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^3, choose from the example of the case where R ³ is a hydrocarbon group is preferable. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In general formula (2), R ⁴ represents hydrogen, halogen, a hydrocarbon group or a heteroatom-containing hydrocarbon group.
Examples of the halogen used as R ⁴ include fluorine, chlorine, bromine and iodine. When R ⁴ is a hydrocarbon group, it generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group used as R ⁴ include a linear aliphatic hydrocarbon group typified by a methyl group or an ethyl group, a branched fat typified by an i-propyl group or a t-butyl group. An alicyclic hydrocarbon group typified by an aromatic hydrocarbon group, a cyclopentyl group or a cyclohexyl group, an aromatic hydrocarbon group typified by a phenyl group, and the like. Among these, 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, or the like.
In the case where R ⁴ is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples in which R ³ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
When the value of a is 2, two R ⁴ may be the same or different. Regardless of the value of a, R ⁴ may be the same as or different from R ³ .

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

Preferable examples of the organosilicon compound (A3a) having an alkoxy group used in the present invention include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et _{) Si (OMe) 2, t} -Bu (n-Pr) Si (OMe) 2, c-Hex (Me) Si (OMe) 2, c-Hex (Et) Si (OMe) 2, c-Pen 2 Si _{(OMe) 2, i-Pr} 2 Si (OMe) 2, i-Bu 2 Si (OMe) 2, i-Pr (i-Bu) Si (OMe) 2, n-Pr (Me) Si (OMe) 2 , T-BuSi (OEt) ₃ , (Et ₂ N) ₂ Si (OMe) ₂ , Et ₂ N—Si (OEt) ₃ ,

And so on.
These organosilicon compounds can be used alone or in combination with a plurality of compounds.

(A3b) Compound having at least two ether bonds The compound (A3b) having at least two ether bonds used in the present invention is a compound disclosed in JP-A-3-294302 and JP-A-8-333413. Etc. can be used. In general, it is desirable to use a compound represented by the following general formula (3).
_{^{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8 ... (3)
(In the formula, R ⁶ and R ⁷ represent a free radical selected from the group consisting of hydrogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group, and R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.)

In General Formula (3), R ⁶ represents a free radical selected from the group consisting of hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group.
The hydrocarbon group used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group used as R ⁶ include a linear aliphatic hydrocarbon group represented by an n-propyl group, a branched aliphatic group represented by an i-propyl group and a t-butyl group. Examples thereof include a hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, Etc. are desirable.
Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure containing 2 or 3 unsaturated bonds in the ring structure can be taken. It may also be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And alicyclic hydrocarbon groups typified by, aromatic hydrocarbon groups typified by phenyl groups, and the like.

In the general formula (3), R ⁷ represents a free radical selected from the group consisting of hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . Preferably it is hydrogen.
In General Formula (3), R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, R ⁸ can be selected from the examples when R ⁶ is a hydrocarbon group. Preferably, it is a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group. Most preferred is a methyl group.
When R ⁶ to R ⁸ are heteroatom-containing hydrocarbon groups, the heteroatom is preferably selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus, and silicon. Further, regardless of whether R ⁶ to R ⁸ are a hydrocarbon group or a heteroatom-containing hydrocarbon group, they may optionally contain a halogen. When R ⁶ to R ⁸ contain a heteroatom and / or halogen, the skeleton structure is preferably selected from the group consisting of examples in the case of a hydrocarbon group. Further, the eight substituents R ⁶ to R ⁸ may be the same as or different from each other.

Preferable examples of the compound (A3b) having at least two ether bonds used in the present invention include 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-dimethoxy Lopan, 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) indene, 1,1 -Bis (phenoxymethyl) -3,6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornadinene, and the like. 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 (A3b) having at least two ether bonds can be used not only alone but also in combination with a plurality of compounds. Moreover, it may be the same as or different from the polyvalent ether compound used as the optional component (A1d) in the solid component (A1).

(4) (A4) Organoaluminum compound The solid catalyst component (A) in the present invention comprises a solid component (A1), a vinylsilane compound (A2), and (A3) an organosilicon compound having an alkoxy group, and / or at least Although it is formed by contacting a compound having two ether bonds, other optional components may be contacted by any method as long as the effects of the present invention are not impaired. An organic aluminum compound (A4) can be mentioned as an example of such an arbitrary component.
As the organoaluminum compound (A4) used as an optional component in preparing the solid catalyst component (A) in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following general formula (5).
R ⁹ _c AlX _d (OR ¹⁰ ) _e (5)
(In the formula, 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 general formula (5), R ⁹ is a hydrocarbon group, preferably 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 ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In general formula (5), X is halogen or hydrogen. Examples of the halogen used as X include fluorine, chlorine, bromine, iodine and the like. Of these, chlorine is particularly preferred.
In the general formula (5), R ¹⁰ is a hydrocarbon group or a crosslinking group by Al. When R ¹⁰ is a hydrocarbon group, R ⁷ can be selected from the same group as exemplified for the hydrocarbon group of R ⁹ . Moreover, it is also possible to use alumoxane compounds represented by methylalumoxane as the organoaluminum compound (E ′), in which case R ⁷ represents a cross-linking group of Al.

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

2. Method for Preparing Solid Catalyst Component (A) The solid catalyst component (A) in the present invention comprises (A1) a solid component, (A2) a vinylsilane compound, and (A3) an organosilicon compound having an alkoxy group, and / or at least It is formed by contacting a compound having two ether bonds. Under the present circumstances, you may contact other arbitrary components, such as (A4) organoaluminum compound, by arbitrary methods in the range which does not impair the effect of this invention. As the contact condition of each component of the solid catalyst component (A), it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. In general, the following conditions are preferred.

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

The amount ratio of each component constituting the solid catalyst component (A) in the present invention may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range. .
The amount of the vinylsilane compound (A2) used is a molar ratio to the titanium component constituting the solid component (A1) (number of moles of vinylsilane compound (A2) / number of moles of titanium atoms), preferably 0.001 to 1,000. And particularly preferably within the range of 0.01 to 100.
The amount used when the organosilicon compound having an alkoxy group (A3a) is used is the molar ratio to the titanium component constituting the solid component (A1) (the number of moles of the organosilicon compound having an alkoxy group (A3a) / titanium atom). The number of moles) is preferably in the range of 0.01 to 1,000, and particularly preferably in the range of 0.1 to 100.
When the compound (A3d) having at least two ether bonds is used, the amount used is a molar ratio to the titanium component constituting the solid component (A1) (number of moles of the compound (A3d) having at least two ether bonds / 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.
The amount used when the organoaluminum compound (A4) is used as an optional component is preferably a molar ratio to the titanium component constituting the solid component (A1) (number of moles of organoaluminum compound (A4) / number of moles of titanium atoms). Is in the range of 0.1 to 100, particularly preferably in the range of 1 to 50.

  Regarding the contact procedure of (A1) a solid component, (A2) a vinylsilane compound, and (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds, an arbitrary procedure may be used. it can. Specific examples include the following procedure (i) to procedure (iii).

Procedure (i): (A1) Method of contacting (A2) a vinylsilane compound with a solid component and then (A3) contacting an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds (ii) ): (A1) Method of contacting (A3) vinyl silane compound after contacting (A3) organosilicon compound having alkoxy group and / or compound having at least two ether bonds with solid component (iii): All The method of contacting these compounds simultaneously can be exemplified. Among these, procedure (i) and procedure (iii) are preferable.

  In addition, (A1) a vinyl silane compound, (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds can be contacted with the solid component any number of times. . In this case, (A2) vinyl silane compound, (A3) organosilicon compound having alkoxy group and / or compound having at least two ether bonds are different even if the compounds used in multiple times of contact are the same. Also good. Even when the organoaluminum compound (A4) is used as an optional component, it can be contacted in any order as described above. Among these, the following procedure (iv) to procedure (vi) are mentioned.

Procedure (iv): (A1) (A2) a vinylsilane compound is contacted with a solid component, (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds is further contacted, and (A4) ) Method of contacting organoaluminum compound (v): (A1) contacting the solid component with (A2) a vinyl silane compound, (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds, Thereafter, (A4) Method of contacting organoaluminum compound (vi): A method of contacting all compounds simultaneously is preferred. (A4) The organoaluminum compound can also be contacted a plurality of times as described above. At this time, the (A4) organoaluminum compounds used a plurality of times may be the same or different.

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

3. Other optional components in the catalyst In the present invention, it is an essential requirement to use the solid catalyst component (A) as a catalyst. However, the organoaluminum compound (B), which will be described below, is organic as long as the effects of the present invention are not impaired. Arbitrary components, such as a silicon compound (C) and the compound (D) which has an at least 2 ether bond, can be used.

(B) Organoaluminum compound As the organoaluminum compound (B) used as an optional component in the catalyst of the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. Preferably, it can be selected from the same group as exemplified in the organoaluminum compound (A4) which is an optional component when 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 but also a plurality of compounds can be used in combination.

(C) Organosilicon compound As the organosilicon compound (C) used as an optional component in the catalyst of the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. Preferably, it can be selected from the same group as exemplified in the organosilicon compound (A3a) having an alkoxy group used in the solid catalyst component (A). At this time, the organosilicon compound (A3a) having an alkoxy group and the organosilicon compound (C) used as an optional component may be the same or different.
As the organosilicon compound (C), not only a single compound but also a plurality of compounds can be used in combination.

(D) Compound having at least two ether bonds The compound (D) having at least two ether bonds used as an optional component in the catalyst of the present invention is disclosed in JP-A-3-294302 and JP-A-8-333413. The compounds disclosed in the above can be used. Preferably, it can be selected from the same group as exemplified in the compound (A3b) having at least two ether bonds used in the solid catalyst component (A). At this time, the compound (A3b) having at least two ether bonds used in preparing the solid catalyst component (A) and the compound (D) having at least two ether bonds used as optional components of the catalyst were the same. Or different.
As the compound (D) having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.

(E) Other compounds As long as the effects of the present invention are not impaired, components other than the organoaluminum compound (B), the organosilicon compound (C), and the compound (D) having at least two ether bonds may be used as an optional catalyst. It can be used as a component. For example, as disclosed in JP-A-2004-124090, by using a compound (E) having a C (═O) N bond in the molecule, an amorphous material such as CXS (cold xylene solubles) The production of sex components can be suppressed. Preferred examples of this compound include tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone, and the like. An organometallic compound having a metal atom other than Al, such as diethyl zinc, can also be used.

4). Use amount of optional component The use amount of the optional component in the catalyst of the present invention may be any as long as the effects of the present invention are not impaired, but generally it is preferably within the following range.
The amount used when the organoaluminum compound (B) is used is preferably a molar ratio to the titanium component constituting the solid catalyst component (A) (number of moles of organoaluminum compound (B) / number of moles of titanium atoms), preferably 1. Is preferably in the range of 10 to 500, particularly preferably in the range of 10 to 500.
The amount used when the organosilicon compound (C) is used is preferably a molar ratio to the titanium component constituting the solid catalyst component (A) (number of moles of organosilicon compound (C) / number of moles of titanium atoms), preferably 0. The range of .01 to 10,000 is preferable, and the range of 0.5 to 500 is particularly preferable.
When the compound (D) having at least two ether bonds is used, the amount used is the molar ratio to the titanium component constituting the solid catalyst component (A) (the number of moles of the compound (D) having at least two ether bonds / titanium). The number of moles of atoms is preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.
When the compound (E) having a C (═O) N bond in the molecule is used, the amount used is a molar ratio with respect to the titanium component constituting the solid catalyst component (A) (C (═O) N bond in the molecule). The number of moles of the compound (E) possessed / the number of moles of titanium atoms) is preferably in the range of 0.001 to 1,000, and particularly preferably in the range of 0.05 to 500.

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

  When using what was prepolymerized as a solid catalyst component (A), prepolymerization can be performed in arbitrary procedures in the preparation procedure of a solid catalyst component (A). For example, (A1) after subjecting the solid component to prepolymerization, (A2) a vinylsilane compound, and (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds can be contacted. . Alternatively, prepolymerization may be performed after contacting (A1) a solid component, (A2) a vinylsilane compound, and (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds. Furthermore, when (A1) a solid component, (A2) a vinylsilane compound, and (A3) an organosilicon compound having an alkoxy group and / or a compound having at least two ether bonds are contacted, prepolymerization may be performed simultaneously. .

Arbitrary conditions can be used for the reaction conditions of a solid catalyst component (A) or a solid component (A1), and said monomer in the range which does not impair the effect of this invention. In general, the following range is preferable.
The amount of prepolymerization is within the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g, based on 1 gram of the solid catalyst component (A) or solid component (A1). The range of is desirable. The reaction temperature during the prepolymerization is -150 to 150 ° C, preferably 0 to 100 ° C. The reaction temperature during the prepolymerization is desirably lower than the polymerization temperature during the main polymerization. In general, the reaction is preferably carried out with stirring, and an inert solvent such as hexane or heptane can also be present.
The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization.

[II] Production Process and Polymerization Conditions As a production process for the polypropylene block copolymer, any process can be used as long as it is a gas phase polymerization process in which heat is removed mainly using latent heat of liquefied propylene.
In the present invention, the gas phase polymerization method does not mean that no liquid is present. The phase for polymerization may be substantially a gas phase, and a liquid may be present within a range not impairing the effects of the present invention. Examples of this liquid include not only liquefied propylene for heat removal but also inert hydrocarbon components such as hexane.
As the gas phase polymerization process, a two-stage gas phase polymerization process is preferable, and the two-stage gas phase polymerization process uses the above-described solid catalyst component (A) and first polymerizes propylene alone in the first stage. Or copolymerizing propylene with one or more comonomers selected from the group consisting of ethylene and α-olefins having 4 to 8 carbon atoms, and then, in the second stage, propylene, ethylene and carbon atoms having 4 to 8 carbon atoms. One or more comonomers selected from the group consisting of α-olefins are copolymerized.

  As a mixing mode, either a method using a fluidized bed or a method using a stirrer may be used. When a stirrer is used, a fluidized bed equipped with a stirrer can also be used. The stirrer may have the stirring shaft facing the vertical direction or the horizontal direction. As the shape of the stirring blade, any paddle, helical, gate, etc. can be used. Among these, the method using a paddle blade or a gate blade with the stirring shaft oriented in the horizontal direction is most preferable.

As for the arrangement of the polymerization reactors, any method can be used as long as the effects of the present invention are not impaired. There are no particular restrictions on the number of reactors, but random co-polymerization of a reactor that performs the first polymerization step for producing a polymer component (a) mainly composed of propylene, and propylene and other monomers (also referred to as comonomers). A reactor for performing the second polymerization step for producing the combined component (b) and one or more reactors are required. In the first polymerization step and / or the second polymerization step, when a plurality of reactors are used, they may be connected in series or in parallel. At this time, it is desirable that at least one reactor for performing the first polymerization step and at least one reactor for performing the second polymerization step be arranged in series.
Further, in the first polymerization step and / or the second polymerization step, as a method for further narrowing the residence time distribution without increasing the number of tanks, a weir for restricting the movement of powder can be provided in the polymerization tank. As a form of the weir, a fixed weir fixed to the polymerization tank may be used, or a rotating weir fixed to the rotating shaft may be used.

  As the polymerization method, either a batch method or a continuous method may be used, but it is desirable to use a continuous method from the viewpoint of productivity. A particularly preferred example is a method in which 2 to 4 polymerization tanks are connected in series and polymerized by a continuous method.

  Any method can be used as a method of removing heat using the latent heat of liquefied propylene. In order to perform heat removal using the latent heat of liquefied propylene, propylene in a substantially liquid state may be supplied to the polymerization tank. Although fresh liquefied propylene can be supplied to the polymerization tank, it is generally desirable to use recycled propylene. The general procedure using recycled propylene is illustrated below. A gas containing propylene is extracted from the polymerization tank, the gas is cooled to liquefy at least a part, and at least a part of the liquefied component is supplied to the polymerization tank. At this time, the component to be liquefied needs to contain propylene, but may contain a comonomer component typified by butene and an inert hydrocarbon component typified by isobutane.

As a method for supplying liquefied propylene, any method can be used as long as propylene in a substantially liquid state is supplied to the polymerization tank. You may supply to the bed of a polypropylene particle, and you may supply to a gaseous-phase part. When supplying to a gas phase part, you may supply to the gas phase part inside a polymerization tank, and may supply to a recycle gas line. In particular, in the case of a stirring and mixing tank in which the stirring shaft is directed in the horizontal direction, it is desirable to supply it to the gas phase part inside the polymerization tank.
In the present invention, removing heat mainly using the latent heat of liquefied propylene does not mean removing heat using only the latent heat of liquefied propylene. Other heat removal methods can be used in combination as long as the effects of the present invention are not impaired. Specifically, a method of removing heat using a jacket provided in the polymerization tank, a method of extracting a part of the gas from the polymerization tank, cooling it with a heat exchanger, and returning the gas to the polymerization tank again can be exemplified. it can. However, in the present invention, heat removal using the latent heat of liquefied propylene needs to be the main. Specifically, in at least one polymerization tank, it is necessary to remove at least half of the heat removal amount by using the latent heat of liquefied propylene.

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 0 ° C. or higher, more preferably 30 ° C. or higher, particularly preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower, particularly preferably 80 ° C. or lower. It is. The polymerization pressure is preferably 1200 kPa or more, more preferably 1400 kPa or more, particularly preferably 1600 kPa or more, preferably 4200 kPa or less, more preferably 3500 kPa or less, particularly preferably 3000 kPa or less. However, the polymerization pressure should not be set lower than the vapor pressure of propylene at the polymerization temperature.
The residence time can be arbitrarily adjusted according to the configuration of the polymerization tank and the product index. Generally, it is set within a range of 30 minutes to 5 hours.
The catalytic activity varies depending on the polymerization conditions such as temperature, pressure and residence time, but is preferably 30,000 gPP / g or more. Preferably, the catalytic activity is in the range of 30,000 gPP / g catalyst to 500,000 gPP / g catalyst, more preferably in the range of 35,000 gPP / g catalyst to 200,000 gPP / g catalyst, most preferably 40, It is in the range of not less than 000 gPP / g catalyst and not more than 100,000 gPP / g catalyst. When the catalytic activity is lower than the above range, the catalyst residue increases, and it is necessary to use a large amount of additives such as a neutralizing agent, which is not economical and not preferable. When the catalytic activity is higher than the above range, it is difficult to locally remove heat from the catalyst feed portion, and foreign matters such as lumps are easily formed, which is not preferable.

The solid catalyst component and other optional components can be supplied to the polymerization tank using a known method. The solid catalyst component may be supplied as it is in a powder form to the polymerization tank, but may be supplied after being diluted with an inert solvent such as hexane or mineral oil.
Since the solid catalyst component has very high activity, it is preferable to dilute and supply it to the polymerization tank. In particular, as a polymer component (a) mainly composed of propylene units, the activity becomes extremely high when producing an ethylene propylene random copolymer or the like, and there is a possibility of causing troubles such as fouling if the dilution is insufficient. is there. In such a case, it consists of an organic silicon compound (C) which is an optional component, a compound (D) having at least two ether bonds, and a compound (E) having a C (═O) N bond in the molecule. It is effective to use at least one compound selected from the group. When these optional components are brought into contact with each other before the solid catalyst component is supplied to the polymerization tank, the fouling prevention effect is further enhanced, which is preferable. At this time, the contacting method of both components is arbitrary, but the optional components are supplied to the line for supplying the solid catalyst components to the polymerization tank, or the optional components are added to the place where the solid catalyst components are diluted with an inert solvent. It is preferable to do.

In the second polymerization step for producing the random copolymer component (b), an activity inhibitor can be used as an optional component. The addition of an activity inhibitor can reduce reactor fouling. In addition, an effect of improving quality such as surface impact strength can be expected. Any compound can be used as the activity inhibitor as long as it can be made lower than the activity in the case where the activity in the second polymerization step is not added by adding to the reactor. Examples of such activity inhibitors include compounds having an active hydrogen group such as alcohol and amine, compounds containing oxygen atoms such as oxygen, ether and ketone. In any case, one or more functional groups may be used (polyalcohol, polyether, polyketone, alcohol having an alkoxy group, etc.). Preferred are alcohol, oxygen, ketone and ether.
Most preferred among these is oxygen. When oxygen is used, it may be diluted with another gas such as nitrogen or propylene. The amount of oxygen added is arbitrary as long as the effects of the present invention are not impaired, but the molar ratio of oxygen to Ti atoms contained in the solid catalyst component (A) is preferably 1 or more and 1000 or less. More preferably, it is 5 or more and 500 or less, and most preferably 10 or more and 100 or less. If the amount of oxygen added is less than this range, the fouling suppression effect is undesirably lowered. If the amount of oxygen added is more than this range, the activity becomes too low and the polymer component (b) cannot be polymerized as much as necessary, which is not preferable.
In the case of producing a polypropylene block copolymer having the same index, it is desirable to add more activity inhibitor from the viewpoint of fouling prevention and product quality. Higher activity in the second polymerization step for producing the random copolymer component (b) is preferable because more activity inhibitor can be added. By using the catalyst system of the present invention, not only the overall activity of the first polymerization step and the second polymerization step, but also the activity in the second polymerization step can be further increased, so more activity inhibitors are added. can do. In addition, when compared to the case where the minimum amount of activity inhibitor is added to prevent fouling, the activity of the second polymerization step is higher than that of the conventional catalyst, and therefore a larger amount of random copolymer The coalescence component (b) can be produced. That is, it becomes possible to stably produce a polypropylene block copolymer having a high content of the random copolymer component (b) as compared with the conventional catalyst system.
As a method for adding the activity inhibitor, any method can be used as long as the effect of the present invention is not inhibited. When oxygen is used, it is desirable to add it to the recycle gas line.

[III] Polypropylene block copolymer The polypropylene block copolymer obtained by the method of the present invention is low in production cost, excellent in moldability and quality, and has a particularly high MFR.
The polypropylene block copolymer obtained by the method of the present invention is, for example, cold xylene in the polymer component (a) mainly composed of propylene produced in the first polymerization step when the two-stage gas phase polymerization process is used. Since there are few amorphous components represented by indicators such as soluble matter (CXS), there is a feature that it is difficult to cause molding troubles such as fuming, eyes, mold stains, and resin burns. Since the amorphous component is small, the crystallinity of the molded product is high and the rigidity is excellent. Furthermore, it has a high melting point and is excellent in heat resistance. Hereinafter, each polymer component will be described in detail.

(I) Polymer component (a)
The polymer component (a) in the block copolymer of the present invention preferably has an MFR of 50 g / 10 min or more, more preferably an MFR of 50 g / 10 min to 1,000 g / 10 min, still more preferably It is 60 g / 10 min or more and 800 g / 10 min or less, and most preferably 100 g / 10 min or more and 500 g / 10 min or less. CXS is preferably 3% by mass or less, more preferably 0.1% by mass or more and 2.5% by mass or less, still more preferably 0.2% by mass or more and 2.0% by mass or less, and most preferably 0.3% by mass. It is not less than 1.8% by mass.
Here, CXS is defined as a value measured by the following method.
The sample (about 5 g) is completely dissolved once in 140 ° C. p-xylene (300 ml). Thereafter, it is cooled to 23 ° C., and the polymer is precipitated at 23 ° C. for 12 hours. After the precipitated polymer is filtered off, p-xylene is evaporated from the filtrate. The polymer remaining after evaporation of p-xylene is dried under vacuum at 100 ° C. for 2 hours. The polymer after drying is weighed, and the value of CXS is obtained as mass% with respect to the sample.
In order to adjust the MFR, the concentration of hydrogen as a chain transfer agent in the polymerization tank may be adjusted. Increasing the hydrogen concentration increases the MFR of the polymer component (a) mainly composed of propylene, and vice versa. When the catalyst of the present invention is used, not only can the MFR be increased under the condition of a relatively low hydrogen concentration, but also there is a feature that a polypropylene having a high stereoregularity and a low CXS can be produced even at a high MFR. In order to further lower CXS within the range defined by the present invention, an organic silicon compound (C) as an optional component, a compound (D) having at least two ether bonds, and C (═O) N in the molecule It is effective to use at least one compound selected from the group consisting of the compound (E) having a bond. As the amount of these optional components used increases, the polymer component (a) composed mainly of propylene having a low CXS can be obtained.

In order to increase the rigidity of the polypropylene block copolymer, the polymer component (a) is preferably a propylene homopolymer. However, a copolymer with a small amount of a comonomer can be used for the purpose of improving hinge characteristics and moldability. Specifically, the polymer component (a) contains a comonomer unit corresponding to one or more comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms in a content of 5% by mass or less. it can. Preferably the comonomer is ethylene and / or 1-butene, most preferably ethylene. Use of an α-olefin having 9 or more carbon atoms as a comonomer is not preferable because the catalytic activity is remarkably lowered. Moreover, when the content of the comonomer unit in the polymer component (a) exceeds 5% by mass, the rigidity is remarkably lowered, which is not preferable.
Here, the content of the comonomer unit can be determined by an arbitrary analysis technique. Specific examples include infrared spectroscopy (IR) and nuclear magnetic resonance analysis (NMR).

(Ii) Polymer component (b)
The polymer component (b) in the block copolymer of the present invention is a random copolymer of propylene and one or more comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. Preferably the comonomer is ethylene and / or 1-butene, most preferably ethylene. Use of an α-olefin having 9 or more carbon atoms as a comonomer is not preferable because the catalytic activity is remarkably lowered. The content of propylene units in the polymer component (b) is 20% by mass or more and 80% by mass or less. When the content of the propylene unit is out of this range, the random copolymer component (b) becomes too hard, so that the impact strength is remarkably lowered. More preferably, the content of propylene units is 25% by mass or more and 75% by mass or less, and particularly preferably 30% by mass or more and 70% by mass or less. Most preferably, the content of propylene units is 35% by mass or more and 65% by mass or less.
In order to adjust the content of the propylene unit in the polymer component (b), the concentration of each monomer in the reactor for polymerizing the polymer component (b) may be changed. The content of propylene units in the polymer component (b) can be analyzed by the same method as the content of comonomer units in the polymer component (a).

The MFR of the polymer component (b) can be any value, but is preferably 0.001 g / 10 min to 100 g / 10 min, more preferably 0.01 g / 10 min to 50 g / 10 min, More preferably, it is 0.1 g / 10 min or more and 10 g / 10 min or less, and most preferably 0.5 g / 10 min or more and 5 g / 10 min or less. If the MFR of the polymer component (b) is too higher than the above range, the block copolymer becomes sticky, which is not preferable. If the MFR of the polymer component (b) is too lower than the above range, the dispersion becomes worse, the gel increases, and the appearance when the block copolymer is molded is remarkably deteriorated.
The MFR of the polymer component (b) can be adjusted by the same method as the MFR of the polymer component (a).

The polypropylene block copolymer in the present invention contains the polymer component (a) and the polymer component (b) in a mass ratio of 10:90 to 84:16. When the content of the polymer component (b) is less than 16% by mass, the impact strength is lowered, which is not preferable. When the content of the polymer component (b) is more than 90% by mass, the rigidity is lowered, which is not preferable. Preferably, the mass ratio of the polymer component (a) to the polymer component (b) is in the range of 30:70 to 83:17, more preferably the polymer component (a) and the polymer component (b). The mass ratio of the polymer component (a) to the polymer component (b) is particularly preferably in the range of the mass ratio of 60:40 to 81:19. Most preferably, the mass ratio of the polymer component (a) to the polymer component (b) is within the range of the mass ratio of 65:35 to 80:20.
In order to adjust the mass ratio of the polymer component (a) and the polymer component (b), the first polymerization step for producing the polymer component (a) and the second polymerization step for producing the polymer component (b) What is necessary is just to control the manufacturing amount ratio. It is well known to the operator that the production amount ratio of both can be controlled by changing the polymerization temperature and residence time.
The mass ratio of the polymer component (a) and the polymer component (b) can be determined by any known method. Specifically, it can be determined from the ratio of the production amounts of the first polymerization step and the second polymerization step. Moreover, it can also analyze by TREF (temperature rising elution fractionation method) using the difference in crystallinity between the polymer component (a) and the polymer component (b).

The MFR of the polypropylene block copolymer can be set to an arbitrary value, preferably 10 g / 10 min to 1,000 g / 10 min, more preferably MFR 20 g / 10 min to 500 g / 10 min, More preferably, it is 25 g / 10 min or more and 100 g / 10 min or less, and particularly preferably 30 g / 10 min or more and 60 g / 10 min or less. If the MFR is too low, the injection moldability is inferior, and if it is too high, the physical properties such as impact strength are adversely affected.
The MFR of the polypropylene block copolymer depends on three factors: the MFR of the polymer component (a), the MFR of the polymer component (b), and the quantitative ratio of the polymer component (a) and the polymer component (b). It is determined uniquely. Therefore, the MFR of the block copolymer can be controlled by adjusting these three factors. In order to improve the balance between quality and moldability, it is desirable to increase the MFR of the block copolymer by increasing the MFR of the polymer component (a).

  In addition, since a high MFR polypropylene block copolymer can be produced with high productivity according to the present invention, the polypropylene block copolymer in the present invention is superior to the conventional method in that it does not have to be subjected to CR treatment. ing. Since it is difficult to produce a high MFR block copolymer with high productivity by the conventional production method, a low MFR block copolymer is produced (with high productivity), and this low MFR block copolymer is produced. A technique for increasing the MFR by treating the coalescence with a radical generator such as peroxide in a granulation step or the like is generally used. Usually, this treatment with peroxide is called CR treatment. When this CR treatment is performed, the MFR of the block copolymer can be increased, but the decomposition quality of the block copolymer is deteriorated in terms of odor, hue, taste, etc., because by-products such as peroxides are by-produced. There is a problem with the point. Another problem is that the random copolymer component (b) of propylene and other monomers is easily crosslinked to form a gel. Therefore, the present invention, which can produce a high MFR polypropylene block copolymer with high productivity without performing CR treatment, shows a high advantage over the prior art.

Moreover, the copolymer obtained by the present invention exhibits excellent particle properties.
That is, in this copolymer, the particle properties of the polymer particles are generally evaluated based on the polymer bulk density, particle size distribution, particle appearance, etc. The copolymer obtained according to the present invention has 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, the polymer particles are suitable. The polymer particle size can take any value, but the average particle size is preferably in the range of 1,000 to 3,000 μm, particularly preferably 1,100 to 2,000 μm. Is desirable.

[IV] Use The polypropylene block copolymer obtained by this invention can be used for arbitrary uses. Especially, it can use suitably with respect to the field | area where a high MFR polypropylene block copolymer is desirable. Particularly preferred examples include molding fields such as injection molding and injection compression molding.
More specific applications include general injection materials such as miscellaneous goods, automotive materials such as bumpers and instrument panels, household appliance materials such as refrigerators and vacuum cleaner housings, and yogurt. Impact-resistant food packaging materials typified by containers, heat-resistant food packaging materials typified by cup noodle containers, textile materials typified by non-woven fabrics for sanitary products, elastic fiber materials typified by supporters, etc. , Etc. can be preferably used.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples. The measuring method of each physical property value in the present invention is shown below.
(1) MFR: Evaluation was performed under the conditions of 230 ° C. and 21.18 N based on JIS-K6921 using a melt indexer manufactured by Takara.
(2) Polymer bulk density: The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
(3) Polymer average particle size The particle size distribution of the powder sample was measured by a sieving method according to JIS-Z8801. In the obtained particle size distribution, the average particle size was defined as the particle size that was 50% by mass on the mass basis.
(4) CXS: A sample (about 5 g) was completely dissolved in 140 ° C. p-xylene (300 ml), cooled to 23 ° C., and a polymer was precipitated at 23 ° C. for 12 hours. After separation by filtration, p-xylene was evaporated from the filtrate, the polymer remaining after evaporation was dried under reduced pressure at 100 ° C. for 2 hours, and the dried polymer was weighed to obtain the value of CXS as mass% with respect to the sample. .
(5) Determination of ethylene content: The average ethylene content in the copolymer was measured using an infrared spectrophotometer according to the following procedure.
(I) Preparation of sample The sample was formed into a sheet having a thickness of 500 µm by a heat and pressure press. The pressing conditions were a temperature of 190 ° C., a preheating time of 2 minutes, a pressing pressure of 50 MPa, and a pressing time of 2 minutes.
(Ii) Measurement of absorbance with an infrared spectrophotometer The amount of absorption was measured using the sheet obtained by the above molding under the following conditions.
Equipment: Shimadzu FTIR-8300
Resolution: 4.0 cm ⁻¹
Measurement range: 4,000 to 400 cm ⁻¹
Absorbance peak area calculation range: 700 to 760 cm ⁻¹
(Iii) Calculation of ethylene content A calibration curve was prepared using a sample whose ethylene content was previously determined by NMR, and the ethylene content was calculated based on this calibration curve.
(6) Calculation of content of propylene ethylene random copolymer component unit in propylene ethylene block copolymer First polymerization step for producing propylene homopolymer component and second polymerization for producing propylene ethylene random copolymer component Calculated from the value of the production amount of the process, the value was obtained as mass%.
(7) Calculation of ethylene content in propylene ethylene random copolymer component From the value of ethylene content in propylene ethylene block copolymer and the content of propylene ethylene random copolymer component unit in propylene ethylene block copolymer The value was obtained by calculation.
(8) Calculation of MFR of propylene ethylene random copolymer component MFR of propylene homopolymer, MFR of propylene ethylene block copolymer, and content of propylene ethylene random copolymer component unit in propylene ethylene block copolymer Was calculated based on the viscosity mixing rule shown below.
100 × LN (MFR of block copolymer)
= (Propylene homopolymer unit content) x LN (Propylene homopolymer MFR)
+ (Random copolymer component unit content) x LN (Random copolymer MFR)
(9) Ti content: The sample was accurately weighed and hydrolyzed, and then measured using a colorimetric method. About the sample after prepolymerization, content was calculated using the mass remove | excluding prepolymerized polymer.
(10) Silicon compound content: The sample was accurately weighed and decomposed with methanol. The silicon compound concentration in the obtained methanol solution was determined by comparison with a standard sample using gas chromatography. From the silicon compound concentration in methanol and the mass of the sample, the content of silicon compound units contained in the sample was calculated. About the sample after prepolymerization, content was calculated using the mass remove | excluding prepolymerized polymer.

Example 1
(1) Preparation of solid component A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified toluene was introduced. To this, 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added at room temperature. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. to carry out a reaction for 3 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. 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 portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (A1) was 2.7% by mass.
Next, a 20 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 100 g of the solid component (A1) slurry was introduced as a solid component (A1). Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 25 g / L. 50 ml of SiCl ₄ was added and a reaction was performed at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane.
Thereafter, purified n-heptane was introduced to adjust the liquid level to 4 L. To this, 30 ml of dimethyldivinylsilane, 30 ml of (i-Pr) ₂ Si (OMe) ₂ and 80 g of Et ₃ Al in an n-heptane diluted solution were added as Et ₃ Al, and a reaction was carried out at 40 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane, and a portion of the resulting slurry was sampled and dried. As a result of analysis, the solid component contained 1.2% by mass of Ti and 8.8% by mass of (i-Pr) ₂ Si (OMe) ₂ .

(2) Prepolymerization Using the solid component obtained above, prepolymerization was performed by the following procedure. Purified n-heptane was introduced into the slurry, and the solid component concentration was adjusted to 20 g / L. After cooling the slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 280 g. After the supply of propylene was completed, the reaction was further continued for 30 minutes. Next, the gas phase was sufficiently 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 (A). This solid catalyst component (A) contained 2.5 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component (A) excluding polypropylene contained 1.0% by mass of Ti and 8.2% by mass of (i-Pr) ₂ Si (OMe) ₂ .

(3) Polymerization of propylene This will be described with reference to the attached flow sheet shown in FIG. A gas phase polymerization reactor using two polymerization tanks was used. The two polymerizers 1 and 10 have a continuous horizontal gas phase polymerizer (length / diameter) equipped with a stirrer having an inner diameter D: 340 mm, a length L: 1260 mm, a rotating shaft diameter: 90 mm, and an internal volume: 110 dm ^3. = 3.7).
After replacing the inside of the polymerization vessel 1, 25 kg of polypropylene powder (average particle size 1500 µm) from which polymer particles of 500 µm or less were removed was introduced, and the solid catalyst component (A) obtained above was used as an n-hexane slurry. Was continuously fed into. The supply rate of the solid catalyst component (A) was adjusted so that the production rate of polypropylene became a constant value. Further, a 15% by mass n-hexane solution of triethylaluminum was continuously supplied so that the molar ratio was 100 with respect to 1 mol of Ti atoms in the catalyst component (A). Further, hydrogen is polymerized so that the molar ratio of the hydrogen concentration in the polymerization vessel 1 to the propylene concentration is 0.08, and the propylene monomer is polymerized so that the pressure in the polymerization vessel 1 is maintained at 2.2 MPa and the temperature is kept at 65 ° C. It was supplied into the vessel 1. Unreacted gas discharged from the polymerization reactor 1 was extracted out of the reactor system through an unreacted gas extraction pipe 4, cooled and condensed, and separated into liquefied propylene and mixed gas. The mixed gas was returned to the polymerization vessel 1 through the recycle gas pipe 2. Further, hydrogen gas for adjusting the molecular weight of the propylene polymer was also supplied from the pipe 2. The liquefied propylene condensed outside the reactor system was supplied from the raw material mixed gas supply pipe 3 together with fresh raw material propylene. The heat of polymerization was removed by the heat of vaporization of liquefied propylene supplied from this pipe 3.
Polypropylene produced in the polymerization vessel 1 is continuously extracted from the polymerization vessel 1 through the polymer extraction pipe 5 so that the retained level of the polymer is 50% by volume of the reaction volume, and is supplied to the polymerization vessel 10 in the second polymerization step. Supplied.
The polymer and propylene gas from the first polymerization step were continuously supplied into the polymerization vessel 10 to carry out propylene ethylene random copolymerization. The reaction conditions were a temperature of 60 ° C. and a pressure of 2.0 MPa. The unreacted gas discharged from the polymerization vessel 10 was extracted out of the reactor system through the unreacted gas extraction pipe 8, cooled and condensed, and separated into liquefied propylene and mixed gas. The mixed gas was returned to the polymerization vessel 10 through the recycle gas pipe 7. Also, ethylene gas and hydrogen gas are supplied from the pipe 7 and adjusted so that the molar ratio of ethylene concentration to propylene concentration in the polymerization vessel 10 is 0.32, and the molar ratio of hydrogen concentration to ethylene concentration is 0.1. did. The liquefied propylene condensed outside the reactor system was supplied from the raw material mixed gas supply pipe 6 together with fresh raw material propylene. The polymerization heat was removed by the vaporization heat of the liquefied propylene supplied from the pipe 6. Furthermore, for adding an activity inhibitor in which oxygen is connected as an activity inhibitor to the pipe 7 so that the molar ratio is 30 with respect to Ti atoms contained in the solid catalyst component (A) supplied to the polymerization vessel 1. It was supplied from the pipe 11.
The propylene block copolymer produced in the second polymerization step was continuously extracted from the polymerization vessel 10 through the polymer extraction pipe 9 so that the retained level of the polymer was 60% by volume of the reaction volume. The extracted powder was separated into gases by the gas recovery machine 12, and the powder part was extracted to the recovery system.
The production rate of the polypropylene block copolymer was 15 kg / hr, the average residence time in the polymerization vessel 1 was 1.6 hr, and the average residence time in the polymerization vessel 10 was 1.0 hr. When the activity was calculated as a value obtained by dividing the production rate by the supply rate of the solid catalyst component (A) (excluding the prepolymerized polymer), it was 50,000 g-PP / g-catalyst.
When the sample taken out partially from the superposition | polymerization device 1 was analyzed, MFR was 120 g / 10min and CXS was 1.6 mass%. When the polypropylene block copolymer finally obtained was analyzed, the MFR was 32 g / 10 min. In addition, the content of the propylene ethylene random copolymer component unit in the polypropylene block copolymer is 25% by mass, the ethylene content in the propylene ethylene random copolymer component is 40% by mass, and the MFR of the propylene ethylene random copolymer component. Was 0.6 g / 10 min. The polypropylene particles were smooth, the polymer bulk density (BD) was 0.45 g / ml, and the average particle size was 1,220 μm.

(Examples 2 to 5)
Using the solid catalyst component (A) of Example 1, polymerization was performed in the same manner as in Example 1 except that the polymerization conditions shown in Table 1 were used. At this time, in Example 5, the silicon compound described in the table was continuously supplied into the polymerization vessel 1. The results are shown in Table 1.

(Comparative Example 1)
(1) Preparation of solid catalyst component Using the solid component (A1) of Example 1, prepolymerization was performed according to the following procedure. A 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the slurry of the solid component (A1) of Example 1 was introduced as the solid component (A1). Purified n-heptane was introduced to adjust the concentration of the solid component (A1) to 20 g / L. After cooling the slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 280 g. After the supply of propylene was completed, the reaction was further continued for 30 minutes. Next, the gas phase was sufficiently 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 (A). This solid catalyst component (A) contained 2.4 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component (A) excluding polypropylene contained 2.2% by mass of Ti.
(2) Polymerization of propylene Polymerization was performed in the same manner as in Example 1 except that the polymerization conditions shown in Table 2 were used using the solid catalyst component (A). The resulting polypropylene particles were quite sticky. The results are shown in Table 2.

(Comparative Examples 2 and 3)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization conditions shown in Table 2 were used. The results are shown in Table 2.

(Comparative Example 4)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the supply amount of oxygen as the activity inhibitor was adjusted so that the molar ratio was 1 with respect to the Ti atoms contained in the solid catalyst component (A). Fouling in the polymerization vessel 10 was severe and could not be stably operated.

As is clear from Tables 1 and 2, when Examples 1 to 5 and Comparative Examples 1 to 3 are contrasted, in the present invention, a high MFR propylene ethylene block copolymer can be obtained with a low hydrogen concentration. It is clear that The catalytic activity is also high, and the properties of the polymer particles obtained are good. Further, the stereoregularity of the propylene homopolymer is high.
Specifically, in Example 1, compared with Comparative Example 1, a propylene ethylene block copolymer having the same MFR can be produced at a lower hydrogen concentration. Further, the catalyst activity is high, and the amount of the activity inhibitor that can be added in the production of the propylene ethylene random copolymer component is also large. Due to this, it can be seen that the properties of the polymer particles obtained are very good. In addition, the CXS of the propylene homopolymer is low and the stereoregularity is high.
In Comparative Example 2, a propylene homopolymer was produced under the same conditions as in Example 1, but the MFR of the propylene homopolymer was low, so that the obtained block copolymer had a low MFR. Comparative Example 3 supplies the same amount of activity inhibitor as Example 1 in order to improve the properties of the polymer particles, but the content of propylene ethylene random copolymer component units is extremely low, which is not preferred. In Comparative Example 4, although the supply amount of the activity inhibitor is lowered in order to increase the content of the lopyreneethylene random copolymer component unit, the properties of the polymer particles are extremely deteriorated and fouling is severe and stable operation cannot be performed.
On the other hand, as shown in Examples 1 to 4, it is apparent that the present invention can be applied to various propylene ethylene random copolymer component settings.
In Example 5, the organosilicon compound (C) is used as an optional component, but performance equivalent to that in Example 1 is obtained.
Therefore, in the examples, in terms of the production of a high MFR propylene ethylene block copolymer, the results are superior to the comparative examples in terms of productivity, catalytic activity, stereoregularity, and particle properties. It can be said that it is obtained.

  Since the polypropylene block copolymer produced using the present invention has a high MFR, it can be used in the molding field such as injection molding and injection compression molding. In particular, general injection materials such as sundries, bumpers, Automotive materials such as instrumental panels, household appliance materials such as housings for refrigerators and vacuum cleaners, impact-resistant food packaging materials such as yogurt containers, heat-resistant food packaging materials such as cup noodle containers, and non-woven fabrics for sanitary products It can preferably be used for stretchable fiber materials such as materials and supporters. Further, since a high MFR polypropylene block copolymer can be produced at a low hydrogen concentration, the productivity is high and the production can be inexpensive.

It is the schematic showing the manufacturing process of the polypropylene used by the Example and the comparative example.

Explanation of symbols

1 Polymerizer (first polymerization process)
2 Recycled gas piping 3 Raw material mixed gas supply piping 4 Unreacted gas extraction piping 5 Polymer extraction piping 6 Raw material mixed gas supply piping 7 Recycled gas piping 8 Unreacted gas extraction piping 9 Polymer extraction piping 10 Polymerizer (second polymerization step) )
11 Pipe for adding activity inhibitor 12 Gas recovery machine 13 Bag filter

Claims (11)

A polypropylene block containing the following polymer component (a) and polymer component (b) in a mass ratio of 10:90 to 84:16 by a gas phase polymerization process in which heat of reaction is mainly removed by the heat of vaporization of liquefied propylene. A method for producing a copolymer comprising:
Solid component (A1) containing titanium, magnesium and halogen as essential components, vinylsilane compound (A2), organosilicon compound having an alkoxy group, and / or compound (A3) having at least two ether bonds A method for producing a polypropylene block copolymer, comprising using the solid catalyst component (A) obtained by contact treatment.
Polymer component (a): a propylene homopolymer or a random copolymer of propylene and one or more comonomers selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, The unit content is 5% by mass or less, and the MFR measured at 230 ° C. and 21.18N is 50 g / 10 min or more. Polymer component (b): Propylene, ethylene and an α-olefin having 4 to 8 carbon atoms. A random copolymer with at least one comonomer selected from the group, wherein the propylene unit content is 20% by mass or more and 80% by mass or less   The gas phase polymerization process is a two-stage gas phase polymerization process, wherein propylene is polymerized alone in the first stage using the solid catalyst component (A), or propylene, ethylene, and carbon number 4 Copolymerized with one or more comonomers selected from the group consisting of -8 α-olefins, and then in the second stage, one selected from the group consisting of propylene, ethylene and α-olefins having 4 to 8 carbon atoms 2. The method for producing a polypropylene block copolymer according to claim 1, wherein the copolymer is copolymerized with the above comonomer. The method for producing a polypropylene-based block copolymer according to claim 1 or 2, wherein the vinylsilane compound (A2) is a compound represented by the following general formula (1).
[CH ₂ = CH-] _m SiX _n R ¹ _j (OR ² ) _k (1)
(In the formula, X represents halogen, R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, a hydrocarbon group or an organosilicon group, and m ≧ 1, 0 ≦ n ≦ 3, 0 ≦ j ≦ 3, 0 ≦ (k ≦ 2, m + n + j + k = 4) The polypropylene-based block copolymer according to any one of claims 1 to 3, wherein the organosilicon compound (A3a) having an alkoxy group is a compound represented by the following formula (2). Production method.
R ³ R ⁴ _a Si (OR ⁵ ) _b (2)
(Wherein R ³ is a hydrocarbon group or a heteroatom-containing hydrocarbon group, R ⁴ is any radical selected from the group consisting of hydrogen, halogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group, R ⁵ is Represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3.) The polypropylene block copolymer according to any one of claims 1 to 4, wherein the compound (A3b) having at least two ether bonds is a compound represented by the following general formula (3): Manufacturing method.
^{_{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8 ... (3)
(Wherein R ⁶ and R ⁷ represent any free radical selected from the group consisting of hydrogen, a hydrocarbon group and a heteroatom-containing hydrocarbon group, and R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. )   The polypropylene system according to any one of claims 1 to 5, wherein the polymer component (b) is a random copolymer having an MFR in the range of 0.5 to 5.0 g / 10 min. A method for producing a block copolymer.   The method for producing a polypropylene-based block copolymer according to any one of claims 1 to 6, wherein the solid catalyst component (A) is prepolymerized.   The method for producing a polypropylene-based block copolymer according to any one of claims 1 to 7, wherein the catalyst activity is 30,000 gPP / g catalyst or more.   The method for producing a polypropylene block copolymer according to any one of claims 1 to 8, wherein the gas phase polymerization process is performed in a reactor having a stirrer.   The polypropylene block copolymer according to any one of claims 1 to 9, wherein the gas phase polymerization process is performed in a horizontal reactor having an agitator rotating around a horizontal axis therein. Production method.   The method for producing a polypropylene block copolymer according to any one of claims 1 to 10, wherein peroxide is not used.

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