TW200413421A - Catalysts for polymerizing olefins and process for producing olefin polymer - Google Patents

Abstract

Solid catalyst components for polymerizing olefins obtained by reacting the following compounds (i), (ii) and (iv) or (i), (ii), (iii) and (iv) are disclosed, in which (i) is a halogen-containing titanium compound; (ii) is an alkoxy-containing magnesium compound obtained by reacting metallic magnesium, an alcohol and a halogen and/or a halogen-containing compound containing at least 0.0001 gram atom of a halogen atom per mol of the metallic magnesium; (iii) is a halogen-containing silicon compound; and (iv) is an electron donating compound represented by the following general formula (I). (in the formula, R1 represents linear or branched alkyl having 1 or more carbon atoms; and R2 and R3 independently represent each liner or branched C1-20 alkyl.)

Description

200413421 (1) (i) Description of the invention [Technical field to which the invention belongs] The present invention relates to a catalyst for polymerizing olefins and a method for producing an olefin polymer, which are used to produce a polymer or copolymer of an α-olefin alone. [Prior art] Generally, olefin polymers are polymerized by Ziegranata [Z i e g 1 e r N a 11 a] catalyst formed of titanium compounds and organoaluminum compounds. For example, in the production of polypropylene, which is one of the olefin polymers, although a solid catalyst component mainly composed of titanium, magnesium, chlorine, and an electron donating compound, an organoaluminum compound as an auxiliary catalyst component, and Isotactic-Polypropylene, a catalyst for organosilicone compounds with alkoxy groups for stereoregularity enhancers, is now attempting to improve the catalyst activity during polymerization, the stereoregularity and improvement of olefin polymers Stable powder type used in the production of olefin polymers. For example, in order to improve the particle size and shape of olefin polymers (Morphology), it is disclosed in Japanese Patent Application Laid-Open No. 63-2 8707, etc., that magnesium is supported on an inorganic oxide such as silicon dioxide. The method of the compound is disclosed in Japanese Patent Application Laid-Open No. 5 8-0008 1 1 and the like, and a method in which a magnesium compound is first dissolved in a solvent such as an alcohol and then precipitated again is used. However, in these methods, processes such as supporting, dissolving, and precipitating a magnesium compound are necessary, so that the steps are extremely complicated. In addition, these methods only improve the catalyst activity at the initial stage of polymerization, so they have the disadvantage of lack of stability of catalyst performance, or the catalyst activity during polymerization and the stereoregularity of olefin polymers. -6- (2) (2) 200413421 The disadvantage of performance cannot occur sufficiently. Therefore, as a method for improving these disadvantages, Japanese Unexamined Patent Publication No. 02-413883 discloses a method of using a reaction product of metal magnesium, alcohol, and a specific amount of halogen as a carrier for the catalyst. In addition, U.S. Patent No. 07-025822 Gazette discloses the production of an olefin polymer by adding an organic acid ester to the reaction product of magnesium alkoxide, halogenating agent and alkoxy 'titanium, and then using Ziegler Natta catalyst containing solid catalyst components obtained by the reaction of titanium halide. method. · However, the polymerization activity of these methods and the stereoregularity of olefin polymers are still insufficient. In addition, Japanese Unexamined Patent Publication No. 1 1-2692 18 discloses that a magnesium compound and a titanium compound are contacted at a temperature of 120 ° C to 150 ° C in the presence of an electron-donating compound, and then The solid catalyst component for polymerized olefins obtained by washing with an inert solvent at a temperature of 100 ° C to 150 ° C reduces the chronological properties of the catalyst activity during polymerization and suppresses the improvement of the olefin polymer. Three-dimensional regularity can get the effect. · However, the polymerization activity of the catalyst is not necessarily sufficient, and further improvement is necessary. Therefore, in order to obtain a catalyst system that can improve the catalyst activity during polymerization, the three-dimensional regularity of the olefin polymer, and the powder form, it is necessary to find a catalyst system that has been improved to meet the above conditions and has high performance. · On the other hand, the propylene-ethylene random copolymer obtained by random copolymerization of propylene and ethylene is superior to propylene alone polymers because it has excellent impact resistance, transparency, and a relatively low melting point, so it has excellent properties. (3) (3) 200413421 and other characteristics, can be widely used in the field of packaging materials using a variety of films. However, the propylene-ethylene random copolymers made by the prior art are not very good in quality, so their use is currently restricted depending on the application. For this reason, currently known methods include, for example, a method of increasing the ethylene content in a propylene-ethylene random copolymer by further improving impact resistance and heat-sealing properties. However, although increasing the ethylene content can improve the impact resistance and heat sealability, the increase in the amount of by-products of the low-molecular-weight amorphous component will increase the tackiness of the film, which will cause so-called damage due to the formation of agglomeration. To the price of goods. In addition, the low molecular weight amorphous component may also be a hindrance factor to low-temperature heat-sealability and impact resistance. In addition, even in the production of propylene-ethylene random copolymers, when the slurry polymerization using propylene as a medium is used for production, adhesion between copolymers and an increase in the viscosity of the polymerization system will not only reduce productivity, but also become production. Important troubles. Furthermore, although catalysts composed of titanium halides and organoaluminum compounds can generally be used to produce polypropylene and propylene-based copolymers, when the polymer contains a large amount of catalyst residues, the color tone of the molded product becomes yellow. This causes a problem of poor appearance. In particular, when the polymer contains a large amount of chlorine atoms, roller fouling or lattice blockage may occur during film formation, thereby deteriorating the appearance quality of the film. In addition, in the past, the improvement of propylene-ethylene block copolymers has been reviewed mainly by improving physical properties such as rigidity, impact resistance, etc.-(4) (4) 200413421, but among them, effective methods There are also those who review from solid structural surfaces. In other words, the influence of the solid structure composed of the propylene alone polymerized part forming the copolymer matrix and the propylene-ethylene copolymerized part forming the rubber-like elastomer on the strength and physical properties is based on the so-called individual component ratio, molecular weight of each part, _LL body regularity is described by the aggregation factors, and reflected in the polymer design, and then fed back to the polymerization technology manufacturer who made the polymer. However, even now, it is expected to further improve its rigidity and impact resistance, and in particular, the appearance of improved products with higher impact resistance is expected. Accordingly, an object of the present invention is to provide a catalyst for polymerizing olefins, and a method for producing an olefin polymer, which can obtain an olefin polymer having high polymerization activity, excellent regularity in the stereo, and excellent powder form. Another object of the present invention is to provide a novel propylene-ethylene copolymerization catalyst and a method for producing a propylene-ethylene copolymer. Another object of the present invention is to provide a propylene-ethylene random copolymer having a high ethylene content and a low molecular weight amorphous component. Another object of the present invention is to provide a propylene-ethylene block copolymer having a balance of physical properties such as excellent rigidity and impact resistance. [Contents of the invention] The disclosure of the invention The best state of the present invention is as follows: (5) (5) 200413421 [olefin polymerization] (1) The following compounds (i), (ii) and (i V) or lower The solid catalyst component for polymerized olefins obtained by the reaction of the compounds (i), (ii), (iii) and (iV) is described. (i) Halogen-containing titanium compounds (ii) Metal magnesium, alcohols, and halogens containing halogen atoms of at least 1,000 lg atoms with respect to 1 mol of the above-mentioned metal magnesium, and / or alkoxy-containing compounds obtained by the reaction of halogen-containing compounds (Iii) halogen-containing silicon compound (i V) is an electron donating compound R1 represented by the following general formula (I)

I R2—〇—c——C——C— 0—R3 ...... (I)

II I II ο I 〇H · [In the general formula (I), R1 is a linear or branched alkyl group having 1 or more carbon atoms, and R2 to R3 are independent of each other and a linear chain having 1 to 20 carbon atoms Or branched alkyl. ] ~ By using such a solid catalyst component, a catalyst with a high polymerization activity can be obtained. Furthermore, an olefin polymer having excellent stereoregularity and powder form can be obtained. For example, by using a magnesium compound (i i) containing an alkoxy group, the form of the olefin polymer can be improved. The magnesium compound (i i) containing an alkane -10- (6) (6) 200413421 oxygen group produced as described in (i i) has an approximately spherical shape, and therefore does not need to be classified. Further, by using an electron donating compound (iV), a high polymerization activity can be found while maintaining high stereoregularity as it is. Since such an electron donating compound (i V) does not contain an aromatic ring, it is possible to reduce safety and health problems. Furthermore, although a halogen-containing silicon compound (iii) is used in accordance with the need, by using this compound, the catalyst activity during polymerization, the improvement of stereoregularity, and the fine powder contained in the olefin polymer polymer can be reduced. the amount. (2) The solid catalyst component for polymerizing olefins as described in the above aspect (1), wherein the aforementioned halogen is iodine. Iodine is extremely convenient to handle. Further, by using iodine, a spherical (i i) component having a narrow particle size distribution can be produced. (3) The solid catalyst component for polymerizing olefins as described in the above-mentioned aspect (1) or (2), wherein the halogen-containing compound is magnesium chloride. Magnesium chloride is extremely convenient in handling. Furthermore, by using magnesium chloride, a spherical (i i) component having a narrow particle size distribution can be produced. (4) The solid catalyst component for polymerized olefins according to any one of the above-mentioned aspects (1) to (3), wherein the halogen-containing silicon compound (i i i) is sand tetrachloride. By using silicon tetrachloride, the catalyst has a spherical shape, and the particle size distribution can also be narrowed. (5) The poly-11 described in any one of the above-mentioned forms (1) to (4)-(7) (7) 200413421 solid catalyst component for olefins, the aforementioned electron donating compound (i V) Diethyl n-butylmalonate. By using diethyl n-butylmalonate, polymer I with higher stereoregularity can be produced at higher activity. (6) When the solid catalyst component for polymerizing olefins described in any one of the forms (1) to (5) above is reacted with the aforementioned compounds (i), (ii), (iV), The halogen titanium compound (i) and the alkoxy group-containing magnesium compound (ii) are contacted, and then contacted with the electron donating compound (i V). On the other hand, when the compounds (i), (ii), (iii), and (iV) are reacted to produce a solid catalyst component for polymerized olefins, it is preferable to contact the compound (ii) and (iii), and then The compound (i V) is contacted, and then the compound (i) is further contacted with fytm. (7) A catalyst for polymerizing olefins containing the following components [A] and [B] or the following components [A], [B], and [C]. [A] The solid catalyst component described in any one of the above-mentioned types (1) to (6) [B] Organoaluminum compound [C] The electron donating compound may be constituted by such a catalyst A catalyst with high polymerization activity is obtained, and an olefin polymer having excellent stereoregularity and powder form can be obtained. In addition, although it contains an electron-donating compound [C] according to need, (8) 200413421 By containing this compound, it is possible to further produce polymers with high stereoregularity or polymers with controllable molecular weight distribution. . (8) A method for producing an olefin polymer using the catalyst described in the above-mentioned form (7) to polymerize olefins. With such a production method, it is possible to produce an excellent stereoregularity and powder with high polymerization activity. Type of olefin polymer. [Propylene-ethylene copolymerization] (9) propylene-ethylene obtained by reacting the following compounds (a), (b), (c) or the following compounds (a), (b), (c), (d) Solid catalyst component for copolymerization. (a) Magnesium compound (b) Titanium compound compound (c) Electron donating compound represented by general formula (Π) R4 (I)

η2—〇—C—C—C—10—R3 II I 11 〇L 〇 [In the general formula (Π), R4 is a linear, branched or cyclic alkyl group having 1 to 2 carbon atoms, and R5 R4 and R5 are alkyl groups having 1 to 2 carbon atoms, and R4 and R5 may be bonded to each other to form a ring. R2 and R3 may be the same or different, and are 1 to 20 linear or branched alkyl groups. . (d) Silicon compound (1 0) The propylene-ethylene copolymerization described in the above-mentioned form (9) -13- (9) (9) 200413421 A solid catalyst component is used, and the solid catalyst component is in the aforementioned compound (b) In the presence of 120 ~ 150 ° C, contact the aforementioned compounds (a) and (c), or the aforementioned compounds (a), (c) and (d), and then at 120 ~ 150 ° The solid catalyst component obtained under C was washed with an inactive solvent. By using the solid catalyst component thus produced, a polypropylene-ethylene random copolymer having a low by-product amount of a low molecular weight amorphous component can be produced. Furthermore, by using the solid catalyst component thus produced, a propylene-ethylene block copolymer containing a polypropylene component having high stereoregularity can be produced. (1 1) The solid catalyst component for propylene-ethylene copolymerization as described in the above-mentioned form (9) or (1 0), the magnesium compound (a) described above is metallic magnesium, alcohols, and 1 mole of the above An alkoxy group-containing magnesium compound obtained by the reaction of a magnesium metal containing a halogen atom having a halogen atom of at least 1,000 g atoms and / or a halogen-containing compound. By using a magnesium compound containing an alkoxy group, a copolymer having an excellent particle shape and a uniform particle size distribution can be produced. (1 2) The solid catalyst component for propylene-ethylene copolymerization as described in any one of the above-mentioned forms (9) to (1 1), in the general formula (Π) of the foregoing, R4 is a carbon number of 1 to 20 A linear, branched, or cyclic alkyl group, and R5 is fluorene or an alkyl group having 1 to 2 carbon atoms. By using such an electron donor, it is possible to efficiently produce a propylene-ethylene random copolymer with low by-products of a low molecular weight amorphous component. Also, by using such an electron donor, it is possible to produce a propylene--14- (10) (10) 200413421 ethylene block copolymer composed of a highly stereoregular polypropylene component and a copolymer having a uniform composition. . (1 3) The propylene-ethylene random solid catalyst component according to any one of the above-mentioned forms (9) to (1 2), wherein the electron-donating compound (c) is n-butylmalonic acid Diethyl ester. By using diethyl n-butylmalonate, a propylene-ethylene random copolymer having lower tackiness can be produced. Further, by using diethyl n-butylmalonate ', a propylene-ethylene block copolymer having a narrow molecular weight distribution can be produced. (1 4) The propylene-ethylene random solid catalyst component described in any one of the above-mentioned forms (9) to (1 2), and the aforementioned electron-donating compound (c) is cyclobutane-1, 1 Dibutyl dicarboxylic acid. By using cyclobutane-1,1-dicarboxylic acid dibutyl ester, a propylene-ethylene random copolymer having a lower viscosity can be produced. Further, by using cyclobutane-1,1-dicarboxylic acid dibutyl ester, a propylene-ethylene block copolymer having a narrow molecular weight distribution can be produced. (1 5) The solid catalyst component for propylene-ethylene copolymerization as described in any one of the above-mentioned forms (9) to (1 4). The solid catalyst component described above is a solid catalyst for random copolymerization of propylene-ethylene. MEDIA COMPONENTS. (1 6) The solid catalyst component for propylene-ethylene copolymerization as described in any one of the above-mentioned forms (9) to (1 4). The solid catalyst component described above is a solid catalyst for propylene-ethylene block copolymerization. MEDIA COMPONENTS. (17) A propylene-ethylene copolymerization catalyst containing the following components [A] and [B] or the following components [A], [B], and [C]. [A] The solid (11) (11) 200413421 as described in any one of the above forms (9) to (1 4), the catalyst component [B] an organoaluminum compound [C] an electron donating compound (1 8 ) The catalyst for propylene-ethylene copolymerization described in the above-mentioned type (1 7), the former catalyst is obtained by contact with olefins in the presence of [A], [B], and [C], and the preliminary polymerization amount 0.1 to 100% by weight of preliminary polymerization catalyst. By using such a preliminary polymerization catalyst, a copolymer having an excellent particle shape and a uniform particle size distribution can be produced. (19) The catalyst for propylene-ethylbenzene copolymerization as described in the above-mentioned type (17) or (18), the catalyst mentioned above is a catalyst for random copolymerization of propylene-ethylbenzene. (20) The catalyst for propylene-ethylene copolymerization as described in the above-mentioned aspect (1 7) or (1 8). The catalyst described above is a catalyst for propylene-ethylene block copolymerization. [Propylene-ethylene random copolymer] (2 1) —A method for producing a propylene-ethylene random copolymer, which is a copolymer of propylene and ethylene randomly using a catalyst as described in the above-mentioned type (19). . (22) A propylene-ethylene random copolymer obtained by the production method described in the above-mentioned aspect (2 1). By such a manufacturing method, a propylene-ethylene random copolymer having excellent low-temperature heat-sealability and impact resistance can be obtained. -16 · (12) (12) 200413421 By using an electron donor represented by the general formula (Π), a copolymer having a small amount of tacky components can be obtained under high activity. (2 3) The propylene-ethylene random copolymer according to the aspect (2 2) described above, wherein the ethylene content is from 0.1 to 4% by weight, and the soluble component at 0 ° C is 1. 0% by weight or less. 0 ° C soluble content is an indicator of the amount of non-crystalline components. Rather than saying that the amount of soluble ingredients of 0 ° 〇 does not contribute to the mechanical properties of the polymer, Wu Ning said that it will become an obstruction factor. In addition, it will become the cause of stickiness on the polymer surface. For this reason, the less this ingredient, the better. (24) The propylene-ethylene pseudo random copolymer according to the above-mentioned aspect (22) or (23), wherein the ethylene content is more than 4% by weight and the content is less than 5% by weight, and the amount of soluble components at 0 ° C is large At 1.0% by weight, it is 2.0% by weight or less. [Propylene-ethylene block copolymer] (25)-a method for producing a propylene-ethylene block copolymer, comprising a process of polymerizing propylene to form a polypropylene component, and polymerizing ethylene and propylene to form ethylene / propylene For the copolymer component manufacturing process, the catalyst described in the above-mentioned type (20) is used in at least one of the foregoing polypropylene burning component forming process and the foregoing ethylene / propylene copolymer component forming process. (26) A propylene-ethylene block copolymer obtained by the production method described in the above-mentioned aspect (2 5). According to the present invention, a propylene-ethylene block copolymer composed of polypropylene with high stereoregularity, -17- (13) (13) 200413421, and an ethylene / propylene copolymer component having a uniform rubber-like elastomer component can be obtained. Thing. Relative to the ethylene content, the ethylene / propylene copolymer component is a relatively uniform rubber-like elastomer component, that is, it is composed of not only several rubber-like elastomers having different hardnesses but also having uniform properties. By using an electron donor represented by the general formula (Π), a propylene-ethylene block copolymer having excellent rigidity and impact resistance can be produced. (27) The propylene-ethylene block copolymer as described in the above aspect (26), wherein the MFR is 10 to 20 g / 10 minutes. When the MFR is 10 to 20 g / 10 minutes, a resin having good fluidity will be formed, and productivity during molding can be improved. Best Mode for Implementing the Invention [Olefin Polymerization] First, the catalyst for olefin polymerization of the present invention and a method for producing an olefin polymer using the catalyst will be described. Lu 1. Catalyst component [A] Solid catalyst component The solid catalyst component refers to the following compounds (i), (ii) and (i V) or below compounds (i), (ii), (iii) and (I V) The person who obtained the reaction. (i) Halogen-containing titanium compound Although the halogen-containing titanium compound is not particularly limited, a compound represented by the following general formula (m) can be suitably used.

TiXp (OR6) 4- p- (π) In the above general formula (dish), x represents a halogen atom, of which a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R6 is a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group '. Alternatively, a group containing a hetero element such as sulfur, nitrogen, oxygen, silicon, and phosphorus may be used. Among them, the hydrocarbon group having 1 to 8 carbon atoms is preferably an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like, and a linear or branched alkyl group is particularly preferable. When R6 is plural, they may be the same or different from each other. Specific examples of R6 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, Allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, phenethyl and the like. p is an integer from 1 to 4. Specific examples of the halogen-containing titanium compound represented by the above general formula (melon) include, for example, titanium tetrahalide, titanium tetrabromide, titanium tetraiodide, and the like; titanium methoxy trichloride, and ethoxy Trihalogenated titanium alkoxy titanium such as titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, and titanium ethoxy tribromide; dimethoxy titanium dichloride, diethyl Dihalogenated titanium dialkoxy titanium, such as oxy titanium dichloride, diisopropoxy titanium dichloride, di-n-propoxy titanium dichloride, and diethoxy dibromide; trimethoxy chloride Monohalogenated trialkoxy titanium, such as titanium oxide, triethoxy titanium chloride, triisopropoxy titanium chloride, tri-n-propoxy titanium chloride, and tri-n-butoxy titanium chloride. Among them, in terms of polymerization activity, -19- (15) (15) 200413421, titanium compounds containing high halogens, especially titanium tetrachloride are preferable. These halogen-containing titanium compounds may be used singly or in combination of two or more kinds. (ii) Magnesium compounds containing alkoxy groups In the present invention, as magnesium compounds containing alkoxy groups, metal magnesium, alcohols, and halogen atoms containing at least 0.001 lg atoms with respect to 1 mole of metal magnesium are used. The compound obtained by the reaction of halogen and / or a halogen-containing compound is not particularly limited, but a compound represented by the following general formula (IV) can be suitably used.

Mg (OR7) qRS.q (IV) In the general formula (IV), R7 represents a hydrocarbon group, and R8 represents a hydrocarbon group or a halogen atom. Here, examples of the hydrocarbon group of R7 and R8 include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, which may be the same or different. Examples of the halogen atom of R8 include chlorine, bromine, iodine, and fluorine. q represents an integer of 1 to 2. Specific examples of the alkoxy-containing magnesium compound represented by the general formula (IV) include dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dihexyl magnesium, and Magnesium octyloxy, diphenoxymagnesium and dicyclohexyloxymagnesium dialkoxymagnesium and diallyloxymagnesium; ethoxyethylmagnesium, phenoxyethylmagnesium, ethoxyphenyl Alkoxyalkyl magnesium, magnesium allyloxyphenyl magnesium, allyloxy alkyl magnesium, alkoxy allyl magnesium, allyloxy allyl-20- (16) (16) 200413421 Methyl magnesium; butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, and alkoxy magnesium chloride of ethoxy magnesium iodide and Aryloxy magnesium chloride and so on. Among these magnesium compounds, in terms of polymerization activity and stereoregularity, dialkoxymagnesium is preferred, and diethoxymagnesium is particularly preferred. In terms of the polymerization activity of the catalyst, the powder form and stereoregularity of the olefin polymer, the alkoxy-containing magnesium compound (ii) is preferably made of metallic magnesium, alcohols, It is obtained by reacting a halogen containing a halogen atom of at least o.oooig and / or a halogen-containing compound. In this case, the shape and the like of the metal magnesium are not particularly limited. Therefore, metallic magnesium of any particle size, such as metallic, bow-shaped, and powdery metallic magnesium, can be used. In addition, there is no particular limitation on the surface state of the magnesium metal, but it is preferable that a film such as magnesium hydroxide is not formed on the surface. The type of the alcohol is not particularly limited, but it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, when ethanol is used, a solid product that significantly enhances catalyst performance can be obtained, which is suitable. Although the purity and water content of alcohols are not limited, if alcohols with high water content are used, magnesium hydroxide will be formed on the surface of metal magnesium, so alcohols with a water content of 1% or less, especially alcohols of 2,000 ppm or less Better. In addition, in order to obtain a better shape, the less the water content, the better. Generally, it is preferably 200 ppm or less. The type of halogen is not particularly limited, but it is preferable to use chlorine, bromine or iodine, with iodine being the most preferable. In addition, the type of the halogen-containing compound is not limited, and any compound containing a halogen atom in the formula of its -21-(17) (17) 200413421 can be used. In this case, although there are no particular restrictions on the type of halogen atom, chlorine, bromine or iodine is preferred. Among the halogen-containing compounds, a halogen-containing metal compound is particularly preferred. As the halogen-containing compound, specifically, MgCh, Mgl2, Mg (OEt) Cl, Mg (OEt) I, MgBr2, CaCl2, NaCl, KBr, and the like can be suitably used. Among them, MgCl2 is particularly preferred. There is no particular limitation on the state, shape, and shape of the particles, and any substance may be used. For example, it can be used in a solution in an alcohol-based solvent (such as ethanol). Although there are no restrictions on the amount of alcohols, it is preferably 2 to 100 mols, and more preferably 5 to 50 mols, relative to 1 mol of metal magnesium. When the amount of the alcohol is too much, the recovery rate of the magnesium compound (i i) containing an alkoxy group in a good form will decrease. If the amount is too small, the stirring in the reaction tank will not be performed smoothly. However, this Morse ratio is not limited. The amount of halogen to be used is 1 mol of metal relative to 1 mol of metallic magnesium, preferably 0.0005 g or more, and more preferably 0.001 g or more. When the O.OOOlg atom is not full, there is no significant difference from the amount used with halogen as a reaction initiator. When the obtained alkoxy-containing magnesium compound (i 1) is used as a catalyst carrier, the catalyst Deterioration of living or olefin polymer may occur. In addition, the amount of halogen-containing compounds used is relative to 1 mol of metal magnesium, and the amount of halogen atoms in the halogen-containing compounds is 0.0000 ig atoms or more, preferably 0.0005 g atoms or more, and 0.00000 g. Above atomic is preferred. When the O.OOOlg atom is not full, there is no great difference from the amount used with halogen as a reaction initiator, and the obtained alkoxy-containing magnesium compound-22- (18) (18) 200413421 (ii) is used as a catalyst. When a carrier is used as a vehicle, the catalyst activity or the type of the olefin polymer may be defective. In the present invention, the halogen and the halogen-containing compound may be used alone or in combination of two or more kinds. Alternatively, a halogen and a halogen-containing compound may be combined. When a halogen and a halogen-containing compound are used in combination in this manner, the total amount of halogen atoms in the halogen and the halogen-containing compound is preferably equal to or greater than 0.001 lg atom, preferably equal to or greater than 0.0005 g atom, relative to 1 mol of metallic magnesium. O.OOlg or more is particularly preferred. · The upper limit of the amount of halogen and halogen-containing compounds used is not particularly limited, as long as it is appropriately selected within the range in which the alkoxy-containing magnesium compound (ii) used in the present invention can be obtained, generally It is preferably less than 0.06 g atoms. In the method for producing an olefin polymer of the present invention, the amount of the halogen and the halogen-containing compound is appropriately selected, and the particle size of the alkoxy group-containing magnesium compound (i i) can be freely controlled. In general, the manufacturing process of the magnesium compound (i 1) containing an alkoxy group is carried out until it is considered that hydrogen is no longer generated (usually 1 to 30 hours). Specifically, when halogen iodine is used, a method of adding solid iodine to a solution of metal magnesium and ethanol, and heating and reacting it, and dropping a solution of iodine into the metal magnesium and ethanol solution, and heating A method for the reaction and a method for reacting while heating an alcohol solution of magnesium metal while dripping an alcohol solution of iodine. In addition, any method is carried out in an inert gas (such as nitrogen, argon) environment, and sometimes it is suitable to use an inert organic solvent (such as a saturated hydrocarbon such as n-hexane • 23- (19) (19) 200413421). In addition, magnesium metal, alcohols, and halogens need not be added in their entirety from the beginning. A particularly suitable type is a method in which alcohol is added in full amount from the beginning, and magnesium is added in several times. In this case, a large amount of hydrogen gas can be prevented in an instant, and safety is highly desirable. In addition, the reaction tank can be miniaturized. In addition, alcohols or halogens caused by the large amount of hydrogen produced in an instant can be prevented from flying together. The number of divisions may be determined in consideration of the size of the reaction tank, and there is no special rule. If the degree of complexity of the operation is considered, it is usually appropriate to use 5 to 10 times. In addition, the reaction itself may be batch or continuous. In addition, as a modification, a small amount of magnesium metal is initially charged into the entire amount of alcohol, and the product produced by the reaction is separated into a separate tank for removal, and then a small amount of magnesium metal is repeatedly introduced. When the magnesium compound (i i) containing an alkoxy group is used for the preparation of the solid catalyst component [A], a dried product may be used, or after filtering, the solvent may be washed with an inactive solvent such as heptane. In any case, the magnesium compound (i i) containing an alkoxy group can be used in the following steps without performing a grading operation or grading operation with a uniform particle size distribution. The magnesium compound (i i) containing an alkoxy group is approximately spherical and has a concentrated particle size distribution. Furthermore, when examining each particle, the difference in sphericity is small. These alkoxy-containing magnesium compounds (i i) may be used alone 'or in combination of two or more. Furthermore, it is also possible to use a support supported on sand dioxide, alumina, polystyrene, etc., and a mixture with a halogen, etc. -24- (20) 200413421 can also be used. (iii) Halogen-containing silicon compound In the production of the solid catalyst component [A], a halogen-containing silicon compound (i i i) is used as required. The halogen-containing silicon compound is not particularly limited, but a compound represented by the following general formula (V) can be used.

Si (OR9) rX4- r- (V) In the general formula (V), X represents a halogen atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R9 is a hydrocarbon group, which may be a saturated group or an unsaturated group, and may be a linear one or a branched or cyclic one. In addition, R9 may contain a different element such as sulfur, nitrogen, oxygen, silicon, and phosphorus. Among these, a hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, an alkenyl group, a cyclodialkyl group, an aryl group, an aralkyl group, or the like. When OR9 is plural, it may be the same as or different from each other. Specific examples of R9 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, Allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, phenethyl and the like. r is an integer from 0 to 3. Specific examples of the halogen-containing titanium compound represented by the general formula (V) are, for example, silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, and ethoxytrichlorosilane. , Diethoxydichlorosilane, triethoxychlorosilane, propoxytrichlorosilane, dipropoxydichlorosilane-25- (21) 200413421 alkane, and tripropoxychlorosilane. Among them, silicon tetrachloride is suitable. These halogen-containing silicon compounds may be used singly or in combination of two or more kinds. (i V) Electron donating compound In the present invention, as the electron donating compound, a malonic acid diester represented by the following general formula (I) is used.

R1 (I) R2 one hundred one C—C—C one hundred one R3

it I II ο I 〇Η [In the general formula (I), r1 is a linear or branched alkyl group having 1 or more carbon atoms, and R2 and R3 are linear or branched independently of 1 to 20 carbon atoms. Branched alkyl group. ] R1 is preferably a carbon number of 1 to 8, and the most carbon number is 2 to 4. Further, R2 and R3 are preferably 2 to 8 carbon atoms, and the most preferable is 2 to 8 carbon atoms. Specific examples of the electron donating compound include methylmalonic acid, ethylmalonic acid, and Dimethyl esters of propylmalonate, isopropylmalonate, n-butylmalonate, isobutylmalonate, sec-butylmalonate, tert-butylmalonate, etc. Ester, di-n-propyl ester, di-isopropyl ester, di-n-butyl ester, di-isobutyl ester, di-t-butyl ester, di-n-pentyl ester, di-n-heptyl ester, di-n-octyl ester, Dinepentyl esters and the like. Among them, n-butylmalonic acid diester is preferred. These compounds may be used singly or in combination. -26- (22) (22) 200413421 may be used in combination of two or more kinds. [B] An organoaluminum compound and the organoaluminum compound [B] used in the present invention are not particularly limited, and alkyl groups, halogen atoms, hydrogen atoms, those having an alkoxy group, aluminoxane ^ ~ (aluminoxane), and Its mixture can be suitably used. Specific examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum; diethylaluminum monochloride, diisopropylaluminum Dialkyl aluminum monochloride such as monochloro, φ diisobutyl aluminum monochloride and dioctyl aluminum monochloride; alkyl aluminum sesquichloride such as ethyl aluminum sesquichloride; methyl alumoxane and the like Chain aluminoxane and the like. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, and specifically, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutyl Aluminium is particularly preferred. These organoaluminum compounds may be used singly or in combination of two or more kinds. [C] Electron donating compound In the catalyst for polymerizing olefins of the present invention, an electron donating compound is used as needed. As such an electron donating compound [C], an organic silicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among them, it is preferable to use an organosilicon compound having an alkoxy group. Specific examples of the organosilicon compound having an alkoxy group include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, and dimethyl (23) (23) 200413421 silane, ethyl isopropyl dimethoxy silane, propyl isopropyl dimethoxy silane, diiso Propyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tertiary Butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butylisobutyl Dimethoxysilane, tert-butyl (sec-butyl) dimethoxysilane, tert-butylpentyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, Tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane, tert-butyl (3,3,3-trifluoromethane Propyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane , Dicyclohexyldimethoxysilane, dicyclohexylt-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldi Methoxysilane, cyclopentyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethyl Oxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, naphthyl-1,1,2-trimethylpropyldimethoxysilane, n-tetradecyl-1,1 2,2-trimethylpropyldimethoxysilane, 1,1,2-trimethylpropylmethyldimethoxysilane, 1,1,2-trimethylpropylethyldimethoxy Silane, 1,1,2-trimethylpropylisopropyldimethoxysilane, 1,1,2-trimethylpropylcyclopentyldimethoxysilane, 1,1,2-trimethylsilane Propylcyclohexyldimethoxysilane, 1,1 2-trimethylpropyltetradecyldimethyl-28- (24) (24) 200413421 oxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxy Methylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyl Trimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxy Silane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, orthospinyltrimethoxysilane, indotrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, ethyltriisopropoxy Methylsilane, methylcyclopentyl (tert-butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, (Isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, vinyltriethoxysilane, ethylene Tributoxysilane, triethoxysilane, 7-chloropropyltrimethoxysilane, 7-aminopropyltrimethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane , 1,1,2,1-trimethylpropylisopropoxydimethoxysilane, 1,1,2-trimethylpropyl (tert-butoxy) dimethoxysilane, tetramethoxysilane , Tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltrisiloxane (Θ —methoxyethoxy) silane, vinyltriacetoxysilane, dimethyltethoxydisilaxane, cyclopentyl (tert-butoxy) dimethoxysilane, tert-butyl ( Isobutoxy) dimethoxysilane, thexyl trimethoxysilane, thexyl isopropoxydimethoxysilane, thexyl (tert-butoxy) dimethoxy sand institute, thexyl methyl dimethoxy sand Institute, thexyl di (25) (25) 200413421 dimethoxysilane, thexyl isopropyldimethoxysilane, thexyl cyclopentyldimethoxysilane, thexyl tetradecyldimethoxysilane thexyl cyclohexyldimethoxysilane, cyclohexylisopropyldimethoxysilane, isobutylisopentyldimethoxysilane, di-n-isobutyldimethoxysilane, cyclopentylisobutyldi Methoxysilane, etc. These organosilicon compounds may be used individually or in combination of 2 or more types. In addition, as such an organic silicon compound, for example, a silicon compound having no Si—O—C bond and an organic compound having a 0—C bond may be reacted in advance, or when an α-olefin is polymerized, The compound obtained by the reaction. Specific examples include compounds obtained by reacting silicon tetrachloride with alcohols. As specific examples of the nitrogen-containing compound, 2,6-diisopropylpiperidine, 2 '6-diisopropyl-4-methyl vein, and N-methyl-2, 2, 6, 6-14 2,6-substituted piperidines of methylpiperidine, etc .; 2,5-diisoylazolysine and N-methyl-2,2,5,5-tetramethylazolysine, etc. 2,5—Substituted azolysine acids; Ν, Ν, Ν ′, Ν, —tetramethylmethylene diamine and methine such as Ν, Ν, Ν ′, Ν, tetraethylmethylene diamine, etc. Diamines; Substituted imidazolysines such as 1,3-diphenylimidazolysine and 1,3-diphenyl-2 · phenylimidazolysine. Specific examples of the phosphorus-containing compound include triethyl phosphate, tri-n-propyl phosphate, tri-isopropyl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, diethyl-n-butyl phosphate, and diethylbenzene phosphate. Phosphites and the like. As specific examples of the oxygen-containing compound, 2,2,5,5-tetramethyltetrahydrofuran and 2,2,5, · 5-tetraethyltetrahydrofuran etc. are substituted by 2,5—30 · (26) (26) 200413421 Tetrahydrofurans; 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentane, 9,9-dimethoxyfluorene, and diphenyldimethoxymethane Oxymethane derivatives, etc. 2. · Manufacturing method of solid catalyst component [A] As the manufacturing method of solid catalyst component [A], as long as the titanium compound (i) containing a halogen and the magnesium compound containing an alkoxy group are made at a specific temperature, (Ii) The silicon compound (iii) and the electron donating compound (i V) containing a specific amount of halogen may be contacted as required, and there is no particular limitation on the order of contact. However, the compound (i) may be contacted with the compound (i i), (iii) ′ (i V) or the compounds (i i), (i V), and then contacted with (1 or more) these compounds. Again, this method is the best. When the compounds (i), (ii), and (iV) are reacted to produce the component [A], the halogen-containing titanium compound (i) is brought into contact with the alkoxy-containing magnesium compound (ii), It is preferable to contact the electron-donating compound (i V) and react. Furthermore, when the compounds (i), (ii), (iii), (iV) are reacted to produce the [A] component, the magnesium compound (ii) containing an alkoxy group and the silicon compound containing a halogen ( After contacting i 1 i), it is then preferably contacted with an electron donating compound (i V), and finally reacted with a halogen-containing titanium compound (i). When contacted in this order, the polymerization activity may be improved. -31-(27) (27) 200413421 These components can be contacted in the presence of an inactive solvent such as a hydrocarbon, or they can be contacted by diluting the components with an inactive solvent such as a hydrocarbon in advance. Examples of the inactive solvent include aliphatic hydrocarbons or alicyclic hydrocarbons such as octane, decane, and ethylcyclohexane; aromatic hydrocarbons such as toluene, ethylbenzene, and xylene; and chlorobenzene and tetrachloride. Halogenated hydrocarbons such as ethane and chlorofluorocarbons, or mixtures of these. Among them, aliphatic hydrocarbons and aromatic hydrocarbons are preferred, and aliphatic hydrocarbons are particularly preferred. Here, the halogen-containing titanium compound (i) is usually 0.5 to 100 mol, preferably 1 to 50 mol, relative to 1 mol of the alkoxy-containing magnesium compound (i i). If the molar ratio is out of the above range, the catalyst activity will be insufficient. In addition, the electron-donating compound (i V) is generally 0.01 to 10 mol, and preferably 0.05 to 1.0 mol relative to 1 mol of the alkoxy-containing magnesium compound (ii). . If this molar ratio deviates from the range described above, the catalyst activity or stereoregularity will be deteriorated. In addition, the amount of halogen-containing silicon compound (i i i) is about 0 to 1 mole relative to the alkoxy-containing magnesium compound (i i) at a molar ratio of halogen / alkoxy group. In addition, the contact reaction of the compounds (i) to (i V) described above is generally carried out at a temperature ranging from 90 to 150 ° C, preferably from 125 to 140 ° C, after the addition. When the contact temperature is outside the above range, the effect of improving catalyst activity or three-dimensional regularity cannot be fully exerted. The contacting is usually performed for 1 minute to 24 hours, and preferably for 10 minutes to 6 hours. The pressure at this time varies depending on the type and contact temperature of the solvent used. -32- (28) (28) 200413421 The pressure range is usually 0 ~ 5Mpa, preferably 0 ~ IMpa. In addition, in the contact operation, it is preferable to perform stirring in terms of contact uniformity and contact efficiency. The same applies to the contact with the halogen-containing titanium compound (i) after the second time. In the contact operation of the halogen-containing titanium compound (i), when a solvent is used, the solvent used is usually 5,000 ml or less, in the range of 10 to 1,000 ml, relative to 1 mole of the halogen-containing titanium compound (i). Better. If the ratio is out of the above range, the uniformity or effectiveness of the contact will deteriorate. In addition, after the first contact reaction of the halogen-containing titanium compound (i), it is usually suitable to wash it with an inactive solvent at 90 to 150 ° C, especially 120 to 140 ° C. If the cleaning temperature is outside the above range, the effect of improving catalyst activity or three-dimensional regularity cannot be fully exerted. Examples of the inactive solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. And halogenated hydrocarbons such as chlorobenzene, tetrachloroethane, and chlorofluorocarbons, or mixtures of these. Among them, aliphatic hydrocarbons and aromatic hydrocarbons are suitable for use. In addition, there is no particular limitation on the cleaning temperature after the second and subsequent contact reactions with the halogen-containing titanium compound (i), but in terms of stereoregularity, it is 90 to 150 ° C, especially 120 To 140. (: It is advisable to wash the inactive solvent. Although the washing method is not particularly limited, it is advisable to use decantation and filtration methods. There is no particular limitation on the amount of inactive solvent, washing time and washing times. Restricted 'with respect to 1 mole of magnesium compounds, usually the solvent used is 100 ~ 100,000ml, preferably 1000 ~ 50,000ml, contact system (29) 200413421 usually 1 minute ~ 24 hours, especially 10 minutes ~ 6 hours If the ratio exceeds the above range, the washing will be incomplete. Although the pressure at this time varies depending on the type of solvent and washing temperature, the range is usually 0 ~ 5Mpa and 0 ~ IMpaG. In addition, in the cleaning operation, it is advisable to stir in terms of uniformity and contact efficiency of the cleaning. In addition, the solid catalyst component obtained can be stored in a dry state or an inactive solvent such as a hydrocarbon. 3. Method for producing olefin polymer There is no particular limitation on the amount of each component of the catalyst for polymerizing olefins of the present invention. The solid catalyst component [A] is converted into a titanium atom and the reaction volume per i L Which usually makes The amount ranges from 0.00005 to 1 ml. The aluminum / titanium atomic ratio of the organoaluminum compound [B] is generally used in the range of 1 to 1,000, preferably 10 to 500. If the atomic ratio exceeds the above range, the catalyst activity is In addition, when the electron-donating compound [C] is used, [C] / [B] (molar ratio) is usually used in an amount ranging from 0.001 to 5.0, preferably 0.01 to 2.0, and 0.05 to 1.0. If the molar ratio is out of the above range, sufficient catalyst activity and stereoregularity will not be obtained. However, the amount of the electron-donating compound [C] can be further reduced during preliminary polymerization. The olefin used in the invention is preferably an α-olefin represented by the general formula (VI): (VI) R10-CH = CH2 (30) (30) 200413421 In the general formula (VI), R1G is a hydrogen atom or The hydrocarbon group may be a saturated unsaturated group, or a linear one or a branched or cyclic one. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-heptane. Ene, 1-octene, 1-decene, 3-methyl-1, 1-pentene, 4-methyl-1, 1-pentene, vinyl ring Alkane, butadiene, isoprene, and stomach, etc. These olefins can be used alone or in combination of two or more. Among the above olefins, ethylene and propylene are particularly preferred. 之 In the present invention In the polymerization of olefins, the polymerization activity, in terms of the regularity of the olefin polymer 2 and the powder type, can be carried out after the preliminary polymerization of the olefin as required, and then the present polymerization. At this time, the solid catalyst component [Α] 'Organic aluminum compound [B] and the electron-donating compound [C]' in the presence of a catalyst mixed at a certain ratio, respectively, the olefin 'is usually at a temperature ranging from 1 to 100 ° C In the process, preliminary polymerization is performed at a pressure of normal pressure to about 5 MpaG, and then olefin-based polymerization is performed in the presence of a catalyst and a preliminary polymerization product. φ There is no particular limitation on the form of polymerization in this polymerization. Any solution polymerization, slurry polymerization, gas phase polymerization, and bulk polymerization are suitable for use. In addition, any batch polymerization or continuous polymerization is suitable for use, under different conditions. Two-stage polymerization or multi-stage polymerization is also suitable. In addition, regarding the reaction conditions, the polymerization pressure is not particularly limited. "In terms of polymerization activity," it is usually atmospheric pressure to 8 MpaG * preferably 0.2 to 5 MpaG, and the polymerization temperature is usually 0 to 200 ° C and 30 to 100 °. C is appropriately selected within a suitable range. Although the polymerization time varies depending on the type of the raw olefin -35- (31) (31) 200413421 or the polymerization temperature, it is usually 5 minutes to 20 hours, and preferably 10 minutes to 10 hours. The molecular weight of the hydrocarbon-burning polymer can be adjusted by adding a chain transfer agent, particularly hydrogen. In addition, inert gas such as nitrogen may be present. In addition, as the catalyst component in the present invention, the solid catalyst component [A], the organoaluminum compound [B], and the electron donating compound [c] are mixed and contacted at a certain ratio, and the olefin can be immediately introduced for polymerization Alternatively, after contacting, it is matured in about 0.2 to 3 hours, and then the olefin is introduced to perform polymerization. The catalyst component can be supplied after being suspended by an inactive solvent or an olefin. In the present invention, the post-polymerization treatment can be carried out in a conventional manner. That is, in the gas-phase polymerization method, after the polymerization, the polymer powder derived from the polymerizer can pass nitrogen gas flow to remove olefins and the like. In addition, it can also be extruded as required. In order to completely deactivate the catalyst, a small amount of water, alcohols, etc. may be added at this time. In the bulk polymerization method, after polymerization, the polymer powder derived from the polymerizer is completely separated from the monomers, and then tabletized. [Propylene-ethylene copolymerization] The catalyst for propylene-ethylene copolymerization of the present invention and a method for producing a propylene-ethylene copolymer using the catalyst will be described. The propylene-ethylene copolymerization of the present invention includes random copolymerization and block copolymerization. Furthermore, the propylene-ethylene random copolymer and propylene-ethylene block copolymer obtained by these production methods will be described. -36- (32) (32) 200413421 1. Catalyst component [A] Solid catalyst component The solid catalyst component contains titanium, magnesium, and an electron donor, that is, the following (a) magnesium compounds, ( b) a titanium compound compound, (c) an electron donor, and (d) a silicon compound corresponding to the need. Magnesium compound As the magnesium compound, a compound represented by the following general formula (W) can be used.

MgRMR12 ... (W) In the general formula (W), R11 and R12 represent a hydrocarbon group, an OR13 group (R13 is a hydrocarbon group) or a halogen atom. More specifically, examples of the hydrocarbon group include alkyl, cycloalkyl, aryl, and aralkyl groups having 1 to 12 carbon atoms. Examples of the OR13 group include R13 having 1 carbon atom. Examples of the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group of ~ 12, as the halogen atom include chlorine, bromine, iodine, and fluorine. R11 and R12 may be the same or different. Specific examples of the magnesium compound represented by the general formula (W) include dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, Ethylbutylmagnesium, diphenoxymagnesium, dicyclohexylmagnesium alkylmagnesium, arylmagnesium; dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium , Magnesium dihexyl oxide, magnesium dioctyl oxide, magnesium diphenoxy and magnesium dialkoxy, magnesium diallyloxy; ethyl-37- (33) (33) 200413421 Magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium bromide Alkyl magnesium halides, aryl magnesium halides, butyl magnesium iodide, etc .; butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, and ethoxylate Alkoxymagnesium chloride, aryloxymagnesium chloride, etc. of magnesium iodide; magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, etc. These magnesium compounds may be used singly, or may be used by being supported on a support such as silica, alumina, polystyrene, or a combination of two or more. Furthermore, it can also be used in mixture with halogen or the like. Among the magnesium compounds, magnesium chloride is the most preferable, or in the general formula (W), R11 and / or R12 is an OR13 group alkoxy group-containing magnesium compound. Such an alkoxy-containing magnesium compound, in terms of the polymerization activity of the catalyst, includes metal magnesium, alcohols, and halogens having a halogen atom of at least 0.001 lg with respect to 1 mol of metal magnesium and The alkoxy-containing magnesium compound obtained by the reaction of the halogen-containing compound is preferred. The type of alcohol, the type of halogen, and the type of halogen-containing compound are the same as those described for the alkoxy-containing magnesium compound (i i) as a catalyst for olefin polymerization. (b) Titanium compound As the titanium compound, a compound represented by general formula (VDI) can be used. -38- (34) (34) 200413421

TiXs (OR14) 4_ s ... (yin) In the above general formula (μ), the 'x' represents a halogen atom. Among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R14 is a hydrocarbon group, which may be a saturated group or an unsaturated group, and may be a linear one or a branched one or a cyclic one. Furthermore, it may have a different element such as sulfur, nitrogen, oxygen, silicon, and phosphorus. However, a hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, an alkenyl group, a cyclophosphyl group, an aryl group, an aromatic group, or the like, and a linear or branched alkyl group is more preferable. When -OR14 is plural, it may be the same or different from each other. Specific examples of R14 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, decyl, allyl, butyl Alkenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, and phenethyl. s is an integer of 0 to 4. Specific examples of the titanium compound represented by the general formula () include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-isopropoxy titanium, and tetra-n-butoxy titanium. Concrete examples described in tetraalkoxy titanium such as tetraisobutoxy titanium, tetracyclohexyl titanium, tetraphenoxy titanium, and the like, and halogen-containing titanium compounds (i) for olefin polymerization catalysts. Among these, high-halogen-containing titanium compounds are particularly preferred, titanium tetrachloride. These titanium compounds may be used singly or in combination of two or more kinds. (0 Electron donor As the electron donor, a malonic acid diester represented by the general formula (Π) can be used. -39-(35) (35) 200413421 R4 r2-oc-c-co-R3. ..... (n)

II H 0 r5 〇 [—In the general formula (Π), R4 is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, R5 is fluorene or an alkyl group having 1 to 2 carbon atoms, and R4 and R5 may be bonded to each other to form a ring, and R2 and R3 may be the same or different, and may be a linear or branched alkyl group having 1 to 20 carbon atoms. ] r4 is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably n-butyl. R5 is better. It is preferable that R 'and R5 are those forming a ring. R2 and R3 are preferably those having 2 to 8 carbon atoms, and the most preferable are ethyl. Specific examples of the above compounds include cyclopentane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, and cyclobutane-1,1-dicarboxylic acid dibutyl ester. , Cyclopropane-1,1 dicarboxylic acid, dimethylmalonic acid, diethylmalonic acid'methylisopropylmalonic acid, methylisobutylmalonic acid, methylmalonic acid, Ethylmalonate, n-propylmalonate, isopropylmalonate, n-butylmalonate, isobutylmalonate, cyclobutylmalonate, cyclopentylmalonate, cyclohexyl Dimethyl ester, diethyl ester, di-n-propyl ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, di-n-pentyl ester, etc. , Di-n-heptyl ester, di-n-octyl ester, di-n-pentyl ester, and the like. These compounds may be used singly or in combination of two or more kinds. -40- (36) (36) 200413421 remembers the malonates, which can be obtained by a known method, for example, the same method as described in "Experimental Chemistry Lecture 4th edition, 22 volumes, p. 59, nine good" The method 'is a method of synthesizing malonate, or it is the same as the method described in "New Experimental Chemistry Lectures, Vol. 14-II, pages 931 and 1003, Jiushan", which is a transesterification reaction. (d) Sand compound As the silicon compound, a silicon compound represented by the following general formula (κ) can be used.

Si (OR15) tX4- (K) In the general formula (K), X represents a halogen atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R15 is a hydrocarbon group, which may be a saturated group or an unsaturated group, and may be a linear one or a branched one or a cyclic one. In addition, although it may contain different elements such as sulfur, nitrogen, oxygen, silicon, and phosphorus, However, a hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, or the like. When R15 is plural, it may be the same or different from each other. Specific examples of R15 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, decyl, allyl, butyl Alkenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, phenethyl and the like. t is an integer from 0 to 4. Specific examples of the titanium compound represented by the general formula (IX) include, for example, silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxy-41 · (37) (37) 200413421 chlorosilane , Ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Among them, silicon tetrachloride is suitable. These halogen-containing silicon compounds may be used singly or in combination of two or more kinds. The molar ratio of the silicon compound / magnesium compound to the silicon compound of component (d) to be used as desired is usually 0.01 or more, preferably 0.1 or more. If the molar ratio is less than 0.01, there may be a problem that the effect of improving catalytic activity or stereoregularity cannot be fully exerted, or that the amount of fine powder in the produced polymer becomes large. In the production of the solid catalyst component [A], in addition to the compound (c), other electron donors may be used. Examples of such an electron donor include electron-donating compounds (C), alcohols, and organic acids described later. [B] Organoaluminum compound The same as the organoaluminum compound used in the catalyst for olefin polymerization. [C] The electron donating compound is the same as the electron donating compound used in the catalyst for olefin polymerization. 2. Modulation of the solid catalyst component The preparation of the solid catalyst component [A] makes the above (a) titanium compound, (b) A magnesium compound, (c) an electron donor, and a corresponding required (d) silicon compound. -42 · (38) (38) 200413421 The known methods include those disclosed in JP-A Sho 5 3 — 43 094, JP-A Sho 55 — 135102, JP-A Sho 55 — 135103, and JP-A Sho 56 — 18606. Methods etc. For example, (1) in the presence of an electron donor and a corresponding pulverization aid used as desired, the magnesium compound or a compound of the magnesium compound and the electron donor may be pulverized, and then the magnesium compound may be pulverized with the titanium compound. A method of reaction; (2) a method of reacting a liquid material of a magnesium compound having no reducing energy with a liquid titanium compound in the presence of an electron donor, and then precipitating a solid titanium composite; (3) a method of making titanium A method of reacting a compound with the former (1) or (2); (4) Further, a method of reacting an electron donor and a titanium compound with the former (1) or (2); (5) in In the presence of an electron donor, a titanium compound, and a corresponding pulverization aid, etc., a method of pulverizing a magnesium compound or a compound between the magnesium compound and the electron donor, and then treating it with a halogen or a halogen compound, etc. modulation. Furthermore, methods described in JP-A-Sho 56-166205, JP-A-Sho 57-63309, JP-A-Sho 57-190004, JP-A-Sho 57-300407, and JP-A-Sho 58-47003 other than these methods can also be used. To modulate the [A] solid catalyst component described above. Here, the amount of the titanium compound (b) used above is usually 0.5 to 100 mol, and preferably 1 to 50 mol relative to 1 mol of the magnesium compound (a). The amount of the electron donor (c) described above is generally 0.01 to 10 mol, preferably 0.05 to 1.0 mol, relative to 1 mol of the magnesium compound (c). Further, silicon tetrachloride may be added as a halide. -43- (39) 200413421 In addition, the titanium compound can be used as a catalyst carrier by contacting the titanium compound more than twice. The above contact catalyst components can also be inactive solvents such as hydrocarbons. Active solvents can be reporters. The solid product may be stored in an inert solvent such as a hydrocarbon. Furthermore, the contacting of the compounds (a) to (d) described above is carried out at 120 to 150 ° C, preferably at 125 to 140 ° C. When the contact temperature is outside the above range, the catalyst activity or the effect of stereoregularity cannot be improved. In addition, the contact force is preferably from minutes to 24 hours, and from 10 minutes to 6 hours. Although it varies depending on the type of the solvent and the contact temperature, it usually ranges from 0 to 5Mpa (Gauge), J (Gauge). Better. In the contact operation, it is preferable to perform stirring in terms of contact efficiency. There is no particular restriction on the order of this contact. For example, it can be contacted in the presence of an inactive solvent such as a hydrocarbon, or it can also be contacted by diluting each component in advance. Examples of such inertness include n-pentane, isopentane, n-hexane, n-heptane, and octane aliphatic hydrocarbons; aromatic mixtures of benzene, toluene, ethylbenzene, and xylene. In addition, the contact with the titanium compound is performed more than twice, and the role as a catalyst carrier can be fully exerted. When contacting the operating medium, the solvent is 5,000 ml or less relative to 1 mol of the halogen-containing titanium compound, and the solid obtained by the magnesium compound is preferably washed with 10 to 10,000 mi as appropriate. This is not in the dry state. The full temperature range of the reaction system is fully exerted. The pressure range at this time has been changed. 均匀 0 ~ 1 Mpa uniformity, and each component is firstly a solvent such as hydrocarbons, such as hydrocarbons such as decane, or these, which are commonly used in magnesium compounds. If the ratio (40) 200413421 is out of the above range, the uniformity or effectiveness of the contact will deteriorate. The solid catalyst component obtained by the above contact is preferably washed at 0 to 150 ° C, especially at 120 to 140 ° C in an inactive solvent. If the cleaning temperature exceeds the above range, the effect of improving catalyst activity or regularity cannot be fully exerted. Examples of the inactive solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as xylene, and tetrachloroethyl. Halogenated hydrocarbons such as alkanes and chlorofluorocarbons or mixtures of these. Among them, aliphatic is preferred. The cleaning method and pressure are the same as the catalyst for olefin polymerization. 3. Manufacturing method of propylene-ethylene copolymer The manufacturing method of the propylene-ethylene random copolymer of the present invention is to make ethylene and ethylene in the presence of a catalyst. Method for copolymerizing propylene. The method for producing a propylene-ethylene block copolymer according to the present invention includes a process of polymerizing propylene to form a polypropylene component, and a process of polymerizing ethylene and propylene to form an ethylene / propylene copolymer component, and forming the component in polypropylene. In at least one of the production process and the ethylene / propylene copolymer component formation process, the method described in the previous catalyst is used. It is best to use the remembered catalyst in both processes. There is no particular limitation on the amount of catalyst component used. The solid catalyst component [A] is converted into titanium atoms and the reaction volume per 1L is usually in the range of 0.00005 to 1 ml. The aluminum / titanium of the organoaluminum compound [B] The original ratio is usually in the range of 1 to 1,000, preferably 10 to 500. In this case, if the V / · fluorene content of the olefin-containing species before the hydrocarbons is low, the catalytic activity will be insufficient if the ratio of the protons (41) (41) 200413421 exceeds the above range. In addition, the electron donating compound [C] such as an organosilicon compound, and the mole ratio of the electron donating compound [C] / organoaluminum compound [B] are usually used in an amount ranging from 0.001 to 5.0, especially 0.01. ~ 1.0 is better. When the molar ratio exceeds the above range, sufficient catalyst activity cannot be obtained. In addition, the catalyst used in the polymerization may be prepared by preliminary polymerization in an olefin. The α-olefin is preferably an α-olefin represented by the general formula (VI). R10-CH = CH2… (VI) In the general formula (VI), R1G is a hydrogen atom or a hydrocarbon group, which may be a saturated group or an unsaturated group, and may be a linear or branched or cyclic group. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl -1-pentene, vinyl cyclohexane, etc. These olefins may be used alone or in combination of two or more kinds. Among the above olefins, ethylene and propylene are particularly preferred. In addition, diene such as butadiene and other various olefins may be used. In the propylene-ethylene copolymerization in the present invention, if necessary, the preliminary polymerization of olefins may be performed before the present polymerization. At this time, the solid catalyst component [A], the organoaluminum compound [B], and the electron donating compound [C] are mixed at a certain ratio, respectively, and the olefin is usually 1 to 1 〇 (Temperature in the TC range (42) (42) 200413421 'can be used for preliminary polymerization at a pressure of normal pressure to about 5Mpa (Gauge) (polymerization time is 1 minute to 10 hours, and 10 minutes to 5 hours Compared with the solid catalyst component, the amount of preliminary polymerization is usually 0 to 1000% by weight, preferably 1.0 to 500% by weight, and the best amount of polymerization is 1.0 to 200% by weight. If the amount of preliminary polymerization exceeds the above range, Then it will not be able to obtain sufficient catalyst activity, if it is too low, the fine powder will increase. Secondly, propylene-ethylene copolymerization (random or embedded In the present invention, in addition to ethylene and propylene, a small amount of α-olefin may be used as required. As the olefin, the aforementioned ^ -olefin may be mentioned. Furthermore, butyl may be used. Diene, such as diene, and various other olefins. The polymerization method in the manufacturing method is not particularly limited, and any solution polymerization, slurry polymerization, gas phase polymerization, and bulk polymerization are suitable for use. Furthermore, as the polymerization method, any batch polymerization or continuous polymerization can be used. In addition, two-stage polymerization or multi-stage polymerization under different conditions is also suitable for use. In the production of propylene-ethylene block copolymers, whether it is batch polymerization or continuous polymerization, generally, first, the propylene separate polymerization part is firstly performed. Then, the copolymerization part is performed. For example, in the case of continuous production, hydrogen gas and a catalyst of a molecular weight modifier are supplied to a raw material propylene gas in a former polymerization tank, and the polymerization amount is controlled during the polymerization time to produce a propylene alone polymerization part. Then move it to the polymerization tank at the later stage, and further add ethylene gas, hydrogen gas and the corresponding catalyst to the copolymer -47-(43) (43) 200413421 propylene gas to obtain the copolymerization part, and then obtain Block copolymers. In the production of the copolymerization part of the present invention, although ethyl acetate can be used alone, it can also be used as needed. The ❹-olefin represented by the general formula (W) in the foregoing description. Furthermore, according to need, diene such as butadiene and other various olefins may be used. Production of the propylene-ethylene copolymer of the present invention The polymerization conditions in the method are the same as those of the above-mentioned olefin polymerization. The φ molecular weight can be adjusted by adding a chain transfer agent, especially hydrogen. It is also possible to adjust inert gas such as nitrogen. Also, ethylene content Pressure, so that the unit content of ethylene in the copolymer becomes as desired, and is adjusted by the amount of ethylene supplied. In addition, the catalyst component in the present invention is [A], [B], and [C], After mixing and contacting at a certain ratio, ethylene and propylene can be introduced for polymerization immediately, or after contacting, it can be matured after about 0.2 to 3 hours, and then ethylene and propylene are introduced for polymerization. The catalyst component can be supplied after being suspended by an inactive solvent or an olefin. The post-polymerization treatment is the same as the olefin polymerization described above. 4. · propylene-ethylene random copolymer The propylene-ethylene random copolymer of the present invention is a polymer obtained by the above-mentioned production method. The ethylene content 'obtained by 13C-NMR is usually 0.1 to 10.0% by weight, and preferably 0.5 to 7.0% by weight. If it is higher than this range, the amount of soluble fraction of the temperature increase method will be increased, and -48- (44) (44) 200413421 will be increased, and the lumpiness will be deteriorated. If it is too low, it will show a state in which its heat sealability cannot be reduced. In addition, the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography is usually 3.5 to 5_0, and preferably 3.5 to 4.5. If the molecular weight distribution (Mw / Mn) is wider than this range, the agglomeration will be deteriorated. Narrower will deteriorate the formability. Furthermore, the melt flow rate (MFR) measured at 23 0 ° C and 2.16 kg based on JIS-K7210 is usually 0.01 to 100 g / 10 minutes, and 0.1 to 500 g / 10 Divided into the best, the best is! ~; [〇〇g / 10minutes. If the MFR is larger than this range, impact resistance will be reduced, and if it is too small, it will be difficult to form. The polymerization activity is preferably 350 kg / g-Ti or more, more preferably 500 kg / g-Ti or more, and most preferably 700 kg / g-Ti or more. 5. · propylene-ethylene block copolymer The propylene-ethylene block copolymer of the present invention has a melt flow rate (MFR) measured at 230 ° C and 2.16 kg based on JIS-K7210. · 1 to 5 00 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes, and the most preferable is 10 to 20 g / 10 minutes. If the MFR is larger than this range, impact properties will be reduced, and if it is too small, it will be difficult to form. The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography is usually 3.5 to 5.0, and preferably 3.5 to 4.5. If Mw / Mn is too small, the fluidity will decrease and the formability will be deteriorated. If it is too large, the low-molecular-weight component increases, and the transparency tends to decrease -49- (45) (45) 200413421. The amount of the propylene-ethylene block copolymer of the present invention is preferably from 5 to 50% by weight based on the amount of the soluble component (also referred to as the non-crystalline portion) at 25 t. If it is larger than this range, the rigidity decreases, and if it is too small, the impact resistance tends to decrease. The ethylene content of the amorphous portion is preferably 15 to 50 mol%. If it exceeds this range, the dispersibility of rubber will be deteriorated, and in this case, physical properties such as rigidity and impact resistance will be lowered accordingly. The propylene-ethylene block copolymer of the present invention preferably has a flexural modulus of 800 MPa (Gauge) or more, and more preferably 100 MPa (Gauge) or more. At room temperature, Izod impact strength is preferably above 7 kJ / m2. The low-temperature Izod impact strength is preferably 4 kJ / m2 or more, and more preferably 6 kJ / m2 or more. Next, the present invention is specifically illustrated by examples, but the present invention is not limited to the examples described below. [Example of olefin polymerization] A method for evaluating physical properties is as follows. (1) Catalyst activity: After the solid catalyst component obtained from the production is sufficiently dried, it is accurately weighed and then fully deashed with 3N sulfuric acid. After that, the insoluble matter was filtered, phosphoric acid as a decolorizing agent was added to the filtrate, and then 3% hydrogen peroxide water was added to make the solution color. FT-IR was used to measure the absorbance of this color-developing solution at 42 Onm to determine the Ti concentration, and the amount of Ti carrier in the solid catalyst component was calculated. Then calculate the catalytic activity of lg titanium based on this Ti support amount of -50 · (46) 200413421. (2) [7?]: Using a clutch type automatic viscometer (share company) in naphthalene full solvent at 1 35 ° C · (3) [mmmm]: I2C-NMR of 1,2,4-trichlorobenzene and heavy benzene (manufactured by Nippon Denshi Co., Ltd. under 130 ° C, the signal is quantified based on the complete decoupling of protons. In addition, the so-called [mmmm ] Refers to A, Macromolecules, Vol. 6, page 925 (refers to the isotactic fraction in the polypropylene subunit obtained from the 13C-NMR spectrum. In addition, the peak of the 13C-NMR spectrum A · Z ambe 11 i is equal to Ma cr 〇m ο 1 ecu 1 es, proposed by (1 97 5). (4) Magnesium compound containing alkoxy group (ii) Magnesium compound containing alkoxy group (ii) suspended in carbon The average particle diameter of hydrogen is measured by the light transmission method. The measured value is expressed on a logarithmic regular paper, and the particle diameter is 50%. (5) Particle form (average micro component) of polyolefin powder: Yuzisuo will be used The number of measured particle size distributions is on the regular accuracy paper, and the 50% particle diameter is calculated as the particle size, and the powder with 2,830 // m or more is used as the coarse fraction. Company's VMR — 053 F. The compound was mixed in a 90:10 mixed solution, using: LA — 5 0 0), using the measured Zambelli of the methyl group equal to 1 973), the pentad in the sub-chain was determined The legal system complies with the average particle diameter of Volume 8, page 68 7: In the compound, the particle diameter distribution is used as the average particle diameter, the coarse component, and the graph is shown as the average particle diameter. Use 2 5 0 // m and use the powder under (47) (47) 200413421 as the differential to find these quantities. [Embodiment] Example 1 (1) Production of magnesium compound containing alkoxy group After fully replacing a glass reactor with a stirrer with an internal volume of approximately 6 L by nitrogen, approximately 2430 g of ethanol and 160 g (6.6 mol) were charged. Ear) of metal magnesium and a 15g (0.12g atom) stele, while stirring and reacting under circulating conditions and heating until hydrogen no longer occurs in the system ', diethoxymagnesium can be obtained. (2) Manufacture of solid catalyst components After replacing the three-necked flask with a stirrer with a volume of 0.5L by nitrogen, 80 ml of dehydrated octane and 16 g of (1) diethoxylate were added. The base magnesium is then heated to 40 ° C, 77 ml of titanium tetrachloride is added dropwise, the temperature is raised to 90 ° C, and 2.8 ml of diethyl n-butylmalonate is added. The solution was stirred for 2 hours at an internal temperature of 1 2 5 ° C, followed by contact operation, and then thoroughly washed with dehydrated octane. Then, 122 ml of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C for 2 hours. After the contact operation was performed again, it was thoroughly washed with dehydrated octane to obtain a solid catalyst component. (3) Propylene polymerization The stainless steel sterilization kettle with a stirrer with an internal volume of 1 L was fully dried and then replaced with nitrogen. At room temperature, 400 ml of dehydrated heptane was added. Then, 2.0 mmole of triethylaluminum, (48) (48) 200413421 0.2 5 mmole of cyclohexylmethyldimethoxysilane, and 0.0025 mmole of titanium atom (2) were used to produce a solid contact. Add hydrogen to O.OMPaG, then introduce propylene, increase the temperature to 8 (TC, 0.8MPaG), and polymerize for 1 hour. Then lower the temperature, remove the pressure, take out the contents, and put 2L of The catalyst was deactivated in methanol. The propylene polymer was filtered and vacuum dried to obtain a propylene polymer. The obtained propylene polymer was measured for its inherent viscosity and stereoregularity. The results are shown in Table 1. Comparative Example 1 (1) Solid Production of catalyst ingredients In a 500-mL three-necked flask with a stirrer after replacing with nitrogen, 13.3 g of magnesium chloride (anhydrous), 70 ml of guiyuan, and 65.5 ml (0.42 mole) of 2-B Hexanol was heated and reacted at 130 ° C for 2 hours to form a homogeneous solution. Then, 3.12 g of phthalic anhydride was added to the solution, and the mixture was stirred and mixed at 130 ° C for another 1 hour. The anhydride is dissolved in the homogeneous solution described above. After cooling to room temperature, the entire homogeneous solution was dropped into 373 ml of titanium tetrachloride stored at -20 ° C over 1 hour. After dropping, the temperature of the obtained homogeneous solution was raised to n over 4 hours. (TC, to 11 ° C, add 2.3 ml of diethyl n-butylmalonate, and then stir for 2 hours while maintaining 1 10 t. After the 2 hour reaction is over, filter while hot and take The solid part was suspended again with 2 75 ml of titanium tetrachloride, and then heated again at -53 · (49) (49) 200413421 1 1 0 ° C for 2 hours. The reaction was completed After that, it was filtered again while hot, and the solid portion was collected and washed with decane and hexane at 110 ° C. This washing was performed until no titanium compound was detected in the washing liquid to obtain a solid catalyst component. (2) Polymerization of propylene In Example 1, except that the solid catalyst component obtained in the above (1) was used, propylene was polymerized in the same manner as in Example 1 and evaluated. The results are shown in Table 1. Examples 2 (1) Manufacture of solid catalyst components. A three-necked flask with a stirrer with an internal volume of 0.5 L was filled with nitrogen. After substituting, add 80 ml of dehydrated octane and i6 g of the diethoxy magnesium prepared in Example 1, and then heat to 40 X :, add 2.4 ml of silicon tetrachloride, and stir for 20 minutes. Then, 1.8 ml of diethyl n-butyl malonate was further added. The solution was heated to 65. <: Then, 77 ml of titanium tetrachloride was added dropwise, and the internal temperature was 125. (: Then, the solution was stirred for 2 hours, and 'contact operation was performed'. After that, it was thoroughly washed with dehydrated octane. Then, 122 ml of titanium tetrachloride was added at an internal temperature of 125. 〇 Stir for 2 hours, and then perform the contact operation again, and wash thoroughly with dehydrated octane to obtain a solid catalyst component. (2) Polymerization of propylene In Example 1, except that the solid catalyst component obtained in the above (1) was used, propylene was polymerized in the same manner as in Example 丨 and evaluated. -54- (50) (50) 200413421 The results are shown in 袠 1. Example 3 (1) Production of solid catalyst component In Example 1, the same method as in Example 丨 was used except that cyclohexyl isobutyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. To make solid catalyst ingredients. (2) Polymerization of propylene In Example 1, propylene was polymerized in the same manner as in Example i except that the solid catalyst component obtained in the above (1) was used, and evaluated. The results are shown in Table 1. Comparative Example 2 (1) Production of solid catalyst component In Example 1, except that dibutyl cyclopentylmalonate was used instead of diethyl n-butylmalonate, the same method as in Example i was used. Manufacture of solid catalyst ingredients. (2) Polymerization of propylene In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component obtained in the above (1) was used, and evaluated. The results are shown in Table 1. -55- (51) 200413421 Table 1 Catalyst-shaped active polymer parts (kg / pp / g-Ti) [V] [mmmm] Compounds Flat polymer Average polymer Crude polymer micro (dl / g) ( %) Average particle size (um) Particle size (μπι) Component (%) Component (%) Example 1 278 0.96 92.9 59 1030 0.1 7.6 Example 2 252 0.98 93.4 62 1100 0.3 3.6 Example 3 293 0.98 94.3 58 1060 0.3 6.1 Comparative Example 1 192 0.95 93 25 260 0.1 85 Comparative Example 2 216 1.02 93.5 61 1090 0.3 8.9

[Example of a propylene-ethylene random copolymer] A method for evaluating physical properties is as follows. (1) Measurement of U] Using the VMR-05 Model 3 automatic viscometer (Kyoto Corporation) in naphthalene solvent at 1 3 5 ° C.

(2) Measurement of Mw / Mn It was measured under the following apparatus and conditions.

G P C (Gel Permeation Chromatography) Measuring Device Yingzhu · Showa Denko ShodexUT806L Infrared Detector: IR Detector for Liquid Chromatograph Infrared Detection Flowcell: KBr cell (Optical Path Length 1 mm) Solvent: o-dichlorobenzene

Measuring temperature: 1 3 5 ° C Flow rate: 1.0 ml / min. 56- (52) (52) 200413421 Sample concentration: 2mg / ml Injection volume: 2/1/1 Infrared absorption wavelength: 3.42 # m (3) Heating The amount of soluble components in the separate method, that is, the apex temperature of the dissolution curve, can be obtained by the temperature-free separation method for polypropylene obtained by polymerization. The sample was prepared by weighing 75 mg of polymer at room temperature and adding it to 10 ml of o-dichlorobenzene, and stirring at 135 to 15 ° C for 1 hour to dissolve it. After injecting 0.5ml of the sample solution into the column at 135 ° C, slowly cool down to 0 at 10 ° C / hr. (: So far, the polymer is crystallized on the surface of the filler. At this time, the amount of the polymer that has not been crystallized but remains is 0 ° c soluble content. (4) 13C-nMR ethylene content Measurement of Amount The content of ethane-flame unit can be obtained by the following method. That is, the 13C-NMR measurement shown below is performed on the sample, and the spectrum is 35 ~ 2lppm [Tetramethyl Base shift of the basic silane (TMS) chemical [7] peaks in the τίΐ region to calculate the triad continuous fraction (mol%) of ethylene (E) and acrylic (P). F eep = [K (T ") / Τ] χ100 f ΡΡΕ = [κ (δ) / Τ] χ100 f εεε = [Κ (S, 5) / 4T + Κ (Ss 6) / 2Τ] χ100 f ρρρ = [Κ () / Τ) χ1〇〇 -57- (53) 200413421

f PEE = [K (r) / T] xl00 f pep = [K (S / s ^) / T] xlOO However, it shows that τ = κ (τ〇〇 + κ (τβ δ) +

K (Sr < 5) / 4T + K (s δ.) / 2 + K () + K (r) + K (). Here, for example, fEPE represents the continuous fraction of EPEtriad (mol%), and K (T55) represents the integrated intensity of the peak attributed to Tη.

Second, the ethylene unit content (% by weight) can be calculated by the following formula using the triad continuous fraction described above. Ethylene unit content (% by weight) = 28 [3 f EEE + 2 (f pee + [ερε) + f ppE + f pep] x1〇〇 / [28 〔3 f eee + 2 (f pee + f EPe) + f PPE + f PEP] + 42 [3 f ppp + 2 (f ppE + f PEP) + fEPE + fpEE]] <13C — NMR measurement>

Take 220mg of the sample into the NMR sample tube, and add 3ml of 1 '2,4-trichlorobenzene / heavybenzene mixed solution (capacity ratio 90/10), then cover the tube cap at 130 ° C The mixed sample was uniformly dissolved, and then 13 C-NMR measurement was performed under the conditions shown below. Device Pulse width Pulse repetition time Spectral width Measured temperature Accumulated times JNM made by Japan Electronics Co., Ltd. — EX4 0 0 9 // S (45 °) 4 seconds

20000Hz 1 3 0 ° C 1000 ~ 10000 times -58- (54) (54) 200413421 Example 4 (1) Production of solid catalyst components A nitrogen-filled glass reactor equipped with a stirrer is used to sufficiently replace the internal volume of about 6L. Then, put about 2430g of ethanol, 160g of magnesium metal and 16g of iodine, and stir while reacting under circulating conditions and heating until no more hydrogen is generated in the system to obtain a solid magnesium compound (diethoxy magnesium) . Next, 16 g of diethoxymagnesium was put into a three-necked flask equipped with a stirrer having an internal volume of 0.5 L which had been replaced by nitrogen. Furthermore, 80 ml of dehydrated octane was added. Then it was heated to 4 ° C, 2.4 ml of silicon tetrachloride was added, and after stirring for 20 minutes, 2.7 ml of diethyl n-butylmalonate was further added. The solution was heated to 80 ° C, and then used. The dropping funnel was further dropped into 77 ml of titanium tetrachloride. Then, the internal temperature was 125 ° C to contact the reaction for 2 hours. Thereafter, the stirring was stopped to precipitate the solid, and the supernatant was removed. Then, 100 ml of dehydrated octane was added, The temperature was raised to 125t while stirring. After holding for 1 hour, the stirring was stopped to precipitate the solid, and the supernatant was removed. The washing operation was repeated 7 times. Furthermore, 122 ml of titanium tetrachloride was added to make the internal temperature 125 ° C Come in contact with the reaction for 2 hours. Second, repeat the washing with 125t of dehydrated octane for 6 times to obtain the solid catalyst component. (2) Polymerization method: The content is 1L and the stainless steel sterilization kettle with a stirrer is sufficient. After drying and replacing with nitrogen, 380 ml of dehydrated heptane (55) (55) 200413421 was added to the inside, and the temperature was raised to 80 ° C while stirring. The propylene, ethylene and hydrogen were adjusted to a flow ratio (I / m in) is 9.90: 0.10: 0.814 and introduced into the system, and discharged at the same time Outside the system, keep the pressure in the system at MPa (Gauge). After replacing the catalyst supply tube with sufficient nitrogen, add 20 ml of dehydrated Geng Yuan, 0.6 mmole of triethylamine, 0.075 mmole of dicyclopentyl di A methoxysilane (DCPDMS), a polymerization catalyst component described in terms of titanium atom of 0.0015mmole, and then pressurized into the system with hydrogen. The temperature was maintained at 80 ° C and the internal pressure was 0.4MPa (Gauge). Polymerization was performed for 1 hour. After stopping the reaction with methanol, the content was taken out in methanol and vacuum dried to obtain a propylene-ethylene copolymer. The results are shown in Table 2-1. Example 5 Except changing the propylene flow rate to 9.83 ( 1 / min), the ethylene flow rate was changed to 0.17 (1 / min), and the chlorine flow rate was changed to 0.720 (i / min), and the rest were performed in the same manner as in Example 4. The results are shown in Table 2-1. Example 6 Except that the C-flow rate was changed to 9.69 (Ι / min), the B-flow rate was changed to 0.31 (Ι / min), and the hydrogen flow rate was changed to 0.81 〇 (丨 / min). Performed in the method of Example 4. The results are shown in Figure 2-1. Example 7 Except solid catalyst The electron donor used in the partial preparation was changed from -60- (56) (56) 200413421 2.7ml of diethyl n-butylmalonate to 3.1ml of dimethylmalonate, the rest All were performed in the same manner as in Example 4. The results are shown in Table 2-1. Example 8 Except that the catalyst used was changed to that prepared in Example 7, the rest were performed in the same manner as in Example 5. Already. The results are shown in Table 2-1. Example 9 Except that the electron donor used in the preparation of the solid catalyst component was changed from 2.7 ml of diethyl n-butylmalonate to 3.6 ml of dibutyl cyclopentylmalonate, the rest were all The same method as in Example 4 was performed. The results are shown in Table 2-1. Example 1 Except that the catalyst used was changed to the one prepared in Example 9, the stomach &amp; was performed in the same manner as in Example 5. The results are shown in Table 2-1. -61 ^ (57) (57) 200413421 Table 2-1 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Solid catalyst component electron donor com.A com.A com.A com.B com.B com.C com.C Reaction temperature ° c 125 125 125 125 125 125 125 Washing temperature ° c 125 125 125 125 125 125 125 Polymerization conditions Polymerization time minutes 60 60 60 60 60 60 60 Polymerization temperature ° c 80 80 80 80 80 80 80 Propylene flow rate 1 / min 9.90 9.83 9.69 9.90 9.83 9.90 9.83 Ethylene flow rate 1 / min 0.10 0.17 0.31 0.10 0.17 0.10 0.17 Hydrogen flow rate 1 / min 0.814 0.720 0.810 0.814 0.720 0.814 0.720 Full pressure MPa 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst mmol 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 TEA mmol 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Silicon compound type DCP DCP DCP DCP DCP DCP DCP DCP DCP Silicon compound mmol 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 Polymerization polymerization activity kg / g-Ti 480 740 1160 520 790 500 770 ethylene content NMR 1.2 2.6 4.4 1.1 2.2 1.2 2.3 [V] dl / g 1.68 1.71 1.61 1.69 1.76 1.76 1.76 Mw / Mn 4.42 4.56 4.38 4.38 4.6 1 4.38 4.63 0 ° C Soluble content Wt% 0.80 0.92 1.44 0.79 0.89 0.80 0.90 com.A Diethyl butylmalonate com.B Dibutyl dimethylmalonate com.C Cyclopentylmalonate Dibutyl acid-62- (58) (58) 200413421 DCP dicyclopentyldimethoxysilane TEA triethylaluminum Example 1 1 Except for the electron donor used for the preparation of the solid catalyst component, 2.7 Except that ml of diethyl n-butylmalonate was changed to 3.2 mi of cyclobutane mono-dicarboxylic acid dibutyl, the rest were performed in the same manner as in Example 4. The results obtained are shown in Table 2-2. Example 1 2 The same procedure as in Example 5 was performed except that the catalyst used was changed to the one prepared in Example 11. The results are shown in Table 2_2. Example 1 3 Except that the silane compound used in the polymerization was changed from cyclopentyldimethoxysilane (DCPDMS) to cyclohexylisobutyldimethoxysilane, the rest were performed in the same manner as in Example 5. . The obtained results are shown in Table 2-2. Example 1 4 (1) Production of solid catalyst components In a three-necked flask with a stirrer with an internal volume of 5,000 mL and substituted with nitrogen, 13.3 g of magnesium chloride ( Anhydrous), 70ml of decane and 65.5ml (0.42mole) of 2-ethylhexanol 'at 130 ° C -63- (59) (59) 200413421 heating reaction for 2 hours to become a homogeneous solution . Thereafter, 3.12 g of phthalic anhydride was added to the solution, and the mixture was stirred and mixed at 130 ° C for 1 hour, and then the phthalic anhydride was dissolved in the above uniform solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into 373 ml of titanium tetrachloride stored at -20 ° C over 1 hour. After dropping, the temperature of the obtained homogeneous solution was raised to 110 t over 4 hours, and to 110 ° C, 3.4 ml of diethyl n-butylmalonate was added, and then-while maintaining 1 1 0 ° C, while stirring for 2 hours. After the completion of the reaction for 2 hours, the hot portion was filtered, and the solid portion was collected. The solid portion was suspended again with 275 ml of titanium tetrachloride, and then heated at 110 ° C for 2 hours. After the reaction was completed, the solution was filtered while still hot. The solid portion was collected and washed with decane and hexane at 110 ° C. This washing is performed until no Chin compound is detected in the washing liquid 'to obtain a solid catalyst component. (2) Polymerization method Polymerization was performed by the same polymerization method as in Example 4. The results are shown in Table 2-2. Example 15 (1) Preliminary polymerization In a three-necked flask equipped with a stirrer with an internal volume of 1 L after the replacement with nitrogen, 4 8 g of the solid catalyst used in Example 4 was charged. Furthermore, 400 ml of dehydrated heptane was added. Heat to 10 ° C 'and add 2.7 ml of triethylaluminum and 2.0 ml of dicyclopentyldimethoxy-64-(60) (60) 200413421 silane. The reaction was carried out by circulating propylene gas at room temperature for 4 hours. Thereafter, the solid content was sufficiently washed with dehydrated heptane to obtain a preliminary polymerization catalyst having a preliminary polymerization amount of 41%. (2) Polymerization was carried out in the same manner as in Example 4. The results are shown in Table 2-2. Comparative Example 3 Same as Example 4 except that the electron donor used in the preparation of the solid catalyst component was changed from diethyl n-butylmalonate to diethyl diisobutylmalonate This method performs the modulation of the solid catalyst. Next, polymerization was performed under the conditions shown in Table 2-2. The results are shown in Table 2-2. Comparative Example 4 Except that the electron donor used in the preparation of the solid catalyst component was changed from diethyl n-butylmalonate to diethyl diisobutylmalonate, the rest were the same as in the Examples Method 4 performs the modulation of the solid catalyst. Next, polymerization was performed under the conditions shown in Table 2-2. The results are shown in Table 2_2. -65- (61) (61) 200413421 Table 2-2 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 3 Comparative Example 4 Solid catalyst component electron donor com.E com.E com .A com.A com.A com.D com.D Reaction temperature ° C 125 125 125 110 125 125 110 Washing temperature ° C 125 125 125 110 125 125 110 Polymerization conditions Polymerization time minutes 60 60 60 60 60 60 60 Polymerization Temperature ° c 80 80 80 80 80 80 80 propylene flow rate 1 / min 9.90 9.83 9.83 9.90 9.90 9.78 9.78 ethylene flow rate 1 / min 0.10 0.17 0.17 0.10 0.10 0.22 0.22 air flow rate 1 / min 0.814 0.720 0.720 0.814 0.814 0.090 0.090 full pressure MPa 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst mmol 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 TEA mmol 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Silicon compound type DCP DCP CHB DCP DCP DCP DCP DCP Silicon compound mmol 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 Polymerization polymerization activity kg / g-Ti 510 760 710 370 390 320 260 Ethylene content NMR 1.1 2.3 2.6 1.2 1.2 1.6 1.7 [V] dl / g 1.75 1.72 1.65 1.70 1.71 1.60 1.61 Mw / Mn 4.40 4.58 4.40 4 .47 4.41 4.46 4.42 (TC soluble content Wt% 0.98 0.90 0.98 0.81 0.82 1.10 1.20 com.A diethyl butyl malonate com.D diisobutyl propylene diester-66- (62) 200413421 c 〇m. E Dicyclobutyl-1 DCP Dicyclopentyl di CHB Cyclohexyl isobutyl TEA Triethylaluminum 1-dicarboxylic acid dibutyl methoxysilyldimethoxysilane Table 2 — 1, 2-2 shows that compared with Comparative Examples 3 and 4, Examples 4 to 15 increase the polymerization activity. In addition, although the polymer having a soluble content of 0 ° C is non-crystalline, it increases with the increase of the ethylene content in the ethylene-propylene random copolymer. However, if Examples 5, 8, 10 and Compared with Comparative Examples 3 and 4, although the former contains a large amount of ethylene, the amount of soluble components at 0 ° C decreases. [Example of a propylene-ethylene block copolymer] A method for evaluating physical properties is as follows. (1) MFR measurement Based on JIS-K7210, measured at 23 ° C and 2.16 kg. (2) Measurement of the amount of xylene soluble components at room temperature The xylene soluble components and insoluble components at room temperature (25 ° C) can be determined by the following method. (D fine scale 5 ± 0.05g sample is put into a 1000ml eggplant-type flask. After adding 1 ± 0.05 g of BHT (antioxidant), put the rotor and 700 ± 10 ml of para-xylene. 0Next The cooler is installed in an eggplant-type flask, and while rotating the rotor, the flask is heated in a 140 ± 5t: oil bath for 120 ± 30 minutes to dissolve the -67- (63) (63) 200413421 sample in para-xylene ◎ After pouring the contents of the flask into a 1000 ml beaker, while stirring the solution in the beaker with a stir bar, let it cool (more than 8 hours) to room temperature (25 ° C), and then filter out the precipitate with a metal mesh. After further filtering the filtrate with filter paper, the filtrate was poured into a 3000 ml flask containing 2000 ± 100 ml of methanol, and the solution was stirred with a stirrer at room temperature (251), and left for more than 2 hours. After extracting the precipitate by a metal mesh filter, air-drying for 5 hours, and then drying it at 100 ± 5t using a vacuum dryer for 240 to 270 minutes, 25 ° C xylene solubles can be recovered. @On the other hand, write the above again. The method of @ is used as a reference, and the precipitation in the above G is filtered by a metal mesh. After dissolving in para-xylene, quickly transfer it to a 3,000 ml flask containing 2000 ± 100 ml of methanol while stirring with a stirrer for more than 2 hours, and then leave it at room temperature (251) overnight. G Next, the precipitate was collected by metal mesh filtration, air-dried for 5 hours, and then dried at 100 ± 5 ° C using a vacuum dryer for 240 to 270 minutes to recover xylene insoluble content at 25 ° C. On the other hand, relative to 25 ° C xylene soluble content (w), if the sample weight is set to A g, the weight of the soluble component recovered in the above ◎ is set to Cg, then

w (% by weight) = 100xC / A The content of insoluble components is expressed as (100-w)% by weight. (3) Measurement of impact strength -68- (64) (64) 200413421 Based on JIS-K7110, using test paper manufactured under injection molding to measure the temperature at 23 0 ° C, -30 ° C Notched Izod impact strength. (4) Measurement of flexural modulus The flexural modulus was measured based on JIS-K7210. Examples related to the measurement of [/?], The measurement of Mw / Mn, and the 13C-NMR ethylene content of xylene soluble components at room temperature (25 ° C), examples of propylene-ethylene random copolymers the same. Example 1 6 (1) Production of solid catalyst components After fully replacing a glass reactor with a stirrer with an internal volume of about 6 L by nitrogen, about 2430 g of ethanol with a water content of 100 ppm and 160 g of metal were introduced. Magnesium and 16 g of iodine can be reacted under the conditions of circulation and heating under the condition of stirring until hydrogen is no longer generated in the system, and a solid magnesium compound (diethoxy magnesium) can be obtained. Call Next, put 16 g of diethoxymagnesium into a three-necked flask equipped with a stirrer whose internal volume has been replaced with nitrogen of 0.5 L. Furthermore, 80 ml of dehydrated octane was added. Then, it was heated to 40 ° C, 2.4 ml of silicon tetrachloride was added, and after stirring for 20 minutes, 2.7 ml of diethyl n-butylmalonate was further added. The solution was warmed to 80 ° C, and then 77 ml of titanium tetrachloride was added dropwise using a dropping funnel. Then, the internal temperature was set to 125 t to perform a contact reaction for 2 hours. Thereafter, the stirring was stopped to precipitate a solid, and the supernatant liquid was taken out. Then, -69- (65) (65) 200413421 was added with 100 ml of dehydrated octane, and the temperature was raised to 125 ° C while stirring. After maintaining for 1 hour, the stirring was stopped to precipitate a solid, and the supernatant liquid was taken out. Repeat this washing operation 7 times. Furthermore, 122 ml of titanium tetrachloride was added so that the internal temperature was 1 2 5 ° C and the reaction was carried out for 2 hours. Secondly, washing was repeated 6 times with 1 2 5 t of dehydrated octane to obtain a solid catalyst component. (2) The polymerization method is sufficiently dried with nitrogen gas, and then a stainless steel sterilization kettle with a stirring device with an internal volume of 5 L replaced by propylene gas is maintained at 7 (TC, and then the pressure is increased to 0.0 5 MPa with propylene gas ( Gauge). In this state, add hydrogen to 0.4 8 MPa (Gauge), or slowly increase the pressure to 2.8 MPa (Gauge) with propylene gas. Second, put 60 ml of catalyst replaced by hydrogen gas into the tube. After taking 20ml of Gengyuan, 4.0mmole of triethylamine, 1mmole of dicyclopentyldimethoxysilane, and a solid catalyst component of 0.02mmole in terms of titanium atom, put them into a sterilization kettle to make the full pressure Propylene was injected at a rate of 2.8 MPa (Gauge) and polymerized for 60 minutes. Thereafter, it was depressurized to outside pressure, and once it was vacuum degassed, ethylene gas / propylene was added at a molar ratio of 4 · 7: 5 · 3. Gas to 1 MPa (Gauge), hold at 70 ° C, 1 MPa (Gauge) for 20 minutes to carry out propylene-ethylene copolymerization. After that, depressurize to outside air pressure and reduce the temperature to normal temperature, open the sterilizer and recover The resulting polymer powder. In the resulting block polypropylene powder Add 1000 ppm calcium stearate (manufactured by Nippon Oil & Fats Co., Ltd.) as a neutralizer, DHT-4 A (manufactured by Kyowa Chemical Co., Ltd.) at I500 ppm, and 75 Oppm as an antioxidant (66) (66) 200413421 P-EPQ (manufactured by Kurari Ando (Co., Ltd.)), 1,500 ppm irganocks100 (made by Chiba Special T Chemicals (Co., Ltd.)), 2000 Ppm as crystallization nucleating agent PTBBA—Al (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), after being fully mixed, melted and kneaded in a 20mm uniaxial kneading extruder to form pellets. Part of the pellets are used for The predetermined structure was analyzed, and then the remaining pellets were injection-molded to make a test piece, and its physical properties were measured. Example 1 7 Except that the copolymerization time in the second stage was set to 40 minutes, the rest were the same as in the example. The method of 16 was performed. The results are shown in Table 3-1. Example 18 The method of Example 16 was performed except that the copolymerization time of the first stage was set to 40 minutes. The results were shown in Table 16. 3-1. Example 1 9 Divide The molar ratio of ethylene to propylene in the second stage was set to 2.7: 7.3, and the copolymerization time was set to 60 minutes, and the rest were performed in the same manner as in Example 16. The results are shown in Table 3-1. Examples 20 In addition to changing the electron donor used in the preparation of the solid catalyst component from -71-(67) (67) 200413421 2.7ml of diethyl n-butylmalonate to 3.1mi of dimethylmalonate Except for dibutyl ester, the rest were carried out in the same manner as in Example 17. The results are shown in Table 3-1. Example 2 1 Except that the catalyst used was changed to that prepared in Example 20, the rest were performed in the same manner as in Example 17. The results are shown in Table 3-1. • Example 22 Except that the electron donor used in the preparation of the solid catalyst component was changed from 2.7 ml of diethyl n-butylmalonate to 3.6 ml of dibutyl cyclopentylmalonate It was carried out in the same manner as in Example 16. The results are shown in Table 3-1. Example 23 The procedure was the same as in Example 17 except that the catalyst used was changed to the one prepared in Example 22. The results are shown in Table 3-1. -72- (68) 200413421 Table 3-1 Examples Example Examples Example Examples Example Implementation 16 17 18 19 20 21 22 Example 23 Solid Electron Donor com.A com.A com.A com .A com.B com.B com.C com.C Reaction temperature of medium component ° C 125 125 125 125 125 125 125 125 Washing temperature ° C 125 125 125 125 125 125 125 125 The first polymerization time is 60 60 30 60 60 60 60 60 Polymerization temperature ° C 70 70 70 70 70 70 70 70 Hydrogen pressure MPa 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Full pressure MPa 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 Catalyst mmol 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 TEA mmol 4 4 4 4 4 4 4 4 Silicon compound type DCP DCP DCP DCP DCP DCP DCP DCP DCP Silicon compound mmol 1 1 1 1 1 1 1 1 Second polymerization time minutes 20 40 40 60 20 40 20 40 Polymerization temperature ° C 70 70 70 70 70 70 70 70 C2: C3 Molar ratio 4.7: 5.3 4.7: 5.3 4.7: 5.3 2.7: 7.3 4.7: 5.3 4.7: 5.3 4.7: 5.3 4.7: 5.3 Full pressure MPa 1 1 1 1 1 1 1 1 Convergence MFR g / l〇16.5 15.8 16.0 15.3 16.2 14.8 16.0 15.3 [V] dl / g 1.52 1.50 1.50 1.52 1.49 1.50 1.52 1.50 Mw / Mn 4.38 4.19 4.43 4.33 4.47 4.56 4.37 4.26 Amorphous weight% 17.6 21.8 32.5 20.8 18.0 20.9 17.8 20.8 mol% of ethylene content 40.2 42.0 40.5 25.1 41.5 40.9 41.7 42.0 Flexural modulus MPa 1360 1100 870 1100 1330 1090 1400 1080 Normal temperature Izod kJ / m2 7.3 14.6 66.5 21.5 7.6 15.2 7.3 14.8 Low temperature Izod kJ / m2 4.2 6.7 20.6 6.6 4.4 6.5 4.4 6.3

com. A butyl malonate-73- (69) (69) 200413421 c om. B dimethyl malonate c om. C cyclopentyl malonate DCP Dicyclopentyldimethoxysilane TEA triethylaluminum Example 24 Except changing the electron donor used when preparing the solid catalyst component from 2.7 ml of diethyl n-butylmalonate to 3.2 ml of Except for cyclobutane-1,1-dicarboxylic acid dibutyl ester, the rest were carried out in the same manner as in Example 16. The results are shown in Table 3-2. Example 2 5 The same procedure as in Example 17 was performed except that the catalyst used was changed to the one prepared in Example 24. The results are shown in Table 3-2. Example 26 The same procedure as in Example 16 was performed except that the silane compound used in the polymerization was changed from cyclopentyldimethoxysilane (DCPDMS) to cyclohexylisobutyldimethoxysilane. . The obtained results are shown in Table 3-2. Example 2 7 (1) Manufacture of solid catalyst components After the nitrogen volume is replaced, the volume is 500mL. • 74- (70) (70) 200413421 Three ports Into a flask, 13.3 g of magnesium chloride (anhydrous), 70 ml of decane, and 65.5 ml (0.42 mole) of 2-ethylhexanol 'were heated and reacted at 130 ° C for 2 hours to obtain a homogeneous solution. After that, 3.12 g of phthalic anhydride was added to the solution, and the mixture was stirred and mixed at 130 ° C for 1 hour, and then the phthalic anhydride was dissolved in the above uniform solution. The homogeneous solution thus obtained was cooled to room temperature, and then dropped into 373 ml of titanium tetrachloride stored at -20 ° C over a period of 1 hour. After dropping, the temperature of the obtained homogeneous solution was raised to 110 ° C over 4 hours, and when the temperature reached 110 ° C, 3.4 ml of diethyl n-butylmalonate was added, and then maintained at 1 10 ° C, stirring for 2 hours. After the completion of the reaction for 2 hours, the hot portion was filtered, and the solid portion was collected. The solid portion was suspended again with 275 ml of titanium tetrachloride, and then heated at 110 ° C for 2 hours. After the reaction was completed, the solution was filtered while still hot. The solid portion was collected and washed with decane and hexane at 110 ° C. This cleaning is performed until no titanium compound is detected in the cleaning solution, and a solid catalyst component is obtained. (2) Polymerization method Polymerization was performed by the same polymerization method as in Example 17. The results are shown in Tables 3 and 2. Example 2 8 (1) Preliminary polymerization In a three-necked flask equipped with a stirrer with an internal volume of 1 L after nitrogen substitution, 4 8 g of the solid catalyst used in Example 16 was charged. (71) (71) 200413421 Furthermore, 400 ml of dehydrated heptane is added. Heat to 10 ° C, and add 2.7 ml of triethylaluminum and 2.0 ml of dicyclopentyldimethoxysilane. The reaction was carried out by circulating propylene gas at room temperature for 4 hours. Thereafter, the solid content was sufficiently washed with dehydrated heptane to obtain a preliminary polymerization catalyst having a preliminary polymerization amount of 40%. (2) Polymerization was carried out in the same manner as in Example 16. The results are shown in Tables 3 and 2. Comparative Example 5 Except for changing the electron donor used in the preparation of the solid catalyst component from diethyl n-butylmalonate to diethyl diisobutylmalonate, and changing the ethylene in the second stage Except that the ratio of ear to ear is 5.0: 5.0, the rest are performed in the same manner as in Example 17. The results are shown in Table 3-2. Comparative Example 6 Except for changing the electron donor used in the preparation of the solid catalyst component from n-butylmalonic acid monoethyl ester to monoisobutyldiac diacetate, and changing the ethylene in the second stage Except that the ear to ear ratio was set to 5.0: 5.0, the rest were performed in the same manner as in Example 27. The results are shown in Tables 3 and 2. -76- (72) 200413421 Table 3-2 Example 24 Example 25 Example 26 Example n Example 28 Comparative Example 5 Comparative Example 6 Solid catalyst component electron donor com.E com.E com.A com .A com.A com.D com.D Reaction temperature ° C 125 125 125 110 125 125 110 Washing temperature ° C 125 125 125 110 125 125 110 The first polymerization time is 60 60 60 60 60 60 60 Polymerization temperature ° C 70 70 70 70 70 70 70 Hydrogen pressure MPa 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Full pressure MPa 2.8 2.8 2.8 2.8 2.8 2.8 2.8 Catalyst mmol 0.02 0.02 0.02 0.02 0.02 0.02 0.02 TEA mmol 4 4 4 4 4 4 4 Silicon compound Type DCP DCP CHB DCP DCP DCP DCP DCP Silicon compound mmol 1 1 1 1 1 1 1 Second polymerization time 20 40 20 40 20 40 40 Polymerization temperature ° C 70 70 70 70 70 70 70 C2: C3 Molar ratio 4.7 : 5.3 4.7: 5.3 4.7: 5.3 4.7: 5.3 4.7: 5.3 5.0: 5.0 5.0: 5.0 Full pressure MPa 1 1 1 1 1 1 1 Polymerization result MFR g / l0 points 16.0 15.3 17.0 16.0 16.1 25.4 24.7 [V] dl / g 1.51 1.50 1.42 1.45 1.51 1.18 1.19 Mw / Mn 4.35 4.25 4.27 4.48 4.46 4.24 4.28 Non Part weight% 17.6 20.6 17.5 20.9 17.7 20.5 21.0 Ethylene content mol% 41.8 42.0 40.0 41.5 40.7 40.5 41.2 Flexural modulus MPa 1300 1070 1300 1090 1350 980 990 Normal temperature Izod kJ / m2 7.3 14.7 7.2 14.4 7.4 6.7 6.5 Low temperature Izod kJ / m2 4.4 6.3 4.2 6.5 4.3 5.7 5.8 -77- (73) 200413421

com. A com. D com. E DCP CHB TEA Butyl malonate Dimethoxysilane cyclohexyl isobutyldimethoxysilane triethylaluminum Industrial applicability According to the present invention, a polymerized olefin can be obtained which can obtain an olefin polymer with high polymerization activity, stereoregularity and excellent @end S state. Catalyst and olefin polymer manufacturing method. According to the present invention, a novel catalyst for propylene-ethylene copolymerization and a method for producing a propylene-ethylene copolymer can be provided. According to the present invention, a propylene-ethylene random copolymer having a high ethylene content and a low amount of low molecular weight amorphous components can be provided. According to the present invention, it is possible to provide a propylene-ethylene block copolymer having a balance of physical properties such as excellent rigidity and impact resistance. [Brief description of the drawings] M 1 is a schematic diagram showing a method for producing a catalyst for polymerizing olefins and an olefin polymer according to the present invention. Fig. 2 is a schematic view showing a method for producing a propylene-ethylene copolymerization catalyst and a propylene-ethylene copolymer according to the present invention. -78-

Claims (1)

200413421 Π) Patent application scope 1. A solid catalyst component for polymerizing olefins, characterized in that the following compounds (i), (ii) and (iV) or the following compounds (i) '(ii), (I 1 i) and (i V) reaction. (i) Halogen-containing titanium compound 4 (ii) Metal magnesium, alcohols, and halogens containing halogen atoms of at least 1,000 lg atoms with respect to 1 mol of the above-mentioned metal magnesium, and / Oxygen-containing magnesium compound (iii) Halogen-containing silicon compound (i V) is an electron donating compound R1 (I) represented by the following general formula () R2—〇—C——C——C—0—R3 II I II ο I 〇Η [In the general formula (I), R1 is a linear or branched alkyl group having 1 or more carbon atoms, and R2 to R3 is a linear or branched alkyl group having 1 to 20 carbon atoms independently of each other]. 2. The solid catalyst component for polymerized olefins according to item 1 of the patent application scope, wherein the halogen of the aforementioned compound (i i) is iodine. 3. For example, the solid catalyst component for polymerized olefins in the scope of patent application, wherein the halogen-containing compound of the aforementioned compound (i i) is magnesium chloride. -79 · (2) (2) 200413421 4 · As in the solid catalyst component for polymerized olefins in the scope of application for item 1 ', wherein the aforementioned halogen-containing silicon compound (i i i) is sand tetrachloride. 5. The solid catalyst component for polymerized olefins according to item 1 of the application, wherein the aforementioned electron donating compound (1 V) is diethyl n-butylmalonate. 6. If the solid catalyst component for polymerized olefins according to item 1 of the patent application 'wherein the aforementioned compounds (i), (ii), (iV) are reacted', the aforementioned halogen-containing titanium compounds (i) and After the aforementioned alkoxy-containing magnesium compound (ii) is contacted, it is then contacted with the aforementioned electron-donating compound (i V). 7 * A catalyst for polymerizing olefins, which is characterized in that it contains the following components [A] and [B] or the following components [A], [B] and [C], [A] as described in item 1 of the scope of patent application Solid catalyst component [B] Organoaluminum compound [C] Electron donating compound. 8 * A method for producing an olefin polymer, characterized in that a catalyst such as item 7 of the patent application is used to polymerize an olefin. 9. A solid catalyst component for propylene-ethylene copolymerization, characterized in that the following compounds (a), (b), (c) or the following compounds (a), (b), (c), ( d) the reaction result, (a) a magnesium compound (b) a titanium compound compound (c) an electron-donating compound represented by the general formula (Π) -80- (3) 200413421 R4 (Π) &amp; r2—〇— C—C—C—0—R3 R5 [In the general formula (Π), R4 is a linear, branched or cyclic alkyl group having 1 to 2 carbon atoms, and R5 is fluorene or 1 to 2 carbon atoms Alkyl groups, R4 and R5 may be bonded to each other to form a ring, and R2 and R3 may be the same or different, and may be a linear or branched alkyl group having 1 to 20 carbon atoms] (d) a sand compound. 10. The solid catalyst component for propylene-ethylene copolymerization according to item 9 of the scope of the patent application, wherein the solid catalyst component is in the presence of the aforementioned compound (b) at 120 to 15 (TC, the previously mentioned compound is used). (A) and (c), or the aforementioned compounds (a), (c) and (d) are contacted, and then the obtained solid catalyst component is washed with an inactive solvent at 100 to 150 ° C. 1 1. The solid catalyst component for propylene-ethylene copolymerization according to item 9 of the scope of the patent application, wherein the magnesium compound (a) described above is a metal magnesium, an alcohol, and the above-mentioned metal magnesium contains 1 · 0 A magnesium compound containing an oxy group obtained by reacting a halogen atom having a halogen atom of more than 00 lg atoms and / or a halogen-containing compound. 12. As a solid catalyst component for propylene-ethylene copolymerization, such as in item 9 of the patent application scope, In the general formula (Π), R4 is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and R5 is an η or alkyl group having 1 to 2 carbon atoms. -81-(4) (4 ) 200413421 1 3 · If the propylene-ethylene random solid catalyst component for item 9 of the patent application scope, The former electron-donating compound (c) is diethyl n-butylmalonate. 14. The propylene-ethylene random solid catalyst component according to item 9 of the patent application scope, among which the aforementioned electron-donating compound (C) is cyclobutane-1,1 dibutyl dicarboxylic acid. 15 · —A catalyst for propylene-ethylene copolymerization, characterized in that it contains the following components [A] and [B] or the following Ingredients [A], [B], and [C], [A] For example, the solid catalyst component [B] Organoaluminum compound [C] Electron donating compound in item 9 of the scope of patent application. The catalyst for propylene-ethylene copolymerization according to item 9, wherein the former catalyst is obtained by contacting α-olefins in the presence of [A], [B], and [C], and the preliminary polymerization amount is 0.1 to 100% by weight. Preparative polymerization catalyst. 17. A method for producing a propylene-ethylene random copolymer, which is characterized in that a catalyst such as item 16 in the scope of patent application is used to randomly copolymerize propylene and ethylene. 18 · —propylene -An ethylene random copolymer, characterized by being obtained by a manufacturing method as described in item 17 of the scope of patent application. The propylene-ethylene random copolymer in the range of item 18, wherein the content of ethylene is from 0.1% by weight to 4% by weight, and the content of soluble component at 0 ° C is 1.0% by weight or less. The propylene-ethylene random copolymer of 18 items -82-(5) (5) 200413421, wherein the ethylene content is more than 4% by weight and the content is less than 5% by weight, and the content of soluble components at 0 ° C is more than 1.0% by weight. 2.0% by weight or less. 21. A method for producing a propylene-ethylene block copolymer, comprising a process of polymerizing propylene to form a polypropylene component, and polymerizing ethylene and propylene to form an ethylene / propylene copolymer. In the component manufacturing process, a catalyst such as item 15 of the scope of patent application is used in at least one of the foregoing polypropylene component forming process and the foregoing ethylene / propylene copolymer component forming process. 22. A propylene-ethylene block copolymer characterized by being obtained by a manufacturing method as claimed in claim 21 of the patent scope. 23. The propylene glycol monoblock copolymer according to item 22 of the application, wherein the MFR is 10 to 20 g / 10 minutes. • 83-