TW200835703A - Process for manufacturing ethylene-propylene block copolymer - Google Patents

Abstract

A process for producing a propylene block copolymer comprising a first step of obtaining an intermediate in an amount equivalent to 20 to 95 wt% of the total amount of the polymer by polymerizing a monomer composition containing propylene as a major component and 5 wt% or less ethylene, in the presence of a catalyst which comprises (A) a solid catalyst component containing magnesium, titanium, a halogen, and an electron-donating compound, (B) an organoaluminum compound shown by the formula R1pAlQ3-p, and (C) an aminosilane compound shown by the formula R2nSi(NR3R4)4-n, and a second step of obtaining a propylene polymer with a total ethylene content of 5 to 50 wt% by polymerizing the intermediate, propylene, and ethylene in an amount of 3 to 300 mol% for 100 mol% of the ethylene. The propylene block copolymer has excellently balanced properties and can be manufactured at a low cost.

Description

200835703 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the invention of a method for producing an ethylene-propylene block copolymer. More specifically, it relates to the propylene or propylene/ethyl bond in the presence of a specific catalyst. A method of producing an ethylene-propylene block copolymer by polymerizing the mixture in at least two steps. [Prior Art]

As a method for improving the impact strength, especially the low-temperature impact strength, while maintaining the superior rigidity and heat resistance of the crystalline polypropylene, it has been known that propylene and other olefins (especially ethylene) are staged. The technique of performing the copolymerization of the owe segments. &These conventional techniques can improve the impact strength, but in the manufacture of ethylene-propylene and the manufacture of the substrate, even if the copolymer is manufactured in multiple stages, if the copolymer (synthesized with the rubber component is increased) It is easy to occur due to the adhesive polymer =: r: rf〇uiing), and it has become a lot of system in continuous operation. Therefore, the production amount of the copolymer is limited to two to the final product, and the physical balance of the final product must be produced by additionally kneading the rubber ::: from the outside. Therefore, it will increase the production of this 'in the patent document i (Japanese Patent (4) Zhao 63 Yunna, in solving the problem of the melting (four) properties of the metal-burning oxidized copolymer, the effect of the effect of the f-fine-acrylic embedded The segment has recently demanded high flow two = two W to produce cut N rigid, 咼 impact resistant 312XP / invention manual (supplement) / 97 · 02 / 96 Μ 0209 6 200835703 properties, and cheap ethylene one by one The improvement of the step. The propylene block copolymer will be required to further enter another L in the special offer 2 (Japan's phase 20 () 5_12 with the proposal has a place, the woman - C - paragraph _ ^ liquid (four) 胄 generate 1 In the dream, the atomic concentration and the chlorine atom concentration are reduced. This technique is to improve the rigidity, heat resistance and impact resistance. However, this method must add a new polymerization device, so it is difficult to match the current cost reduction. The demand of the market. =刖': The method of obtaining a low-cost and excellent balance of physical properties, which is required by the market, is based on the direct reaction of ethylene-acrylic The side of the final product that achieves a balance of physical properties The method (the following % is "straight polymerization method"). However, in the prior art, if the ethylene-propylene block copolymer is to be produced by the direct polymerization method, in order to maintain the melt flow of the ethylene-propylene block copolymer of the final product. (hereinafter referred to as mfr), when propylene is polymerized in the first step (first stage), it is necessary to obtain a polypropylene having a sufficiently low molecular weight (MFR value > 200 g/l〇min) and high stereoregularity. In the technology, in order to obtain a polypropylene having a low molecular weight, that is, a MFR is large, a large amount of A will be required, so that the multi-(four) monolithic polymerization will exceed the limit of the pressure-resistant design of the first-stage reactor, so that it is substantially impossible. In particular, in a loop reactor (l〇〇P react〇r) or the like, there is a limit to the solubility of hydrogen in liquefied propylene, and a large amount of argon is used to generate a gas phase portion in the reactor to make the device inoperable. Further, in the prior art, a large amount of hydrogen must be supplied to the ethylene-propylene block copolymer reaction apparatus after the second step, and therefore, it is difficult to control the rubber component 312XP of the copolymer after the second step. Piece Molecular weight of /97-02/96140209 7 200835703. In order to solve this problem, Patent Document 3 (Nikkei-2-2) discloses the use of organic compounds. However, this method is used by Special organoaluminum compounds, and the beneficial method avoids the increase in manufacturing costs, so it is difficult to meet the requirements of the recent market.... In order to solve this problem, in Patent Document 4 (International Patent W02004-sec 2), it is revealed that there is a loan. The compound represented by 吏=Μ010·21") is used as a contact component for the polymerization of a rare hydrocarbon: a small amount of hydrogen is added to add a homopolymer having high stereochemistry and high stereoregularity, and the effect thereof is exemplified. The time-dependent inactivation of 妒 变 二 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合It may not be sufficient and requires further improvement. Second, the manufacturing cost of π salty low ethylene-propylene block copolymer, the above-mentioned long two cattle 2 properly maintain the smelting fluidity of the final product, and the methane value of the polypropylene portion of the homopolymerized portion) At least become > 200, go again, argon 7 s 1 ^ component needs 15~5Q 2 2 = improved impact strength, Oak Bu. Because of the Tung Li%, the MFR of the final product requires at least 30 to be the molecular weight of the rubber component, but the straight H-shell of the copolymer of the C-stage is the same as the above-mentioned method of the fine-canned copolymer = ground = The manufacturing method of the following baking method can be used to fundamentally solve the problem of the 制造 私 私 ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦守 曰 5 5 Catalyst activity, even in the first step (homogeneous 312 ΧΡ / invention manual (supplement) / 97 · 〇 2 / 96 ΐ 4 〇 2 (8) 200835703 phase) after the first - Feng _ γ, order,, $ — The activity of the catalyst in the reaction (co-polymerization stage) is still very south, and the sub-Asia has superior properties. (Patent Document 1) 曰本 I4 / Tte + 寻利特开开 63-101405 (Patent Document 2) 曰太森泰丨B曰. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The method of manufacturing is to produce an ethylene-propylene block copolymer having superior properties at a low cost. SUMMARY OF THE INVENTION Under the relevant content, the inventors of the present invention have repeatedly conducted intensive studies, and as a result, the use of a solid catalyst having three magnesium, titanium, halogen, and electron-donating compounds has been used as a knife, an organic compound, Further, the catalyst formed by the amine-based compound having a specific structure and the ethylene-propylene block copolymerization can solve the problems of the above-mentioned conventional techniques, and the present invention has been completed. That is, the present invention provides a method for producing an ethylene-propylene block copolymer, which is characterized in that the first step is a catalyst formed of the following components (1), (B) and (C). In the presence of a monomer which can contain a propylene main body of 5% by weight or less of ethylene, to obtain an intermediate corresponding to 20 to 95% by weight of the total polymer; and a second step, which is based on the intermediate In the presence of propylene and ethylene, an ethylene-propylene block copolymer having a total ethylene content of 3 to 60% by weight is obtained; (A) a solid touch component containing magnesium, titanium, a halogen, and an electron donating compound. ; 312XP / invention manual (supplement) /97-02/96140209 9 200835703 (B) in the following general formula (Ο: fpAlQs-p (1) (wherein, R1 represents a carbon number of 1 to 4 of the burning base Q An organic aluminum compound represented by a rat atom or a halogen atom • P is 0 0< pS 3; (C) is represented by the following general formula (2): R2nSi (NR3R4Vn (2) (wherein R2 represents carbon a straight or branched alkyl group of 1 to 20, a cycloalkyl group and a derivative thereof, a vinyl group, an allyl group, an aralkyl group, which may be the same or different R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and a derivative thereof, a vinyl group, an allyl group or an aralkyl group, which may be the same or different; a linear or branched alkyl group having 1 to 20, a cycloalkyl group and a derivative thereof, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different: ^ and ^ may also be combined to form a ring;胺 is an integer of 0 or 1 to 3; at least one of the NR3R4 groups is an amine decane compound represented by a quaternary amine group. The catalyst used in the method for producing an ethylene-propylene block copolymer of the present invention is a catalyst. At the same time, it has high stereochemistry, high hydrogen reaction, high catalytic activity and catalyst activity. It can produce high performance and low cost ethylene-propylene block copolymer by direct polymerization. BEST MODE FOR CARRYING OUT THE INVENTION The catalyst component (A) of the present invention (hereinafter referred to as "component (A) contains magnesium, titanium, halogen, and an electron donor compound, and can be obtained by:). And (c) electron donor compound is grafted; for example, a Λ-h-^ 鎸 鎸 合作 is a porphyry compound (hereinafter sometimes referred to as " Sub-(4)"), such as magnesium dihalide, dialkyl magnesium, dentate base, magnesium, dialkoxymagnesium '', sclerosing alkoxy magnesium, or fatty acid magnesium, etc. 312XP/ Hair duck, book, bribe cow) /97-02/96140209 10 200835703 : Medium 'preferably a mixed magnesium-based magnesium dihalide, magnesium dihalide and dialkoxy magnesium, especially good for di-silk magnesium; as two Alkoxymagnesium, bovine, for example, methyl milk magnesium, diethoxy town, dipropoxy magnesium, ruthenium = methoxy, ethoxy propoxy, butoxy ethoxy lock 4, 4 inches is preferably diethoxy magnesium. Further, the "di-alkoxymagnesium" may be a reaction (4) in the presence of a halogen-containing organometallic or the like. The above two alkoxy groups may be used alone or in combination of two or more. Ϊ́ίί ‘A suitable magnesium alkoxide can be used in the form of granules or powder, and an amorphous or spherical shape can be used. For example, in the case of using a spherical di-oxygen group, it is possible to obtain a more favorable particle shape and a narrow particle size separation; = material powder ί, to enhance the handling of the polymer powder during the polymerization operation, The problem of clogging of the filter in the separation device caused by the formation of the fine powder contained in the polymer powder is solved. ^Spherical bismuth-based magnesium is not necessarily a true spherical shape, and may also be used in the shape of a moon or a potato. Specifically, the ratio of the particle to the minor axis diameter (L/W) is 3 or less, preferably 2, more: and the average particle diameter of the above-mentioned two-site oxymagnesium can be used as m妁 is preferably 5~150#m. In the case of globular dialkoxymagnesium, the average: diameter is H00", preferably 5 to 5 Å (four), more preferably 1 〇. It is preferable that the particle size of the cloth narrow is less than that of the fine powder and the coarse powder, and the particle size is 10f to be the underarm. Specifically, the particle of 5" or less is 20% or less, preferably 丄U/6 or less. 100 or more particles are 1% or less, which is preferably 5% or less compared with 3_ invention specification (supplement)/97-彳02/96140209 11 200835703. Furthermore, the particle size distribution is D90/D10 (here, D90 system) The particle size of 90% of the cumulative particle size, and the D10 is 10% or less in terms of the particle size of the cumulative particle size) is preferably 3 or less, preferably 2 or less. The method for producing the above spherical bis-alkaline magnesium is exemplified in For example, Japanese Patent Laid-Open Publication No. SHO-58-132132, JP-A-62-51 633, JP-A-3-74341, JP-A-4-36839, No. 1, No. 8-73388, and the like. The tetravalent titanium halide compound used in the preparation of the component (A) of the invention (8) (hereinafter sometimes referred to as "component (8)") is a general formula

Ti (0R5)nX4-n (wherein R5 represents an alkyl group having a carbon number of 4, χ represents a halogen atom, and 1 is an integer of 0$η$4), or a titanium alkoxide group One or two or more of each of the selected compounds. Specifically, as the functionalized titanium, for example, titanium tetrahalide such as tetrachlorinated phloem, quaternary osmosis, or titanium tetrachloride; as the halogenated oxy-oxyl group, ==, ethoxylated titanium oxychloride , titanium titanyl trichloride, three: dimethoxy titanium dichloride, diethoxy titanium dichloride, minus (tetra) titanium, di-n-butoxy titanium dichloride, trimethoxy titanium chloride The same milk: titanium lactide, titanium tripropoxide chloride, tri-n-butoxy chloride i: preferably tetradentate titanium, particularly preferably titanium tetrachloride. These 4 titanated a substances may be used alone or in combination of two or more.备::: The electrons used in the preparation of the solid catalyst component 00 are supplied to the steep compound (hereinafter sometimes referred to as "the organic compound of the % sub-donor or the nitrogen atom, for example, alcohol", phenol, 3 Oxygen esters, ketones, acid servants, phenols, ethers, (four) compounds, discs, acid amines, nitriles, isocyanate 12 Bay face book (supplement) / 97 •Cai Shi 12 200835703 Ester, organic ruthenium compound containing Si-0-C bond or Si-Ν-C bond, etc. Specifically, for example, methanol, ethanol, n-propanol, 2-B Alcohols such as hexyl hexanol; phenols such as phenol and cresol; mercapto ether, ethyl ether, propyl bond, butyl bond, pentyl bond, diphenyl bond, 9,9-bis(methoxy oxime) Base, bismuth, 2-isopropyl-2-isopropyl-1,3-dimethoxypropane, etc.; 曱 曱 旨, acetate B, acetic acid vinegar, propylene acetate , octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoic acid

a monocarboxylic acid ester of phenyl ester, methyl p-benzoate, methyl p-toluate, methyl anisate, ethyl diguate; diethyl malonate, dipropyl malonate , dibutyl malonate, diisobutyl malonate, diamyl malonate, di-pivalyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate Ester, diethyl isobutyl bromomalonate, diethyl diisopropyl malonate, diethyl dibutyl malonate, diethyl diisobutylmalonate, diisoamyl propyl Diethyl diacrylate, diethyl isopropyl butyl malonate, dimethyl isopropyl isoamylmalonate, diethyl bis(3-chloro-n-propyl)malonate, double Diethyl 3-bromo-n-propyl)malonate, diethyl maleate, butyl succinate, dimethyl succinate, diethyl succinate, dipropylene succinate , adipic acid diterpene g, diethyl adipate, dipropyl adipate, hexamethylene sulfonate, dioctyl adipate, dioctyl adipate, dioctyl phthalate Ester, g toffee-g day, | too St-g-derivative derivative, etc. a ketone of a base ethyl ketone, a mercapto butyl ketone, an acetophenone or a diphenyl ketone; an acid chloride of a decanoic acid dichloride, a benzoic acid-g 2 T-deuteride, or the like; acetaldehyde , B, 510, benzoic acid, etc. ^来· aldehydes, mercaptoamine, ethylamine, tributylamine, 312XP/invention manual (supplement 13 200835703 brigade, aniline, u bite Amines such as enoic acid amines, decyl succinates, etc., && month females, acetonitrile, benzonitrile, benzonitrile and other nitriles; visceric acid methyl vinegar, isocyanuric acid ethyl ester, etc. The isocyanate; phenyl alkoxy decane, alkoxy alkoxy oxime, phenylalkyl alkoxy decane, cycloalkyl alkoxy decane, cycloalkyl alkyl alkoxy sulphate, etc. Si-0-C bonded organic compound; bis(alkylamino) dialkoxy decane, bis(cycloalkylamino) dialkoxy oxime, alkyl (alkylamino) An organic dream compound containing a Si-NC bond, such as an alkoxy group, a dialkylamino group, an alkoxy decane or a cycloalkylaminotrialkoxide. Preferably, among the above electron-donating compounds, Using esters, In particular, an aromatic dicarboxylic acid diester is particularly preferably a decanoic acid diester and a decanoic acid diester derivative. Specific examples of such decanoic acid diesters include didecyl phthalate and diethyl decanoate. , di-n-propyl phthalate, diisopropyl phthalate, di-n-propyl phthalate, 酞g-iso-butyl acrylate, g-ethyl ethyl decyl ester, methyl isopropyl ester, ethyl decanoate (n-propyl) ester, ethyl (n-butyl) citrate, ethyl isobutyl acrylate, di-n-pentyl phthalate, diisoamyl phthalate, di-pivalyl citrate, citric acid Dihexyl ester, di-n-heptyl phthalate, di-n-octyl phthalate, bis(2,2-dimethylhexyl) phthalate, bis(2-ethylhexyl) phthalate, di-n-decanoate Anthracene ester, diisoindole bis(2,2-dimethylheptyl) phthalate, n-butyl (isohexyl) phthalate, n-butyl phthalate (2-ethylhexyl) Ester, n-pentyl (hexyl) citrate, n-pentyl (isohexyl) decanoate, isoamyl (heptyl) decanoate, n-pentyl-yl (2-ethylhexyl) phthalate, N-pentyl (isodecyl) decanoate, isoamyl decanoate (n-decyl), n-pentyl decanoate Undecyl)ester, isopentyl decanoate (p-hexyl) ester, n-hexyl decanoate (2,2-dimethylhexyl) vinegar, n-hexyl decanoate, (different 312XP/invention specification (supplement)/ 97·02/96140209 14 200835703, n-heptyl phthalate (2-ethylhexanoic acid n-heptyl (neoxanyl), etc. decanoic acid diester can be used as 1 decyl) ester, decanoic acid n-hexyl (positive Mercapto) ester, n-heptyl (isodecyl) phthalate: 2-ethylhexyl (isodecyl) phthalate, one or more. Further, examples of the citric acid di-organism include the following: two vinegar groups of acid diesters are formed; one or two nitrogen atoms of the heart 〇 μ Γ are carbon alkyl groups or gas atoms, A halogen atom such as a bromine atom or a fluorine atom is substituted. By using the niobic acid derivative as an electron-donating compound and modulating the _body_component', it is possible to further increase the effect of the amount of hydrogen on the smelting flow rate, that is, to enhance the hydrogen reaction, even if The amount of hydrogen added during the polymerization is the same amount or less, and the melt flow rate of the polymer can still be increased. Specifically, 'for example, 4 - methyl phthalic acid dioxon, 4 - ethyl dinonyl decanoate, 4, 5-dimercaptoic acid dipivalate, 4, diethyl fluorene Di-n-pentyl acid ester, diethyl 4-chloropyrumate, di-n-butyl 4-chlorophosphonate, di-n-pentyl 4-chlorodecanoate, diisobutyl 4-chlorodecanoate, 4-barraconic acid Diisohexanoate, 4-isooctyl 4-chlorodecanoate, diethyl 4-bromodecanoate, di-n-butyl bromide, di-p-amyl 4-bromanoate, diisobutyl 4-bromedonate , isohexyl bromophthalate, diisooctyl 4-bromanoate, diethyl 4, 5-dichlorodecanoate, di-n-butyl phthalate, 4, 5-dichlorodecanoic acid Diisohexyl ester, 4, 5-dichlorodecanoic acid diisooctyl vinegar, among which, preferably 4-bromopentanoic acid neopentyl ester, 4~filled|tanoic acid di-n-butyl vinegar, and 4-different self-acid Butai vinegar. Further, the above-mentioned esters are preferably used in combination of two or more kinds. In this case, the total number of carbon atoms of the ester base used in the case is preferably 4 or more compared with other vinegars, and it is preferable to combine the esters. . 312XP/Invention Manual (Supplement)/97-02/96140209 15 200835703 In the invention, the preferred embodiment is such that the above u), (8) and (4) are present in the case of "Beyond (10) and sometimes referred to as "Component (4)"). Under the (four) touch, hunt this, the method of the weekly production (A) 'as this component (4), and the body is preferably the use of a stupid, dimethyl strepto, ethyl benzene, hexane, g-burning material boiling point 50~ 150X: a hydrocarbon compound. In addition, & harassment is used for two or more types. X is a particularly preferred preparation method that can be used alone or mixed as described above. For example, the following (f) is used to form a (four) liquid, and the mixed solution formed of the component (8) and the component (4) is brought into contact with the suspension, and thereafter, the present invention is used. (4) The adjustment of the catalyst component U) In addition to the above-mentioned components, it is preferred to carry out the polymerization of (four) oxygen (hereinafter sometimes referred to as "component:)"). The stereoregularity = crystallinity, and can reduce the fine powder of the polymer. Polyoxymethane system ^ (4) oxygen-fired bond (_si_G bond) polymer in the main chain, also known as n / oxygen oil, which has a viscosity at 25. 02~io〇cmvs (2~1 0000 centist〇kes), liquid or sticky (4) chain, partially hydrogenated, cyclic or oxy-fired at room temperature. And taken as a chain polycime, which can be exemplified by dimethyl polyoxime, methylphenyl oxime; and as a partially hydrogenated polyoxyalkylene, a hydrogenation rate of 10 to 80% can be exemplified: a hydrogen hydride polyoxyalkylene; as the cyclic polyoxane, hexamethyl$% dioxane, octamethylcyclotetraoxane, decamethylcyclopentane oxime '2, 4, 6 —Dimethylcyclotrioxane, 2, 4, 6, 8-tetramethylcyclotetrazepine 3_Invention Manual (supplement)/97-02/961 Side 9 16 200835703 Alkane, as a modified poly The cerium oxygen burning can be exemplified by a higher fatty acid substituted dimethyl oxa oxy 1 epoxy substituted dimethyl oxazepine, and a polyoxyalkylene group substituted dimethyl ketone oxime. Among these, a decyl ruthenium pentoxide and a dimethyl hydrazide are preferable, and a decyl quinoxaoxane is particularly preferable. In the invention, the components (3), (b) & (c), or the optional component (d) or the component (e) are brought into contact to form the component (A), and the following will be directed to the hair. The modulation method of the component (A) of the month is described. Specifically, for example, the magnesium compound (a) may be suspended in an alcohol or a halogenated hydrocarbon solvent, and the price may be increased! The method of obtaining the component (A) by contacting the electrons of the perhalogen compound (8) or the hydrocarbon compound (4) with the electrons of the bismuth citrate and the steepening & substance (c) and/or the tetravalent titanium halogen compound (b). In this method, by using a spherical magnesium compound, the component (A) having a spherical shape and a narrow particle size distribution can be obtained, and even if a spherical shape, a magnesium compound is used, for example, a solution is used by using a spray device. Alternatively, the suspension may be subjected to a so-called spray drying method, that is, a so-called spray drying method, and the particles may be formed into a spherical component having a narrow particle size distribution (A). The contact of each component is carried out in an inert gas atmosphere under a condition of removing moisture or the like in a vessel equipped with a stirrer. Contact temperature The temperature at which the components are contacted may be the same temperature as the reaction temperature or a different temperature. In the case where only contact and stirring are mixed, and in the case where the reforming treatment is carried out by dispersing or suspending, the contact temperature may be a lower temperature region than the vicinity of the room temperature, but the reaction is made after the contact. And get the product. In the case of 'the temperature is preferably 40 to 130 ° C. When the temperature at the time of the reaction is less than 40 ° C, the reaction cannot be sufficiently carried out, and as a result, the performance of the prepared solid catalyst component is insufficient, and if it exceeds 13 Torr. 〇, then use 312XP / invention manual (supplement) /97-〇2/96140209 17 200835703 ::::: the hair becomes obvious 'and it is difficult to control the reaction. The response time is ίίί, preferably 10 minutes or more, more preferably minutes or more. The method for preparing the preferred component (Α) of t ^毛明, for example, a method of preparing a component (A) by contacting and reacting with a knife; or =;: (:) suspending the component (4), followed by A method of preparing a component (A) by contacting the component (6) with () contact and reaction. Further, the component (8) or the component (b) and the knife c are brought into contact with the component (A) thus prepared, thereby improving the performance of the final solid catalyst component. In this case, it is preferred to carry out in the presence of the hydrocarbon compound (d). As a preferred preparation method of the component (1) in the present invention, for example, a component (a) and a component (c) and a hydrocarbon compound (4) having a boiling point of 5 〇 to 15 rc are used to form a suspension, and the compound (*) and the component (4) are formed. The resulting mixed solution is brought into contact with the suspension, and thereafter subjected to a preparation method of the reaction. As a preferred preparation method of the component (A) in the present invention, for example, the method shown below can be mentioned. A suspension is formed from the component (a) and the component (c) and the alkylated S material (d) having a boiling point of 5 〇 to i5 〇t. First, a mixed solution is formed from the component (c) and the hydrocarbon compound (d) having a boiling point of 5 Torr to °C, and the above suspension is added to the mixed solution. Thereafter, the resulting mixed solution is heated to carry out a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid material was washed with a liquid hydrocarbon compound at a normal temperature, and the washed solid matter was used as a solid product. After that, the solid matter after the washing is further subjected to the step (b) and the hydrocarbon compound (d) having a boiling point of 50 to 150 t in '2 〇 to 1 〇〇 ° (: contact is made and the temperature is raised, Reaction treatment (second reaction treatment), reverse 312XP/invention specification (supplement)/97-02/96140209 18 200835703 After completion, the operation of washing with a liquid hydrocarbon compound at normal temperature is repeated 1 to 10 times. Further, the component (A) can also be obtained. According to the above, a particularly preferred preparation method of the solid catalyst component (A) of the present invention is a method in which a dialkoxy group (a) is suspended in a hydrocarbon compound having a boiling point of 50 to 150 ° C ( d) 'After contacting the suspension with the tetravalent titanium halogen compound (b), the reaction is carried out before or after contacting the side suspension with the tetravalent titanium halogen compound (b). When one or two or more kinds of the electron-donating compound (〇) such as an ester are reacted in contact with -2〇~13 (contacting with rc as needed, if necessary), a solid product (1) is obtained. In this case, it is preferred to carry out the ripening reaction at a low temperature before or after contacting the electron-donating compound or two or more kinds of contacts. After the solid product (1) is washed with a liquid alkylation & normal temperature (intermediate washing), the tetravalent titanium compound (b) is again present in the presence of a hydrocarbon compound at -2 Torr to 1 Torr. (The solid product (2) can be obtained by contacting the rc by contact. Further, the intermediate washing and the reaction treatment can be repeated several times as needed. Second, the solid product is subjected to decantation at normal temperature. The liquid catalyst component is washed to obtain a solid catalyst component (A). The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method, so it cannot be said in an ordinary manner. Each of the 1 molar magnesium compound (a), the tetravalent titanium halogen compound (b) is 〇 5 to 100 moles, preferably 〇 5 to 50 moles, more preferably 1 to 10 moles of 'electron-donating compound (c) 〇· 〇1~1〇莫耳, preferably 0·01~1 molar, better 0·02~0. 6摩尔, the hydrocarbon compound (d) is 0. 001~500 m, preferably 0. 001~100 Mo, better 〇·〇〇5~10 Moer, polyoxane (e) is ΜΗ~l〇〇g, preferably 0·05~80g, better 312XP/invention manual (supplement ) /97-02/96140209 19 200835703 1 ~ 50g. Further, the solid catalyst component (A) of the present invention contains the content of the electron donating compound and is helmet, ', wu, halogen atom, 0. 5~8. 0% by weight, preferably 1 〇~8 英寸 | = 疋, preferably titanium amount %, more preferably 15 〜25% by weight, tooth atom is inside 】 & good 15~4 〇 heavy, special (four) weight %, more preferably 45: ^ The total of the donor compounds is G. 5 to 3G and '% by weight of electrons, and the weight of the mixture is particularly good. The total amount of the earth is 2525. The olefin polymerization medium of the present invention is formed, and it may be simply referred to as "the compound of the component". As the butyl group of the formula (2), as the Q, a gas atom, a chlorine atom or a heart ethyl group is preferably exemplified by a specific example of a compound such as a lingen, a compound of the organic compound (8), and a bovine such as monomethyl aluminum or the like. Ethyl aluminum, diethylaluminum chloride, triampe lanthanum, ethylaluminum, diethylaluminum halide can be used in one or two kinds, and is more preferably diethylaluminum or triisobutylaluminum. The compound (6) represented by the above general formula (2) (hereinafter sometimes referred to as "component C") used in forming the olefin polymerization catalyst of the present invention is not a burn of an electron donating compound used in the prior art. Oxygen is a compound, and is an amine-based compound. In the general formula (2), as the organism of the naphthenic earth, for example, a cyclopentyl group substituted with a mercapto group can be mentioned. Examples of such an amine-based calcined compound include, for example, (alkylamino) tricarbocarb, (alkylamino)dialkylcycloalkylnonane, (alkylamino)alkylbicycloalkane. Base 312XP / Invention Manual (supplement) /97-02/96140209 20 200835703 Alkane, (alkylamino) tricycloalkyl decane, (alkylamino) (dialkylamino) dialkyl group And (alkylamino) (dialkylamino) bicycloalkyl squid, spirulina (alkylamino) dialkyl carbaryl, bis(alkylamino) ruthenium group, chopped, - bis(alkylamino)bicycloalkyl chopping, bis(alkylamino)(dialkylamino)alkyldecane or bis(alkylamino)(dialkylamino)cycloalkyl Decane, bis(cycloalkylamino)dialkylnonane, bis(cycloalkylamino)alkylcycloalkylnonane, bis(cycloalkylamino)bicycloalkyl chopane, ginseng (alkylamine) Alkyl oxime, ginseng (alkylamino) cycloalkyl chopping, cesium (alkylamino) alkyl chopping, ginseng (alkylamino) cycloalkyl decane, ginseng (cycloalkyl) Amino)alkylnonane, ginseng (cycloalkylamino group) a cycloalkyl decane, anthracene (alkylamino) decane, gin(alkylamino)dialkylamine sec-second, ginseng (cycloalkylamino)dialkylamine sec-second, double (secondary) Amino group) bis(alkylamino) chopping, dialkylamino ginseng (alkylamino) decane, bis(perhydroisoquinolinyl) bis(alkylamino) decane, bis (perhydrogen) Quinolinyl) bis(alkylamino)decane, bis(cycloalkylamino)bis(alkylamino)decane, anthracene (alkylamino)decane, dialkylamine-based (alkylamino group) a decane, a bis(alkyl substituted perhydroisoquinolyl) bis(alkylamino) decane, a bis(alkyl substituted perindolinolyl) bis(alkylamino) decane, a bis(cycloalkane) Amino) bis(alkylamino)decane, 1,1-di(alkylamino)dialkyl substituted anthracene. Among these, bis(alkylamino)dicyclopentyl oxime, bis(alkylamino)diisopropyldecane, bis(alkylamino)di-tert-butylnonane, ^ bis(alkylamino)t-butylethyl decane, bis(alkylamino)t-butyl decyl carbaryl, bis(alkylamino)dicyclohexyl chopped, bis(alkylamine) Cyclohexyldecyl decane, bis(alkylamino)bis(decalinyl)decane, bis(alkane 312XP/invention specification (supplement)/97-02/96140209 21 200835703 arylamino)cyclopentyl Cyclohexyl sulphur, bis(perhydroisoindolyl) (alkylamino) alkyl decane, bis(perhydroquinolinyl)(alkylamino)alkyl decane, bis(alkyl-ylamino) a dicyclopentyl decane, bis(alkylamino)diisopropyldecane, bis(alkylamino)di-tert-butylnonane, bis(alkylamino)tributylethyldecane, Bis(alkylamino)t-butylmethyldecane, bis(alkylamino)dicyclohexyldecane, bis(alkylamino)cyclohexylmethyldecane, bis(alkylamino)bis(decahydronaphthalene) Base) decane, double ( Alkylamino)cyclopentylcyclohexyldecane, bis(alkylamino)cyclohexylthiacylnonane, anthracene (fluorenylamino) hydrazine, ginseng (alkylamino) ruthenium, ginseng (alkylamino)cycloalkyl-based, bis(dialkylamino)bis(alkylamino)decane, dialkylamino gin (alkylamino) oxime, bis(perfluoroisoquine) Alkyl) bis(alkylamino) oxime, more preferably bis(alkylamino)dicyclopentyldecane, bis(alkylamino)diisopropyldecane, bis(alkylamino)di Third butyl decane, bis(alkylamino)t-butylethyl decane, bis(alkylamino)t-butylmethyldecane, bis(alkylamino)dicyclohexyldecane, bis(alkyl Amino)cyclohexylmethyldecane, bis(alkylamino)bis(decaphthylnaphthalenyl)decane, bis(alkylamino)cyclopentylcyclohexyl-monostyl, bis(perhydroisoindole) ) (alkylamino) calcined sec-second, bis(perhydroquinolinyl)(alkylamino)alkylnonane. Specific examples of the above amine group > 5 kiln compound are shown below.参(methylamino)decyl decane, ginseng (decylamino)ethyl decane, ginseng (methylamino)-n-decane, ginseng (methylamino)isopropyl decane, ginseng Amino group) n-butyl decyl decane, ginseng (methylamino) isobutyl decane, ginseng (decylamino) tributyl sulphate, ginseng (methylamino) cyclopentyl sulphate, ginseng (Methylamino)cyclohexyldecane, s(nonylamino)vinyl decane; 312XP/Invention Manual (Supplement)/97-02/96140209 22 200835703 Reference (ethylamino)nonyl decane, ginseng Ethylamino)ethyl decane, ginseng (ethylamino) n-propyl decane, ginseng (ethylamino) isopropyl decane, ginseng (ethyl amino) n-butyl decane, gin (ethyl) Amino)isobutylnonane, ginseng (ethylamine 'yl)cyclopentyldecane, ginseng (ethylamino)cyclohexyldecane, ginseng (ethylamino)vinylnonane, ginseng (ethylamino) Phenyl decane; △ 苓 (n-propylamino) decyl decane, cis (n-propylamino) ethyl decane, wheat (n-propylamino) n-propyl decane, ginseng (n-propyl amide) Isopropyl decane, wheat (n-propylamino) n-butyl decane, cis (n-propylamino) isobutyl decane, ginseng (n-propylamino) cyclopentyl decane, ginseng Propylamino)cyclohexyl chopping, ginseng (n-propylamino) ethylene chopping; wheat (isopropylamino)methyl decane, ginseng (isopropylamino) ethyl decane, ginseng Isopropylamino) n-propyl decane, cis (isopropylamino) isopropyl decane, hydrazine (isopropylamino) n-butyl decane, cis (isopropylamino) isobutyl decane, Tea (isopropylamino)cyclopentyl decane, ginseng (isopropylamino)cyclohexyl chopping, ginseng (isopropylamino)glycosyl secant; ginseng (n-butylamino) isopropyl Base decane, ginseng (t-butylamino) ethyl decane, ginseng (t-butylamino)methyl decane, cis (cyclopentylamino) ethyl decane, ginseng (cyclopentylamino) Isopropyl decane, cis (cyclohexylamino) ethyl decane, cis (cyclohexylamino) isopropyl decane, cis (cyclohexylamino) benzyl decane, gin (cyclohexylamino) phenyl decane Participation Amino)vinyl fluorene-alkane; bis(methylamino)(dimethylamino)methyl sulphur, bis(methylamino)(diethylamino)methyl decane, bis(Ψ Amino) (▼-ethylethylamino) methyl decane, bis (methylamino) (di-n-propylamino) methyl decane, bis (A 312XP / invention specification (supplement) / 97-02 /90140209 23 200835703 Amino) (methyl-propylamino) decyl decane, bis(decylamino)(decyl isopropylamino)methyl decane, bis(decylamino) 曱-N-butylamino)-methyldecane, bis(methylamino)(ethyl-n-butylamino)methyldecane, bis-(decylamino)(ethylisobutylamino)phosphonium Base decane, bis(methylamino)(ethyl second butylamino)decyl decane, bis(methylamino)(ethyltributylamino)decyl decane, bis(decylamine) (Methylcyclopentylamino) methyl decane, bis(decylamino)(ethylcyclopentylamino)methyl decane, bis(decylamino)(methylcyclohexylamino) Mercaptodecane, bis(methylamine-yl) ( Cyclohexylamino)methyl decane; bis(methylamino)(dimethylamino)ethyl decane, bis(methylamino)(diethylamino)ethyl decane, bis(methyl Amino) (methylethylamino) ethyl decane, bis(methylamino)(di-n-propylamino)ethyl decane, bis(decylamino)(mercapto-n-propylamino) Ethyl decane, bis(methylamino)(decylisopropylamino)ethyl decane, bis(methylamino)(methyl-n-butylamino)ethyl decane, bis(decylamino) (Ethyl n-butylamino) ethyl decane, bis(methylamino)(ethyl isobutylamino)ethyl decane, bis(methylamino) (ethyl second butylamino) Ethyl decane, bis(methylamino)(ethyltributylamino)ethyl decane, bis(decylamino)(fluorenylcyclopentylamino)ethyl decane, bis(methyl) Amino)(ethylcyclopentylamino)ethyldecane, bis(methylamino)(methylcyclohexylamino)ethyldecane, bis(decylamine) group (ethylcyclohexylamino) Ethyl decane; - bis(decylamine) (isobutylamino)methyl decane, bis(decylamino)(isobutylamino)ethyl decane, bis(methylamino)(isobutylamino) n-propyl decane, Bis(decylamino)(isobutylamino)isopropyl decane, double 312XP / invention specification (supplement) / 97_02/96140209 24 200835703 (methylamino) (isobutylamino) n-butyl Terpine, bis(methylamino)(isobutylamino)t-butyldecane, bis(methylamino)(isobutylamino)iso-butyldecane, bis(methylamino) (Isobutylamino)t-butyldecane, bis((fluorenylamino)(isobutylamino)thiacylidene, bis(decylamino)(isobutylamino)cyclopentane Basestone, bis(methylamino)(isobutylamino)cyclohexyl sulphate, bis(indenylamino)(isobutylamino)perfluoronaphthyl sulphate, bis(methylamine) (isobutylamino)adamantanyl decane; bis(decylamino)(t-butylamino) sulfhydryl, bis(methylamine-yl)(dibutylamino) Ethyl second burning, bis(methylamino) (Tertiary butylamino) n-propyl decane, bis(methylamino) (t-butylamino) isopropyl hydrazine bis(methyl sulfanyl) (dibutylamino) Butyl sulphate, bis(methylamino)(t-butylamino)dibutylnonane, bis(methylamino)(t-butylamino)isobutylnonane, bis(indenyl) Amino) (t-butylamino) first butyl sulphate, bis(methylamino) (t-butylamino) thiazide, bis(decylamino) (third butyl) Amino group) cyclopentyl decane, bis(methylamino)(second butylamino)cyclohexyl oxime, bis(methylamino)(t-butylamino)perhydronaphthyl decane, Bis(methylamino)(t-butylamino)gold dialkyl-based fever; bis(methylamino)dimethyl decane, bis(decylamino)diethyldecane, bis(decylamine) Divinyl decane, bis(methylamino)di-n-decane, bis(methylamino)diisopropyldecane, bis(methylamino)di-n-butyl bis-bis(methyl) Amino) diisobutyl sulphur, double Aminobutyl)dibutylbutane, bis(indenylamino)di-tert-butyldecane, bis(methylamino)di-n-neopentylnonane, bis(methylamino)dicyclopentyl Decane, bis(indenyl 312XP / invention specification (supplement) /97-02/96140209 25 200835703 amino) dicyclohexyldecane, bis(methylamino)di-4-methoxyphenylnonane; Aminomethyl)methylethyl decane, bis(methylamino)methyl tert-butane decane, bis(methylamino)methylphenyl decane, bis(methylamino)ethyl- Tributyl decane, bis(methylamino)t-butylmethyl decane, bis(decylamino)t-butylethyl decane, bis(methylamino)methylcyclopentyl decane, bis (A) Ethylamino)cyclopentyldecane, bis(indenylamino)cyclopentylcyclohexyldecane, bis(methylamino)T-cyclohexyldecane, bis(methylamino)di(decahydronaphthalene) , decane, bis(methylamino) thiazylmethyl decane; bis bis(ethylamino)dimethyl decane, bis(ethylamino)diethyl decane, bis(ethylamino) Diethylene Decane, bis(ethylamino)di-n-decane, bis(ethylamino)diisopropyldecane, bis(ethylamino)di-n-butylnonane, bis(ethylamino)diamine Butyl decane, bis(ethylamino)dibutylbutyrene, bis(ethylamino)di-tert-butylnonane, bis(ethylamino)dicyclopentyldecane, bis(ethyl Amino)dicyclohexyldecane, bis(ethylamino)-(decahydronaphthyl)lithium; bis(ethylamino)methylethyldecane, bis(ethylamino)methyl Butyl decane, bis(ethylamino)nonylphenyl decane, bis(ethylamino)ethyl second butyl decane, bis(ethylamino)t-butylmethyl decane, bis(ethylamine) Base) second butyl ethyl decane, bis(ethylamino)nonylcyclopentyl decane, bis(ethylamino)cyclopentylcyclohexyldecane, bis(ethylamino)nonyl hexyl decane decane , bis(ethylamino)t-butylisobutyl decane, bis(ethylamino)cyclohexylthiacyl decane; bis(n-propylamino)dimethyl decane, bis(n-propyl) amine Diethyl decane, bis(n-propylamino)divinyl decane, bis(n-propylamino) bis-n- 26 312XP/invention specification (supplement)/97·〇2/96140209 200835703 propyl decane, Bis(n-propylamino)diisopropyldecane, bis(n-propylamino)di-n-butyl ketone, bis(n-propylamino)diisobutyl sulphide double propylamino) Dibutyl decane, bis(n-propylamino)di-tert-butyl fluorene, bis(n-propylamino)di-n-neopentyl decane, bis(n-propylamino)-cyclopentyl iridium Calcined, bis(n-propylamino)dicyclohexyl sulphur; bis(isopropylamino)dimethyl decane, bis(isopropylamino)diethyl decane, bis(isopropylamino) Divinyl decane, bis(isopropylamino)di-n-decane, bis(isopropylamino)diisopropyldecane, bis(isopropylamino)di-n-butylnonane, double Isopropylamino)diisobutylnonane, bis(isopropylamino)dibutylbutane, bis(isopropylamino)di-t-butyltin, bis(isopropylamino) Dixinpentyl Shixia, bis(isopropylamino)dicyclopentyldecane, bis(isoylamino)dicyclohexyldecane, bis(isopropylamino)bis(decalinyl)decane, double (iso) Propylamine) bis(tetrahydronaphthyl), sulphur, bis(isopropylamino) dimethyl ketone, bis(isopropylamino)diphenyl sulphide; bis(isopropylamine)曱 曱 乙基 乙基 石 、, bis (isopropylamino) fluorenyl tert-butyl oxime, bis(isopropylamino)ethyl tert-butyl oxime, bis (isopropylamino) a second butyl mercapto decane, bis(isopropylamino)dibutylethyl decane, bis(isopropylamino)decyl neodecyl decane, bis(isopropylamino) fluorenyl Cyclopentyldecane, bis(isopropylamino)isopropylcyclopentyldecane, bis(isopropylamino)isobutylcyclopentyldecane, bis(isopropylamino)cyclopentylcyclohexyl Decane, bis(isopropylamino)methylcyclohexyldecane; hydrazine (methylamino) zebra, hydrazine (ethylamino) sec, hydrazine (n-propylamino) decane, hydrazine Propylamino) decane, hydrazine Amino) decane, 312XP / invention specification (supplement) / 97·02/9 ό 140209 27 200835703 肆 (isobutylamino) decane, hydrazine (t-butylamino) decane, hydrazine (n-hexylamino)炫; ' ( (methylamino) (ethylamino) decane, cis (decylamino) (n-propylamino) decane, gin (methylamino) (isopropylamino) decane , ginseng (methylamino) (n-butylamino) decane, ginseng (methylamino) (second butylamino) decane, gin (methylamino) (t-butylamino) decane , ginseng (methylamino) (neopentylamino) decane, ginseng (decylamino) (di- 4-methoxyphenylamino) oxime, ginseng (methylamino) (diethyl) Amino) sec, ginseng (methylamino) (diisopropylamino) decane, ginseng (methylamino) (diisobutylamino) decane, ginseng (methylamino) (two Dibutylamino) shixi, ginseng (decylamino) (t-butylamino) decane, ginseng (methylamino) (perhydroisoquinolinylamino) oxime, ginseng Methylamino) (perhydro hydrazino) Xishao, ginseng (methylamino) (dicyclopentylamino) shixi, ginseng (methylamino) (dicyclohexylamino) shixi, ginseng (methylamino) (third Butylethylamino) decane, ginseng (methylamino) (t-butyl-n-propylamino) decane, ginseng (methylamino) (t-butylethylamino) decane, ginseng Mercaptoamine) (t-butylisopropylamino) oxime, oxime (ethylamino) (decylamino) oxime, ginseng (ethylamino) (n-propylamino) decane , ginseng (ethylamino) (isopropylamino) decane, ginseng (ethylamino) (n-butylamino) decane, ginseng (ethylamino) butyl amide, Ginseng (ethylamino) (t-butylamino) decane, ginseng (ethylamino) (neopentylamino) chopping, ginseng (ethylamino) (diethylamino) 'Sinter, ginseng (ethylamino) (diisopropylamino) shixi, ginseng (ethylamino) (diisobutylamino) shixi, ginseng (ethylamino) (two Second butylamino group) Shi Xia, ginseng (ethylamino) (two Butylamine) shixi burning, ginseng (ethylamine 312XP / invention specification (supplement) / 97-02/96140209 28 200835703 base) (monocyclopentylamino) shixi burning, ginseng (ethylamino) (dicyclohexylamino) Shixi burning, labeling (ethylamino) (perhydroisoquinolinyl) oxime, ginseng (ethylamine * group) (perhydroquinolinyl) decane, gin (ethyl Amino) (t-butylethylamino) ^ decane, cis (n-propylamino) (decylamino) decane, cis (n-propylisopropylamino) decane, ginseng (n-propyl) Amino) (t-butylamino) decane, tea (n-propylamino) (n-butylamino) decane, ginseng (n-propylamino) (second butylamino) decane, ginseng N-propylamino)(cyclopentylamino)decane, cis (n-propylamino) (cyclohexylamino) shixi, ginseng (n-propylamino) (di-ethylamino) decane , ginseng (n-propylamino) (diisopropylamino) decane, ginseng (n-propylamino) (diisobutylamino) decane, ginseng (n-propylamino) (a second butyl) Amine, ginseng, ginseng (dicyclopentylamino) decane, wheat (n-propylamino) (dicyclohexylamino) decane, ginseng (n-propylamino) (perhydroisoquinolinyl) decane, ginseng Propylamino)(perhydroquinolinyl), bis (methylamino) bis(ethylamino), bis(methylamino)bis(n-propylamino)decane , bis(indenylamino)bis(isopropylamino)"infraline, bis(decylamino)bis(n-butylamino)decane, bis(methylamino)β-bis(isobutyl) Alkyl) decane, bis(indenylamino) bis (material 'bis(methylamino)bis(tributylamino)))bis(cyclopentylamino)decane, bis(methyl Amino) bis(cyclohexylamino) decane, bis(methylamino)bis(perfluoroisoquinolinyl)nonane, bis(methylamine*yl)bis(tetrahydroisoquinolinyl)decane, double (mercaptoamino) bis(perhydroquinoline) 'Shi Xizhuo bis(decylamino) bis(monoethylamino) sulphur, bis(methylamino) bis(di-n-propyl Amino) decane, bis(methylamino) double Bis(methylamino)bis(di-n-butylsyl) I, =;; amides 312XP/Invention Manual (supplement)/97-02/96140209 29 200835703 bis(isobutylamino) ) Shixia, bis(indenylamino)bis(di-dibutylamino)-osin, bis(indenylamino)bis(di-t-butylamino)decane, bis(methyl) Amino)bis(dicyclopentylamino)decane, bis(indenylamino)bis(di-cyclohexylamino)decane; bis(ethylamino)bis(n-propylamino)decane, double (ethylamino)bis(isopropylamino)decane, bis(ethylamino)bis(n-butylamino)decane, bis(hexylamino)bis(isobutylamino)decane, Bis(ethylamino)bis(t-butylamino)decane, bis(ethylamino)bis(t-butylamino)oxime, bis(ethylamino)bis(cyclopentyl) Amino) decane, bis(ethylamino)bis(cyclohexylamino)fluorene, bis(ethylamino)bis(perhydroisoquinolinyl), sulphur, bis(ethylamino) bis (perhydroquinolinyl) Shixi burning, bis(ethylamine Bis(cyclooctamethyleneimido)decane, bis(ethylamino)bis(diethylamino) tartan, bis(ethylamino)bis(di-n-propylamino) shi Burned, bis(ethylamino)bis(diisopropylamino)decane, bis(ethylamino)bis(di-n-butylamino)decane, bis(ethylamino)bis(diisobutyl) Alkyl) decane, bis(ethylamino)bis(t-butylamino)ethyl cerium, bis(ethylamino)bis(t-butylamino)isopropyl decane, bis ( Ethylamino)bis(t-butylamino)isobutylnonane, bis(ethylamino)bis(di-dibutylamino)decane, bis(ethylamino)bis (second third) Butylamine), sylvestre, bis(ethylamino)bis (monopentylamine), bis(ethylamino)bis(dicyclohexylamino) - chopped, double ( N-propylamino)bis(cyclopentylamino)decane, bis(n-propyl-amino)bis(cyclohexylamino)carbazide, bis(n-propylamino)bis (all oxime) Lynn) dream burning, double (n-propylamino) double (all hydrogen ) fever, bis(n-propylamino)bis(diethylamino)decane, bis(propylamino)bis (di-n-propyl 3 UXP/invention specification (supplement)/97-02/96140209 30 200835703 Aminoalkyl) decane, bis(n-propylamino)bis(diisopropylamino)decane, bis(n-propylamino)bis(di-n-butylamino) zebra, double (positive Propylamine) • bis(diisobutylamino)decane, bis(n-propylamino)bis(di-dibutyl-amino)decane, bis(n-propylamino)bis (di-di Tributylamino) decane, bis(n-propylamino)bis(dicyclopentylamino)decane, bis(n-propylamino)bis(monohexylamino) chopping, ginseng Amino group) (methylamino) shixi burning, ginseng (diethylamino) (decylamino) decane, ginseng (di-n-propylamino) (methylamino) decane, ginseng (two ^Isopropylamino)(methylamino)decane, ginseng(di-n-butylamino)(methylamino)decane, ginseng (diisobutylamino)(methylamino)decane, ginseng (t-butylamino group) (methylamino group) Alkane, ginseng (cyclopentylamino) (decylamino) oxime, hexamethylamino)(methylamino) decane; ginseng (dimethylamino)(ethylamino) decane, ((diethylamino)(ethylamino)decane, cis (di-n-propylamino)(ethylamino)decane, ginseng(diisopropylamino)(ethylamino)decane, ((di-n-butylamino)(ethylamino)decane, ginseng (diisobutylamino)(ethylamino)decane, ginseng (t-butylamino)(ethylamino)decane , ginseng (cyclopentylamino) (ethylamino) oxime, ginseng (cyclohexylamino) (ethylamino) decane, ginseng (dimethylamino) (n-propylamino) decane, Ginseng (diethylamino) (n-propylamino) decane, ginseng (n-propylamino) (n-propylamino) shixi, ginseng (diisopropylamine) (positive propyl) Alkyl) decane, ginseng (di-n-butylamino) (n-propylamino)-decane, ginseng (diisobutylamino) (n-propylamino) decane, ginseng (t-butylamine) (n-propylamino) decane, ginseng Pentylamino)(n-propylamino) decane, cis (cyclohexylamino)(n-propylamino)decane; 312XP/invention specification (supplement)/97_〇2/96140209 31 200835703 1'b Bis-decylamino-second-heterocyclic ring-burning, I-dimethylamino-based heterocyclic pentylene burning, 1, bis-methylamino-based fluorene-hexene-burning, bis-diethylamine-based heterocyclic pentylene burning, 1, bis-diethylamine Base ♦ heterocyclic hexanyl, methylamino-ethyl ethyl carbazide heterotetracycline (tetra), methylamino group + ethylamino group (tetra) cyclohexyl, 1,1-bis(ethylamino)-2, 5-dimethyl Heterocyclic pentane, i, bis(ethylamino)-2,6-diindenyl hexacyclohexane, i, bis(ethylamino)_2,5-diethyl fluorene heterocycle Pentane, hydrazine, b-bis(ethylamino)_2, 6-diethyl hydrazine, etc. In the present invention, in order to further improve the catalytic performance of the catalyst formed of the component (A), the component (B) and the component (C), an organic ruthenium compound other than the component (c) may be used in combination (hereinafter sometimes) It is called "ingredient (D)"). When the organic hydrazine compound of the above component (D) is specifically exemplified, di-n-propyl-decyloxydecane, diisopropyldimethoxydecane, di-n-butyldimethoxydecane, and di-n-butyl are preferably used. Butyl diethoxy decane, t-butyl (fluorenyl) dimethoxy decane, t-butyl (ethyl) dimethoxy decane, dicyclohexyl decyl decane, cyclohexyl (methyl a dimethoxy decane, a cyclopentyl (ethyl) decyloxy decane, a cyclopentyl (cyclohexyl) dimethoxy decane, a 3-methyl hexyl (cyclopentyl) decyloxy decane, 4-monodecylcyclohexyl (cyclopentyl) dimethoxy decane, 3, 5-dimercaptocyclohexyl (cyclopentyl) dimethoxy decane, bis(diethylamino) decyloxydecane , bis(di-n-propylamino)-methoxydecane, bis(di-n-butylamino)dimethoxydecane, bis(di-t-butylamino)dimethoxy decane, double (two Cyclopentylamino)dimethoxy zeoxime, bis(monorudylamino)dimethoxy zeoxime, bis(di-2-dimethylcyclohexylamino)dimethoxy decane, double (isoquinolyl)dimethoxyindole 312XP/Invention Manual (supplement)/97-〇2/96140209 32 200835703 Alkane, bis(quinolinyl)dimethoxydecane, bis(ethyl-n-propylamine) Dimethoxydecane, bis(ethylisopropylamino)dimethoxydecane, bis(ethyl-n-butylamino)dimethoxydecane, bis(ethylisobutylamino) Dimethoxy bis(ethyl 2,4-butylamino)dimethoxy-lower, bis(isobutyl-n-propylamino)dimethoxydecane, bis(ethylcyclopentylamino) Methoxydecane, bis(ethylcyclohexylamino)dimethoxyoxydecane, ethyl (diethylamino)dimethoxydecane, n-propyl (diisopropylamino)dimethoxy One stone, isopropyl (di-t-butylamino) dimethoxy, cyclohexyl (> diethylamino) dimethoxy decane, ethyl (di-t-butylamino) Dimethyl decyl decane, ethyl (perhydroisoquinolinyl) dioxy decane, n-propyl (perhydroisoindole, dimethicone, I propyl (perhydrohetero) dimethyl, Base decane, n-butyl (perhydroisoquinoline) Dimethoxydecane, ethyl (perhydroporphyrinyl)-methoxydecane, n-propyl (perhydroquinolinyl) dimethoxy (tetra), isopropyl (perhydroindolyl) dimethyl Oxygen oxime @, n-butyl (perhydro hydrazino) dimethoxy zexiyuan, bis(diethylamino)diethoxy oxane, =(-n-propylamino)diethoxy Decane, bis(di-n-butylamino)diethoxydecane, bis(di-t-butylamino)diethoxydecane, bis(dicyclopentylamino)diethoxydecane, bis ( Dicyclohexylamino)diethoxydecane, bis(di-2-methylcyclohexylamino)diethoxydecane, bis(diisoquinolinyl)diethoxydecane, bis(diquinoline) Diethoxy decane, bis(ethyl-n-propylamino)diethoxy valence, bis(ethylisopropylamino)diethyl sulphate, bis(ethyl-n-butylamino) Diethoxylate, bis(ethylisobutylamino)diethoxysecond sinter, bis(ethyl-tert-butylamino)diethoxy sulphur, bis(isobutyl-n-propyl) Amino) diethoxy stone, double (B 312X) P/Invention Manual (Repair 33 200835703 Cyclopentylamino) Diethoxydecane, bis(ethylcyclohexylamino)diethoxylate, n-propyl (diisopropylamino) Ethoxy sec-second, ethyl (perhydroisoquinolyl) diethoxy decane, n-propyl (all oxaquinolyl) diethylene > oxoxane, isopropyl (perylene isoquinoline) Diethoxy decane, n-butyl (pernitroisoindolyl) diethoxy carbaryl, ethyl (all-azinyl) diethoxy decane, n-propyl (per quinolinolyl) Diethoxy decane, isopropyl (perhydroquinolinyl) diethoxy decane, n-butyl (perhydroquinolinyl) diethoxy decane, thicytyl trimethoxy decane, diethyl Aminotrimethoxy decane, _di-n-propylaminotrimethoxy decane, di-n-butylaminotrimethoxy decane, di-t-butylaminotrimethoxy decane, dicyclopentyl Aminotrimethoxy oxalate, dicyclohexylaminotrimethoxy oxanthene, bis-2-nonylcyclohexylaminotrimethoxy decane, isoquinolinyltrimethoxy decane, quinolyl Trimethoxy decane , diethylaminotriethoxydecane, di-n-propylaminotriethoxydecane, di-n-butylaminotriethoxydecane, ethyl-tert-butylaminotriethoxydecane, Ethyl tert-butylaminotriethoxydecane, dicyclopentylaminotriethoxydecane, dicyclohexylaminotriethoxydecane, di-β-2-mercaptocyclohexylaminotriethyl Oxydecane, perhydroisoquinolyltriethoxydecane, perhydroquinolinyltriethoxydecane, bis(t-butylamino)dimethoxyoxydecane, bis(cyclohexylamino)di曱oxydecane, bis(t-butylamino)diethoxydecane, bis(cyclohexylamino)diethoxyanthracene, trivinylmethyldecane, tetravinylnonane, methyl ether , ethyl ether, .  Propyl ether, butyl ether, pentyl ether, diphenyl ether, 9,9-bis(decyloxyfluorenyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dioxane A group of the above-mentioned organic sulfonium compound (D) may be used alone or in combination of two or more. 312ΧΡ/发明发明(补件)/97·02/96140209 34 200835703 The method for producing the ethylene-propylene block copolymer of the present invention, which is formed by ==, (〇, or ? required component (1)): Contacting, and -, the mono-biliary which can contain propylene body of 5% by weight or less of ethylene is polymerized, and the i-th step corresponding to the inter-body of 2 to 95 of the total polymer is obtained, and the intermediate is In the presence, make Cri. : A method in which ethylene is polymerized to obtain a copolymer having a total ethylene content of 3 to knees and a propylene graft. Ethylene in the case of heavy metals - the amount of each component constituting the catalyst in the first step

Under the influence of the influence, it may be arbitrary, and there is no particular limitation. = The titanium atom in the knife A) is 丨m, and the component (8) is in the range of ❹ 咖 莫 莫, preferably 5G 〜1_莫耳. Ingredient ingredients (〇 use 0′′ 02~10 m, preferably 0.0 b 2 ^ ear L) mother 1 Mo, component (D) is used 〇.0001~1〇莫u; i~1 mo, Very good. benefit. .5 range of Moh; Medium 'Using G.GG Bu 10 Moar, preferably u05】Mohr, bucket inch 佺0.01~0.5 Moule range. The contact order of the mouth 77 is arbitrary, but the preferred system is in contact with the touch, or the component (6) and the component (d) are arbitrarily arbitrarily (obtained (8), and the other component (4) and = (4) and the component are 2^mBMmmm(mm/97^2/96i4〇2〇9 200835703 makes it contact, and it is also preferable to form a catalyst. By thus pre-constructing the component (A), the component (β) or the component ( When the contact treatment with the component (D) is carried out, the hydrogen reaction of the catalyst and the crystallinity of the polymer are further improved. The polymerization conditions in the first step, the copolymerization temperature is 2 〇 (rc or less, 150) c below, more preferably 50~i〇〇°c, the polymerization pressure is 1〇MFa or less, preferably 6MPa or less, more preferably 11~5. ^ Further, it can be a continuous polymerization method, a batch-human method Any one of the polymerization reaction is carried out by slurry polymerization or solution polymerization of propane, butane, isobutylidene, hexanol, Gengyuan, or smoldering inert hydrocarbon solvent, or at the polymerization temperature. The liquid olefin is used as a bulk polymerization or gas phase polymerization of the medium. Further, the polymerization in the i-th step is one stage or multiple stages. The first step is preferably C. In the case of homopolymerization, the polymerization is preferably a bulk polymerization or a gas phase polymerization. In the first step, it is preferred to carry out the homopolymerization of propylene, and the ethylene may contain micro liters, that is, 5% by weight or less. Polymerization with ethylene can be supplied to a reaction vessel by supplying a mixture of propylene and ethylene, and the alkene and ethylene can be continuously and continuously supplied to the reaction vessel. In the case of bulk polymerization, the mixture of propylene and ethylene, ethylene content & 5% by weight or less, (iv) 3% by weight or less 'In the case of gas phase polymerization, based on the amount of the rolling stock supplied to the reaction vessel, the amount of propylene # 术, 〇 〜 0.08 NL / min, preferably 〇 〇 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐 隐Usually, it is in the form of a bag. The device or the like continuously separates unreacted monomers from the solid polymer. The second step is in the presence of the intermediate obtained in the step!, and the two are returned to the 312XP/invention specification (supplement). /97·02/9614〇2〇9 200835703 Polymerization with ethylene Relative to 3 to 300% by mole, particularly preferably _〇莫耳=2 is preferably 3 to 60% by weight, compared with the bucket.) and the total ethylene content of the ene-propylene block copolymer Good 10~40% by weight of B, difficult. The best use of the second step is the impact of the ethylene used in the second step on the impact of the obtained polymer. The rigidity of the polymer to be served is lowered, so it is not good. The co-polymerization temperature in the second step is the same as the first step, and the method is the same as the above-mentioned first step. Next, the copolymerization of propylene and gold propylene is carried out, and it is preferred to use propylene and ❹r p ♦ in combination with the rolling phase polymerization. In the second step t, the polymerization may be carried out by supplying a mixture of propylene and ethylene to the trough, or by arranging the propylene and the acetamidine continuously: 2:=! In order to adjust the molecular weight, a bond such as chlorine may be added. = Sheet 1; In the case of co-polymerization, when the multi-stage polymerization tank is used, the above-mentioned catalyst components (1) to (6) can be used for the first! In the case where the polymerization tank used in the step is the second step of forming the multistage polymerization tank, there is no particular limitation. However, in each of the polymerization tanks, the components (8) and (C) may be additionally supplied as needed. (D), component (c) and or component (c). As described above, in the first step, an intermediate amount corresponding to 2 to 95% by weight, preferably 30 to 85% by weight, based on the total polymer is formed to obtain a specific amount of the intermediate, followed by the second step. Among them, a copolymer containing various amounts of total ethylene content is obtained, and a copolymer having various compositions is produced, whereby a polymer having different properties such as elasticity, rigidity, surface characteristics, and low-temperature impact properties can be obtained. The ratio of the propylene to the berry in the first step and the second step, or the ratio of the polymer produced in the second step and the second 312XP/invention specification (supplement)/97-02/96140209 37 200835703 step and the second step can be borrowed It is appropriately controlled by the grade of the target polymer, and in particular, in the second step, since a copolymer (rubber component) of propylene and ethylene can be sufficiently produced, a high rubber component ratio and a good balance of elasticity and rigidity can be obtained. Superior ethylene-propylene block copolymer.

Further, as a method of controlling the amount of the intermediate polymer in the above numerical range in the first step and the total polymer, the method of controlling the total ethylene content in the above numerical range in the second step and the total polymer For example, a method of controlling the reaction time of the first step and the reaction time of the second step in combination with the polymerization activity of the catalyst in the first step and the second step; in the continuous polymerization apparatus, the average in the apparatus a method of estimating the amount of polymer produced by the product of the polymerization rate and the average residence time; or a method of controlling the supply amount of propylene in the step (step pp) and the supply of propylene and ethylene in the second step; The method of quantitatively analyzing the composition of the gas and the composition of the outlet, and automatically controlling the composition thereof. The formation of a shell in the final product from the homopolymerization of propylene to the ethylene-propylene block copolymerization may be carried out by adding a known electron-based compound such as an alcohol read, a weide or a ketone to the polymerization system. The specific example can be exemplified by ethanol, isopropyl alcohol, etc., and the amount used is (B) l mole relative to ^', which is 〇.〇1〇莫耳, preferably 〇. Moer. Further, in the production of the ethylene-propylene block copolymer, the second step is performed (the third step is sometimes referred to as the third step, the first person, and the other is called "the present time". In order to further improve the activity of the catalyst and the degree of particle traits generated by the company, it is best to enter the _, 彳 and 丁 备. Pre-polymerization

312ΧΡ/^^8δ^·(Μ#)/97-〇2/96140209 38 200835703 犄' The same olefin or styrene monomer as the present polymerization can be used. Specifically, in the presence of an olefin, the component (A), the component (B), and/or the component (c) are contacted so that the component (A) is 0.01 to 1 g per lg. The olefin is subjected to preliminary polymerization, and the component 3) and/or the component (c) are contacted to form a catalyst. Further, when the component (D) is used in combination, the component (A), the component (B) and the component '(D) may be contacted in the presence of an olefin in the preliminary polymerization, and then used in the polymerization. Ingredient (C). In the pre-polymerization of the earth, the contact order of each component and the monomer is arbitrary, and it is preferably contained in a preliminary polymerization system in which a gas atmosphere is set in an inert gas atmosphere or a polymerization of propylene or the like, and the component (8) is first charged, and secondly, After the component (C) or the component (D) is contacted, the component (A) is contacted, and then a olefin such as propylene is passed through and/or one or two or more other rare hydrocarbons are contacted. The preheating temperature is arbitrary, and is not particularly limited, and is preferably _10 ΐ to 7 (the range of TC, more preferably Ot 〜 5 (the range of TC.) 围 _ cite the example of the cockroach to more specifically describe the present invention, but only this For example, the characteristics of the polymer are determined by the following method (the evaluation of the stereoregularity of the homopolypropylene (10) (the weight will be aggregated in the first step PP) A ^PP < compound sample (c)g, dissolved in heating: 3 = = but after (2). C) the weight of the insoluble portion (8) g, by the lower arm ^ ^ ^ ") - aD) g / a ) gxlG(), to obtain dif-benzene (polymerization activity of the catalyst of the PP part) "Gui Lixian". Catalyst activity is calculated by the following formula: Catalyst activity = polymer 312XP / invention manual ())/97-02/961.09 39 200835703 (E)g/solid catalyst component g/l hour. The polymerization activity of the catalyst in the PP part is the polymerization activity in the first step (homopolymerization stage) in Table 1. Further, the measurement of the melt flowability (MFR) of the obtained PP portion and the obtained ethylene-propylene block copolymer was carried out in accordance with the method of ASTM D1238. The melt flowability of the olefin block copolymer (ICP) is expressed by ICP (MFR) in Table 1. (Evaluation of the amount of ethylene-propylene block copolymer produced in the ethylene-propylene block copolymerization reaction) The evaluation of the amount of polymer produced per ethylene-propylene block polymerization time calculated by the following formula is represented by the block ratio. The block ratio (%) is determined by measuring the high pressure dad weight (F) g and the end of the PP polymerization stage. Then, the weight of the high pressure dad (G) g after removing the unreacted monomer, the weight of the autoclave after the copolymerization for 60 minutes (I) g, and the weight of the high pressure dad (K) g after the copolymerization for 120 minutes were calculated by the following formula. Homopolymer g = (GF)g Block rate after copolymerization for 60 minutes (%) = (IG) gAI-F) gxl00 Block rate after copolymerization for 120 minutes (%) = (KG) g / ( KF)gxlOO (Evaluation of EPR content and ethylene content) The content of the ethylene-propylene rubber component (hereinafter referred to as EPR) in the block copolymer was measured by the following method: 1 - liter volume flask equipped with a stirrer and a cooling tube In the ethylene-propylene block copolymer, about 2. 5g, .2, 6-di-tert-butyl-p-cresol 8mg, p-diphenylbenzene 250ml, At the boiling point of the solvent, the mixture was stirred until the block copolymer was completely dissolved. Next, the flask was cooled to room temperature and allowed to stand for 15 hours to precipitate a solid matter. This was centrifuged 312XP/invention specification (supplement)/97·02/ %140209 40 200835703 The second part is the solid part and the liquid phase part. The solid part is taken into the beaker and acetone is added thereto. After mixing for 15 hours at room temperature, the solid matter is filtered and dried, and the weight is measured. Heavy knife,

(reset it as 〇. EpR in block copolymer

t = the ethylene content of the insoluble solid β, which is 13c-swelled: other than in the table of the examples...thin...) (determination of the ultimate viscosity (π) (di/g) of EPR) EPR The ultimate viscosity (π) is determined by using a Ubbelohde viscometer in the tenth naphthalene to determine the reducing viscosity for the concentration of i · 〇, 〇 · 2 and 0. 5 g / di, and secondly to reduce the viscosity relative to the concentration. The drawing was carried out, and the ultimate viscosity was obtained by extrapolation of the concentration to zero. (Reference Example 1) <Synthesis of the amine-based calcined compound of (C)> In the reaction of dicyclopentyldimethoxydecane with a salt of 2-fold molar ethylamine, the synthesis was carried out by a certain method. The yield of the obtained bis(ethylamino)dicyclohexyldecane was 84.6%, and the boiling point was ll 8 ° C / 2. 4 mmHg. The elemental analysis values () of C, U, and N are theoretical values. c: 66. 〇 5% (66.07%), Η: 11. 86 ° / 〇 (11. 88%) ^ Ν : 11. 02% (11. 01%) (Reference Example 2) <Component (C) Synthesis of Amine Groups&gt;5 Sparkling Compounds> Li Salt 312XP of Diisopropyldimethoxy decane and 2 Mole Ethylamine/Invention Manual (Supplement)/97-02/90140209 41 200835703 In the reaction, bis(ethylamino)diisopropyl rock was synthesized by a certain method, and purified by vacuum distillation to obtain a target compound having a purity of *96% by gas chromatography. The elemental analysis value () of c, Η, and N is the theoretical value. • C : 59·31% (59·34%), Η: 12·96% (12.95%), n: 13·82% (13·84%) (Reference Example 3) <Component (C) Synthesis of Aminodecane Compounds > Synthesis of bis(indenylamino)cyclohexylfluorene by a certain method in the reaction of ketone thiol-methoxy sec-second with 2 times mole of decylamine The decane was purified by vacuum distillation to obtain a target compound having a purity of 95% by gas chromatography. The elemental analysis value () of C, Η, and N is the theoretical value. C: 57·97% (58·00%), Η: 11·97% (11·70%), Ν: 15.02% (15.03%) (Reference Example 4) <Amino decane compound of the component (C) Synthesis &gt; In the reaction of the third salt of the third butylmethyldimethoxycarbazide with the Li salt of the ethylamine of 2 times mole, the bis(ethylamino)th-butyl-decyldecane is synthesized by a certain method. Purification and separation were carried out by vacuum distillation to obtain a target compound having a purity of 97% by gas chromatography. The elemental analysis values of C, Η, and N are theoretical values. C: 57· 36% (57·38%), Η: 12·82% (12·84%), ^ Ν: 14·85% (14·87%) - (Reference Example 5) <Component (Α) Synthesis of solid catalyst> Round 312χΡ/inventive instruction (supplement)/97-02/96140209 42 200835703 bottom flask, fully substituted with nitrogen and having a capacity of 200 ml of a blender, charged with diethoxymagnesium 1 〇g and toluene 8〇mi, made into a cloudy cancer. Next, titanium tetrachloride is added to the suspension solution to raise the temperature. When the temperature reaches 62 ° C, diethyl citrate 1· 〇mi is added, and then the temperature is raised. • When the temperature reaches 110 ° C, citric acid is added. Dioctyl ester 3 · 5ml, and then heated to 112 ° C. Thereafter, while maintaining the temperature at 112 ° C, the reaction was carried out while stirring i 5 hours. After completion of the reaction, the mixture was washed twice with 9 (rc toluene l〇〇ml), and 2 〇ml of titanium tetrachloride and 8 〇πα of toluene were added again, and the temperature was raised to 10 ° C, and the mixture was stirred for 2 hours to carry out a reaction. After completion, the solid catalyst component was obtained by washing 4 times of 100 ml of rc of heptane heptane to obtain a solid catalyst component. Further, the solid solution in the solid catalyst component was separated, and the titanium content in the solid fraction was measured. 2.6% by weight. (Example 1) <Synthesis of ethylene-propylene block copolymer> (Preparation polymerization and first step) Pressurization and application of a nitrogen gas (99·9999%) of 30 kg/cm2 The pressure was repeated 10 times, and the weight of the autoclave (reactor) equipped with the completely substituted internal volume 2. 〇L mixer and the pressurized polymer sample take-out device was measured. Secondly, triethylaluminum was charged into the reactor. (hereinafter referred to as TEA), the bis(ethylamino)dicyclopentyldecane obtained by Reference Example 1 (hereinafter referred to as BEADC), and the solid catalyst component obtained in McC. 5, 钛26 mm by titanium atom 1, forming a polymerization catalyst. At this time, the molar ratio of T i, tea, ♦ and BEAD in the solid content of the solid catalyst (Ti/TEA/BEADC) was set to 1/600/120. Thereafter, 4 L of hydrogen gas and 1.4 L of liquefied propylene were charged, and after pre-polymerization for 5 minutes at 20X, propylene polymerization was carried out at 70 ° C for 1 hour. , release the non-anti-312XP / invention manual (supplement) /97-02/96140209 43 200835703 should be the monomer. Second, the high-purity nitrogen pressure to 〇 · 5MPa, followed by depressurization, 'and repeat this operation 5 Then, the reactor was made into a nitrogen gas atmosphere. The weight of the high pressure dad was calculated, and the generation (weight) of the PP was calculated. Considering the stirring efficiency of the copolymer, the average PP in the reactor was about 200 g. The PP was taken out from the polymer take-out device under nitrogen, and it was used as a sample for evaluation of the average PP. (Second step) Next, in the coexistence of PP and the catalyst system of about 200 g, propylene, ethylene, and ruthenium were used. In this order, according to the gas supply speed ratio of propylene / ethylene / hydrogen = 2.0 / 1.4 / 0.06 (NL / min), the total pressure is 1.2MPa, continuously supplied to the reactor, at 70 ° C for up to 2 hours Copolymerization. The copolymerization system is set to each of the reaction time of 30 minutes, 60 minutes, 90 minutes, and 12 minutes. After the completion of the batch polymerization, the gas supply was stopped, the weight of the reactor was measured, and the weight of the copolymer was evaluated as the amount of the copolymer produced at each time, and the block ratio was calculated. At the same time, the polymerization amount required for the analysis was taken out. For the composition of the copolymer, the composition of the copolymer was observed and observed with time. The results are shown in Table 1. Further, in the first step of Example 1, the amount of the intermediate polymer was 215 g x l 007 443 · 3 g = 48.5 wt. %. (Reference Example 6) • <Preparation of Solid Catalyst> - In a round bottom flask equipped with a stirrer and sufficiently substituted into a nitrogen gas volume of 500 ml, 4.76 g of anhydrous magnesium chloride, 25 ml of decalin, and 2-ethylhexyl group were charged. Alcohol 23.4m Bu was reacted at 130 ° C for 2 hours, made into 312XP / invention instructions (supplement) / 97-02 / 96140209 44 200835703 even = liquid human, in the 5 Hai uniform solution added with phthalic anhydride 丨.丨丨g, the reaction was carried out at 130 C for 1 hour, and then, the solution was placed in a round bottom flask equipped with a stirrer and sufficiently substituted with a nitrogen gas, and the total amount was dropped for 1 hour until it was kept. _2 (rc tetrachlorinated in 2 〇〇mi. Secondly, the mixed solution was heated to 11 Torr over 4 hours, then 2.68 ml of diisobutyl citrate was added and reacted for 2 hours. After the reaction was over, borrowed The liquid portion was removed, and the remaining solid component was washed with decachloronaphthalene and hexane at 11 (rc) until no free titanium compound could be detected, and the mixture was filtered and dried to obtain a powdery solid catalyst component. The content of titanium in the solid catalyst component was measured and found to be 3.1 wt%. Example 2) <Formation and Polymerization of Polymerization Catalyst> A polymerization catalyst was formed and a 2-hour block copolymerization was carried out in the same manner as in Example 1 except that the solid catalyst component obtained in Reference Example 6 was used. The results obtained are shown in Table 1. (Reference Example 7) <Preparation of solid catalyst> In a round bottom flask equipped with a stirrer and sufficiently substituted with a nitrogen gas volume of 10 μm, the Grenada shavings were placed. Next, 32 g of magnesium was added. Next, a mixture of 120 g of butyl chloride and 500 ml of dibutyl ether was dropped in the magnesium for 4 hours at 50 C, and then reacted at 6 (TC for 1 hour). After the reaction was completed, The reaction solution was cooled to room temperature, and the solid content was removed by filtration to obtain a sedative compound solution. Next, in a round-bottomed flask having a capacity of 500 ml, which was sufficiently substituted with a nitrogen gas, was charged with 24 〇ml of tetrahexane and tetrabutoxygen. 312XP / invention manual (supplement) /97·02/96140209 45 200835703 base titanium 5 · 4g and tetraethoxy decane 61 · 4g to make a homogeneous solution, at this time the town compound solution 15Om 1 at 5 ° C for a duration Drip and react for 4 hours, then at room temperature After the reaction mixture was filtered at room temperature, the liquid portion was removed, and the remaining solid portion was washed 8 times with 240 ml of hexane, and dried under reduced pressure to give a solid product. Next, 8 6 g of the solid product was placed in a round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas in an amount of 1 〇〇mi, and then toluene and diisobutyl phthalate 5·8 ml were added thereto. The reaction was carried out for 1 hour. Thereafter, after removing the liquid portion by filtration, the remaining solid portion was washed 8 times with toluene 85 m. After the completion of the washing, 21 ml of toluene, 0. 48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride were placed in the flask, and the mixture was reacted at 95 ° C for 8 hours. After the completion of the reaction, solid-liquid separation was carried out at 95 ° C, and the solid portion was washed twice with 48 ml of toluene, and then subjected to the same reaction under the same conditions for the above mixture of diisobutyl phthalate and titanium tetrachloride. The mixture was washed 8 times with 48 ml of hexane, filtered and dried to obtain a powdery solid catalyst component. The content of titanium in the solid catalyst component was measured and found to be 2.% by weight. (Example 3) <Formation and Polymerization of Polymerization Catalyst> The formation of a polymerization catalyst and a 2-hour block copolymerization were carried out in the same manner as in Example 1 except that the solid catalyst component obtained in Reference Example 7 was used. ; The results obtained are shown in Table 1. - (Example 4) <Synthesis of ethylene-propylene block copolymer> In addition to the gas supply speed ratio in the substituted block copolymerization section: propylene/b 312XP/invention specification (supplement)/97-02/90140209 46 200835703 Aene/hydrogen = 2. 0 Λ · 4/0·06 (NL/min), and the same as in Example 1 except that propylene/ethylene/氲=2.0/1.4/0.12 (NL/min) was used. The synthesis of the ethylene-propylene block copolymer was carried out. The results are shown in Table 1. Here, the copolymerization in the second step was batch polymerization, and polymerization was carried out for 60 minutes and for 120 minutes, respectively. Hereinafter, Examples 5 and 6 and Comparative Examples 2 and 3 are also the same. (Example 5) <Synthesis of ethylene-propylene block copolymer> In addition to the gas supply rate ratio in the sub-block copolymerization section: propylene/ethylene/hydrogen=2.0/1.4/0.06 (NL/min), The synthesis of the ethylene-propylene block copolymer was carried out in the same manner as in Example 1 except that propylene/ethylene/hydrogen two 2.0/1.4/0.18 (NL/min). The results are shown in Table 1 实施 (Example 6) <Synthesis of ethylene-propylene block copolymer> The bis(ethyl group) obtained in Reference Example 2 was used except for the substitution of bis(ethylamino)dicyclopentyldecane. The synthesis of the ethylene-propylene block copolymer was carried out in the same manner as in Example 1 except for the amino group diisopropyl decane. The results are shown in Table 2. (Example 7) <Synthesis of ethylene-propylene block copolymer> In addition to the substitution of bis(ethylamino)dicyclopentyldecane, the bis(methylamino)cyclohexyldecyldecane obtained in Reference Example 3 was used. The same procedure as in Example 1 was carried out, and the synthesis of the ethylene-propylene block copolymer was carried out 2 312 XP / invention specification (supplement) / 97-02/96140209 47 200835703. The results are shown in Table 2. (Example 8) <Synthesis of ethylene-propylene block copolymer> In addition to the substitution of bis(ethylamino)dicyclopentyldecane, the bis(ethylamino)t-butylmethyldecane obtained in Reference Example 4 was used. The synthesis was carried out in the same manner as in Example 1 except that the synthesis of the ethylene-propylene block copolymer was carried out for 2 hours. The results are shown in Table 2. (Comparative Example 1) <Synthesis of ethylene-propylene block copolymer> The same procedure as in Example 1 except that instead of bis(ethylamino)dicyclopentyldecane, cyclohexylmethyldimethoxydecane was used. The synthesis was carried out while the ethylene-propylene block copolymer was carried out. The results are shown in Table 2. (Comparative Example 2) <Synthesis of ethylene-propylene smear copolymer> In addition to the substitution of bis(ethylamino)dicyclopentyl sulphate, dicyclopentamethoxy decane was used, and the others were carried out. In the same manner as in Example 1, the synthesis of the ethylene-propylene block copolymer was carried out. The results are shown in Table 2. (Comparative Example 3) <Synthesis of Ethylene-Propylene Block Copolymer> Except that bis(ethylamino)dicyclopentyl sulphate was substituted, and dimetheryl triethoxy decane was used, and the examples and the examples 1 was carried out in the same manner, and the synthesis of the acetamidine-propylene-derived segment copolymer was carried out. The results are shown in Table 2. 312XP/Invention Manual (supplement)/97-02/96140209 48 200835703

EPR 1-1 1_1 O LO CD inch inch · LO a CD LO · CO inch · LO inch · CO &lt; NI CO CD CO CJD cvi CJD oi 1 CO Ethylene content (wt%) in XI CO CO oo CO Cd LO cd cd cd CD inch · 3 CJD CO CO inch inch · inch CO οα cd LO cd in EPR oa od CO r—^ oo CO oo CO ◦ cd CO CD CO inch cd CO OB CO οα cd CO CO LD* CO LO CO t—H cd CO oo LO CO CO CD CO oo LO CO &amp; i (MFR) | . 呀οα r—4; 1 ( l a4 CD LO oo 卜 · CO 寸 cd 卜 CNI 00 1 i oo CT&gt; CO C^I &lt;〇oo rH &lt;NJ t-H od block rate (wt%) LO C&lt;1 &lt;NI oa LO CO ri CO inch LO t-H LO CO rH LO C75 § oo cd CO inch ci&gt; LO 1 &lt; oi CO CO ! &lt; inch oa CO CO LO 卜 寸 oo cji inch CO CD LO copolymerization time (min.) o CO 〇&gt; CO o 〇CNI rH ◦ (Nl t— H cz&gt; (XI § cz&gt; CNI tH § o CNI t-H § OJ T-l CD (Nl r-H cz&gt; oa t-H Π 1 (MFR) LO LO LO inch LO inch o tH LTD CO 1 - H o inch T—H o LO o LO o inch o CO tH CD CO 03 (N1 CD OO o oo t—H Ou Γ XS(wt°/〇) inch T &lt; CO i 4 CO 'ϊ—Η CO tH LO r—^ CO 1—H oa ψ&quot; i CO t—H CV3 rH (&gt;3 r \ &lt;NJ rH oa rH C^&gt; CD OJ r—H 1 copolymerization stage polymerization activity (g-PP /g-Cat · h) &lt;〇CZ5 cz&gt; oa inch Q o (Nl 05 CO CD cz&gt; CO inch CD 〇CO inch! CD CZ5 ◦ oi 03 o CD CD oJ inch c=&gt;cz&gt;σ&gt; CO CZ) CZ) CO 05 CO CD 〇LO (XI inch oo CD inch o CD 〇T-^ cz&gt; CD CO CD inch CD Cl? 03 t-H inch o O CO 呀 Example &lt;NJ CQ LQ CO oo 6 inch 608 inch 196/39 Bu 6/(生紫)_^鉴^激/&lt;1}^1£ 200835703 _ i (ζ&lt;)

EPR 1-1 1_1 卜(ΝΪ c^&gt;c&lt;i CD CO CO LO CO CO CO rH CO CO CO 1—( XG •1—1 tH oi Od CO CD CO c&lt;i CD c&lt;i CO (N1 rH inch φΐ loveο ί in EPR OO cJ CO CO oa CO &lt;3&gt; r-H CO OO d CO rH cii CO CD ii CO t-H OO CO CO CO 1-1 (MFR) UD H TH T-H OO 卜 oa cd CO CNl t-H rH D- CO 卜 t-H block rate (wt%) oa LO rH CO inch (NI CO y—i CO Bu·CO Bub· οα T—H cvi 寸T —H OO i—H 〇〇· CN1 Copolymerization time (min.) ◦ CO ◦ CO oo (NJ g &lt;〇▼—Η § CZ&gt; 03 H Oh (MFR) LO oa CO C&lt;1 CD oa ii CSi CO ai Ο ai CD OO CD 卜 XS(wt°/〇) 卜 t—H OO OO 卜 CJi CZ) ◦' LO r—H LO rH polymerization activity in the copolymerization stage (g-PP/g-Cat · h) 46, 900 cz&gt; CZ) oa OO inch 47,600 ◦ cz&gt; Bu CO 53,000 inch CD LO 42,800 oo czT inch comparison example &lt;N1 CO 〇ς 60SH96/sr-6/ff4ii)_K?is^MXCNIe 200835703 As a result, it is understood that the ethylene-propylene block copolymer obtained by the present invention is ethylene-propylene as compared with the comparative example of the prior art. The copolymerization of the olefin block increases the combined time and block rate, and the polymerization activity is maintained for a long time. Moreover, under the same hydrogen amount, the MFR of the homopolypropylene is more than 7 times that of the comparative example, so it is caused by hydrogen. The chain mobility (hydrogen reaction) is extremely superior. Compared with the comparative example, even if the MFR of the homopolypropylene is large, the XS (non-biphenylene soluble fraction) evaluated for stereoregularity is 1.5% by weight or less, and the stereoscopic value is three-dimensional. The EPR generated by the copolymerization of the ethylene-propylene block is also easy to control, and the MFR of the ethylene-propylene block copolymer having a high EPR content is increased. By the method of the present invention, a high-performance, inexpensive ethylene-propylene block copolymer can be produced in a direct polymerization. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of modulating the polymerization medium of the present invention.

312XP/Invention Manual (supplement)/97-02/96140209 51

Claims (1)

200835703 X. Patent application scope: 丨· A method for producing an ethylene-propylene block copolymer, characterized by having: the first step, which is carried out by the following components (A), (B) and (C) In the presence of a medium, a monomer capable of containing propylene by weight of 5% by weight or less is polymerized to obtain an intermediate corresponding to 2 to 95% by weight of the total polymer; and a second step , in the presence of the intermediate, propylene and ethylene are polymerized to obtain a propylene copolymer having a total ethylene content of 3 to 6 % by weight; 馨 (A) § has town, titanium, halogen and electron supply The solid catalyst component of the compound; χ (Β) is an organoaluminum compound represented by the following general formula (1): fpAiQ3 ρ (!); (wherein R1 represents an alkyl group having a carbon number of 1 to 4, and Q represents hydrogen. An atom or a halogen atom, P is a real number of 0 < p S 3 ; (C) an amine group based on the following general formula (2): R2nSi(NRf )4_n (2); &amp; (wherein R2 represents a linear or branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group and a derivative thereof, a vinyl group, an allyl group, and an aralkyl group. , which may be the same or different; R3 represents a halogen atom, a linear or branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group, a derivative thereof, a vinyl group, a propyl group, an aryl group, or The same or different; R4 represents a linear or branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group and a derivative thereof, a vinyl group, an allyl group, an aralkyl group, which may be the same or different; R3 And R4 may also combine to form a ring; η is an integer of 0 or 1 to 3; at least one of the NR3R4 groups is a 2-stage amine group). 312XP / invention manual (supplement) /97-02/96140209 52 200835703, the scope of patent claims! The amount of ethylene used in the above second step is the amount of ethylene used in the second step, which is 3 to lion mole %. . The method for producing an ethylene-propylene block copolymer according to the first aspect of the invention, wherein the solid catalyst component (A) is obtained by using a magnesium compound (a) and a titanium compound (b) And the electron-donating compound (c) is then prepared. The method for producing an ethylene-propylene block copolymer according to the first aspect of the invention, wherein the amino decane compound is bis(ethylamino)dicyclopentyl kiln (ethylamino group) Diisopropyl zebra, bis(ethylamino)cyclohexylmethyl decane or bis(ethylamino)t-butylmethyldecane, bis(ethylamino)(t-butylamino)B Base decane. Further, a method for producing an ethylene-propylene block copolymer according to the first aspect of the patent application, wherein the total ethyl content is 5 to 5 〇 by weight of the final product 〇 312XP/Invention Manual (supplement)/97-02/96140209 53