 Propylene homopolymer
专利摘要:
The present invention relates to a propylene homopolymer having high stereoregularity and excellent processability in sheet or film forming, wherein a melt flow rate (MFR) is 0.1 to 20 g / 10 min; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is calculated by the following formula (1) from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. 3 mol% propylene homopolymer: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm which are absorption strengths by isoblock chain, respectively). 公开号:KR19990022344A 申请号:KR1019970708824 申请日:1997-03-31 公开日:1999-03-25 发明作者:다쿠오 가타오카；마사요시 사이토 申请人:아라이 요이치；도호 티타늄 가부시키가이샤； IPC主号:
专利说明:
Propylene homopolymer As essential components, olefins are polymerized in the presence of a solid catalyst component containing a titanium halide, a magnesium compound and an electron donor compound, and a catalyst containing a third component such as an organoaluminum compound and a silicon compound. Many proposals have been made for the process. In addition, processes have been intensively studied to produce crystalline polyolefins with high stereoregularity in high yield in the presence of such catalysts. For example, JP-A-63-3010 (JP-A used herein means a Japanese patent application published before being examined), JP-A-1-221405, JP-A-1-315406 Nos., JP-A-3-227309, JP-A-3-70711 and JP-A-4-8709 disclose solid catalyst components prepared from dialkoxy magnesium and titanium tetrachloride as the main starting materials, and organic aluminum. In the presence of a catalyst for olefin polymerization consisting of a third component such as a compound and a silicon compound, a process for producing a polymer having a high stereoregularity in high yield is described. In addition, various proposals for a catalyst for olefin polymerization consisting of a solid catalyst component comprising an aluminum halide compound, a magnesium compound and a titanium halide compound as essential components, and a third component such as an organoaluminum compound and an organic acid ester and a silicon compound Have been. For example, JP-A-55-161807 describes a catalyst composed of magnesium chloride, titanium halide, organic acid ester, halogenated hydrocarbon compound and aluminum halide compound. JP-A-61-31402 includes reacting a reaction product of an aluminum halide compound with a silicon compound with a magnesium compound, and then reacting the reaction product with a halogenated titanium compound, a phthalate ester, an organoaluminum compound, and a silicon compound. In the presence of a catalyst consisting of a solid catalyst component obtained by a manufacturing process, a process for producing a polymer having a high stereoregularity in high yield is described. The various techniques described above are highly active enough to omit the so-called deashing step, which is a process for removing catalyst residues such as chlorine and titanium remaining in polymers produced by propylene polymerization in the presence of a catalyst. The focus is on the development of catalyst components, while at the same time focusing on improving the yield of polymers that are stericly ordered and increasing the persistence of the polymerization activity. These techniques can provide good results for these purposes. On the other hand, for propylene polymers, JP-A-7-25946, for example, describes high crystallinity, high stereoregularity and very long mesoform lengths of components insoluble in boiling n-heptane. propylene polymers have been described. The propylene polymer produced by the above-mentioned conventional techniques has a high heat denaturation temperature, a high melting point, a high crystallization temperature, and thus exhibits a very good effect on the stiffness and heat resistance. Accordingly, the propylene polymer prepared by the above-described conventional techniques can be used in various molding methods such as extrusion, blow molding, injection molding, etc. into sheets, films, and the like. However, some problems with the molding of polypropylene still remain unresolved. In particular, when the above-mentioned polymer having a high rigidity is applied to extrusion molding into a sheet, a film, or the like, problems such as breaking during high-speed molding and a decrease in transparency of the molded article may occur. As a way to solve these problems, it is usually known to reduce the stereoregularity of the propylene polymer to reduce the energy required to process the propylene polymer. However, such a solution is undesirable because the propylene polymer contains a large amount of atactic polymers and thus worsens rather than improves the quality of the product. An example of another solution that has been tried is a method in which the polymerization system contains a small amount of ethylene as a copolymer monomer. Although this method can somewhat control the crystallinity and density of the resulting polymer, undesirable phenomena such as complicated manufacturing process, increased manufacturing cost, and increased production rate of atactic polypropylene with very low stereoregularity There is a disadvantage that causes. In addition, in order to improve the transparency of the propylene polymer, a method of adding various nucleating agents to the produced propylene polymer has been attempted in JP-A-2-265905 and JP-A-2-29444. However, this method has a disadvantage in that odor is generated during processing by the addition of the crystal generating agent. In addition, since the added crystallization agents are not sufficiently dispersed in the polymer, this method has a weak point in improving transparency. As mentioned above, these conventional techniques are inadequate in solving the above-mentioned problems. Therefore, there is a strong need to develop propylene homopolymers with a high stereoregularity that can be easily processed into high quality sheets or films. The present invention relates to propylene homopolymers. In particular, the present invention relates to propylene homopolymers having a low xylene-soluble component and extremely high isoblock content in the xylene-insoluble component. The present inventors have diligently studied the solution to the above-mentioned problems. As a result, propylene homopolymers have been found which have high stereoregularity and high isoblock content, thereby facilitating molding, in particular into sheets or films. This completed the present invention. The present invention is a novel propylene homopolymer, having a melt flow rate (MFR) of 0.1-20 g / 10 min; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is calculated by the following formula (1) from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. 3 mol% propylene homopolymer: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm which are absorption strengths by isoblock chain, respectively). The propylene homopolymer of the present invention is particularly useful as a material for sheet or film production. In addition, the present invention provides a propylene prepared by polymerizing propylene in the presence of an organic aluminum compound (B) and an organosilicon compound (C) with a solid catalyst component (A) containing magnesium, titanium, halogen and electron donors as essential components. As homopolymer, the melt flow rate (MFR) is 0.1-20 g / 10 min; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is at least 3 mole%, calculated by Equation (1) below from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. Relates to propylene homopolymers: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm which are absorption strengths by isoblock chain, respectively). The present invention also provides a propylene homopolymer prepared by polymerizing propylene in the presence of a catalyst comprising the following components (A), (B) and (C), wherein the melt flow rate (MFR) is 0.1-20 g / 10 min; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is at least 3 mole%, calculated by Equation (1) below from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. Relates to propylene homopolymers: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm, respectively, which are absorption strengths by isoblock chain): (A) a solid catalyst component prepared from the following components (a)-(d): (a) Magnesium compound represented by the following general formula: Mg (OR 1 ) 2 (Wherein R 1 represents a C 1-4 alkyl group or aryl group); (b) at least one aluminum compound selected from the group consisting of aluminum compounds represented by the following general formulas: Al (OR 2 ) m X 1 3-m (Wherein R 2 represents a C 1-4 alkyl or aryl group; X 1 represents a halogen atom; m represents a real number of at least 0 to 3 or less); R 3 n AlX 2 3-n (Wherein R 3 represents an alkyl group of C 1-4 ; X 2 represents a hydrogen atom or a halogen atom; n represents a real number greater than 0 and less than or equal to 3); (c) a titanium compound represented by the following general formula: Ti (OR 4 ) p X 3 4-p (Wherein R 4 represents an alkyl group of C 1-4 ; X 3 represents a halogen atom; p represents 0 or an integer of 1 to 3); And (d) diesters of aromatic dicarboxylic acids; (B) the organoaluminum compound represented by the following general formula: R 5 q AlY 3-q (Wherein R 5 represents an alkyl group of C 1-4 ; Y represents one selected from a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom; q represents a real number greater than 0 and less than or equal to 3); And (C) organosilicon compounds represented by the following general formula: R 6 r Si (OR 7 ) 4-r (Wherein R 6 is the same or different from each other, and each represents a C 1-12 alkyl group, cycloalkyl group, phenyl group, vinyl group, allyl or aralkyl group; R 7 is the same or different from each other, An alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group each of C 1-4 ; r represents 0 or an integer of 1 to 3). Hereinafter, embodiments of the present invention will be described in detail. The propylene homopolymer of the present invention is a polymer produced by polymerizing propylene alone as a monomer, and is distinguished from a copolymer produced by blending propylene with a copolymerization monomer such as ethylene to polymerize. The propylene homopolymer of the present invention has a melt flow rate of 0.1 to 20 g / 10 minutes, preferably 0.3 to 15 g / 10 minutes, and more preferably 0.5 to 10 g / 10 minutes. Melt flow rate (MFR) is measured at 230 ° C with a load of 2.16 kg according to JIS K6758. In addition, the propylene homopolymer of the present invention has a xylene-soluble component content of 6% by weight or less, preferably 2.0 to 5.0% by weight, more preferably 3.0 to 5.0% by weight. In addition, the propylene homopolymer of the present invention has a relatively high stereoregularity as described above, but isoblock content [IB] in the xylene-insoluble component is at least 3 mol%, preferably 3.5 to 20 mol%, more Preferably it is 3.5-10 mol%. Here, the isoblock has a monomer unit defect homopolymerized in the polymer chain, so that the methyl group (monomer unit defect) in the polymerized propylene monomers, as shown in the following formula, It shows the crystal structure of the methyl group and other polymers in other polymerized propylene monomers in planar view. (In the following formula, Me represents a methyl group (-CH 3 ).) Isoblocks are stereoblock and atablock (JE Ewen, Journal of American Chemical Society 106, 6355 (1984) / V. Busico, Macromolecules 27, 4521 (1994) / V. Busico, Macromolecules 28, 1887 (1995) / T. Keiji, Y. Doi, Macromol. Chem. Rapid Commun. 2, 293 (1981)). In the above formula, m (meso: meso) and r (racemi: racemic) states are as follows. The structural units by the absorption intensities Pmmmr, Pmmrr and Pmrrm in the 13 C-NMR spectrum are represented by (i), (ii) and (i) in the following equations. Therefore, the isoblock content [IB] in the above-mentioned crystalline structure can be calculated from the absorption strengths Pmmmr, Pmmrr and Pmrrm in the 13 C-NMR spectrum by the following equation (1): [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein among, [Pmmmr], [Pmmrr] and [Pmrrm] are, respectively, 13 of the absorption intensity of Pmmmr, Pmmrr and Pmrrm by isobutyl block chain at C-NMR, all of the absorption intensity (Pmmmm, Pmmmr, Prmmr, Relative strength ratio (in mole%) to the sum of Pmmrr, Prmrr, Pmmrm, Prmrm, Prrrr, Pmrrr and Pmrrm) The propylene homopolymer of the present invention is measured by a dynamic stress rheometer (DSR), and preferably has a polydispersity index (PI) of 3.0 to 8.0, more preferably 3.5 to 8.0. Indicates. The polydispersity index (PI) is a variable associated with the molecular weight distribution (weight average molecular weight / number average molecular weight) of the polymer. The higher the polydispersity index, the better the processability. In addition, as an index showing the stereoregularity of the propylene homopolymer of the present invention, the content of the insoluble component extracted by boiling n-heptane is preferably 90.0 to 99.9% by weight, more preferably 94.0 to 99.8% by weight, particularly preferably. Preferably it is 94.5 to 99.4 weight%. The method for producing the propylene homopolymer of the present invention is not particularly limited. In practice, however, the propylene homopolymers of the present invention are, for example, solid catalyst components (A) containing magnesium, titanium, halogens and electron donors as essential components, organoaluminum compounds (B) and organosilicon compounds (C). It can be prepared by polymerizing propylene in the presence of a catalyst for olefin polymerization formed by. Hereinafter, various components constituting the catalyst for olefin polymerization used to prepare the propylene homopolymer of the present invention will be described. Solid catalyst component (A) can be prepared by contacting a magnesium compound, a titanium compound and an electron donor with each other. More specifically, the following components (a) to (d) can be used. (a) Magnesium compound represented by the following general formula: Mg (OR 1 ) 2 (Wherein R 1 represents a C 1-4 alkyl group or aryl group); (b) at least one aluminum compound selected from the group consisting of aluminum compounds represented by the following general formulas: Al (OR 2 ) m X 1 3-m (Wherein R 2 represents a C 1-4 alkyl or aryl group; X 1 represents a halogen atom; m represents a real number of at least 0 to 3 or less); R 3 n AlX 2 3-n (Wherein R 3 represents an alkyl group of C 1-4 ; X 2 represents a hydrogen atom or a halogen atom; n represents a real number greater than 0 and less than or equal to 3); (c) a titanium compound represented by the following general formula: Ti (OR 4 ) p X 3 4-p (Wherein R 4 represents an alkyl group of C 1-4 ; X 3 represents a halogen atom; p represents 0 or an integer of 1 to 3); And (d) diesters of aromatic dicarboxylic acids. General formula for constituting the solid catalyst component (A) (hereinafter sometimes referred to as component (A)): Mg (OR 1 ) 2 (wherein two R 1 are the same or different from each other, and each C 1-4 Examples of the magnesium compound (hereinafter referred to as component (a) in some cases) represented by the alkyl group or the aryl group of the above include dialkoxy magnesium and diaryloxymagnesium. More specifically, at least one dimethoxymagnesium, diethoxy magnesium, di-n-propoxyshimamium, di-iso-propoxymagnesium, di-n-butoxymagnesium, di-iso-butoxymagnesium, diphenoxy Magnesium, ethoxy methoxymagnesium, ethoxy-n-propoxymagnesium, n-butoxyethoxymagnesium, iso-butoxyethoxymagnesium, diphenoxymagnesium, etc. can be used. Among these magnesium compounds, diethoxy magnesium and di-n-propoxyshima magnesium are particularly preferable. The dialkoxy magnesium used in the preparation of the solid catalyst component (A) here may be granular or powdered. The particle shape of dialkoxy magnesium may be amorphous or spherical. When spherical dialkoxy magnesium is used, a polymer powder having a better particle shape and a narrower particle size distribution is obtained. Therefore, the resulting polymer powder becomes easy to handle during the polymerization operation, and problems such as blocking caused by the fine particles contained in the resulting polymer powder can be solved. The above-mentioned spherical dialkoxy magnesium does not necessarily need to be circular, but may also be elliptical or pebble-like. More specifically, the sphericity of the particles is calculated by the ratio (l / w) of the major axis length (l) to the minor axis length (w), and is 3 or less, preferably 1 to 2, and more. Preferably it is 1-1.5. In addition, the average particle diameter of the above-mentioned dialkoxy magnesium may be 1 to 200 μm, preferably 5 to 150 μm. The average particle diameter of the above-mentioned spherical dialkoxy magnesium may be 1-100 micrometers, Preferably it is 5-50 micrometers, More preferably, it may be 10-40 micrometers. In addition, in the particle size thereof, it is preferable that the above-mentioned spherical compound contains very fine particle size distribution by containing less fine powder or coarse powder. Specifically, the particle size distribution comprises 20% or less, preferably 10% or less, particles having a particle size of 5 μm or less, and 10% or less, preferably 5% or less of particles having a particle size of at least 100 μm. Included in the amount. Calculate the particle size distribution as ln (D90 / D10), where D90 represents the particle size when the integrated particle size reaches 90%, and D10 represents the particle size when the integrated particle size reaches 10%. 3 or less, preferably 2 or less. The aforementioned dialkoxy magnesium does not necessarily need to be used as starting material in preparing the solid catalyst component (A). For example, the aliphatic one in the presence of a catalyst of metallic magnesium and iodine, such as C 1 ~ 4 alcohol obtained by the reaction, can be used in the manufacture of a solid catalyst component (A). Here, in producing the solid catalyst component (A), the aluminum compound (hereinafter referred to as component (b) in some cases) used as component (b) is represented by the following general formulas (I) and (II) It includes at least one selected from the group consisting of aluminum compounds represented: Al (OR 2 ) m X 1 3-m (Ⅰ) Wherein R 2 represents an alkyl group of C 1-4 , an aryl group such as a phenyl group, or an aralkyl group in which one or two C 1-3 alkyl groups are substituted; when m is 2 or more, a plurality of R 2 are the same Or X 1 represents a halogen atom such as chlorine and bromine, m represents a real number of at least 0 to 3 or less); R 3 n AlX 2 3-n (II) Wherein R 3 represents an alkyl group of C 1-4 ; X 2 represents a hydrogen atom or a halogen atom; n represents a real number greater than 0 and less than or equal to 3; when n is 2 or more, a number of R 3 s are the same or can be different). Examples of the aluminum compound represented by general formula (I) described above include aluminum trihalide, alkoxyaluminum dihalide, dialkoxyaluminum halide and trialkoxyaluminum. Specific examples of these aluminum compounds include aluminum trichloride, aluminum tribromide, aluminum triodide, diethoxyaluminum chloride, di-iso-propoxyaluminum chloride, dibutoxyaluminum chloride, ethoxyaluminum dichloride, iso-propoxyaluminum Dichloride, butoxyaluminum dichloride, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri-iso-propoxyaluminum, tributoxyaluminum and tri-iso-butoxyaluminum. Among these aluminum compounds, aluminum trichloride, di-iso-propoxyaluminum chloride, iso-propoxyaluminum dichloride, triethoxyaluminum and tri-iso-propoxyaluminum are particularly preferred. Examples of the aluminum compound represented by the general formula (II) include trialkylaluminum, dialkylaluminum halides and alkylaluminum dihalides. Specific examples of these aluminum compounds include triethylaluminum, tri-iso-butylaluminum, diethylaluminum hydride, di-iso-butylaluminum hydride, diethylaluminum chloride, di-iso-butylaluminum chloride, ethylaluminum di Chloride, propylaluminum dichloride, ethylaluminum sesquichloride and butylaluminum sesquichloride. Among these aluminum compounds, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and ethylaluminum sesquichloride are particularly preferred. As the above-mentioned component (b), one or more selected from the group consisting of the aforementioned compounds of the general formulas (I) and (II) can be used. Component (b) may be in direct contact with other components, or may be diluted with an organic solvent such as aromatic hydrocarbons (eg toluene, xylene) or aliphatic hydrocarbons (eg hexane, heptane) before use. Component (c) used to prepare the solid catalyst component (A) is a titanium compound represented by the following general formula (hereinafter referred to as component (c) in some cases): Ti (OR 4 ) p X 3 4-p Wherein R 4 represents an alkyl group of C 1-4 ; X 3 represents a halogen atom such as chlorine and bromine; p represents an integer of 0 or 1 to 3; and if p is 2 or more, a plurality of R 4 May be the same or different). Examples of these titanium compounds include titanium tetrahalide and alkoxy titanium halides. Specific examples of titanium tetrahalides include TiCl 4 , TiBr 4 and TiI 4 . Specific examples of alkoxytitanium halides include Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , Ti (OC 3 H 7 ) Cl 3 , Ti (O- (n) C 4 H 9 ) Cl 3 , Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 , Ti (OC 3 H 7 ) 2 Cl 2 , Ti (O- (n) C 4 H 9 ) 2 Cl 2 , Ti (OCH 3 ) 3 Cl, Ti (OC 2 H 5 ) 3 Cl, Ti (OC 3 H 7 ) 3 Cl and Ti (O- (n) C 4 H 9 ) 3 Cl. Among these titanium compounds, titanium tetrahalide is preferred. TiCl 4 is particularly preferred. These titanium compounds may be used alone or as a mixture. Component (c) may be used after being dissolved or diluted in an organic solvent such as an aromatic hydrocarbon (for example, toluene, xylene) or an aliphatic hydrocarbon (for example, hexane, heptane) before use. Particularly preferred examples of diesters of aromatic dicarboxylic acids (hereinafter optionally referred to as component (d)) as component (d) used to prepare the solid catalyst component (A) are straight chains of C 1-12 of phthalic acid. Or branched alkyl diesters. Specific examples of such phthalic acid diester include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, ethyl methyl phthalate, and butyl ethyl. Phthalate, methyl (iso-propyl) phthalate, ethyl (n-propyl) phthalate, ethyl (n-butyl) phthalate, di-n-pentylphthalate, di-iso-pentylphthalate, di-n-hexylphthalate, di-iso -Hexylphthalate, di-n-heptylphthalate, di-iso-heptylphthalate, di-n-octylphthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonylphthalate, Di-iso-decylphthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl (iso-hexyl) phthalate, ethyl (iso-octyl) phthalate, n-butyl (iso-octyl) phthalate, n-pentyl ( Hexyl) phthalate, n-pentyl (iso-hexyl) phthalate, iso-pentyl (heptyl) phthalate Latex, n-pentyl (iso-octyl) phthalate, n-pentyl (iso-nonyl) phthalate, iso-pentyl (n-decyl) phthalate, n-pentyl (undecyl) phthalate, iso-pentyl (iso-hexyl) phthalate n-hexyl (iso-octyl) phthalate, n-hexyl (iso-nonyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (iso-octyl) phthalate, n-heptyl (iso-nonyl) phthalate , n-heptyl (neo-decyl) phthalate and iso-octyl (iso-nonyl) phthalate. These phthalic acid diesters can be used alone or as a mixture. Of these phthalic acid diesters, diethylphthalate, di-n-butylphthalate, di-iso-butylphthalate and bis (2-ethylhexyl) phthalate are preferred. When 2 or more types of these components (d) are used as a mixture, these combination is not specifically limited. Where phthalic acid diesters are used, the combination thereof is preferably at least 4 different between the one phthalic acid diester and the other phthalic acid diester, adding up the carbon atoms contained in the two alkyl groups. Specific examples of such combinations are summarized below. (1) diethyl phthalate and di-n-butyl phthalate (2) diethyl phthalate and di-iso-butyl phthalate (3) diethyl phthalate and di-n-octyl phthalate (4) diethyl phthalate and bis (2-ethylhexyl) phthalate (5) di-n-butylphthalate and di-n-octylphthalate (6) di-n-butyl phthalate and bis (2-ethylhexyl) phthalate (7) diethyl phthalate, di-n-butylphthalate and bis (2-ethylhexyl) phthalate (8) diethyl phthalate, di-iso-butylphthalate and bis (2-ethylhexyl) phthalate. In addition to the components described above, polysiloxanes (hereinafter, optionally referred to as component (e)) can be used to prepare the solid catalyst component (A). As such polysiloxanes, one or more polysiloxanes (hereinafter sometimes referred to as component (e)) represented by the following general formula can be used: (Wherein x represents an average degree of polymerization of 2 to 30,000; R 8 to R 15 are each mainly composed of methyl groups and are partially composed of phenyl groups, hydrogen, higher fatty acid residues, epoxy-containing groups or poly) May be substituted with an oxyalkylene group). In the above-described compounds of the general formula, R 11 and R 12 may form a cyclic polysiloxane of methyl group. One or more polysiloxanes (hereinafter referred to as component (e) in some cases) represented by the above general formula can be used. The above-mentioned polysiloxanes are generally known as silicone oils and have a chain, partial viscosity of 25 to 10,000 cSt, preferably 2 to 1,000 cSt, more preferably 3 to 500 cSt at 25 ° C. Hydrocyclic, cyclic or modified polysiloxanes, which are liquid or viscous at room temperature. Examples of chained polysiloxanes include dimethylpolysiloxanes and methylphenylpolysiloxanes. Examples of partially hydrogenated polysiloxanes include methyl-hydrogenpolysiloxanes having a hydrogenation rate of 10-80%. Examples of cyclic polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane . Examples of modified polysiloxanes include C 6-30 higher fatty acid-substituted dimethylsiloxanes, epoxy group-substituted dimethylsiloxanes and polyoxyalkylene group-substituted dimethylsiloxanes. Specific examples of these polysiloxanes include TSF400, TSF401, TSF404, TSF405, TSF4045, TSF410, TSF411, TSF433, TSF437, TSF4420, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100, TSF483 and TSF484 [Toshiba Silicone Co ., Ltd. Commercially available products], and KF96, KF96L, KF96H, KF69, KF92, KF961, KF965, KF56, KF99, KF94, KF995, KF105, KF351, HIVAC-F4 and HIVAC-F5 [Shin-Etsu Chemical Co., Ltd. Commercial item]. Such polysiloxanes can be used in the form of solutions in organic solvents such as toluene, xylene, hexane and heptane. Solid catalyst component (A) can be prepared by contacting components (a), (b), (c), (d) and optionally (e) with one another. Such a contact process can proceed without an inert organic solvent, but it is preferable to proceed in the presence of the above-described organic solvent in consideration of the ease of the process operation. Examples of inert organic solvents usable herein include saturated hydrocarbons such as hexane, heptane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; And halogenated hydrocarbons such as o-dichlorobenzene, methylene chloride, carbon tetrachloride and dichloroethane. In particular, the aromatic hydrocarbon whose boiling point is 90-150 degreeC is preferable. Specific examples of such aromatic hydrocarbons include toluene, xylene and ethylbenzene. As for the ratio of the various components, the ratio of component (b) is 0.01 to 10 g, preferably 0.05 to 2.0 g, per 1 g of component (a). The proportion of component (c) is 0.01 to 200 ml, preferably 0.5 to 100 ml, per 1 g of component (a). The proportion of component (d) is 0.01 to 1.0 g, preferably 0.1 to 0.5 g per 1 g of component (a). The ratio of the optional component (e) is 0.01 to 5.0 g, preferably 0.05 to 1.0 g, per 1 g of component (a). The amount of the inert organic solvent to be used is not particularly limited, but is preferably 0.1 to 10 times the volume of the component (c) in consideration of handling problems. Each of these components may be added batchwise upon contact. Alternatively, one or more compounds may be appropriately selected and used. These components can be contacted in an inert gas atmosphere containing no moisture while stirring in a vessel equipped with a stirrer. If these components are modified by simply stirring and mixing, or by dispersing or suspending these components, they can be contacted at relatively low temperatures near room temperature. When these components are brought into contact with each other and then reacted to obtain a reaction product, it is preferred that the components be brought into contact at a temperature in the range of 40 to 130 ° C. If the reaction temperature is less than 40 ° C, the reaction cannot proceed sufficiently, and the resulting solid catalyst component will have insufficient physical properties. On the contrary, when the reaction temperature exceeds 130 ° C., the solvent to be used is volatilized heavily, thus making it difficult to control the reaction. The reaction time is at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes. In order to produce the solid catalyst component (A), component (a), component (b), component (c), component (d) and optional component (e) are brought into contact with each other. The order of contact of these components is not particularly limited and is optional. Specific examples of the contact order of these components are as follows. 1. Components (a), (b), (c) and (d) are brought into contact with each other simultaneously. 2. The component (c) is repeatedly contacted with the solid reaction product obtained by bringing components (a), (b), (c) and (d) into contact with each other. 3. Repetitive contact of component (d) with the solid reaction product obtained by first contacting components (a), (b) and (c) with each other. 4. Contact component (d) with the solid reaction product obtained by first contacting components (a), (b) and (c) with each other. Then, the reaction product and component (c) are repeatedly contacted. 5. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c) and (d) with each other. 6. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c) and (d) with each other. Then, the reaction product and component (c) are repeatedly contacted. 7. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c) and (d). Then, the reaction product is repeatedly contacted with components (b) and (c). 8. Repetitive contact of components (b) and (c) with the solid reaction product obtained by first contacting components (a), (b), (c) and (d) with each other. 9. The components (a), (b), (c), (d) and (e) are brought into contact with each other simultaneously. 10. Repeated contact of component (c) with the solid reaction product obtained by contacting components (a), (b), (c), (d) and (e) with each other. 11. Contact components (d) and (e) with the solid reaction product obtained by first contacting components (a), (b) and (c) with each other. 12. Contact components (d) and (e) with the solid reaction product obtained by first contacting components (a), (b) and (c) with each other. Then, the reaction product and component (c) are repeatedly contacted. 13. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c), (d) and (e) with each other. 14. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c), (d) and (e) with each other. Then, the reaction product and component (c) are repeatedly contacted. 15. Contact component (b) with the solid reaction product obtained by first contacting components (a), (c), (d) and (e) with each other. Then, the reaction product is repeatedly contacted with components (b) and (c). 16. The components (a), (b), (c), (d) and (e) are brought into contact with each other and the solid reaction product obtained is repeatedly contacted with components (b) and (c). Of the various components, the contact order of component (e) is arbitrary. In practice, however, in order to reduce the content of particulates in the polymer while maintaining high activity, high stereoregularity and the desired isoblock content, components (a), (c) and (d) are first obtained by contacting each other. Preference is given to contacting the solid reaction product with component (e). At the aforementioned contact, component (b) and / or component (c) is brought into contact with the solid reaction product at a temperature of 40-130 ° C. for at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes During the contact. In this step, components (b) and (c) may be added directly to the reaction product or in the form of a solution obtained by appropriate dilution with the above-mentioned inert organic solvent. The latter method is more preferred. In a preferred embodiment, the solid reaction product obtained in the previous step of contacting and reaction can be washed with the aforementioned inert organic solvent and then repeatedly contacted with component (b) and / or component (c). Hereinafter, the specific example of the manufacturing process of a solid catalyst component (A) is demonstrated. (1) Diethoxymagnesium as component (a) and aluminum trichloride as component (b) are suspended in an aromatic hydrocarbon solvent such as toluene at a temperature range of -10 ° C to 30 ° C. To the obtained suspension, titanium tetrachloride is added as component (c). In this process, titanium tetrachloride is preferably added in an amount of ½ or less of the volume of the solvent in which component (a) is suspended. The suspension is heated to a temperature of 40 to 100 ° C., to which dibutyl phthalate is added as component (d). Subsequently, diethyl phthalate is added to a suspension in the temperature range of 60-80 degreeC. Then, dimethylpolysiloxane is added to the suspension as component (e). The suspension is heated to a temperature of 100-120 ° C. and then allowed to stand for 30 minutes to 3 hours to react to obtain a solid reaction product. The solid reaction product is washed with titanium tetrachloride diluted with toluene and then washed with toluene for at least 1 minute in the temperature range of 40-130 ° C. Toluene and titanium tetrachloride are added to the solid reaction product and brought into contact with the solid reaction product. The reaction system is heated to a temperature of 100 to 120 ° C, and then left to react for 30 minutes to 3 hours. Aluminum trichloride can be added to the reaction product as component (b) again. Finally, the solid reaction product is washed with heptane to give solid catalyst component (A). (2) As component (a), diethoxy magnesium is suspended in an aromatic hydrocarbon solvent such as toluene at a temperature range of -10 ° C to 30 ° C. To the obtained suspension, titanium tetrachloride is added as component (c). In this process, titanium tetrachloride is preferably added in an amount of ½ or less of the volume of the solvent in which component (a) is suspended. Then, in the temperature range of 30-60 degreeC, di-iso-octylphthalate is added to suspension as component (d). Further, diethyl phthalate is added to the suspension in the temperature range of 60 to 80 ° C. The suspension is then heated to a temperature of 80-100 ° C., to which dimethylpolysiloxane is added as component (e). The mixture is heated to a temperature of 100-120 ° C., and then left to stand there and reacted for 30 minutes to 3 hours to obtain a solid reaction product. The solid reaction product is washed with titanium tetrachloride diluted with toluene and then washed with toluene for at least 1 minute in the temperature range of 40-130 ° C. Then, to the obtained solid reaction product, aluminum trichloride as component (b) is added and contacted with the solid reaction product. In this step, it is preferable that component (b) is added in the form of a solution in an organic solvent such as toluene and brought into contact with each other so that uniform contact can be performed. Then titanium tetrachloride is added to the solid reaction product. The reaction system is heated to a temperature of 100 to 120 ° C, and then left to react for 30 minutes to 3 hours. The solid reaction product is washed with heptane to give solid catalyst component (A). The solid catalyst component (A) of the present invention thus prepared is preferably washed with an inert organic solvent such as heptane to remove unreacted materials. Then, the washed solid catalyst component (A) is mixed with the components (B) and (C) described later after drying or as it is to prepare a catalyst for olefin polymerization of the present invention. As the organoaluminum compound (B) constituting the catalyst for olefin polymerization, an organoaluminum compound represented by the following general formula can be used: R 5 q AlY 3-q Wherein R 5 represents an alkyl group of C 1-4 ; Y represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom; q represents a real number greater than 0 and less than or equal to 3; R 5 may be the same or different). Examples of the organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide and ethylaluminum hydride. These organoaluminum compounds may be used alone or as a mixture of two or more thereof. Among these organoaluminum compounds, triethylaluminum and tri-iso-butylaluminum are preferred. As the organosilicon compound (C) constituting the catalyst for olefin polymerization, an organosilicon compound represented by the following general formula can be used: R 6 r Si (OR 7 ) 4-r Wherein R 6 is the same as or different from each other, and each represents a C 1-12 alkyl group, a cycloalkyl group (preferably a C 3-6 cycloalkyl group), a phenyl group, a vinyl group, an allyl group or an aralkyl group; R 7 Are the same as or different from each other, and each represents a C 1-4 alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group; r represents 0 or an integer of 1 to 3). Examples of the organosilicon compound (C) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane and alkoxysilane. Specific examples of the organosilicon compound (C) described above include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, Tri-iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso- Butyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2 -Ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyl diethoxysilane, dicy Lopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexylethyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n- Pentyl) diethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-propyl) diethoxysilane, Cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane Phenylmethyldiethoxysilane, Neylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane , 2-ethylhexyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyl Trimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethyl Hexyltriethoxysilane, phenyltrimethoxysilane, pe Triethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyl diethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclo Pentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl ) Dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxysilane, bis (3,5- Dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane and tetraethoxysilane. Among these organosilicon compounds, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxy Silane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyl diethoxysilane, cyclohexylethyl Dimethoxysilane, cyclohexylethyl diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyl diethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl diethoxysilane, cyclohexylcyclo Pentyldimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxy Silane and This silane is preferred to Trad. These organosilicon compounds (C) can be used alone or as a mixture. In the preparation of the propylene homopolymer of the present invention, the polymerization of propylene is carried out in the presence of a catalyst consisting of the solid catalyst component (A), organoaluminum compound (B) and organosilicon compound (C) described above. The use ratio of various components is arbitrary and is not specifically limited within the range which does not impair the effect of this invention. Generally, the ratio of an organoaluminum compound (B) is 1-1,000 mol per mole of titanium atoms in a solid catalyst component (A), Preferably it is 50-500 mol. The ratio of the organosilicon compound (C) is 0.001 to 2 mol, preferably 0.01 to 0.5 mol, per mole of the component (B). The catalyst described above is formed of the solid catalyst component (A), organoaluminum compound (B) and organosilicon compound (C) described above. In addition, as an electron donor (external electron donor) which can be used at the time of superposition | polymerization, the organic compound containing oxygen or nitrogen can be used as a mixture with the organosilicon compound (C) mentioned above. Specific examples of such organic compounds include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles and isocyanates. Specific examples of these organic compounds include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol; Phenols such as phenol and cresol; Ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and diphenyl ether; Methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl benzoate, ethyl benzoate, propyl benzo Ate, butylbenzoate, octylbenzoate, cyclohexylbenzoate, phenylbenzoate, methyl p-toluylate, ethyl p-toluylate, p-methoxyethylbenzoate, p-e Monocarboxylic acid esters such as oxyethylbenzoate, methyl anisate and ethyl aniseate; Diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, di-iso-decyl adipate, dioctyl adipate, dimethyl phthalate, di Dicarboxylic acid esters such as ethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate and didecyl phthalate; Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone; Acid halides such as phthalic acid dichloride and terephthalic acid dichloride; Aldehydes such as acetaldehyde, propionaldehyde, octyl aldehyde and benzaldehyde; Amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine; Amides such as acetamide and acrylamide; And nitriles such as acetonitrile, benzonitrile and tolunitrile. Prior to the propylene polymerization (called main polymerization) in the presence of a catalyst consisting of the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C), the catalytic activity and the stereoregularity of the polymer to be produced In order to further improve the properties, particle shape and the like, it is preferable to perform prepolymerization. In the aforementioned prepolymerization, the solid catalyst component (A) described above is used as a mixture with a part of the organoaluminum compound (B) described above. In this process, all or part of the above-mentioned organosilicon compounds (C) can be used as a mixture with these components. The order of contact of the various components in the prepolymerization is arbitrary. In a preferred embodiment, the organoaluminum compound (B) is charged to the prepolymerization system and then the organoaluminum compound (B) is contacted with the solid catalyst component (A) followed by contact with propylene. In the case of prepolymerization using the organosilicon compound (C), the organoaluminum compound (B) is filled in the prepolymerization system, and then the free aluminum compound (B) is brought into contact with the organosilicon compound (C). , Solid catalyst component (A) and finally contact with propylene. Prepolymerization of propylene is carried out by mixing with the aforementioned catalyst components in an inert hydrocarbon solvent. Examples of inert hydrocarbon solvents usable herein include propane, butane, heptane, hexane, octane, decane, dodecane, cyclohexane, benzene, toluene, xylene and mineral oil. Among these inert hydrocarbon solvents, aliphatic hydrocarbons such as hexane and heptane are preferred. The prepolymerization described above is carried out in an inert gas such as nitrogen and argon or in a propylene atmosphere. When prepolymerization is carried out in the inert hydrocarbon solvent described above, a small amount of propylene is first dissolved in the solvent. More specifically, propylene is dissolved in an inert hydrocarbon solvent in an amount of 0.01 to 1.0 g, preferably 0.03 to 0.5 g, more preferably 0.05 to 0.3 g, per g of solid catalyst component (A). In this process, the amount of propylene dissolved in the solvent is 1-50%, preferably 3-30%, more preferably 5-15% of the amount of polymer finally produced in the prepolymerization. As mentioned above, propylene is dissolved in a solvent. The organoaluminum compound (B) and optionally the organosilicon compound (C) are then added to the solution. Then, the solid catalyst component (A) is added to the mixture to bring these components into contact with each other. The mixture is then contacted with a predetermined amount of propylene to prepolymerize. In the above-mentioned prepolymerization process, the usage-amount of an organoaluminum compound (B) is less than the usage-amount of the organoaluminum compound (B) in main polymerization. That is, it is 0.5-50 mol, Preferably it is 1-25 mol, More preferably, it is 2-10 mol per mol of titanium atoms in a solid catalyst component (A). The usage-amount of the organosilicon compound (C) in prepolymerization is 0-10 mol, preferably 0-5 mol, More preferably, 0-1 mol per mol of titanium atoms in a solid catalyst component (A). The concentration of the solid catalyst component (A) in the prepolymerization is preferably 0.01 to 50 g, preferably 0.05 to 30 g, more preferably 0.1 to 15 g per liter of the inert hydrocarbon solvent described above. The prepolymerization temperature is 0 to 40 ° C, preferably 5 to 35 ° C, more preferably 10 to 30 ° C. The prepolymerization reaction time can be made long enough that a certain amount of polymer can be obtained. Actually, 0.1 to 10 hours is normal, preferably 0.5 to 2 hours. It is also preferable to carry out the prepolymerization so that the polymer is produced in an amount of 1 to 20 g, preferably 1.5 to 15 g, more preferably 2 to 10 g, per g of the solid catalyst component (A). Following the prepolymerization described above, the main polymerization of propylene is carried out in the presence of a polymerization catalyst formed of a prepolymerization catalyst, an organoaluminum compound (B) and an organosilicon compound (C). The polymerization is carried out by slurry polymerization, liquid polymerization, or gas phase polymerization. At the time of polymerization, hydrogen can be used as a molecular weight controller. Polymerization temperature is 200 degrees C or less, Preferably it is 100 degrees C or less. The polymerization pressure is 10 MPa or less, preferably 5 MPa or less, and more preferably 3 MPa or less. The propylene homopolymer of the present invention thus obtained has various additives blended into conventional propylene polymers, such as antioxidants, antistatic agents, lubricants, ultraviolet absorbers, light stabilizers, fire retardants, anti-sticking agents (anti -blocking agent) and fillers as necessary. The propylene homopolymer of the present invention can be used as a starting material for injection molded articles, unoriented films, oriented films, stretch sheets, etc., which are manufactured by injection molding, extrusion molding, blow molding, orientation, and the like. Can be. In particular, the propylene homopolymer of the present invention is easy to mold into sheets or films. Sheet forming may be performed by a T-die roll forming method, an inflation method, or the like. Film molding may be performed by an air-cooled inflation method, a two-stage air-cooled inflation method, a T-die film forming method, a water-cooled inflation method, or the like. Thus, the propylene homopolymer of the present invention can be processed into sheets or films that are excellent in transparency, anti-blocking properties, and the like. The xylene-soluble component (XS), isoblock content (IB) and polydispersity index (PI) in the xylene-insoluble component were measured by the following method. (1) Method of measuring xylene-soluble component 4.0 g of the polymer was dissolved in 200 ml of paraxylene at a boiling point (138 ° C.) within 2 hours. Then, the obtained solution was cooled to a temperature of 23 ° C. Soluble and insoluble components were separated from each other by filtration. The separated soluble component was heated and then dried to give a polymer as a xylene-soluble component (XS) (% by weight). (2) Method for measuring isoblock content in xylene-insoluble component by 13 C-NMR spectrum The insoluble component obtained in Method (1) was dried to obtain a polymer, and the isoblock content was measured. Isoblock content was measured using JNM-GSX270, which is commercially available from JEOL Ltd. The sign of Pmmmr, Pmmrr and Pmrrm, the absorption intensities by isoblock chains in the 13 C-NMR spectrum in xylene-insoluble components, is defined according to A. Zambellis et al., Macromolecules, 13, 267, (1980). The measurement conditions are as follows. Measuring mode: Proton decoupling method (SGBCM) Pulse angle: 45 ° (8.25㎲) Pulse repetition time: 7 seconds Number of integration: 10,000 Solvent: 1,2,4-trichlorobenzene and heavy benzene 70: 30% by volume mixture Internal standard: hexamethyldisiloxane Sample concentration: 200 mg / 3.0 ml of solvent Measurement temperature: 120 ℃ (3) How to measure the polydispersity index (PI) by DSR The polydispersity index (PI) was measured under the following conditions by a Type SR-500 dynamic stress flow meter (DSR) sold by RHEOMETRICS Inc. The sample mixed the compounding agent in order to suppress the heat denaturation. Measurement Mode: Frequency sweep Measuring temperature: 200 ℃ Measuring stress: 2,000dyn / ㎠ Measuring frequency range: 100 to 0.1 rad / s Formulation: 4 g of 2,6-di-t-butyl-p-cresol DLTP (Lasmit) 8g 2 g of calcium stearate Mark 260 (adecastab) 6 g Acetone 200ml These compounding agents are mixed to form a slurry and then blended into the polymer. Compounding ratio: 5 ml of compounding agent (slurry) per 5 g of polymer Hereinafter, an Example and a comparative example are given and this invention is demonstrated more concretely. Example 1 Preparation of Solid Catalyst Components A suspension was prepared by filling a 500 ml-volume round flask equipped with a stirrer, in which internal air was completely replaced with nitrogen gas, with 10 g of diethoxy magnesium, 1.5 g of aluminum trichloride and 90 ml of toluene. The flask was then filled with 22 ml of titanium tetrachloride at room temperature. The reaction system was heated to a temperature of 80 ° C. under stirring and reacted at this temperature. Subsequently, 3.3 ml of di-n-butylphthalate and 3.0 ml of dimethylpolysiloxane having a viscosity of 50 cSt at room temperature were added to the reaction system. The reaction system was again heated to a temperature of 110 ° C. and reacted at this temperature for 2 hours. The supernatant was removed after the reaction was completed. The solid reaction product was then washed three times with 88 ml of toluene at 75 ° C. Thereafter, 89 ml of toluene and 22 ml of titanium tetrachloride were added to the reaction system. The reaction system was then stirred at a temperature of 100 ° C. for 1.5 hours. The reaction product obtained was then washed eight times with 83 mL of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti content in the solid catalyst component was measured. As a result, it was 3.3 weight%. In addition, the Al content in the solid catalyst component was 0.5% by weight. Preparation and Polymerization of Polymerization Catalyst 700 ml of n-heptane was charged into a 1,800 ml-volume stainless steel autoclave equipped with a stirrer, where the internal air was completely dried with nitrogen gas and then replaced with propylene gas. The autoclave was charged with 2.10 mmol of triethylaluminum, 0.21 mmol of cyclohexylmethyldimethoxysilane and the solid catalyst component described above in terms of Ti, and then held in an propylene gas atmosphere to form a polymerization catalyst. Subsequently, the reaction system was prepolymerized for 30 minutes at the temperature of 20 degreeC, stirring at the propylene pressure of 0.2 MPa. Thereafter, the autoclave was charged with 80 ml of hydrogen to increase the propylene pressure of the reaction system to 0.7 MPa, and then the reaction system was polymerized at a temperature of 70 ° C. for 2 hours. The pressure drop as the polymerization progressed was supplemented by continuous supply of propylene alone. By this method the pressure in the reaction system was maintained at a predetermined value during the polymerization. Propylene was polymerized according to the polymerization process described above. The polymer thus produced was collected by filtration, and then dried under reduced pressure to obtain a solid polymer. Separately, the filtrate was concentrated to obtain a polymer dissolved in a polymerization solvent. The amount of polymer thus obtained is represented by (A) and the amount of solid polymer is represented by (B). The obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane. The amount of polymer obtained is represented by (C). The polymerization activity (Y) per solid catalyst component is represented by the following formula: (Y) = [(A) + (B)] (g) / amount of solid catalyst component (g) The boiling n-heptane-insoluble component content (HI) is represented by the following formula: (HI) = (C) (g) / (B) (g) In addition, the melt flow rate (MFR), bulk density (BD), xylene-soluble component (XS), isoblock content (IB) and polydispersity index in the xylene-insoluble component with respect to the prepared solid polymer (B). (PI) was measured. The results are shown in Table 1. Example 2 Preparation of Solid Catalyst Components A suspension was prepared by filling a 500 ml-volume round flask equipped with a stirrer, in which internal air was completely replaced with nitrogen gas, with 10 g of diethoxy magnesium, 1.0 g of aluminum trichloride and 90 ml of toluene. The flask was then filled with 20 ml of titanium tetrachloride at room temperature. The reaction system was heated to a temperature of 50 ° C. under stirring and reacted at this temperature. Next, 4.5 ml of di-iso-octylphthalate was added to the reaction system. After heating the reaction system to a temperature of 110 ° C, 4.0 ml of dimethylpolysiloxane having a viscosity of 50 cSt at room temperature was added thereto. Then, the reaction mixture was reacted for 2 hours. The supernatant was removed after the reaction was completed. The solid reaction product was then washed three times with 88 ml of toluene at 75 ° C. Thereafter, 80 ml of toluene, 1.0 g of aluminum trichloride, and 30 ml of titanium tetrachloride were added to the reaction system. The reaction system was then reacted with stirring at a temperature of 105 ° C. for 2 hours. The reaction product was then washed eight times with 80 mL of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti content in the solid catalyst component was measured. As a result, it was 2.9 weight%. In addition, the Al content in the solid catalyst component was 0.8% by weight. Preparation and Polymerization of Polymerization Catalyst The propylene polymerization process in Example 1 was performed similarly except using diphenyldimethoxysilane instead of cyclohexylmethyldimethoxysilane. Then, the obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 3 Preparation of Solid Catalyst Components A suspension was prepared by filling a 500 ml-volume round flask equipped with a stirrer, in which internal air was completely replaced with nitrogen gas, with 10 g of diethoxy magnesium, 0.8 g of aluminum trichloride and 90 ml of toluene. The flask was then filled with 22 ml of titanium tetrachloride at room temperature. The reaction system was heated to a temperature of 80 ° C. under stirring and reacted at this temperature. Then, 4.8 ml of di-iso-octylphthalate was added to the reaction system. After heating the reaction system to a temperature of 110 ° C, 6.0 ml of dimethylpolysiloxane having a viscosity of 100 cSt at room temperature was added thereto. Then, the reaction mixture was reacted for 2 hours. The supernatant was removed after the reaction was completed. The solid reaction product was then washed three times with 88 ml of toluene at 75 ° C. Thereafter, 89 ml of toluene, 0.8 g of aluminum trichloride, and 22 ml of titanium tetrachloride were added to the reaction system. The reaction system was then reacted with stirring at a temperature of 100 ° C. for 1.5 hours. The reaction product obtained was then washed eight times with 83 mL of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti content in the solid catalyst component was measured. As a result, it was 2.5 weight%. In addition, the Al content in the solid catalyst component was 0.8% by weight. Preparation and Polymerization of Polymerization Catalyst The propylene polymerization process in Example 1 was performed similarly except using cyclohexyl cyclopentyl dimethoxysilane instead of cyclohexyl methyldimethoxysilane. Then, the obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 4 Preparation of Solid Catalyst Components A suspension was prepared by filling a 500 ml-volume round flask equipped with a stirrer, in which internal air was completely replaced by nitrogen gas, with 10 g of diethoxy magnesium and 80 ml of toluene. The flask was then filled with 20 ml of titanium tetrachloride at room temperature. The reaction system was heated to a temperature of 50 ° C. under stirring and reacted at this temperature. Subsequently, 5.2 ml of di-iso-octylphthalate was added to the reaction system. After heating the reaction system to the temperature of 70 degreeC, 0.2 ml of diethyl phthalate and 4.0 ml of dimethyl polysiloxanes with the viscosity of 100 cSt at room temperature were further added here. Then, the reaction system was heated to a temperature of 112 ° C., and then reacted at this temperature for 2 hours. The supernatant was removed after the reaction was completed. The reaction product was then run for 15 minutes with 80 ml of toluene and 20 ml of titanium tetrachloride at 100 ° C. The reaction product was washed three times with 100 ml of toluene. Thereafter, 0.8 g of tri-iso-propoxy aluminum, 80 ml of toluene and 20 ml of titanium tetrachloride were added to the reaction system. The reaction system was then reacted with stirring at a temperature of 100 ° C. for 2 hours. The reaction product obtained was then washed eight times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti content in the solid catalyst component was measured. As a result, it was 4.2 weight%. In addition, the Al content in the solid catalyst component was 1.1% by weight. Preparation and Polymerization of Polymerization Catalyst The polymerization catalyst preparation step and the propylene polymerization step in Example 1 were carried out in the same manner except that the solid catalyst component obtained above was used. Then, the obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 5 Preparation of Solid Catalyst Components A suspension was prepared by filling a 500 ml-volume round flask equipped with a stirrer, in which internal air was completely replaced by nitrogen gas, with 10 g of diethoxy magnesium and 80 ml of toluene. The flask was then filled with 20 ml of titanium tetrachloride at room temperature. The reaction system was heated to a temperature of 50 ° C. under stirring and reacted at this temperature. Subsequently, 5.2 ml of di-iso-octylphthalate was added to the reaction system. After heating the reaction system to the temperature of 70 degreeC, 0.2 ml of diethyl phthalate and 4.0 ml of dimethyl polysiloxanes with the viscosity of 100 cSt at room temperature were further added here. Then, the reaction system was heated to a temperature of 112 ° C., and then reacted at this temperature for 2 hours. The supernatant was removed after the reaction was completed. Then, the flask was filled with 80 ml of toluene, 20 ml of titanium tetrachloride, and 0.5 g of diethylaluminum chloride, and then the reaction system was run at a temperature of 110 ° C for 30 minutes. The supernatant was then removed. The reaction product was washed three times with 100 ml of toluene. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were added to the reaction system. The reaction system was then reacted with stirring at a temperature of 100 ° C. for 2 hours. The reaction product obtained was then washed eight times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti content in the solid catalyst component was measured. As a result, it was 5.9 weight%. In addition, the Al content in the solid catalyst component was 1.8% by weight. Preparation and Polymerization of Polymerization Catalyst The polymerization catalyst preparation step and the propylene polymerization step in Example 1 were carried out in the same manner except that the solid catalyst component obtained above was used. Then, the obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 6 In the process in Example 4, the solid catalyst component was prepared in the same manner except that 1.0 g of triethoxyaluminum was used instead of tri-iso-propoxyaluminum. Then, the polymerization was carried out in the presence of the obtained solid catalyst component. The obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 7 In the process in Example 4, a solid catalyst component was prepared in the same manner except that 0.5 g of aluminum trichloride and 0.5 g of tri-iso-propoxy aluminum were used instead of tri-iso-propoxy aluminum. . Then, the polymerization was carried out in the presence of the obtained solid catalyst component. The obtained propylene homopolymer was evaluated. The results are shown in Table 1. Example 8 In the process in Example 2, the solid catalyst component was prepared in the same manner except that no dimethylpolysiloxane was used. Then, the polymerization was carried out in the presence of the obtained solid catalyst component. The obtained propylene homopolymer was evaluated. The results are shown in Table 1. Comparative Example 1 In the process in Example 1, the solid catalyst component was prepared in the same manner except that aluminum trichloride and dimethylpolysiloxane were not used. Then, polymerization was carried out in the presence of the obtained solid catalyst component. The results are shown in Table 1. Evaluation PropertyExampleComparative Example 1 One2345678 Polymerization Activity (Y) (g / g Catalyst)37,50043,00042,00027,60020,50022,50026,30029,80022,800 Boiling n-heptane-insoluble ingredient (HI) (% by weight)96.396.896.696.896.697.296.995.899.5 Melt Flow Rate (MFR) (g / 10min)2.51.73.02.53.22.23.14.01.9 Volume density (BD) (g / ml)0.410.380.380.410.390.390.380.360.40 Xylene-soluble component (XS) (% by weight)3.53.03.14.24.64.34.14.02.5 Isoblock Content (IB) in Xylene-Insoluble Ingredients (mol%)3.33.03.73.84.23.73.63.50.9 Polydispersity Index (PI)4.54.35.04.64.74.24.34.33.4 Example 9 Prepolymerization and main polymerization were carried out in the presence of the solid catalyst component prepared in Example 1 to obtain a propylene homopolymer. Prepolymerization 300 ml of n-heptane was charged into a 1,500 ml-volume stainless steel autoclave equipped with a stirrer, where the internal air was completely dried with nitrogen gas and then replaced with propylene gas. 50 mL of propylene gas was injected into the autoclave to dissolve propylene in n-heptane. Subsequently, 0.80 mmol of triethylaluminum was charged to the autoclave. The mixture was stirred for 30 minutes. The autoclave was then charged in an amount of 0.12 mmol, in terms of Ti, of the solid catalyst component described above. Subsequently, the reaction system was polymerized for 60 minutes while stirring at the temperature of 30 degreeC, continuing injecting propylene. The amount of polymer obtained was 4.8 g per g of solid catalyst component. Main polymerization 700 ml of n-heptane was charged into a 1,800 ml-volume stainless steel autoclave equipped with a stirrer, where the internal air was completely dried with nitrogen gas and then replaced with propylene gas. Then, the autoclave was charged with 2.10 mmol of triethylaluminum, 0.21 mmol of cyclohexylmethyldimethoxysilane, and 0.0053 mmol of the above-described prepolymerization catalyst in terms of Ti, and maintained in a propylene gas atmosphere to form a polymerization catalyst. Thereafter, the autoclave was charged with 150 ml of hydrogen to increase the propylene pressure of the reaction system to 1.1 MPa, and then the reaction system was polymerized at a temperature of 70 ° C. for 4 hours. The pressure drop as the polymerization progressed was supplemented by continuous supply of propylene alone. By this method the pressure in the reaction system was maintained at a predetermined value during the polymerization. Propylene was polymerized according to the polymerization process described above. The polymer thus produced was collected by filtration and then dried under reduced pressure to obtain a solid polymer and to be evaluated. The results are shown in Table 2. Example 10 In the propylene polymerization step of Example 9, prepolymerization was carried out in the presence of the solid catalyst component prepared in Example 2, and the same procedure was carried out except that the amount of triethylaluminum used in the prepolymerization was 0.20 mmol. The obtained propylene homopolymer was evaluated. The results are shown in Table 2. Example 11 In the propylene polymerization step of Example 9, prepolymerization was carried out in the presence of the solid catalyst component prepared in Example 3, the amount of triethylaluminum was 3.3 mmol, and the amount of the solid catalyst component was converted to Ti in the prepolymerization. The same procedure was followed except that it was 0.83 mmol. The obtained propylene homopolymer was evaluated. The results are shown in Table 2. Example 12 In the propylene polymerization step of Example 9, prepolymerization was carried out in the presence of the solid catalyst component prepared in Example 4, and triethylaluminum was added at the time of prepolymerization, followed by addition of 0.048 mmol of cyclohexylmethyldimethoxysilane. Except that, it was carried out in the same manner. The obtained propylene homopolymer was evaluated. The results are shown in Table 2. Comparative Example 2 In the prepolymerization and main polymerization processes in Example 9, the same procedure was followed except that the solid catalyst component prepared in Comparative Example 1 was used. The results are shown in Table 2. Evaluation PropertyExampleComparative Example 2 9101112 Polymerization Activity (Y) (g / g Catalyst)33,30029,50035,10032,70017,300 Boiling n-heptane-insoluble ingredient (HI) (% by weight)97.297.196.697.299.7 Melt Flow Rate (MFR) (g / 10min)2.53.42.42.91.9 Volume density (BD) (g / ml)0.400.400.390.410.33 Xylene-soluble component (XS) (% by weight)3.23.03.13.52.5 Isoblock Content (IB) in Xylene-Insoluble Ingredients (mol%)3.63.53.94.01.0 Polydispersity Index (PI)4.74.55.24.83.5 As is apparent from the above, the propylene homopolymer prepared according to the present invention has a melt flow rate (MFR) of 0.1 to 20 g / 10 min, low xylene-soluble components, and extremely low isoblock content (IB) in the xylene-insoluble components. high. Thus, the present invention can provide a propylene homopolymer that can be easily processed into sheets, films, and the like, without solutions such as ethylene coexistence as copolymer monomers.
权利要求:
Claims (4) [1" claim-type="Currently amended] A melt flow rate (MFR) of 0.1-20 g / 10 minutes; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is calculated by the following formula (1) from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. 3 mol% propylene homopolymer: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm which are absorption strengths by isoblock chain, respectively). [2" claim-type="Currently amended] A propylene homopolymer prepared by polymerizing propylene in the presence of an organoaluminum compound (B) and an organosilicon compound (C) with a solid catalyst component (A) containing magnesium, titanium, halogen and electron donors as essential components. (MFR) is 0.1-20 g / 10 min; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is at least 3 mole%, calculated by Equation (1) below from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. Propylene Homopolymer: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm which are absorption strengths by isoblock chain, respectively). [3" claim-type="Currently amended] A propylene homopolymer prepared by polymerizing propylene in the presence of a catalyst comprising the following components (A), (B) and (C), the melt flow rate (MFR) being from 0.1 to 20 g / 10 minutes; The xylene-soluble component content is 6% by weight or less; The isoblock content [IB] is at least 3 mole%, calculated by Equation (1) below from Pmmmr, Pmmrr and Pmrrm, which are absorption strengths by isoblock chains in xylene-insoluble components in the 13 C-NMR spectrum. Propylene Homopolymer: [IB] = [Pmmmr] + [Pmmrr] + [Pmrrm] (1) (Wherein, [Pmmmr], [Pmmrr] and [Pmrrm] are the relative strength ratios (mol%) of Pmmmr, Pmmrr and Pmrrm, respectively, which are absorption strengths by isoblock chain): (A) a solid catalyst component prepared from the following components (a)-(d): (a) Magnesium compound represented by the following general formula: Mg (OR 1 ) 2 (Wherein R 1 represents a C 1-4 alkyl group or aryl group); (b) at least one aluminum compound selected from the group consisting of aluminum compounds represented by the following general formulas: Al (OR 2 ) m X 1 3-m (Wherein R 2 represents a C 1-4 alkyl or aryl group; X 1 represents a halogen atom; m represents a real number of at least 0 to 3 or less); R 3 n AlX 2 3-n (Wherein R 3 represents an alkyl group of C 1-4 ; X 2 represents a hydrogen atom or a halogen atom; n represents a real number greater than 0 and less than or equal to 3); (c) a titanium compound represented by the following general formula: Ti (OR 4 ) p X 3 4-p (Wherein R 4 represents an alkyl group of C 1-4 ; X 3 represents a halogen atom; p represents 0 or an integer of 1 to 3); And (d) diesters of aromatic dicarboxylic acids; (B) the organoaluminum compound represented by the following general formula: R 5 q AlY 3-q (Wherein R 5 represents an alkyl group of C 1-4 ; Y represents one selected from a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom; q represents a real number greater than 0 and less than or equal to 3); And (C) organosilicon compounds represented by the following general formula: R 6 r Si (OR 7 ) 4-r (Wherein R 6 is the same or different from each other, and each represents a C 1-12 alkyl group, cycloalkyl group, phenyl group, vinyl group, allyl or aralkyl group; R 7 is the same or different from each other, An alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group each of C 1-4 ; r represents 0 or an integer of 1 to 3). [4" claim-type="Currently amended] A sheet or film prepared by molding the propylene homopolymer according to any one of claims 1 to 3.
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同族专利:
公开号 | 公开日 TW440567B|2001-06-16| EP1288233B1|2004-03-17| DE69723516T2|2004-01-29| EP0831103B1|2003-07-16| AT245172T|2003-08-15| EP1288233A1|2003-03-05| DE69723516D1|2003-08-21| ES2217235T3|2004-11-01| DE69728194T2|2004-07-29| US6090903A|2000-07-18| PT831103E|2003-11-28| PT1288233E|2004-06-30| EP0831103A4|2001-07-11| KR100417792B1|2004-04-29| EP0831103A1|1998-03-25| WO1997038030A1|1997-10-16| BR9706576A|1999-07-20| AT261997T|2004-04-15| DE69728194D1|2004-04-22|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题
法律状态:
1996-04-04|Priority to JP8-108366 1996-04-04|Priority to JP10836696 1997-03-31|Application filed by 아라이 요이치, 도호 티타늄 가부시키가이샤 1997-03-31|First worldwide family litigation filed 1999-03-25|Publication of KR19990022344A 2004-04-29|Application granted 2004-04-29|Publication of KR100417792B1
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