KR100430848B1 - Improved Olefin Polymerization and Copolymerization Catalysts - Google Patents

Abstract

The present invention provides a magnesium compound solution by dissolving a magnesium compound and a group of Group IlIA in a periodic solvent in a mixed solvent of a cyclic ether, at least one alcohol, a phosphorus compound, and an organosilane, and 2) a magnesium compound solution is a transition metal compound or silicon. The present invention relates to a solid complex titanium catalyst for α-olefin polymerization and copolymerization obtained by reacting a compound or a tin compound or a mixture thereof to precipitate solid particles, and then reacting the precipitated solid particles with a titanium compound and an electron donor.

The catalyst of the present invention has a large average particle size, a narrow particle distribution, high catalytic activity, and excellent stereoregularity of the polymer polymerized using the catalyst.

Description

Improved Catalysts for Olefin Polymerization and Copolymerization

The present invention relates to a titanium solid complex catalyst supported on a support comprising a catalyst component for α-olefin polymerization and copolymerization, more particularly magnesium, which further improves catalytic activity and stereoregularity.

Until now, many catalysts for olefin polymerization and copolymerization and polymerization have been reported, but in order to improve the physical properties of the produced polymers or to produce polymers requiring special physical properties, further development of new catalysts is required.

Catalysts for the polymerization of olefins containing magnesium are known to give high catalytic activity and stereoregularity and are suitable for gas phase polymerization. In addition to catalytic activity and stereoregularity, catalysts for gas phase polymerization are important in terms of particle shape, size and particle distribution. In particular, small particle catalysts may cause problems during catalyst transfer, and very large particles may form polymers such as agglomerates or skeins during polymerization, and thus it is necessary to prepare catalysts having a narrow particle distribution. For example, in order to produce an impact copolymer of ethylene and propylene having a high ethylene content of about 1000 microns in average polymer size, a catalyst for copolymerization having an average particle size of about 30 to 55 microns is required. In addition, the catalyst should be excellent in mechanical properties against wear in the polymerization process and the apparent density should be good enough. Therefore, in the polymerization catalyst development, the development of a catalyst having a simple but controlled particle size of the catalyst is important above all.

Catalytic activity and stereoregularity in alpha olefin polymerization have been a lot of previous research as a very important basic element of the catalyst. As a result, most of today's commercial production of polyolefins, especially polypropylene, eliminates the need to remove catalyst residues and atactic components. Recently, however, many uses of polypropylene having higher physical properties, particularly rigidity, have been developed. For this purpose, development of a catalyst having higher stereoregularity is required.

Many olefin polymerization catalysts and catalyst preparation processes based on titanium and based on titanium have been reported. In particular, a method of using a magnesium solution to obtain the olefin polymerization catalyst with the above-mentioned particles is well known. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol amine, a cyclic ether, or a carboxy oxide in the presence of a hydrocarbon solvent. In the case of using alcohol, U.S. Patent No. 4,330,649,5,106,807, Reference is made to 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 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). And there is a disadvantage that the stereoregularity must be complemented.

As described above, there is a need for the development of a new olefin polymerization catalyst which is simple for the gas phase polymerization, while having a simple manufacturing process, high polymerization activity, stereoregularity, large average particle size, and small particle size distribution.

It is an object of the present invention to provide a novel catalyst solid component for olefin polymerization and copolymerization, which is prepared by a simple manufacturing process, further improves catalytic activity and stereoregularity of the prepared polymer, and has a large catalyst average particle size and a narrow particle distribution. It is.

It is also an object of the present invention to provide a process for producing a catalyst solid component for olefin polymerization and copolymerization which further increases the activity and stereoregularity of the catalyst and has a large catalyst average particle size and a narrow particle distribution.

Other objects and benefits of the present invention will become more apparent with reference to the following description and claims of the present invention.

The catalyst for olefin polymerization and copolymerization having high catalytic activity and stereoregularity and high catalyst average particle size and narrow particle distribution, which is to be provided in the present invention, comprises: (i) from a mixture of a magnesium compound having no reducibility and a Group IIIA periodic table; Preparing a solution comprising magnesium, and (ii) reacting the magnesium solution with a compound comprising halogen, such as a transition metal compound or silicon chloride, or mixtures thereof, to precipitate solid particles, and (iii) The particles are reacted with a titanium compound and an electron donor and then washed with a hydrocarbon solvent to produce a simple and effective manufacturing process for obtaining solid catalyst particles with controlled particle morphology.

In the present invention, a solution containing magnesium is obtained by dissolving a magnesium compound having no reducibility and a Group IIIA compound of the periodic table in the presence or absence of a hydrocarbon solvent in a mixed solvent of a cyclic ether, at least one alcohol, a phosphorus compound, and an organosilane.

Examples of non-reducible magnesium compounds used in the preparation of magnesium compounds include magnesium halides such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; Alkylmagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, amylmagnesium halide and the like; Alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide, and octoxymagnesium halide; Aryloxymagnesium halides such as phenoxymagnesium halide and methylphenoxymagnesium halide; Alkoxy magnesium, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, and octoxy magnesium; Aryloxymagnesium, such as phenoxy magnesium and dimethylphenoxy magnesium; Magnesium carboxylate salts, such as magnesium laurate and magnesium stearate, are exemplified. 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 method of preparing 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, etc .: 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 thionyl chloride 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 groups, and aryloxymagnesium chloride It is preferable to have a C ₆ to C ₂₀ aryloxy group.

And periodic table IIIA compounds used together with magnesium compounds in the preparation of magnesium compound solutions include boron halides such as boron fluoride, boron chloride, and boron bromide; And aluminum halides such as aluminum fluoride, aluminum bromide, aluminum chloride, aluminum iodide, but aluminum halides are preferred, particularly aluminum chloride. The molar ratio of the magnesium compound to the Group IIIA compound of the periodic table is preferably 1: 0.25 or less, and more preferably 1: 0.15 or less.

Examples of the hydrocarbon solvent that can be used in the preparation of the magnesium solution include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; Alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane; Halogenated hydrocarbons such as benzene, toluene, xylene, ethylbenzene, trichloroethylene, carbon tetrachloride, and chlorobenzene are exemplified.

When converting a magnesium compound into a magnesium solution, a mixed solvent of cyclic ethers, one or more alcohols, phosphorus compounds and organosilanes is used in the presence or absence of hydrocarbons as described above.

Examples of the cyclic ether which may be used in the present invention include cyclic ethers having 2 to 15 carbon atoms, in particular tetrahydrofuran, 2-methyl tetrahydrofuran, and tetrahydropyran, but the most preferred cyclic ether is tetrahydrofuran. Examples of the alcohol include 1 to 1, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol and cumyl alcohol. Alcohol containing 20 carbon atoms is mentioned, Preferred alcohol is an alcohol containing 1-12 carbon atoms. The desired catalyst average particle size and particle distribution vary depending on the ratio of alcohol and cyclic ether, but in order to obtain the catalyst particle size claimed in the present invention, the total amount of alcohol and cyclic ether in preparing a magnesium solution is at least 0.5 mol per mol of the magnesium compound. , Preferably about 1.0 to 20 moles, more preferably about 2.0 to 10 moles. If it is less than 0.5 mol, it is difficult to manufacture a magnesium solution, and if it exceeds 20 mol, the catalyst particle size becomes small. And the molar ratio of the cyclic ether and the at least one alcohol is from 1: 0.05 to 1: 0.95. If it is less than 1: 0.05, it is difficult to manufacture a spherical catalyst, and if it is more than 1: 0.95, there is a problem that the catalytic activity is poor.

One or more alcohols used in the present invention may be used when some or all of them dissolve the magnesium compound. Alternatively, one or more alcohols may be added to some or all of the magnesium solution in which the magnesium compound is dissolved. However, when the magnesium solution is reacted with the transition metal compound in step (ii) to precipitate the solid particles, the total content of the at least one alcohol described above must be maintained.

Specifically, it is preferable that the at least one alcohol consists of an alcohol having 1 to 3 carbon atoms having a relatively low molecular weight and an alcohol having 4 to 20 carbon atoms having a relatively high molecular weight. The molar ratio of the total alcohol and the relatively low molecular weight alcohol is 1: 0.01 to 1: 0.40, preferably 1: 0.01 to 1: 0.25. Preferred relatively low molecular weight alcohols are methanol or ethanol, while relatively high molecular weight alcohols are butanol or isoamyl, alcohols or 2-ethyl hexanol.

The phosphorus compound used for this invention is represented by the following general formula.

Here, X is a halogen atom, R ¹ , R ² , R ³ , R ⁴ is a hydrocarbon having 1 to 20 carbon atoms, alkyl, alkenyl, aryl and the like, each may be the same or different. And a + b + c = 3, 0≤a≤3, 0≤b≤3, 0≤c≤3, d + e + f = 3, 0≤d≤3, 0≤e≤3, 0≤ f≤3. Examples thereof include phosphorus trichloride, phosphorus tribromide, diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite, diphenylbromophosphite, methyldichlorophosphite, phenylchlorophosphite, trimethylphosphite, tri Ethyl phosphite, trinormal butyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, oxychloride, triethyl phosphate, tri- normal butyl phosphate, triphenyl phosphate, etc. Other phosphorus compounds may also be used. The amount of these used is suitably 0.01 mol to 0.25 mol per mol of the magnesium compound, more preferably 0.05 mol to 0.2 mol per mol. If it is less than 0.01 mole, the polymerization activity of the catalyst is inferior, and if it is more than 0.25 mole, it is difficult to produce a spherical catalyst.

The organosilane used to prepare the magnesium solution is R _n SiR ' _4-n where R is hydrogen or alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl, aryl group or halosilyl or halosilyl alkyl group having 1 to 8 carbon atoms. R 'is OR or halogen, and n = 0-4.

Specific examples of this organosilane include trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, tetraethoxysilane, tetrabutoxysilane and the like. In the present invention, the organosilane is used as a shape control agent, which is useful for controlling the particle distribution of the catalyst by inhibiting the production of fine catalyst particles or very large catalyst particles.

The amount of organosilane used is preferably 0.01 mol to 0.25 mol per mole of magnesium compound, more preferably 0.05 mol to 0.2 mol. If it is less than 0.01 mole, the effect as a shape control agent is weak, and when it exceeds 0.25 mole, it is difficult to manufacture the catalyst of the shape desired by this invention.

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

The magnesium compound solution prepared as described above has a transition such as a general formula Ti (OR) _a X _4-a titanium compound in which R is a hydrocarbon group, X is a halogen atom, and a is a number of 0≤a≤4. It reacts with the metal compound to precipitate solid particles having a certain particle shape, a large size and a narrow particle distribution. In the general formula, R represents an alkyl group having 1 to 10 carbon atoms. Types of titanium compounds satisfying the above general formula include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , Til ₄ : Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Halogenated alkoxytitanium such as Br ₃ , and Ti (O (iC ₄ H ₉ )) Br ₃ ; Dihalogenated alkoxy such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ , and Ti (OC ₂ H ₅ ) ₂ Br ₂ titanium ; Tetraalkoxytitaniums such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , and Ti (OC ₄ H ₉ ) ₄ are exemplified. Mixtures of the above titanium compounds may also be used in the present invention. Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium compounds are titanium tetrachloride.

Magnesium compound solutions can also be prepared using silicon tetrahalides, silicon alkyl halides, tin tetrahalides, tin alkyl halides, tin hydrohalides, and mixtures thereof, or mixtures thereof with titanium tetrahalide, which have a large average particle size Narrow solid components can be precipitated.

The amount of titanium compound, silicon compound, tin compound, and mixtures thereof used to precipitate the magnesium compound solution is suitably 0.1 to 200 moles per mole of the magnesium compound, preferably 0.1 to 100 moles, more preferably 0.2 Moles to 80 moles. When the magnesium compound solution and the titanium compound, the silicon compound, the tin compound, or a mixture thereof are reacted, the shape, size, and particle distribution of the solid component (carrier) precipitated by the reaction conditions are greatly changed. Therefore, it is preferable that the reaction of the magnesium compound solution with the titanium compound, the silicon compound, the tin compound or a mixture thereof is performed at a sufficiently low temperature so that the solid product is not immediately produced and the reaction product is heated to gradually generate 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. By doing in this way, the support body which is excellent in particle shape size and distribution can be obtained.

The resulting carrier is reacted with a titanium compound in the presence of a suitable electron donor to prepare a catalyst. This reaction typically proceeds in two stages: first reacting the magnesium carrier with the titanium compound or with the titanium compound and the appropriate electron donor, then separating the solid component and then converting the solid component into the titanium compound and the electron donor After reacting with again, the solid component is separated and dried to obtain a catalyst. Alternatively, the reaction may be carried out with a titanium compound in a presence or absence of a hydrocarbon or halogenated hydrocarbon solvent for a predetermined time, followed by an electron donor.

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

Examples of the electron donor suitable for preparing the catalyst for olefin polymerization having excellent stereoregularity of the present invention include compounds containing 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. Electron donors which can preferably be 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 2 to 10 carbon atoms such as diisobutyl phthalate, diethyl phthalate, ethyl butyl phthalate, dibutyl phthalate are suitable. These electron donors can be used in mixtures of two or more, and can also be used in the form of adducts or complexes of other compounds. The amount of 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 catalyst prepared by the process presented in the present invention is advantageously used for the polymerization of olefins such as ethylene, 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 (i) a solid complex titanium catalyst according to the present invention consisting of magnesium, titanium, halogen, and an internal electron donor, and (ii) Group II and III organometallics of the periodic table as promoters. Compound and (iii) a catalyst system composed of an external electron donor component consisting of an organosilicon compound.

The solid complex titanium catalyst component of the present invention may be prepolymerized with an α-olefin prior to use in the polymerization reaction. The prepolymerization is carried out in the presence or absence of the above catalyst component, an organoaluminum compound such as triethylaluminum, and an organosilicon compound electron donor under conditions of sufficiently low α-olefin pressure 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.

Organometallic compounds which are beneficial as promoters when polymerizing with the catalysts according to the invention can be represented by the general formula of MR _n , where M is a periodic table II such as magnesium, calcium, zinc, boron, aluminum, potassium A group IIIA group IIIA metal component, R represents an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl and decyl, and n represents the valence of the metal component. As more preferable organometallic compound, trialkylaluminum having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and a mixture 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. Such electron donors include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, oxygen such as aldehydes, ketones, silanes, amine amine oxides, amides, diols, phosphate esters, silicon, nitrogen, sulfur, and phosphorus atoms. Organic compounds and mixtures thereof. Particularly beneficial electron donors are organosilicon compounds, which can be represented by the general formula of SiR ₄ , where R is represented by R 'or OR' and R 'is an alkyl group having 1 to 20 carbon atoms. Examples of these include aromatic silanes such as diphenyldimethoxysilane, phenyltriethoxysilane, phenylethyldimethoxysilane and phenylmethyldimethoxysilane; Isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxy Aliphatic silanes such as silane, dicyclohexyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and mixtures thereof.

The polymerization reaction is possible 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. In the case of liquid phase slurry polymerization, the preferred concentration of the solid complex titanium catalyst (i) on the polymerization reaction system is about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, of titanium atoms of the catalyst per 1 liter of solvent. Solvents include alkyl 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 (i) is about 0.001 to 5 millimoles, preferably about 0.001 to 1.0 millimoles, more preferably about 0.01 to 0.5 millimoles of titanium atoms of the catalyst per 1 liter of the polymerization zone. good. The preferred concentration of the organometallic compound (ii) is from about 1 to 2000 moles per mole of titanium atoms in the catalyst (i), calculated in terms of aluminum atoms, more preferably from about 5 to 500 moles, more preferably from organosilicon compounds (iii) The concentration is about 0.001 to 40 moles, more preferably about 0.05 to 30 moles per mole of aluminum atoms in the organometallic compound (ii), 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 2-50 atmospheres is suitable.

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

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.

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

(i) step: preparation of magnesium compound solution

A mixture of 15 g of MgCl ₂ , 4.2 g of AlCl ₃ and 550 ml of toluene was added to a 1.0 L reactor equipped with a mechanical stirrer, which was replaced with a nitrogen atmosphere, and stirred at 400 rpm. After 1.5 ml of ethoxide and 3.0 ml of tributyl phosphate were added thereto, the temperature was raised to 105 ° C. and then reacted for 4 hours. The homogeneous solution obtained after the reaction was cooled to room temperature.

( ii) step: preparing a solid carrier

The magnesium solution was transferred to a 1.6 L reactor, where the temperature of the reactor was maintained at 13 ° C. After stirring was maintained at 350rpm, 15.5mL of TiCl 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 support was allowed to settle. After separating the supernatant, the solid carrier was washed twice with 75 ml of toluene.

(iii) Step: Preparation of Catalyst

Toluene 100ml and TiCl ₄ were added to the solid carrier, and the temperature of the reactor was raised to 110 ° C and heated for 1 hour. After the stirring was stopped, the solid support was allowed to settle, the supernatant was separated, 100ml of toluene and 100ml of TiCl ₄ were added thereto, and 2.9ml of diisophthalate was injected at 70 ° C. The temperature of the reactor was raised to 120 ° C. and then stirred for 1 hour. After the stirring was stopped, the supernatant was separated, 100 ml of toluene was injected, and the temperature of the reactor was lowered to 70 ° C. and stirred for 30 minutes. After the reaction, the stirring was stopped, the supernatant was separated, and 100 ml of TiCl ₄ was injected, followed by stirring at 70 ° C. for 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.

The particle size distribution of the catalyst was measured using a laser particle analyzer (Mastersizer X, Malvern Instruments) and had a distribution of d ₁₀ = 26.2 μm, d ₅₀ = 48.1 μm, and d ₉₀ = 70.7 μm. Where d ₁₀ , d ₅₀ and d ₉₀ mean that 10, 50 and 90 percent of the particles have particles smaller than 26.2 μm, 48.1 μm and 70.7 μm, respectively, and d ₅₀ is defined as the median particle size.

<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 27 mg of the catalyst prepared above 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, triethylaluminum (aluminum / titanium molar ratio = 450) and cyclohexylmethyldimethoxysilane (silane / aluminum molar ratio = 0.1) 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.

The polymerization activity (kg polypropylene / g catalyst), calculated as the weight of the resulting polymer in weight per kilogram (kg), was 6.9 and the weight of the polymer not extracted in boiling n-heptane for 3 to 6 hours ( The% stereoregularity of the polymer, expressed as g) ratio, was 99.4%.

Example 2

In preparing the magnesium solution of Example 1, a catalyst was prepared in the same manner as in Example 1 using AlCl ₃ 2.1g, and the polymerization was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had a distribution of d ₁₀ = 29.3 µm, d ₅₀ = 53.6 µm, and d ₉₀ = 89.7 µm. Polymerization activity was found to be 6.5 kg polypropylene / g catalyst and the stereoregularity of the polymer was 99.4%.

Comparative Example 1

In preparing the magnesium solution of Example 1, a catalyst was prepared in the same manner as in Example 1 without using AlCl ₃ , and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the obtained catalyst had a distribution of d ₁₀ = 27.3 μm, d ₅₀ = 45.9 μm, and d ₉₀ = 77.6 μm. And the polymerization activity was found to be 7.9kg polypropylene / g catalyst, the stereoregularity of the polymer was 93.4%.

Example 3

The catalyst was prepared by changing only 37 ml of tetrahydrofuran to prepare a magnesium solution during the preparation of the catalyst of Example 1, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 25.9 μm, d ₅₀ = 39.3 μm, and d ₉₀ = 63.7 μm. The polymerization activity was found to be 7.7 kg polypropylene / g catalyst and the stereoregularity of the polymer was 98.8%.

Example 4

In preparing the magnesium solution of Example 1, the catalyst was prepared by changing the silicon tetraethoxide to 3.2 ml in the preparation of the catalyst of Example 1, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 31.5 µm, d ₅₀ = 50.2 µm, and d ₉₀ = 86.4 µm. The polymerization activity was found to be 6.9 kg polypropylene / g catalyst, and the stereoregularity of the polymer was 99.3%.

Example 5

In preparing the magnesium solution of Example 1, the catalyst was prepared in the same manner as in Example 1 by changing the silicon tetraethoxide to 6.4 ml in the preparation of the magnesium solution, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the obtained catalyst had a distribution of d ₁₀ = 27.8 µm, d ₅₀ = 52.2 µm, and d ₉₀ = 89.2 µm. Polymerization activity was found to be 6.2 kg polypropylene / g catalyst and the stereoregularity of the polymer was 99.1%.

Comparative Example 2

In preparing the magnesium solution in Example 1, a catalyst was prepared in the same manner as in Example 1 without using silicon tetraethoxide, and the polymerization was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 30.4 µm, d ₅₀ = 50.9 µm, and d ₉₀ = 87.9 µm. The polymerization activity was found to be 4.2 kg polypropylene / g catalyst and the stereoregularity of the polymer was 96.8%.

Example 6

The catalyst was prepared as in Example 1 using 1.5 ml of tributyl phosphate when preparing a magnesium solution during the preparation of the catalyst of Example 1, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the obtained catalyst had a distribution of d ₁₀ = 28.4 µm, d ₅₀ = 46.5 µm, and d ₉₀ = 81.5 µm. Polymerization activity was found to be 6.1 kg polypropylene / g catalyst and the stereoregularity of the polymer was 99.2%.

Example 7

In preparing the magnesium solution of Example 1, a catalyst was prepared in the same manner as in Example 1, using 4.5 mmol of tributyl phosphate when preparing a magnesium solution, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 25.9 μm, d ₅₀ = 45.7 μm, and d ₉₀ = 80.6 μm. The polymerization activity was found to be 5.7 kg polypropylene / g catalyst, and the stereoregularity of the polymer was 99.0%.

Comparative Example 3

In preparing the magnesium solution of Example 1, a catalyst was prepared in the same manner as in Example 1 without using tributyl phosphate, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 23.9 µm, d ₅₀ = 47.7 µm, and d ₉₀ = 85.6 µm. The polymerization activity was found to be 3.8 kg polypropylene / g catalyst, and the stereoregularity of the polymer was 98.5%.

Example 8

In the preparation of the catalyst of Example 1, a catalyst was prepared as in Example 1 using TiCl ₄ 18.0 ml in the preparation of the solid catalyst carrier, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 26.8 µm, d ₅₀ = 48.2 µm, and d ₉₀ = 97.6 µm. The polymerization activity was found to be 6.9 kg polypropylene / g catalyst, and the stereoregularity of the polymer was 99.5%.

Example 9

In the preparation of the catalyst of Example 1, a catalyst was prepared in the same manner as in Example 1 using SiCl ₄ 8.1 ml and TiCl ₄ 7.8 ml in the solid catalyst carrier manufacturing process, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the obtained catalyst had a distribution of d ₁₀ = 17.8 µm, d ₅₀ = 28.2 µm, and d ₉₀ = 52.8 µm. Polymerization activity was found to be 7.2 kg polypropylene / g catalyst, and the stereoregularity of the polymer was 99.4%.

Example 10

In the preparation of the catalyst of Example 1, a catalyst was prepared in the same manner as in Example 1 using SiCl _{4 and} 8.1 mL of TiCl ₄ in the solid catalyst carrier manufacturing process, and the polymerization reaction was carried out in the same manner as in Example 1.

The particle distribution of the catalyst obtained had distributions of d ₁₀ = 26.8 µm, d ₅₀ = 46.9 µm, and d ₉₀ = 76.8 µm. The polymerization activity was found to be 6.8 kg polypropylene / g catalyst and the stereoregularity of the polymer was 99.4%.

Comparative Example 4

(i) step: preparation of magnesium compound solution

5 g of MgCl ₂ and 400 ml of tetrahydrofuran were injected into a 1.0 liter reactor equipped with a mechanical stirrer substituted with a nitrogen atmosphere, and the mixture was stirred at 400 rpm. The temperature was raised to the boiling point of tetrahydrofuran to completely dissolve MgCl _2, and the homogeneous solution obtained was cooled to room temperature.

(ii) step: preparing a solid carrier

The magnesium compound solution was transferred to a 1.6 L reactor in which the temperature of the reactor was maintained at 13 ° C. After stirring was maintained at 350rpm, 30ml of TiCl ₄ was added thereto, and the temperature of the reactor was raised to 90 ° C. The reaction was allowed to react at 90 ° C. for 1 hour, and then stirring was stopped to allow the resulting solid component to sink. After separating the supernatant, the solid component was washed twice with 75 ml of hexane.

(iii) Step: Preparation of Catalyst

Heptane 150ml and TiCl ₄ were added to the solid component, and the temperature of the reactor was raised to 80 ° C. At this temperature, 1.97 mL of diisophthalate was injected and the temperature of the reactor was raised to 100 ° C. and then heated for 2 hours. After stirring was stopped, the solid component was allowed to settle, the supernatant was separated, and washed five times with 100 ml of purified hexane. The catalyst was stored after drying in a nitrogen atmosphere. The particle distribution of the catalyst obtained had a distribution of d ₁₀ = 6.8 μm, d ₅₀ = 14.8 μm, and d ₉₀ = 27.8 μm, but the particles showed irregular shapes.

<Polymerization>

Propylene was polymerized in the same manner as in Example 1 using the same amount as in Example 1 based on the titanium atoms in the solid complex catalyst. The polymerization activity was found to be 5.5 kg polyformene / g catalyst and the stereoregularity of the polymer was 95.7%.

Comparative Example 5

(i) step: preparation of magnesium compound solution

15 g of MgCl ₂ and 150 ml of n-decane were added to a 1.0 liter reactor equipped with a mechanical stirrer replaced with a nitrogen atmosphere, stirred at 400 rpm, and 75 ml of 2-ethyl-1-hexanol was added thereto. After raising the temperature to 120 ° C and reacted for 2 hours, 6 ml of diisobutyl phthalate was injected and reacted for another 1 hour. The homogeneous solution obtained after the reaction was cooled to room temperature.

(ii) step: preparing a solid carrier

The magnesium compound solution was transferred to a 1.6 L reactor in which the temperature of the reactor was maintained at 13 ° C. After stirring was maintained at 350rpm, 30ml of TiCl ₄ was added thereto, and the temperature of the reactor was raised to 90 ° C. The reaction was allowed to react at 90 ° C. for 1 hour, and then stirring was stopped to allow the resulting solid component to sink. After separating the supernatant, the solid component was washed twice with 75 ml of hexane.

(iii) Step: Preparation of Catalyst

Heptane 150ml and TiCl ₄ were added to the solid component, and the temperature of the reactor was raised to 80 ° C. 5.61 mL of diisophthalate was injected at this temperature, and then the temperature of the reactor was raised to 100 ° C. and then heated for 2 hours. After stirring was stopped, the solid component was allowed to settle, the supernatant was separated, and washed five times with 100 ml of purified hexane. The catalyst was stored after drying in a nitrogen atmosphere. The particle distribution of the catalyst obtained had a distribution of d ₁₀ = 8.7 μm, d ₅₀ = 16.8 μm, and d ₉₀ = 35.4 μm, but the particles showed irregular shapes.

<Polymerization>

Propylene was polymerized in the same manner as in Example 1 using the same amount as in Example 1 based on the titanium atoms in the solid complex catalyst. The polymerization activity was found to be 4.9 kg polypropylene / g catalyst and the stereoregularity was 96.3%.

The catalyst of the present invention has a simple manufacturing process, a large average particle size, and a narrow particle distribution. In addition, the catalyst of the present invention has high polymerization activity, and excellent stereoregularity of the polymer polymerized using the catalyst.

Claims (12)

Magnesium halide compounds and halide compounds of group IIIA elements of the periodic table include cyclic ethers, one or more alcohols, general formula PX _a R ¹ _b (OR ² ) _c or POX _d R ³ _e (OR ⁴ ) _f (where X is a halogen atom R ¹ , R ² , R ³ , and R ⁴ are hydrocarbons having 1 to 20 carbon atoms, and are alkyl, alkenyl, and aryl, each of which may be the same or different, and a + b + c = 3, 0 ≦ a≤3, 0≤b≤3, 0≤c≤3, d + e + f = 3, 0≤d≤3, 0≤e≤3, 0≤f≤3) and the organosilane Dissolved in a mixed solvent to prepare a magnesium compound solution, 2) reacting the magnesium compound solution with a transition metal compound or silicone compound or tin compound or a mixture thereof to precipitate solid particles, 3) Solid complex titanium catalyst for α-olefin polymerization and copolymerization obtained by reacting precipitated solid particles with a titanium compound and an electron donor. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the halide compound of the Group IIIA element of the periodic table of step 1) is an aluminum halide, and is used at 0.25 mol or less per mol of the magnesium halide compound. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the cyclic ether of step 1) is a cyclic ether having 2 to 15 carbon atoms and the alcohol is a alcohol having 1 to 20 carbon atoms. The molar ratio of the magnesium compound of step 1) and the total amount of the cyclic ether and the at least one alcohol is 1: 0.5 to 1:20, and the molar ratio of the cyclic ether and the at least one alcohol is 1: 0.05 to Solid complex titanium catalyst for α-olefin polymerization and copolymerization which is 1: 0.95. According to claim 1, wherein the alcohol of step 1) comprises a relatively small molecular weight alcohol having 1 to 3 carbon atoms and a relatively high molecular weight alcohol having 4 to 20 carbon atoms, the molar ratio of the total alcohol and a relatively low molecular weight alcohol A solid complex titanium catalyst for α-olefin polymerization and copolymerization having a ratio of 1: 0.01 to 1: 0.4. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 5, wherein the alcohol having a relatively high molecular weight is butanol or isoamyl alcohol or 2-ethylhexanol, and the alcohol having a relatively low molecular weight is methanol or ethanol. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the phosphorus compound of step 1) is used in an amount of 0.01 mol to 0.25 mol per mol of the magnesium halide compound. The method according to claim 1, wherein the organosilane of step 1) is represented by the general formula R _n SiR ' _4-n , wherein R is hydrogen or alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl, aryl group or having 1 to 8 carbon atoms. A solid complex titanium catalyst for α-olefin polymerization and copolymerization, wherein said is a halosilane or halosilyl alkyl group, R 'is OR or halogen, and is an organosilane of n = 0-4. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the organosilane of step 1) is used in an amount of 0.01 mol to 0.25 mol per mol of the magnesium halide compound. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the transition metal compound of step 2) is titanium tetrachloride or silicon tetrachloride or a mixture thereof. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the titanium compound of step 3) is titanium tetrachloride. The solid complex titanium catalyst for α-olefin polymerization and copolymerization according to claim 1, wherein the electron donor of step 3) is dialkyl phthalate.