KR19980086391A - Olefin polymerization and copolymerization method - Google Patents

Abstract

The present invention provides a process for polymerizing or copolymerizing olefins in the presence of a catalyst comprising (a) a solid complex titanium catalyst consisting of magnesium, titanium, halogen and an internal electron donor, and (b) an organometallic compound and (c) an external electron donor. In the solid complex titanium catalyst of (a), (i) the magnesium compound is prepared as a magnesium-containing solution in the presence of a mixed solvent of cyclic ether and alcohol, and ii) the magnesium-containing solution is reacted with a transition metal compound to After the particles are precipitated, iii) a catalyst is prepared by reacting the precipitated solid particles with a transition metal compound and an internal electron donor, and vinyltriethoxysilane and dicyclopentyldimethoxysilane as the external electron donor of (c). The present invention relates to a method for polymerizing or copolymerizing olefins, which is used.

According to the method of the present invention, a polymer having a high apparent density and a wide molecular weight distribution can be produced.

Description

Olefin polymerization and copolymerization method

The present invention relates to a process for preparing olefin polymers having a broad molecular weight distribution.

In the case of preparing an olefin polymer using a titanium catalyst supported on magnesium, the molecular weight distribution of the prepared polymer is generally narrower than that of an unsupported catalyst.

Thus, such polymers are excellent in mechanical properties, while inferior in processability. Many attempts have been made to make up for such drawbacks, and the representative method is to prepare polymers having a wide molecular weight distribution by preparing olefin polymers having different molecular weight distributions in several polymerization reactors. However, this method is disadvantageous in that it takes a long time and has difficulty in maintaining the quality of the polymer. Therefore, development of a method for producing an olefin polymer having a wide molecular weight distribution in one polymerization reactor is desired.

In general, a magnesium-supported catalyst system for olefin polymerization is divided into three types: (a) a solid complex titanium catalyst containing magnesium, (b) an organometallic compound, and (c) an external electron donor.

Attempts to change the catalyst system in order to broaden the molecular weight distribution can be considered by dividing each component. First, a catalyst capable of producing a polymer having a broad molecular weight distribution can be prepared by changing the main catalyst or the carrier of the catalyst in the preparation of the solid complex titanium catalyst. For example, a catalyst prepared by using a mixture of MgCl ₂ and MnCl ₂ to the catalyst Joshi based on MgCl ₂ in the raw material for the carrier, or (J. Mol Cat A:.. Chemical 104, 205 (1996)), or There is a method of mixing a hafnium and titanium known to produce a polymer having a higher molecular weight than titanium to form a solid complex catalyst using the main catalyst (Japanese Patent Publication No. 85-110104). In the case of using a mixed main catalyst, the range is expanded, and a catalyst having a magnesium compound supported by TiCl ₄ and Cp ₂ TiCl ₂ (Cp = cyclopentadienyl) as a main catalyst also has a wider molecular weight distribution than TiCl ₄ alone. It is reported to produce a polymer having a polymer (Japanese Patent Application Laid-open No. Hei 4-222,804).

As the organometallic compound, which is one of the components of the supported catalyst system, aluminum compounds are commonly used, and a method of mixing an aluminum compound with another compound and using it as a catalyst system has also been reported as a method of broadening the molecular weight distribution of a polymer. As the other compounds, triethylborane (US Pat. No. 5,330,947), diethyl zinc, and the like are shown to have good effect.

Another attempt is to change the external electron donor that is often used in the α-olefin polymerization. In this case, a method of producing an olefin polymer having a wide molecular weight distribution by using a silane compound having a special structure as an external electron donor (JP-A-5-331,234) or by mixing two or more specific silane compounds (Korea) Patent Publication No. 93-665) is also reported.

However, the method of using the specific catalyst and two or more specific silane compounds as an external electron donor in the case described above has a disadvantage in that the activity of the catalyst is very low. Therefore, in this case, a solid complex titanium catalyst having a very high catalytic activity even when used with two or more specific silane compounds is required.

Many olefin polymerization catalysts and catalyst preparation processes based on titanium and based on titanium have been reported. Many methods using a magnesium solution to obtain such an olefin polymerization catalyst are known. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol, an amine, a cyclic ether, or a carboxy oxide in the presence of a hydrocarbon solvent. US Pat. Nos. 4,330,649, 5,106,807, and Japanese Unexamined Patent Publication Reference is made to SO 58-83006. In addition, U.S. Patent Nos. 4,315,874, 4,399,054, 4,071,674, and 4,439,540 also report methods for preparing magnesium solutions. Tetrahydrofuran, a cyclic ether, is a complex with a magnesium chloride compound (e.g., U.S. Pat.Nos. 4,482,687, 4,277,372, 3,642,746, 3,642,772, and European Patent 131,832). Patents 4,158,642, 4,148,756, and solvents (US Pat. Nos. 4,477,639, 4,518,706) and the like. The use of silicone compounds as a component of catalysts in obtaining solid catalyst components from such magnesium solutions is described in US Pat. Nos. 4,071,672, 4,085,276, 4,220,554, 4,315,835, and the like.

U.S. Pat. Nos. 4,946,816, 4,866,022, 4,988,656, 5,013,702, 5,124,297 are related to each other, and in these patents the process for preparing a catalyst first comprises (i) magnesium carboxylate or magnesium from magnesium alkylcarbonate. (Ii) precipitating the magnesium solution in the presence of a transition metal halide and organosilane additive, and (i) reprecipitating the solid component precipitated again using a mixed solution containing tetrahydrofuran, I) Reprecipitated particles are reacted with a transition metal component and an electron donor compound to prepare a catalyst having a uniform catalyst particle. However, this method has a disadvantage in that there are many catalyst preparation steps and the manufacturing process is complicated.

Japanese Laid-Open Patent Publication No. 63-54004 and U.S. Patent No. 4,330,649 are prepared in a solution state by reacting a magnesium compound with one or more of alcohol, organic carboxylic acid, aldehyde, and amine in the presence of an organic hydrocarbon solvent in preparing a magnesium solution. The final catalyst component is described by reacting this solution with a titanium compound and an electron donor.

U.S. Pat.Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186, 5,130,284 are known to provide excellent olefin polymerization catalysts by reacting electron donors such as magnesium alkoxides, dialkyl phthalates, phthaloyl chlorides, and titanium chloride compounds. It is reported to manufacture.

U.S. Patent Nos. 4,298,718, 4,176,289, 4,544,717, and 4,636,486 introduce a process for preparing a polymerization catalyst by reacting an active magnesium chloride with a titanium compound.

As discussed above, in order to produce a polymer having a broad molecular weight distribution, proper matching of the entire catalyst system should be made. The present invention is to propose a method for preparing an olefin polymer having a very high polymerization activity and a wide molecular weight distribution using a combination of a catalyst having a very high polymerization activity and a specific organosilicon compound used in the past as an external electron donor. do. The method for producing the solid complex titanium catalyst used herein is not known from existing patents or literature.

It is an object of the present invention to provide a process for producing olefin polymers and copolymers having a much higher catalytic activity and a broader molecular weight distribution than the existing proposed methods.

Another object of the present invention is to provide a method of producing a polymer having a high apparent density and a wide molecular weight distribution of a polymer produced by controlling the shape of the catalyst particles.

The above object of the present invention is to polymerize an olefin in the presence of a catalyst comprising (a) a solid complex titanium catalyst consisting of magnesium, titanium, halogen and an internal electron donor, and (b) an organometallic compound and (c) an external electron donor. Or a method of copolymerization, wherein the magnesium compound (i) is prepared as a solid complex titanium catalyst of (a) in the presence of a mixed solvent of cyclic ether and alcohol, and ii) the magnesium-containing solution is mixed with a transition metal compound Reacting to precipitate solid particles, i) using a catalyst prepared by reacting the precipitated solid particles with a transition metal compound and an internal electron donor, and in particular, as the external electron donor of (c), vinyltriethoxysilane And dicyclopentyldimethoxysilane.

Hereinafter, the present invention will be described in detail.

The solid complex titanium catalyst for olefin polymerization and copolymerization having excellent catalytic activity, stereoregularity and catalyst particle distribution used in the present invention is (i) preparing a solution containing magnesium from a magnesium compound having no reducibility, and (ii) The magnesium-containing solution is reacted with the transition metal compound to precipitate solid particles, and (iii) the precipitated solid particles are reacted with the transition metal compound and the internal electron donor, and then washed with a hydrocarbon solvent to control the particle shape. It is prepared by a simple and effective manufacturing process for obtaining the catalyst particles.

Solutions containing magnesium dissolve magnesium compounds using mixed solvents of cyclic ethers such as tetrahydrofuran and alcohols in the presence or absence of inert aromatic hydrocarbons such as benzene, toluene or aliphatic hydrocarbons such as hexane, heptane, decane, etc. Are prepared.

Examples of magnesium compounds having no reducing properties include magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium halides such as magnesium bromide, methyl magnesium halide, ethyl magnesium halide, propyl magnesium halide, butyl magnesium halide, isobutyl magnesium halide, and hexyl halide magnesium. Alkylmagnesium halides such as amyl magnesium halide, methoxymagnesium halides, ethoxymagnesium halides, isopropoxymagnesium halides, butoxymagnesium halides, and alkoxymagnesium halides, such as octoxymagnesium halides, phenoxymagnesium halides, and methylphenoxy Aryloxymagnesium halides, such as shimagium halides, ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, and alkoxyma, such as octoxy magnesium Neseum, phenoxy magnesium, and there may be mentioned carboxylic acid salts such as magnesium and aryloxy magnesium lauryl magnesium and stearic acid magnesium such as magnesium dimethylphenoxy example. Two or more of the magnesium compounds may be used in a mixture. Magnesium compounds are also effective when used in the form of complexes with other metals.

The compounds listed above may be represented by simple chemical formulas, but in some cases, they may not be represented by simple formulas depending on the preparation of magnesium compounds. In this case, it can be regarded as a mixture of magnesium compounds listed generally. For example, a compound obtained by reacting a magnesium compound with a polysiloxane compound, a halogen-containing silane compound, an ester, an alcohol, and the like, a compound obtained by reacting a magnesium metal with an alcohol, a phenol, or an ether in the presence of halo silane, phosphorus pentachloride, or hathaionyl salt These can also be used in the present invention. Preferred magnesium compounds are magnesium halides, in particular magnesium chloride, alkyl magnesium chloride, preferably having C ₁ to C ₁₀ alkyl groups, alkoxy magnesium chlorides, preferably having C ₁ to C ₁₀ alkoxy, and aryloxy magnesium chloride And preferably those having C ₆ to C ₂₀ aryloxy. The magnesium solution used in the present invention can be prepared as a solution using the mixed solvent of alcohol and cyclic ether in the above-described magnesium compound in the presence or absence of a hydrocarbon solvent.

Types of hydrocarbon solvents used here include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene, cycloaliphatic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane, benzene, toluene And aromatic hydrocarbons such as xylene, ethylbenzene, cumene, and cymene, and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.

When the magnesium compound is converted into a magnesium solution, a mixed solvent of an alcohol and a cyclic ether is used in the presence of the aforementioned hydrocarbon. By using this mixed solvent, a magnesium compound can be converted into a magnesium solution more easily when used alone. Alcohol type includes one such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl benzyl alcohol, cumyl alcohol And alcohols containing from 20 to 20 carbon atoms. Preferred alcohols are alcohols containing from 1 to 12 carbon atoms. Examples of the cyclic ethers include tetrahydrofuran, 2-methyl tetrahydrofuran and terahydrofuran, but preferred cyclic ethers are tetrahydrofuran. The desired catalyst particle shape, average size, and particle distribution depend on the type of alcohol and the cyclic ether, the total amount, the ratio of the alcohol and the cyclic ether, the type of the magnesium compound, the ratio of the magnesium and the cyclic ether, etc. The total amount of ether and alcohol is at least 0.5 mole, preferably about 1.0 mole to 20 moles, more preferably about 2.0 moles to 10 moles, per mole of magnesium compound, and the molar ratio of cyclic ether to alcohol is 1: 0.05 to 1: 0.95 is good.

In preparing the magnesium solution, the reaction of the magnesium compound with the alcohol and the cyclic ether mixed solvent is preferably carried out in a hydrocarbon medium, and the reaction temperature varies depending on the type and amount of the alcohol and the cyclic ether, but is at least about -25 ° C, preferably It is preferably carried out at -10 ° C to 200 ° C, more preferably at about 0 ° C to 150 ° C for about 15 minutes to 5 hours, preferably about 30 minutes to 3 hours.

Magnesium compound solution prepared as described above is a transition metal compound, for example, _a titanium compound of the general formula Ti (OR) _a X _{4-a in} the liquid state (R is a hydrocarbon group, X is a halogen atom, and a is 0≤a Number 4) and recrystallize into catalyst particles having a constant particle shape and size and excellent particle distribution. In the general formula, R represents an alkyl group having 1 to 10 carbon atoms. Examples of the titanium compound satisfying the general formula include titanium tetrahalide such as TiCl ₄ , TiBr ₄ , and Til ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Br ₃ , and trihalogenated alkoxytitanium such as Ti (O (iC ₄ H ₉ ) Br ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H) ₉ ) dihalogenated alkoxytitanium such as ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , and Ti (OC ₄ H ₉ ) ₄ The same tetraalkoxy titanium may be exemplified, and mixtures of the titanium compounds described above may also be used in the present invention Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium tetrachloride.

Magnesium compound solutions can also be recrystallized into solid components having good particle shape and distribution using silicon tetrahalides, silicon alkyl halides, tin tetrahalides, tin alkyl halides, tin hydrohalides and mixtures thereof or mixtures with titanium tetrahalides. You can.

The amount of the titanium compound, the silicon compound, the tin compound, or a mixture thereof used to recrystallize the magnesium compound solution is suitably 0.1 mol to 200 mol, preferably 0.1 mol to 100 mol, more preferably 0.1 mol per mol of the magnesium compound. 0.2 mol to 80 mol. When reacting a magnesium compound solution with a titanium compound, a silicon compound, a tin compound, or a mixture thereof, the shape, size, and particle distribution of the solid component recrystallized by the reaction conditions are greatly changed. Therefore, the reaction of the magnesium compound solution with the titanium compound, the silicon compound, the tin compound, or a mixture thereof is preferably performed at a sufficiently low temperature so that the solid product is not immediately produced and the reaction product is heated to gradually produce the solid component. Preferably, the contact reaction is preferably performed at -70 ° C to 70 ° C, and more preferably at -50 ° C to 50 ° C. After the contact reaction, the reaction temperature was gradually raised to fully react for 0.5 hours to 5 hours at 50 ° C to 150 ° C. In this way, a carrier having excellent particle shape, size and distribution can be obtained.

The resulting carrier is reacted with a transition metal compound such as a titanium compound in the presence of a suitable internal electron donor to prepare a catalyst. This reaction typically proceeds in two steps, for example, first reacting the carrier with a titanium compound or reacting the carrier with a titanium compound and an appropriate internal electron donor, then separating the solid component and then After reacting with the titanium compound and the internal electron donor once again, the solid component is separated and dried to obtain a catalyst. Alternatively, the carrier and the titanium compound may be reacted for a predetermined time in the presence or absence of a hydrocarbon or a halogenated hydrocarbon solvent, followed by the addition of an internal electron donor.

Beneficial transition metal compounds for the reaction with the carriers obtained in the present invention are titanium compounds, especially titanium halides, and alkoxy halide titanium having 1 to 20 carbon atoms in the alkoxy functional group. In some cases, mixtures thereof may also be used. Of these, titanium halides and alkoxy halide alkoxy titanium having 1 to 8 carbon atoms of the alkoxy functional group are preferable, and titanium tetrahalide is more preferable.

Examples of the type of internal electron donor suitable for preparing the catalyst for olefin polymerization having excellent stereoregularity include compounds including oxygen, nitrogen, sulfur, and phosphorus. Examples of such compounds are organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, phosphate esters, and mixtures thereof, as electron donors. Preferred internal electron donors used in the present invention are aromatic esters. More specifically, alkyl benzenes such as methyl benzoate, methyl bromo benzoate, ethyl benzoate, ethyl chloro benzoate, ethyl bromo benzoate, butyl benzoate, isobutyl benzoate, hexyl benzoate and cyclohexyl benzoate Esters and halobenzene acid esters are useful, and dialkyl phthalates having from 2 to 10 carbon atoms such as diisobutyl phthalate, diethyl phthalate, ethyl butyl phthalate, dibutyl phthalate are suitable. These internal electron donors may be used in mixtures of two or more, and may be used in the form of adducts or complexes of other compounds. The amount of internal electron donor used may vary and is about 0.01 to 10 moles, preferably about 0.01 to 5 moles, more preferably 0.05 to 2 moles per mole of magnesium compound.

The solid complex titanium catalyst prepared by the process presented in the present invention is advantageously used for the polymerization of olefins such as ethylene and propylene. In particular, this catalyst is a stereoregular polymerization of α-olefins having 3 or more carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, copolymerization of these mutually, copolymerization of ethylene and their copolymerization , Copolymerization of propylene with less than 20 moles of ethylene or other α-olefins, and copolymerization thereof with polyunsaturated compounds such as conjugated or unconjugated dienes.

The polymerization reaction in the presence of the catalyst of the present invention comprises (a) a solid complex titanium catalyst according to the present invention consisting of magnesium, titanium, halogen, and an internal electron donor, prepared as described above, and (b) Groups II and III of the Periodic Table. Group organometallic compounds, and (c) two or more organosilicon compounds, in particular using a catalyst system consisting of an external electron donor component consisting of vinyltriethoxysilane and dicyclopentyldimethoxysilane.

The solid complex titanium catalyst component of the present invention may be prepolymerized with 2-olefins before being used as a component in the polymerization reaction. Prepolymerization is carried out in the presence or absence of an electron donor of an organoaluminum compound, such as triethylaluminum or an organosilicon compound, with the above catalyst components at sufficiently low temperatures and α-olefin pressure conditions in the presence of a hydrocarbon solvent such as hexane. . Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. In addition, the prepolymerization may increase the activity and stereoregularity of the catalyst. The weight ratio of polymer / catalyst after prepolymerization is usually from 0.1: 1 to 20: 1.

The organometallic compound beneficial in the present invention may be represented by the general formula of MP _n , wherein M is a periodic table group II or IIIA metal component such as magnesium, calcium, zinc, boron, aluminum, gallium, and R is methyl, C1-C20 alkyl groups, such as ethyl, butyl, hexyl, octyl and decyl, n represents the valence of a metal component. As more preferred organometallic compounds, trialkylaluminum having 1 to 6 alkyl groups such as triethylaluminum and triisobutylaluminum and mixtures thereof are advantageous. In some cases, an organoaluminum compound having one or more halogen or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride may be used.

In general, in order to optimize the activity and stereoregularity of the catalyst in the polymerization of α-olefins, especially propylene, an external electron donor is frequently used. Examples of such electron donors include oxygen, silicon, nitrogen, sulfur, phosphorus atoms such as organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, silanes, amines, amine oxides, amides, diols, and phosphate esters. The organic compound containing these and a mixture thereof are mentioned. Examples of organosilicon compounds used as external electron donors include aromatic silanes such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, and phenylmethyldimethoxysilane, isobutyltrimethoxysilane and diisobutyl Dimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, 2 Aliphatic silanes such as norbornane triethoxysilane, 2-norbornane methyldimethoxysilane and vinyl triethoxysilane, and mixtures thereof. In the present invention, the vinyltriethoxysilane and dicyclopentyldimethoxysilane in the organosilicon compound are used together as the external electron donor. Thus, the vinyltriethoxysilane and the dicyclopentyldimethoxysilane are used as the external electron donor. By using it, the molecular weight distribution of the produced polymer could be widened more effectively than when combining other silane compounds.

The polymerization reaction can be carried out by gas phase or bulk polymerization in the absence of an organic solvent or by liquid phase slurry polymerization in the presence of an organic solvent. These polymerization methods are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons. Preferred concentrations of the solid complex titanium catalyst (a) in the case of liquid phase slurry polymerization are about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, of titanium atoms of the catalyst per liter of solvent. Solvents include alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethyl Alkylaromatics such as benzene, halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, and mixtures thereof are advantageous. In the case of gas phase polymerization, the amount of the solid complex titanium catalyst (a) is about 0.001 mmol to 5 mmol, preferably about 0.001 mmol to 1.0 mmol, more preferably about 0.01 mmol, to 0.5 to 1 titanium of the catalyst per 1 liter of the polymerization zone. It is good to use millimoles. The preferred concentration of the organometallic compound (b) is about 1 to 2000 moles per mole of titanium atoms in the catalyst (a), calculated as aluminum atoms, more preferably about 5 to 500 moles, more preferably organosilicon compound (c) The preferred concentration of is about 0.001 to 40 moles, more preferably about 0.06 to 30 moles per mole of aluminum atoms in the organometallic compound (b) calculated as silicon atoms.

In order to obtain a high polymerization rate, the polymerization reaction is carried out at a sufficiently high temperature regardless of the polymerization process. Generally, about 20 ° C to 200 ° C is suitable, and more preferably 20 ° C to 95 ° C. As for the pressure of the monomer at the time of superposition | polymerization, atmospheric pressure-100 atmospheres are suitable, More preferably, the pressure of 2 atmospheres-50 atmospheres is suitable.

In the present invention, additives may be used in some cases to control the molecular weight of the resulting polymer. An exemplary additive is hydrogen, the use of which can be determined as commonly known.

The product obtained by the polymerization method of the present invention is a solid isotactic poly α-olefin, which has a wide molecular weight distribution and a high yield of the polymer, so that the removal of catalyst residues is not required, and the stereoregularity of the polymer is also excellent. No separation of the polymer is necessary. This polymerization product also has excellent apparent density and fluidity.

Example 1

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.

The solid complex titanium catalyst component was prepared through the following three steps.

(Iii) step

Preparation of Magnesium Solution

A mixture of 15 g of MgCl ₂ and 450 ml of toluene was added to a 1.01 reactor equipped with a mechanical stirrer replaced with a nitrogen atmosphere, stirred at 400 rpm, 100 ml of tetrahydrofuran and 26.6 ml of butanol were added thereto, and the temperature was raised to 105 ° C. The reaction was carried out for the next 3 hours. The homogeneous solution obtained after the reaction was cooled to room temperature.

(Ii) step

Preparation of Solid Support

The magnesium solution was transferred to a 1.61 reactor in which the temperature of the reactor was maintained at 15 to 27 ° C. After stirring was maintained at 350rpm, 20ml of TlCl ₄ was added thereto, and the temperature of the reactor was raised to 90 ° C. Solid carriers were produced during this process. After the reaction was conducted at 90 ° C. for 1 hour, stirring was stopped and the resulting solid component was allowed to settle. After removing the supernatant, the solid component was washed twice with 75 ml of toluene.

(Iii) step

Titanium (IV) Compound Treatment

92 ml of toluene and 87 ml of TiCl ₄ were added to the solid component, and the temperature of the reactor was adjusted to 70 ° C. 1.7 ml of diisophthalate was injected at this temperature, and then the temperature of the reactor was raised to 100 ° C. and then heated for 1 hour. After stirring was stopped, the solid component was allowed to settle, the supernatant was separated, 92 mL of toluene and 87 mL of TiCl ₄ were treated, and 1.0 mL of diisophthalate was added at 70 ° C. The temperature of the reactor was raised to 105 ° C. and stirred for 1 hour. After the stirring was stopped, the supernatant was separated, 92 ml of toluene was injected, and the temperature of the reactor was lowered to 70 ° C. and stirred for 30 minutes. After the reaction was stopped, the supernatant was separated and 87 ml of TiCl ₄ was injected, followed by stirring at 70 to 30 minutes. The catalyst thus prepared was washed five times with 75 ml of purified hexane. The catalyst was stored after drying in a nitrogen atmosphere.

[polymerization]

After the high-pressure reactor with a capacity of 2 liters was dried in an oven and assembled in a hot state, a glass vial containing 38 mg of catalyst was mounted in the reactor, and nitrogen and vacuum were alternately added three times to make the reactor into a nitrogen atmosphere. After 1000 ml of n-hexane was injected into the reactor, 10 mmol of triethylaluminum, 0.75 mmol of vinyltriethoxysilane and 0.25 mmol of dicyclopentyldimethoxysilane were added as an external electron donor. Propylene pressure of 20 psi was added and the catalyst vial was broken by a stirrer and polymerization was performed at room temperature for 5 minutes while stirring at 630 rpm. After adding 100 ml of hydrogen, the temperature of the reactor was increased to 70 ° C., the propylene pressure was adjusted to 100 psi, and polymerization was performed for one hour. After completion of the polymerization, the temperature of the reactor was lowered to room temperature, and excess ethanol solution was added to the polymerization contents. The resulting polymer was collected separately and dried in a vacuum oven at 50 ° C. for at least 6 hours to obtain a polypropylene of white powder.

Polymerization activity (kg polypropylene / g catalyst) was calculated as the ratio of the weight of the resulting polymer (g) to weight (g) of the catalyst used, and the stereoregularity (%) of the polymer was n-heptane boiling for 3 to 6 hours. It was calculated as the weight (g) ratio of the polymer that was not extracted.

The above polymerization results are shown in Table 1 together with the apparent density (g / ml), melt index (g / 10 min) and molecular weight distribution (Mw / Mn) by GPC of the polymer.

Example 2

The polymerization was carried out in the same manner as in Example 1, using 0.5 mmol of vinyltriethoxysilane and 0.5 mmol of dicyclopentyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1. It was.

Example 3

The polymerization was carried out in the same manner as in Example 1, using 0.25 mmol of vinyltriethoxysilane and 0.75 mmol of dicyclopentyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1. It was.

Example 4

The polymerization was carried out in the same manner as in Example 1, using 0.5 mmol of vinyltriethoxysilane, 0.5 mmol of dicyclopentyldimethoxysilane, and 200 ml of hydrogen as a catalyst prepared in Example 1 and an external electron donor. Is shown in Table 1.

Example 5

The polymerization was carried out in the same manner as in Example 1, using 0.5 mmol of vinyltriethoxysilane, 0.5 mmol of dicyclopentyldimethoxysilane, and 400 ml of hydrogen as a catalyst prepared in Example 1 and an external electron donor. Is shown in Table 1.

Example 6

The polymerization was carried out in the same manner as in Example 1, using 0.25 mmol of vinyltriethoxysilane and 0.25 mmol of dicyclopentyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1. It was.

Comparative Example 1

The polymerization was carried out in the same manner as in Example 1, using 1.0 mmol of vinyltriethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1.

Comparative Example 2

The polymerization was carried out in the same manner as in Example 1 using 1.0 mmol of dicyclopentyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1.

Comparative Example 3

The polymerization was carried out in the same manner as in Example 1, using 1.0 mmol of cyclohexylmethyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1.

[Comparative Example 4]

The polymerization was carried out in the same manner as in Example 1 using 0.5 mmol of vinyltriethoxysilane and 0.5 mmol of cyclohexylmethyldimethoxysilane as the catalyst prepared in Example 1 and the external electron donor, and the results are shown in Table 1. .

[Comparative Example 5]

The polymerization was carried out in the same manner as in Example 1, using 0.5 mmol of vinyltriethoxysilane and 0.5 mmol of diphenyldimethoxysilane as the prepared catalyst and the external electron donor prepared in Example 1, and the results are shown in Table 1. It was.

VTS: Vinyltriethoxysilane

DCDS: Dicyclopentyldimethoxysilane

CMDS: Cyclohexylmethyldimethoxysilane

DPDMS: Diphenyldimethoxysilane

Claims (4)

A method of polymerizing or copolymerizing olefins in the presence of a catalyst comprising (a) a solid complex titanium catalyst consisting of magnesium, titanium, halogen and an internal electron donor, and (b) an organometallic compound and (c) an external electron donor. The solid complex titanium catalyst of (a) iii) preparing a magnesium compound as a magnesium-containing solution in the presence of a mixed solvent of cyclic ether and alcohol, and ii) reacting the magnesium-containing solution with a transition metal compound to precipitate solid particles. And (iii) a catalyst prepared by reacting the precipitated solid particles with a transition metal compound and an internal electron donor, wherein vinyltriethoxysilane and dicyclopentyldimethoxysilane are used together as the external electron donor of (c). Polymerization or copolymerization method of olefins, characterized in that The method of claim 1, wherein the mixed solvent of cyclic ether and alcohol is used in 0.5 g or more per mol of the magnesium compound, and the molar ratio of cyclic ether and alcohol is 1: 0.05 to 1: 0.95. Copolymerization method. The method of claim 1, wherein the transition metal compound of ii) is titanium tetrachloride or silicon tetrachloride, and the transition metal compound of ii) is titanium tetrachloride. The method of polymerization or copolymerization of olefins according to claim 1, wherein an aromatic ester is used as the internal electron donor in i).