JP4557260B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

  According to the present invention, a polyolefin polymer having a particle size of 45 μm or less and hardly containing a finely divided polymer can be obtained in a high yield, and particularly when subjected to copolymerization of propylene and ethylene or other olefins, The present invention relates to a solid catalyst component for olefin polymerization capable of maintaining good polymer fluidity even when the content ratio is increased, a polymerization catalyst containing the catalyst component, and a method for polymerizing olefins using the same.

  Conventionally, in the polymerization of olefins, many solid catalyst components for olefin polymerization have been proposed which contain magnesium, titanium, and halogen as essential components. These conventional techniques mainly focus on improving activity and stereoregular polymers, and are composed of this type of highly active catalyst component and electron donating compounds represented by organoaluminum compounds and silicon compounds. When polymerization of olefins is carried out using a polymerization catalyst of composition, the resulting polymer contains a lot of fine powder because of the fine powder of the solid catalyst component itself and particle breakage due to heat of reaction at the time of polymerization. In many cases, it causes process failures such as blockage of piping. In particular, when a porous catalyst having a large specific surface area and a large pore volume is selected as the structure of the solid catalyst component, a sufficient amount of catalytic activity can be expected. There was a tendency to become prominent. However, when designing a solid catalyst component in the direction of obtaining a polyolefin polymer with a small amount of fine powder, it is common to select synthesis conditions that increase the particle density from the viewpoint of preventing polymer particle destruction during polymerization. Met. However, when such a solid catalyst component is used, particularly when applied to the copolymerization of propylene and other olefins such as ethylene, the particle density of the polymer is high, reflecting the structure of the solid catalyst component. Since the pore volume is reduced, the content of the rubber component held in the polymer particles is limited, and stickiness of the polymer particles becomes noticeable when other olefins such as ethylene are inserted in a certain amount or more. In many cases, problems such as adhesion in the reactor and clogging in the polymer transport process become serious problems in process operation.

  From an industrial point of view, homopolymerization of olefins such as propylene and copolymerization of propylene and other olefins are often switched in time series to produce a wide variety of resins in a single line. However, at this time, a single solid catalyst component is used as a catalyst species, and the process operation can be economically performed without causing the above-mentioned fine powder trouble or stickiness problem in copolymerization. A solid catalyst component having high performance and high versatility has been desired.

In the prior art, for example, Patent Literature 1 (Patent No. 2521836), Patent Literature 2 (Patent No. 3016816), Patent Literature 3 (Japanese Patent Laid-Open No. 10-176023), Patent Literature 4 (Japanese Patent Laid-Open No. 10-60041), Patent Reference 5 (Japanese Patent Laid-Open No. 2002-356507) and the like disclose a method for producing a solid catalyst component having specific physical characteristics, but whether or not the above-described problems can be comprehensively solved. It has not been clarified.
Japanese Patent No. 2521836 Japanese Patent No. 3016816 Japanese Patent Laid-Open No. 10-176023 Japanese Patent Laid-Open No. 10-60041 JP 2002-356507 A

  That is, the object of the present invention is to maintain a high degree of polymer stereoregularity and yield when subjected to olefin polymerization, and there is almost no finely divided polymer, so that propylene and ethylene or other olefins can be used together. Solid catalyst and catalyst for olefin polymerization, which is a component of an olefin polymerization catalyst capable of maintaining good polymer fluidity even when the content ratio of the rubber component is increased when subjected to polymerization, and olefin using the same It is to provide a polymerization method.

  In such a situation, the present inventor reduced the fine particles generated when forming the solid catalyst component in the solid catalyst preparation step as much as possible, and at the same time improved the surface strength and stability of the particles that became the solid catalyst component, and at the same time As a result of diligent investigations into a porous internal structure, the solid catalyst component obtained by contacting with a halogenated titanium compound while polymerizing an alkoxy group-containing magnesium compound in combination with a surfactant component and alcohol is polymerized. In other words, the present inventors have found that the above problems can be solved comprehensively, and have completed the present invention.

That is, the present invention is di-alkoxy Shima magnesium compound (a), a suspension is contacted in the presence of a surface-active ingredient (b) and alcohols (c) an inert organic solvent (d), then 該懸 after contact with Nigoeki and tetravalent titanium halide (e) and the electron donor compound other than alcohol (f), contacting further tetravalent titanium halide compound (e), characterized in that it is obtained by A method for producing a solid catalyst component for olefin polymerization is provided.

As the alkoxy group-containing magnesium compound (a) (hereinafter sometimes simply referred to as “component (a)”) used in the present invention, the following general formula (2);
Mg X _n (OR ² ) _2-n (2)
(Wherein, X represents a halogen atom, R ² represents an alkyl group, and n is 0 ≦ n <2). Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group. , Isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, It is an iodine atom. Suitable compounds include dimethoxy magnesium, methoxy chloro magnesium, diethoxy magnesium, ethoxy chloro magnesium, dipropoxy magnesium, propoxy chloro magnesium, dibutoxy magnesium, butoxy chloro magnesium, diphenoxy magnesium, phenoxy chloro magnesium and the like.

The average particle size of the alkoxy-containing magnesium compound is 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. The specific surface area is, 5 to 100 m ² / g, preferably 10 to 80 m ² / g, particularly preferably 20 to 50 m ² / g. The shape of the alkoxy-containing magnesium compound to be used is arbitrary, but it is desirable to use a spherical shape, an elliptical cross-sectional shape or a potato shape.

  As the surfactant component (b) (hereinafter sometimes simply referred to as “component (b)”), a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, Fluorine-based surfactants, reactive surfactants, silicone oils and modified silicone oils can be used, and one or more selected from these can be used.

  Specifically, examples of the cationic surfactant include aliphatic primary to tertiary amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolium salts, and the like. Examples of the anionic surfactant include fatty acid soaps, N-acylamino acids or salts thereof, carboxylates such as polyoxyethylene alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates. Salts, sulfonates such as alkyl disulphates of sulfosuccinates, alkylsulfoacetates, sulfated oils, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, monoglyculates, etc. Examples thereof include phosphoric acid ester salts such as sulfate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene phenyl ether phosphates, and alkyl phosphates.

  Examples of the amphoteric surfactant include carboxybetaine type, aminated rubonate, inidazilinium betaine, lecithin, alkylamine oxide and the like. Examples of the nonionic surfactant include polyoxyethylene mono- or dialkyl ethers having 1 to 18 carbon atoms in the alkyl group, polyoxyethylene secondary alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sterol ethers, Ether esters such as polyoxyethylene lanolin derivatives, polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid alkanolamide sulfates, Polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester , Propylene glycol fatty acid esters, ester type such as sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, nitrogen-containing type such as polyoxyethylene alkyl amines, and the like.

  Examples of the fluorosurfactant include fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, and N-perfluorooctanesulfonyl glutamate disodium. Examples of the reactive surfactant include polyoxyethylene allyl glycidyl nonyl phenyl ether and polyoxyethylene propenyl phenyl ether.

  Silicone oils include dimethyl silicone oil, fatty acid modified silicone oil, alkyl modified silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, methylphenyl silicone oil, chain polydimethylsiloxane, cyclic polydimethylsiloxane, methylphenyl silicone oil. And polyether-modified silicone oil, amino-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, and fluorine-modified silicone oil.

  The surfactants exemplified above can be used alone or in combination of two or more. Among these, nonionic surfactants having an HLB (hydrophilic / lipophilic balance) value of usually 3 to 20 are preferably used, and nonionic surfactants that are sufficiently soluble in the solvent to be used vary depending on the treatment method. It is desirable to select an agent. For example, when processing in polar organic solvents, such as alcohol, ethers, and acetone, the hydrophilic nonionic surfactant whose HLB value is 10-20 is used preferably. Moreover, when processing in organic solvents, such as hydrocarbons, such as hexane and heptane, the slightly lipophilic nonionic surfactant whose HLB value is 3 to 15 is preferable.

  Among the above, the preferred surfactant used in the present invention is a nonionic surfactant, and a slightly lipophilic nonionic surfactant having an HLB value of 3 to 15 is particularly preferred. Specifically, polyoxyethylene alkyl phenyl ethers such as nonylphenol ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyglycerin fatty acid esters such as polyglycerol monostearate, sorbitan monolaurate, sorbitan Examples include sorbitan fatty acid esters such as monostearate and sorbitan distearate, and one or more selected from these are particularly preferred.

  Examples of the alcohol (c) (hereinafter sometimes simply referred to as “component (c)”) include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-methyl-2-propanol, and ethylhexanol, and benzyl alcohol. , Aromatic alcohols such as phenethyl alcohol, etc., among which aliphatic alcohols are particularly preferred.

  Examples of the inert organic solvent (d) (hereinafter sometimes simply referred to as “component (d)”) include saturated hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, and methylcyclopentane. Examples thereof include aromatic hydrocarbon compounds such as compounds, benzene, toluene, xylene, and ethylbenzene, and halogenated hydrocarbon compounds such as methylene chloride and 1,2-dichlorobenzene. Of these, aromatic hydrocarbon compounds such as toluene and xylene are most preferred.

The tetravalent titanium halogen compound (e) used for the preparation of the solid catalyst component (A) in the present invention has a general formula Ti (OR ³ ) _n A _4-n (wherein R ³ has 1 to 4 carbon atoms). Represents an alkyl group, A represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and n is an integer of 0 or 1 to 3). One type or two or more types of compounds.

  Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide as titanium halides, and methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride as alkoxy titanium halides. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dibutoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tributoxy titanium chloride, and the like. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  The electron donating compound (f) (hereinafter sometimes simply referred to as “component (f)”) used in the preparation of the solid catalyst component (A) in the present invention is an organic other than an alcohol containing an oxygen atom or a nitrogen atom. Examples of the compound include phenols, ethers, esters, ketones, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si—O— bond.

  Specifically, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1, Ethers such as 3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, Monocarboxylic acid esters such as octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, diiso Diethyl propylmalonate, dipropyl diisopropyl malonate, diisopropyl diisopropyl malonate, dibutyl diisopropyl malonate, diisobutyl diisopropyl malonate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, phthalic acid Dimethyl, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, ethyl methyl phthalate, methyl phthalate (iso-propyl) ), Ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate, di-iso-pentyl phthalate, di-neo phthalate Pentyl, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate Di-iso-decyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, N-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n- Decyl), n-pentylundecyl phthalate, iso-pentyl phthalate (iso-hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl), n-heptyl phthalate (2 -Ethylhexyl), n-heptyl phthalate (iso-nonyl), dicarboxylic acid esters such as n-heptyl phthalate (neo-decyl), 2-ethylhexyl phthalate (iso-nonyl), acetone, methyl ethyl ketone, methyl butyl ketone , Ketones such as acetophenone, benzophenone, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic acid amide, stearic acid amide, etc. Imides such as amides, acetonitrile, benzonitrile, tolunitrile, isocyanates such as methyl isocyanate, ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, Mention may be made of organosilicon compounds containing Si—O— bonds such as polysiloxane.

  Below, the example of the preparation method of the solid catalyst component (A) of this invention is described. The solid catalyst component (A) is a suspension formed by contacting the alkoxy group-containing magnesium compound (a), the surfactant component (b), and the alcohol (c) in the presence of an inert organic solvent (d). Then, it is obtained by contacting with a tetravalent titanium halogen compound (e) and an electron donating compound (f) other than an alcohol, and further contacting with a tetravalent titanium halogen compound (e). The compound (a), the surfactant component (b) and the alcohol (c) are contacted in the presence of an inert organic solvent (d) to form a suspension, and then 1 mol per 1 mol of the alkoxy group-containing magnesium compound. Less than the tetravalent titanium halogen compound (e) and the electron donating compound (f) other than alcohol, and further contact the tetravalent titanium halogen compound (e). Those obtained by Rukoto are preferred. The tetravalent titanium halogen compound (e) to be contacted first and the tetravalent titanium halogen compound (e) to be subsequently contacted may be the same compound or different compounds.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The amount ratio of the component (b) used is 0.001 to 2 g, preferably 0.005 to 0.5 g, with respect to 1 g of the component (a), and is 0.005 with respect to 1 ml of the component (d). The amount is 0001 to 0.01 g, preferably 0.005 to 0.5 g. The amount of component (c) used is 0.001 to 5 ml, preferably 0.005 to 1.0 ml, with respect to 1 g of component (a), and 0.0001 with respect to 1 ml of component (d). -0.05 ml, preferably 0.005-1.0 ml. About the usage-amount of a component (d), although it can set arbitrarily in the range in which a solid component can form a suspension state, 1 ml-50 ml with respect to 1 g of a normal component (a), Preferably it is 2 ml-20 ml. Used in a range. The use amount ratio of the component (e) that is first brought into contact with the suspension constituted by the components (a) to (d) must be less than 1 mol per 1 mol of the component (a), preferably 0. .01 to less than 1 mol, more preferably 0.05 to 0.5 mol. When the amount of component (e) used first in contact with the suspension is 1 mole or more per mole of component (a), the ultrafine powder having a particle size of 45 μm or less is sufficiently reduced in the resulting polymer. I can't let you.

  The usage-amount of a component (f) is 0.01-10 mol with respect to 1 mol of components (a), Preferably it is 0.01-1 mol, More preferably, it is 0.02-0.6 mol. Next, the amount of component (e) used is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, per mol of component (a).

  The contact temperature can be arbitrarily set within a range in which a rapid reaction is not caused between the components, but is usually performed in the range of −20 ° C. to 100 ° C. Moreover, about the reaction temperature after a contact, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  In the present invention, the order in which the component (a) is brought into contact with the component (b), the component (c), and the component (d) is not particularly defined and is arbitrarily set. Further, the order in which the suspension is brought into contact with the component (e) and the component (f) is not particularly defined. Regarding the use of component (f), after contacting component (a) with less than 1 mole of component (e) and component (f) with respect to component (a) and then contacting component (e) Further, the component (f) can be repeatedly contacted. The solid material thus obtained is washed (final washing) with a hydrocarbon compound that is liquid at room temperature to obtain the solid catalyst component (A). The hydrocarbon compound used for washing is preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is liquid at room temperature. Specifically, the aromatic hydrocarbon compound may be a saturated hydrocarbon such as toluene, xylene, or ethylbenzene. Examples of the compound include hexane, heptane, cyclohexane and the like. Preferably, it is desirable to use an aromatic hydrocarbon compound for the intermediate cleaning and a saturated hydrocarbon compound for the final cleaning.

  Further, the content of titanium, magnesium and halogen atoms in the solid catalyst component (A) in the present invention is not particularly defined, but preferably titanium is 0.5 to 8.0% by weight, preferably 0.7 to 7%. 0.0 wt%, more preferably 1.0 to 6.0 wt%, magnesium 8 to 50 wt%, more preferably 10 to 40 wt%, particularly preferably 15 to 30 wt%, still more preferably 15 to 25 It is desirable that the weight percentage is 20 to 90 wt%, more preferably 30 to 85 wt%, particularly preferably 40 to 80 wt%, and still more preferably 45 to 75 wt%. When the electron donating compound is used, the total content is in the range of 0.5 to 40% by weight.

In the present invention, the average particle diameter of the solid catalyst component (A) is 1 to 300 μm, preferably 5 to 100 μm, and the specific surface area (BET method) is 0.1 to 500 m ² / g, preferably 1 to 300 m. ² / g and pore volume (BET method) are 0.01 to 0.5 ml / g, preferably 0.05 to 0.3 ml / g. Since the structure of the solid catalyst component (A) is prepared by the specific method described above, the generation of fine powder is small even though both the specific surface area and the pore volume are large. For this reason, particularly when copolymerization of propylene and ethylene or other olefins is performed, good polymer fluidity can be maintained even if the content ratio of the rubber component is increased.

  As the organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention, a compound represented by the above general formula (1) can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.

  In forming the olefin polymerization catalyst of the present invention, the external electron donating compound (C) is used together with the organoaluminum compound (B) for the purpose of improving the stereoregularity of the polyolefin. These may be the same as the electron donating compound (f) that can be used for the preparation of the above-described solid catalyst component, among which 9,9-bis (methoxymethyl) fluorene, 2-isopropyl Ethers such as 2-isopentyl-1,3-dimethoxypropane, esters such as methyl benzoate and ethyl benzoate, and organosilicon compounds are used.

  Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, Tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxysilane Di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-Dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclo Nthyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5 -Dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldie Toki Silane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, Cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Ethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane , T-butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysila , It can be exemplified tetrapropoxysilane, tetrabutoxy silane. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldi Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylsilane Lopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used. It can be used in combination of more than one species.

  Next, the olefin polymerization catalyst of the present invention is formed by the above-described solid catalyst component (A) for olefin polymerization, the organoaluminum compound (B), and the external electron donating compound (C), and in the presence of the catalyst. The olefins are polymerized or copolymerized. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The external electron donating compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, per mol of the component (B).

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Furthermore, in the present invention, when the olefin is polymerized using the catalyst formed from the solid catalyst component (A) for olefin polymerization, the organoaluminum compound (B), and the external electron donating compound (C) (also referred to as main polymerization). .), In order to further improve the catalytic activity and the particle properties of the polymer to be produced, it is possible to carry out preliminary polymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the components and monomers is arbitrary, but preferably, the organoaluminum compound (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, Next, after contacting the external electron donating compound (C) and further contacting the solid catalyst component (A) for olefin polymerization, contact olefin such as propylene and / or one or other two or more olefins. The method of making it desirable is preferable.

  When olefins are polymerized in the presence of the olefin polymerization catalyst formed according to the present invention, there is almost no ultrafine powder having a particle size of 45 μm or less in the resulting polymer compared to the case of using a conventional catalyst. Can be obtained in high yield. In addition, when copolymerization of propylene and ethylene or other olefins is performed, good polymer fluidity can be maintained even if the content ratio of the rubber component is increased. In continuous operation of the process, problems such as clogging of the filter in the polymer recovery process and gas recycling system, accumulation in the system vessel and piping, etc. are remarkably reduced, and a reduction in equipment maintenance load can be expected. In addition, improvement in polymer quality level can be expected by ensuring long-term stability of operation.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

(Preparation of solid catalyst component)
20 g of spherical diethoxymagnesium powder with an average particle size of 35 μm, 140 ml of normal temperature toluene, 0.4 ml of ethanol, and 0.3 g of sorbitan monolaurate were sequentially placed in a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer. The mixture was charged and stirred, and the temperature was raised to 40 ° C. to obtain a suspension. Next, this suspension was cooled to -5 ° C, 2.5 ml of di-n-butyl phthalate was added thereto, and then 10 ml of titanium tetrachloride was stirred while maintaining the temperature in the system at -5 ° C. Slowly added at. Thereafter, when the temperature was raised to 80 ° C. at 1 ° C./min, 3.5 ml of di-n-butyl phthalate was added, and the temperature was further raised and reacted at 110 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 3 hours. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. Table 1 shows the results of measuring the titanium content, average particle diameter, specific surface area, and pore volume of the solid catalyst component. Specific surface area and pore volume were measured by ASAP2405 manufactured by Shimadzu Corporation using the BET method.

[Propylene polymerization]
An autoclave with a stirrer with an internal volume of 2.0 liters that was completely replaced with nitrogen gas was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, 1.5 liters of hydrogen gas, and 1.2 liters of liquefied propylene. I entered. Next, 3.0 mg of the solid catalyst component was charged into a solid catalyst component charging vessel mounted on the top of the autoclave, and flushed with 0.2 liter of liquefied propylene to introduce into the autoclave, and polymerization was conducted at 70 ° C. for 1 hour. I did it. Table 3 shows the polymerization activity per gram of the solid catalyst component, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer, the average particle size of the produced polymer, the amount of fine powder of −45 μm or less, and the bulk density. In addition, the ratio (HI) of the boiling insoluble n-heptane insoluble content in the produced polymer is the percentage of the polymer insoluble in n-heptane when the produced polymer is extracted with boiling n-heptane for 6 hours. ).

(Preparation of solid catalyst component)
The solid catalyst component of Example 1 was used.

[Propylene-ethylene / propylene block copolymer]
An autoclave with a stirrer with an internal volume of 2.0 liters that was completely replaced with nitrogen gas was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, 1.5 liters of hydrogen gas, and 1.2 liters of liquefied propylene. I entered. Next, 5.0 mg of the solid catalyst component was charged into a solid catalyst component charging vessel mounted on the top of the autoclave, and flushed with 0.2 liter of liquefied propylene to introduce it into the autoclave and polymerized at 70 ° C. for 1 hour. I did it. Then, after purging propylene in the autoclave and replacing with nitrogen gas five times, while supplying ethylene gas, propylene, and hydrogen gas at an ethylene / propylene / hydrogen molar ratio of 0.7 / 1.0 / 0.03 Polymerization was carried out at 70 ° C. for 2 hours at a pressure of 1.2 MPa. Table 5 shows the polymerization activity per gram of the solid catalyst component, the content of ethylene / propylene rubber (EPR), the average particle size of the produced polymer, the amount of fine powder of −45 μm or less, the bulk density, and the polymer fluidity index.

  The content of ethylene propylene rubber component (EPR) in the propylene block copolymer was measured by the following method. To a 1 liter flask equipped with a stirrer and a condenser tube, about 2.5 g of the copolymer, 8 mg of 2,6-di-t-butyl-p-cresol, and 250 ml of p-xylene were charged, Stir until the polymer is completely dissolved. Next, the flask was cooled to 20 ° C. and left for 15 hours to precipitate a solid. This was separated into a solid and a liquid phase part by a centrifuge. Thereafter, the separated solid was taken in a beaker, 500 ml of acetone was poured in, stirred for 15 hours at room temperature, the solid was filtered and dried, and the weight was measured (this weight is designated as B). Further, the same operation was performed on the separated liquid phase portion, and a solid was precipitated and the weight was measured (this weight is C). The content (% by weight) of the ethylene propylene rubber component (EPR) in the copolymer was calculated by the formula [C (g) / [B (g) + C (g)] × 100].

  As shown in FIG. 2, the flowability of the propylene block copolymer is as follows. Funnel 1 having a damper 2 interposed at the outlet position (upper diameter: 91 mm, damper position diameter: 8 mm, inclination angle: 20 °, high up to the damper position 114 mm) is set at the top, and a device in which a container-like receiver 3 (inner diameter: 40 mm, height: 81 mm) is installed at the bottom of the damper 2 with a space of 38 mm is used. After putting 50 g of the polymer in, the damper 2 was opened, the polymer was dropped into the receiver 3, and the time for all the polymers to fall was measured. Propylene homopolymer obtained by polymerizing this operation using the same solid catalyst component as that used for the polymerization of the propylene block copolymer and the propylene block copolymer (in the production of the propylene block copolymer of Example 2, propylene (Polymer obtained by carrying out only the polymerization reaction of No. 1), the drop times were T1 and T2, respectively, and the value obtained by T2 / T1 was shown as fluidity.

(Preparation of solid catalyst component)
20 g of spherical ethoxymagnesium chloride powder with an average particle size of 35 μm, 140 ml of normal p-xylene, 0.6 ml of isopropanol, 0.3 g of sorbitan distearate in a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer Were sequentially added and stirred, and the temperature was raised to 40 ° C. to obtain a suspension. Next, this suspension was cooled to -5 ° C, and after adding 3.0 ml of di-2-ethylhexyl phthalate, 5 ml of titanium tetrachloride was stirred with the temperature inside the system kept at -5 ° C. Slowly added. Thereafter, when the temperature was raised to 80 ° C. at 1 ° C./min, 2.5 ml of diethyl phthalate was added, and the temperature was further raised and reacted at 95 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed four times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of p-xylene were newly added, the temperature was raised to 115 ° C., and the mixture was allowed to react with stirring for 2 hours. It was. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The results of analyzing this solid catalyst component in the same manner as in Example 1 are shown in Table 1.

[Propylene polymerization]
Polymerization was performed in the same manner as in Example 1 using the solid catalyst component. The results are shown in Table 3.

  Using the solid catalyst component of Example 3, propylene-ethylene / propylene block copolymerization was conducted in the same manner as in Example 2. The results are shown in Table 5.

(Preparation of solid catalyst component)
20 g of spherical diethoxymagnesium powder with an average particle size of 22 μm, 140 ml of normal temperature toluene, 0.5 ml of n-butanol, and 1.2 ml of dimethylpolysiloxane were placed in a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer. Sequentially, the mixture was stirred and heated to 40 ° C. to obtain a suspension. Next, this suspension was cooled to -5 ° C, and 2.0 ml of di-iso-decyl phthalate was added thereto, and then 10 ml of titanium tetrachloride was stirred while maintaining the temperature in the system at -5 ° C. Slowly added at. Thereafter, when the temperature was raised to 80 ° C. at 1 ° C./min, 3.5 ml of di-n-butyl phthalate was added, and the temperature was further raised and reacted at 110 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, the temperature was raised to 115 ° C., and the reaction was carried out with stirring for 3 hours. After the completion of the reaction, the solid catalyst component was obtained by washing 10 times with 100 ml of methylcyclopentane at 40 ° C. The results of analyzing this solid catalyst component in the same manner as in Example 1 are shown in Table 1.

[Propylene polymerization]
Polymerization was performed in the same manner as in Example 1 using the solid catalyst component. The results are shown in Table 3.

  Using the solid catalyst component of Example 5, propylene-ethylene / propylene block copolymerization was performed in the same manner as in Example 2. The results are shown in Table 5.

(Preparation of solid catalyst component)
20 g of spherical diethoxymagnesium powder with an average particle size of 35 μm, 140 ml of normal temperature toluene, 0.4 ml of ethanol, and 0.3 g of sorbitan monolaurate were sequentially placed in a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer. The mixture was charged and stirred, and the temperature was raised to 40 ° C. to obtain a suspension. Next, this suspension was cooled to -5 ° C, 1.5 ml of di-n-butyl phthalate was added thereto, and then 10 ml of titanium tetrachloride was stirred while maintaining the temperature in the system at -5 ° C. Slowly added at. Thereafter, when the temperature was raised to 80 ° C. at 1 ° C./min, 3.5 ml of di-n-butyl phthalate was added, and the temperature was further raised and reacted at 110 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane 1 was further added. 0.0 ml was added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 3 hours. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The results of analyzing this solid catalyst component in the same manner as in Example 1 are shown in Table 1.

[Propylene polymerization]
Polymerization was performed in the same manner as in Example 1 using the solid catalyst component. The results are shown in Table 3.

Propylene-ethylene / propylene block copolymerization was carried out in the same manner as in Example 2 except that the solid catalyst component of Example 7 was used and di-iso-propyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. The results are shown in Table 5.
Examples 9-11

  Propylene-ethylene / propylene block copolymerization was carried out in the same manner as in Example 2 except that the solid catalyst component of Example 1 was used and the polymerization time in the ethylene / propylene copolymerization stage was changed. The results are shown in Table 7. In the table, the results of Example 1 are also shown for comparison.

Comparative Example 1
[Preparation of solid catalyst component and propylene polymerization]
A solid catalyst component was prepared and propylene was polymerized in the same manner as in Example 1 except that sorbitan monolaurate was not used. The analysis results of the solid catalyst component are shown in Table 2, and the propylene polymerization results are shown in Table 4.

Comparative Example 2
[Preparation of solid catalyst component and propylene-ethylene / propylene block copolymer]
Using the solid catalyst component of Comparative Example 1, propylene-ethylene / propylene block copolymerization was carried out in the same manner as in Example 2. The results are shown in Table 6.

Comparative Example 3
[Preparation of solid catalyst component and propylene polymerization]
A solid catalyst component was prepared and propylene polymerization was performed in the same manner as in Example 1 except that ethanol was not used. The analysis results of the solid catalyst component are shown in Table 2, and the propylene polymerization results are shown in Table 4.

Comparative Example 4
[Preparation of solid catalyst component and propylene-ethylene / propylene block copolymer]
Using the solid catalyst component of Comparative Example 3, propylene-ethylene / propylene block copolymerization was conducted in the same manner as in Example 2. The results are shown in Table 6.

Example 12
[Preparation of solid catalyst component and propylene polymerization]
A solid catalyst component was prepared and propylene polymerization was conducted in the same manner as in Example 1 except that 30 ml was used instead of 10 ml of titanium tetrachloride used initially for contact with diethoxymagnesium. The analysis results of the solid catalyst component are shown in Table 1, and the propylene polymerization results are shown in Table 3.

Example 13
[Preparation of solid catalyst component and propylene-ethylene / propylene block copolymer]
Using the solid catalyst component of Example 12, propylene-ethylene / propylene block copolymerization was conducted in the same manner as in Example 2. The results are shown in Table 5.

Comparative Example 5
[Preparation of solid catalyst component and propylene polymerization]
20 g of anhydrous magnesium chloride with a specific surface area of 40 m ² / g was charged into a 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas, and 300 ml of titanium tetrachloride was added and the temperature was raised to 110 ° C. over 3 hours. did. After raising the temperature, 8.4 ml of diisobutyl phthalate was added, and the mixture was further reacted at 110 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours with stirring. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The results of analyzing this solid catalyst component in the same manner as in Example 1 are shown in Table 2. Further, the same propylene polymerization as in Example 1 was performed using the solid catalyst component of Comparative Example 5. The results are shown in Table 4.

Comparative Example 6
[Preparation of solid catalyst component and propylene-ethylene / propylene block copolymer]
Propylene-ethylene / propylene block copolymerization was carried out in the same manner as in Example 2 using the solid catalyst component of Comparative Example 5. The results are shown in Table 6.

It is a flowchart figure which shows the process of preparing the polymerization catalyst of this invention. It is the schematic of the apparatus used for the fluidity | liquidity evaluation of a polymer.

Claims (6)

Di alkoxy Shima magnesium compound (a), the surfactant component (b) and the alcohol (c) to form a suspension is contacted in the presence of an inert organic solvent (d), then the suspension and tetravalent A solid catalyst component for olefin polymerization obtained by contacting with a titanium halogen compound (e) and an electron donating compound (f) other than alcohol and then further contacting with a tetravalent titanium halogen compound (e) Manufacturing method . The method for producing a solid catalyst component for olefin polymerization according to claim 1 , wherein the surfactant component (b) is a nonionic surfactant. The method for producing a solid catalyst component for olefin polymerization according to claim 1 or 2 , wherein the alcohol (c) is an aliphatic alcohol. The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 3 , wherein the tetravalent titanium halogen compound (e) is titanium tetrachloride. The amount of the first tetravalent titanium halide is brought into contact (e) it is, in any one of claims 1 to 4, characterized in that less than 1 mol above di alkoxy island magnesium compound 1 mole The manufacturing method of the solid catalyst component for olefin polymerization of description. The amount of the tetravalent titanium halogen compound (e) to be contacted first is 0.01 mol or more and less than 1 mol with respect to 1 mol of the dialkoxymagnesium compound. The manufacturing method of the solid catalyst component for olefin polymerization of any one.

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