KR100651622B1 - Method for producing a poly-1-olefin in the presence of a Ziegler catalyst and said Ziegler catalyst - Google Patents

Abstract

The present invention is 1-olefin of the formula R ⁴ CH = CH ₂ in the presence of a catalyst, at a pressure and temperature of 0.5 to 50bar of from 20 to 200 ℃, suspension, solution or gas phase (where, R ⁴ is hydrogen or C 1 To an alkyl group of from 10 to 10). This catalyst consists of a reaction product [component (a)] of a magnesium alkoxide and a transition metal compound and an organometallic compound [component (b)]. Component (a) is obtained by the reaction of a gelatinous dispersion of magnesium alkoxide with a transition metal compound of titanium, zirconium, vanadium or chromium in an inert hydrocarbon. According to the process of the invention, the gelatinous dispersion is prepared by stirring a suspension of a powder of magnesium alkoxide having an average particle size [d ₅₀ ] of less than 15 μm with a stirring device in an inert hydrocarbon in which magnesium alkoxide particles are not dissolved or using a high performance shear device. By shearing. Magnesium alkoxide powder is obtained by anhydrous grinding of magnesium alkoxide powder having an average particle size [d ₅₀ ] of at least 15 μm, preferably in the range of 100 to 1000 μm, in an inactivated mill. The invention also relates to a catalyst suitable for carrying out the process of the invention.

Ziegler catalyst, 1-olefin, gelatinous dispersion, transition metal, particle size distribution.

Description

Method for producing a poly-1-olefin in the presence of a Ziegler catalyst and the Ziegler catalyst and said Ziegler catalyst}

The present invention relates to a process for the preparation of poly-1-olefins in the presence of a Ziegler catalyst prepared from gelatinous magnesium alkoxide dispersions.

Magnesium alkoxide Mg (OR ¹ ) (OR ² ) or “complex” by reacting magnesium alkoxide with a compound of titanium, zirconium, vanadium or chromium, Group 1, 2 or 13 of the periodic table [eg, Handbook of Chemistry and Together with an organometallic compound from Physics, 76th Edition (1995-1996), to produce a good catalyst for olefin polymerization.

Processes for polymerizing 1-olefins in the presence of a mixed catalyst having component (a) prepared by the reaction of magnesium alkoxides with tetravalent halogen containing titanium compounds are known (US Pat. No. 3,644,318). Magnesium alkoxide is used in the same form as commercially available. Polymers obtainable in this way have a narrow molecular weight distribution.

Also known are methods of preparing Ziegler catalysts in which dissolved magnesium alkoxides react with halogen-containing Ti or V compounds and transition metal alkoxides (see EP-A 0 319 173). The catalyst particles formed in this process are spherical and have an average particle size of 10 to 70 mu m.

Finally, transition metal components used in the reaction products of tetravalent halogen-containing titanium compounds and magnesium alkoxides containing at least 40% by weight of particles having a diameter of less than 63 μm are also known (EP-A-0 223 011). Magnesium alkoxides having this particle size are obtained, in particular, by milling commercially available products in a ball mill. Magnesium alkoxides are used as suspensions in inert hydrocarbons.

EP-A 0 532 551 also shows that when magnesium alkoxides are used in the form of gelatinous dispersions, Ziegler catalysts are obtained which have very high activity and which can control the particle size distribution of the polymer. It is described. This gelatinous dispersion suspends commercially available magnesium alkoxide in inert hydrocarbons and disperses this suspension with a high performance shear mechanism under protective gas (Ar or N ₂ ) (e.g. ^TM Ultra-Turrax or ^TM Dispax, IKA- Obtained by Maschinenbau Janke & Kunkel GmbH), dispersing for several hours or days with strong cooling.

Nevertheless, the known catalysts are still unsatisfactory, as the energy of the preparation of the gelatinous magnesium alkoxide is unsatisfactorily high and must be lowered by suitable means.

Accordingly, it is an object of the present invention to prepare polyolefins in the presence of a Ziegler catalyst wherein the first component is a reaction product of a gelatinous magnesium alkoxide dispersion and a transition metal compound, wherein the magnesium alkoxide dispersion is prepared in a simpler and more economical manner. To develop a process for the production of polyolefins, characterized in that the polymers produced using this catalyst have a narrower particle size distribution than in the prior art.

An object of the invention is a catalyst consisting of a reaction product of magnesium alkoxide with a transition metal compound [component (a)] and an organometallic compound [component (b)], wherein component (a) is a titanium, zirconium, vanadium or chromium Prepared by reacting a transition metal compound with a gelatinous dispersion of magnesium alkoxide in an inert hydrocarbon] at a temperature range of 20 to 200 ° C. and a pressure range of 0.5 to 50 bar, wherein a 1-olefin of formula R ⁴ CH═CH ₂ , R ⁴ is hydrogen or an alkyl radical having 1 to 10 carbon atoms) to prepare a poly-1-olefin by suspension polymerization, solution polymerization or gas phase polymerization, wherein a gelatinous dispersion of magnesium alkoxide is in an inert grinder. magnesium alkoxide particles have an average particle size in an inert hydrocarbon that is not dissolved in [d _50] the above 15㎛, preferably when from 100 to 1000㎛ That is how to obtain a magnesium alkoxide by dry milling the powder, the average particle size [d _50] is less than 15㎛ suspension of magnesium alkoxide powder, characterized in that the stirring by using a stirrer or obtained by shearing using a high-performance shearing device Is achieved by.

Gelatinous magnesium alkoxide dispersions prepared according to the present invention by stirring a suspension of pulverized magnesium alkoxide powder in an inert hydrocarbon in which magnesium alkoxide is not soluble are agitated using a stirring apparatus or sheared using a high performance shearing apparatus, the gelatinous magnesium alkoxide dispersion prepared in the hydrocarbon fraction at the same temperature The precipitation of solids is slower than the suspension of pulverized magnesium alkoxide powder used in the same inert hydrocarbons, which are themselves identical, represented by weight percent, of the initially introduced solids to solids, and the solids in the dispersion after complete precipitation of the solids The spatial ratio of (expressed in volume%) is higher.

Gelatinous dispersions of the type according to the invention can be prepared by stirring a suspension of magnesium alkoxide powder ground in an inert hydrocarbon in which magnesium alkoxide does not dissolve in an inactivation vessel by stirring using a stirring device or shearing using a high performance shear device. Produced, with the same average number of particles present in each volume increment of the mixture. Stirring with a stirring device or shearing with a high performance shear device is preferably in the range of 1 to 24 hours, preferably 2 to 20 hours, in the temperature range of 10 to 150 ° C., preferably 20 to 100 ° C. according to the invention. The magnesium alkoxide particles are run in an inert hydrocarbon that does not dissolve for hours.

The invention also relates to a catalyst used in the process of the invention as described above.

Component (a) is prepared using commercially available magnesium alkoxides. The present magnesium alkoxide is a “simple” magnesium alkoxide of the formula Mg (OR ¹ ) (OR ² ), wherein R ¹ and R ² are the same or different and are alkyl radicals of 1 to 6 carbon atoms. Mg (OC ₂ H ₅ ) ₂ , Mg (OiC ₃ H ₇ ) ₂ , Mg (OnC ₄ H ₉ ) ₂ , Mg (OCH ₃ ) (OC ₂ H ₅ ) and Mg (OC ₂ H ₅ ) (OnC ₃ H ₇ ) as an example. In addition, the formula Mg (OR) _n X _m [where X is halogen, (SO ₄ ) _1/2 , OH, (CO ₃ ) _1/2 , (PO ₄ ) _1/3 or Cl, R is R ¹ or R ² with meanings, and n + m is 2].

However, it is also possible to use "complex" magnesium alkoxides. The term “complex” magnesium alkoxide refers to magnesium alkoxide containing one or more metals of Group 1, 2, 13 or 14 of the periodic table in addition to magnesium. Complex magnesium alkoxides of this type include [Mg (OiC ₃ H ₇ ) ₄ ] Li ₂ ; [Al ₂ (OiC ₃ H ₇ ) ₈ ] Mg; [Si (OC ₂ H ₅ ) ₆ ] Mg; [Mg (OC ₂ H ₅ ) ₃ ] Na; [Al ₂ (OiC ₄ H ₉ ) ₈ ] Mg; [Al ₂ (O 2 -C ₄ H ₉ ) ₆ (OC ₂ H ₅ ) ₂ ] Mg.

Complex magnesium alkoxides (alkoxy salts) are prepared by known methods.

Simple magnesium alkoxides are preferred, in particular Mg (OC ₂ H ₅ ) ₂ , Mg (OnC ₃ H ₇ ) ₂ or Mg (OiC ₃ H ₇ ) ₂ .

Commercially available Mg (OC ₂ H ₅ ) ₂ generally has the following components.

Mg content 21-22 wt%

MgCO ₃ ≤ 1 wt%

C ₂ H ₅ OH content <0.3 wt%

The average particle diameter is 400 µm and contains 90% or more of particles having a particle diameter of 200 to 1200 µm.

Commercially available magnesium alkoxides having an average particle diameter of about 400 μm are ground according to the invention in the inactivated mill until the ground material has an average particle diameter [d ₅₀ ] of less than 15 μm.

For the purposes of the present invention, the grinder is considered to be deactivated when the proportion of the atmospheric environment gas in the total space of the grinding apparatus in contact with the magnesium alkoxide during the grinding process is less than 1% by inert gas replacement. For the purposes of the present invention, inert gases are considered in particular nitrogen and argon.

For the purposes of the present invention, particularly suitable mills are, for example, ball mills, impact mills, opposed jet mills, spiral jet mills or jet mills. In particular, "Mechanische Verfahrenstechnik, Trocken- und Nassprozesse" No. of the company brochure [Hosokawa Alpine AG, Augsburg, Germany]. 017/10 297.2d, of which an opposing jet mill is available from the company.

Suitable inert hydrocarbons according to the present invention are aliphatic or cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane and aromatic hydrocarbons such as toluene and xylene, and the oxygen, sulfur compounds and water carefully Removed hydrogenated diesel oil or gasoline fractions may also be used.

Gelatinous dispersions may be prepared from Ti compounds [particularly TiCl ₄ , Ti (OR) ₄ ], Zr compounds [particularly Zr (OR) ₄ ], V compounds [particularly VCl ₄ , VOCl ₃ ] or chromium compounds [particularly CrO ₂ Reaction with Cl ₂ ] in one or multiple stages.

Here, the gelatinous magnesium alkoxide dispersion is reacted in the presence of a transition metal compound and an inert hydrocarbon in a temperature range of 20 to 100 ° C., preferably 60 to 90 ° C. while stirring with a high speed stirrer as necessary. 0.05 to 5 moles, preferably 0.1 to 3.5 moles, of transition metal compound are used per mole of magnesium alkoxide. The reaction time is 0.5 to 8 hours, preferably 2 to 6 hours.

A solid is obtained that does not dissolve in hydrocarbons and contains magnesium and transition metals referred to in this invention as component (a). Component (a) forms a suspension with a hydrocarbon (solid / liquid).

The polymerization catalyst used according to the invention is prepared by mixing component (a) with an organometallic compound [component (b)] of the periodic table Group 1, 2 or 13 metals. Component (a) can be reacted directly with component (b) as a suspension, but can also first be separated off as a solid, stored and resuspended in future use.

Component (b) used is preferably an organoaluminum compound. Suitable organoaluminum compounds are dialkylaluminum monochlorides of formula R ³ ₂ AlCl or alkylaluminum sesquichlorides of formula R ³ ₃ Al ₂ Cl ₃ , wherein R ³ is alkyl having 1 to 16 carbon atoms Radicals). Examples that may be mentioned are (C ₂ H ₅ ) ₂ AlCl, (iC ₄ H ₉ ) ₂ AlCl and (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . It is also possible to use mixtures of these compounds.

On the other hand, organoaluminum compounds which do not contain chlorine such as trialkylaluminum AlR ³ ₃ or dialkylaluminum hydrides of the general formula AlR ³ ₂ H, wherein R ³ is an alkyl radical having 1 to 16 carbon atoms are also suitable. For example, Al (C ₂ H ₅ ) ₃ , Al (C ₂ H ₅ ) ₂ H, Al (C ₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , Al (iC ₄ H ₉ ) ₂ H, Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₂ H ₂₅ ) ₃ , Al (C ₂ H ₅ ) (C ₁₂ H ₂₅ ) ₂ and Al (iC ₄ H ₉ (C ₁₂ H ₂₅ ) ₂ .

It is also possible to use mixtures of organometallic compounds of the Group 1, 2 or 13 metals of the periodic table, in particular mixtures of different organoaluminum compounds.

The following mixtures may be mentioned by way of example: Al (C ₂ H ₅ ) ₃ and Al (iC ₄ H ₉ ) ₃ , Al (C ₂ H ₅ ) ₂ Cl and Al (C ₈ H ₁₇ ) ₃ , Al (C ₂ H ₅ ) ₃ and Al (C ₈ H ₁₇ ) ₃ , Al (C ₄ H ₉ ) ₂ H and Al (C ₈ H ₁₇ ) ₃ , Al (iC ₄ H ₉ ) ₃ and Al (C ₈ H ₁₇ ) ₃ , Al (C ₂ H ₅ ) ₃ and Al (C ₁₂ H ₂₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ and Al (C ₁₂ H ₂₅ ) ₃ , Al (C ₂ H ₅ ) ₃ and Al (C ₁₆ H ₃₃ ) ₃ , Al (C ₃ H ₇ ) ₃ and Al (C ₁₈ H ₃₇ ) ₂ (iC ₄ H ₉ ), Al (C ₂ H ₅ ) ₃ and isoprenylaluminum [= isoprene and Al (iC ₄ H ₉ ) ₃ or Al (iC ₄ H ₉ ) ₂ H].

Before the polymerization, the components (a) and (b) can be mixed in a stirred tank reactor in the temperature range of -30 to 150 ° C, preferably -10 to 120 ° C. It is also possible to mix components (a) and (b) directly in the polymerization reactor in the temperature range of 20 to 200 ° C. However, the addition of component (b) preactivates component (a) with the first fraction of component (b) before the polymerization reaction in the temperature range of -30 to 150 ° C and the addition of the same or another component (b). The fraction may be carried out in two stages of addition to the polymerization reactor in the temperature range of 20 to 200 ° C.

The polymerization catalysts used according to the invention are 1-olefins of the formula R ⁴ -CH = CH ₂ , wherein R ⁴ is a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms (e.g. ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene).

Ethylene is preferably polymerized alone or with a mixture of at least 50% by weight of ethylene and up to 50% by weight of another 1-olefin of the formula R ⁴ -CH = CH ₂ . In particular, it is polymerized with ethylene alone or with a mixture of at least 90% by weight of ethylene and up to 10% by weight of another 1-olefin of the formula R ⁴ -CH = CH ₂ .

The polymerization is carried out in a known manner in a temperature range of 20 to 200 ° C., preferably 50 to 150 ° C., in solution, in suspension or in the gas phase, continuously or discontinuously, in one or more steps. The pressure is 0.5 to 50 bar. The polymerization is preferably carried out in a pressure range of 1.5 to 30 bar, which is of particular industrial importance.

The reaction product of component (a) or component (a) with component (b) is used at a concentration of 0.0001 to 1 mmol, preferably 0.001 to 0.5 mmol of transition metal per dm ^{3 of the} dispersion medium on a transition metal basis. However, in principle higher concentrations may be used.

Suspension polymerization is carried out in an inert dispersion medium customary for Ziegler low pressure processes such as, for example, aliphatic hydrocarbons or cycloaliphatic hydrocarbons, which may be mentioned, for example, butane, pentane, hexane, heptane, isooctane, Cyclohexane and methylcyclohexane. It is also possible to use gasoline or hydrogenated diesel oil fractions with careful removal of oxygen, sulfur compounds and moisture.

As with gas phase polymerization, suspension polymerization can be carried out directly by prepolymerization which is advantageously carried out by suspension or after catalyst prepolymerization.

The molecular weight of the polymer is controlled by known methods, preferably hydrogen is used for this.

Due to the high activity of the catalyst used, the method according to the invention produces very low transition metals and polymers with very low halogen content, which results in very good color stability and corrosion test results.

In addition, the process according to the invention makes it possible to produce catalysts which can optimally match the catalyst particle size distribution and the particular level of particle morphology of the formed polymer powder and surprisingly the hydrogen sensitivity of the catalyst.

According to the invention, particularly surprisingly narrow particle size distributions, expressed as S values according to the improved particle morphology, DIN 66 144, are obtained so that there are no fractions with too large particle sizes and fine fractions, and the catalyst productivity is high. Bulk density is comparable to the bulk density according to the prior art.

Thus, the gelatin according to the invention prepared by anhydrous grinding in inert hydrocarbons in which the magnesium alkoxide particles are not dissolved and subsequently stirring the suspension of the ground magnesium alkoxide using a stirring device or shearing using a high performance shear device. In the case of using a magnesium magnesium alkoxide dispersion, the morphological properties of the polymer powder can be controlled, which is a useful advantage in industrial processes (transferring the factory polymer powder is simpler and provides better fluidity). ). High catalyst productivity results in lower catalyst residual content in the product.

In addition, less energy is required in the preparation of gelatinous magnesium alkoxide dispersions.

In the following working examples to more clearly explain the present invention to those skilled in the art, the Mg: Ti: Cl ratio in characterizing the catalyst is measured by conventional analytical methods. Powder particle size and particle size distribution are measured by screen analysis according to DIN 66 144.

Example 1 (according to the invention)

Preparation of catalyst component (a) using gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion obtained by stirring a suspension of milled Mg (OC ₂ H ₅ ) ₂ in an inert hydrocarbon

A throughput of about 6 kg / hour in a 100 AFG-type opposing jet grinder (manufactured by Hosogawa Alpine AG, Augsburg, Germany) in a diesel oil 1.0dm ³ having a boiling point in the range of 140 to 170 ° C. Commercially available suspension of 57 g of Mg (OC ₂ H ₅ ) ₂ ground to an average particle diameter of about 5.4 μm in a 2dm ³ stirred vessel equipped with a reflux condenser, a 2-blade stirrer and an inert gas blanket (argon). Stirred at 100 rpm (rpm per minute) at room temperature for 20 hours. The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 30 minutes after the stirrer was turned off.

The Mg (OC ₂ H ₅ ) ₂ dispersion was heated to 85 ° C. at 150 rpm stirring rate, and 0.15 mol of concentrated TiCl ₄ was metered in over 4 hours. The resulting suspension was then heated to 110 ° C. for 1 hour. The preparation of the catalyst component (a) was thus completed.

Subsequently, 0.35 moles of Al ₂ (C ₂ H ₅ ) ₃ Cl _{3 in} 200 cm 3 of diesel oil (hydrogenated gasoline fraction with boiling range from 140 to 170 ° C.) was metered in over a period of 2 hours at a temperature of 110 ° C. and a stirring speed of 250 rpm. It was. The temperature was then maintained at 110 ° C. for an additional 2 hours.

The solid suspension was cooled to room temperature. The molar ratio Mg: Ti: Cl of solids was about 1: 0.3: 2.4.

Example 2 (according to the invention)

Catalyst component (a) was prepared by the method described in Example 1 using a gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion obtained by stirring a suspension of milled Mg (OC ₂ H ₅ ) ₂ in an inert hydrocarbon. Commercially available Mg (OC ₂ H ₅ ) ₂ ground to an average particle diameter of about 5.4 μm in a diesel oil (hydrogenated gasoline fraction) having a boiling point in the range of 140 to 170 ° C. at a temperature of 85 ° C. and a stirring rate of 100 rpm. Stir for hours.

The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 60 minutes after the stirrer was turned off.

The molar ratio of solids of the solid suspension prepared in this way was Mg: Ti: Cl about 1: 0.3: 2.3.

Example 3 According to the Invention

Preparation of catalyst component (a) using gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion obtained by stirring a suspension of milled Mg (OC ₂ H ₅ ) ₂ in an inert hydrocarbon

A commercially available Mg (OC ₂ H ₅₎ ground to an average particle diameter of about 5.4 μm at a throughput of about 6 kg / hour in a 100 AFG type opposing jet grinder (Augosbruck, Germany). ) of a suspension of 57g ₂ having a boiling point range from 100 to 120 ℃ diesel oil (hydrogenated gasoline fraction) 1.0dm ³ in refluxing condenser, of 100rpm in a 2-blade agitator and an inert gas blanket (argon), equipped with a 2dm ³ stirred vessel Stirred at room temperature for 20 hours at room temperature.

The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 20 minutes after the stirrer was turned off.

The Mg (OC ₂ H ₅ ) ₂ dispersion was heated to 85 ° C. at 150 rpm stirring rate, and 0.15 mol of concentrated TiCl ₄ was metered in over 4 hours. The resulting suspension was then heated to 110 ° C. for 1 hour. The preparation of the catalyst component (a) was thus completed.

Subsequently, 0.35 moles of Al ₂ (C ₂ H ₅ ) ₃ Cl _{3 in} 200 cm 3 of diesel oil (hydrogenated gasoline fraction having a boiling point in the range of 100 to 120 ° C.) was metered in over a period of 2 hours at a temperature of 110 ° C. and a stirring speed of 250 rpm. It was. The temperature was then maintained at 110 ° C. for an additional 2 hours.

The solid suspension was cooled to room temperature. The molar ratio Mg: Ti: Cl of solids was about 1: 0.3: 2.4.

Example 4 According to the Invention

Catalyst component (a) was prepared by the method described in Example 3 using a gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion obtained by stirring a suspension of milled Mg (OC ₂ H ₅ ) ₂ in an inert hydrocarbon. Commercially available Mg (OC ₂ H ₅ ) ₂ milled to an average particle diameter of about 5.4 μm at 20 ° C. in a diesel oil (hydrogenated gasoline fraction) having a boiling point in the range of 100 to 120 ° C. at a stirring speed of 100 rpm and 20 rpm. Stir for hours.

The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 45 minutes after the stirrer was turned off.

The molar ratio Mg: Ti: Cl of solids of the solid suspension prepared in this way was about 1: 0.3: 2.5.

Comparative Example 1

Preparation of catalyst component (a) using a suspension of pulverized Mg (OC ₂ H ₅ ) ₂ in inert hydrocarbon without dispersion step

100 AFG type opposing in 1.0dm ³ of diesel oil (hydrogenated gasoline fraction) with boiling point in the range from 140 to 170 ° C. in a 2dm ³ stirred vessel equipped with a reflux cooler, a 2-blade stirrer and an inert gas blanket (Argon). 57 g of commercially available Mg (OC ₂ H ₅ ) ₂ was ground at a jet grinder (Augusbruck, Germany, Hosogawa Alpine Age) at a throughput of about 6 kg / hr with an average particle diameter of about 5.4 µm at 100 rpm (100 rpm). Stirred at revolutions per minute), the mixture was stirred at room temperature for 10 minutes.

The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 10 minutes after the stirrer was turned off.

The suspension was heated to 85 ° C. at 150 rpm stirring rate and 0.15 moles of concentrated TiCl ₄ was metered in over 4 hours. The resulting suspension was then heated to 110 ° C. for 1 hour. The preparation of the catalyst component (a) was thus completed.

Subsequently, 0.35 moles of Al ₂ (C ₂ H ₅ ) ₃ Cl _{3 in} 200 cm 3 of diesel oil (hydrogenated gasoline fraction with boiling range from 140 to 170 ° C.) was metered in over a period of 2 hours at a temperature of 110 ° C. and a stirring speed of 250 rpm. It was. The temperature was then maintained at 110 ° C. for an additional 2 hours.

The solid suspension was cooled to room temperature. The molar ratio Mg: Ti: Cl of solids was about 1: 0.3: 2.5.

Comparative Example 2

Preparation of catalyst component (a) using gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion obtained by dispersing a commercially available suspension of Mg (OC ₂ H ₅ ) ₂ in an inert hydrocarbon using a high performance shear apparatus

137 g of commercially available Mg (OC ₂ H ₅ ) ₂ was suspended in diesel oil (hydrogenated gasoline fraction with boiling range from 140 to 170 ° C.) (total volume 1.0 dm ³ ). The suspension is converted to a dispersion using a high speed disperser ( ^TM Ultra-Turrax) externally cooled using an ice bath in a cylindrical glass vessel under inert gas (Ar) to exclude moisture and air (O ₂ ). (Lasting time about 8 hours). The dispersion has gelatinous roughness.

The gelatinous dispersion 0.42dm ³ [containing 57 g Mg (OC ₂ H ₅ ) ₂ ] was transferred to a 2dm ³ stirred vessel equipped with a reflux condenser, a 2-blade stirrer and an inert gas blanket (argon). 0.58 dm ³ of diesel oil (hydrogenated gasoline fraction) having a boiling point in the range from 140 to 170 ° C. was added and the mixture was stirred at room temperature for 10 minutes at a stirring rate of 100 rpm.

The precipitation time at room temperature of the thus obtained gelatinous Mg (OC ₂ H ₅ ) ₂ dispersion was about 60 minutes after the stirrer was turned off.

The gelatinous dispersion was heated to 85 ° C. at a stirring speed of 150 rpm, and 0.15 mol of concentrated TiCl ₄ was metered in over 4 hours. The resulting suspension was then heated to 110 ° C. for 1 hour. Thus, the preparation of the catalyst component (a) was completed.

0.35 moles of Al ₂ (C ₂ H ₅ ) ₃ Cl _{3 in} 200 cm 3 of diesel oil (hydrogenated gasoline fraction with boiling point in the range from 140 to 170 ° C.) was metered in over 2 hours at a temperature of 110 ° C. and a stirring speed of 250 rpm. The temperature was then maintained at 110 ° C. for an additional 2 hours.

The solid suspension was cooled to room temperature. The molar ratio Mg: Ti: Cl of solids was about 1: 0.3: 2.5.

Example 5

Polymerization Experiments Using Catalysts of Examples 1-4 and Two Comparative Examples

Polymerization experiments were carried out discontinuously in a 200 dm ³ reactor. The reactor is equipped with an impeller and a baffle. The temperature of the reactor was measured and automatically kept constant. The polymerization temperature was 85 ± 1 ° C.

The polymerization reaction was carried out in the following manner.

Diesel oil 100dm ³ was introduced into the reactor under an N ₂ blanket and heated to 85 ° C. Promoter Al (C ₂ H ₅ ) ₃ (component b) was added under an inert gas blanket (nitrogen) so that a promoter concentration of 0.50 mmol / dm ³ was present in the reactor. An amount of catalyst component (a) corresponding to 2.0 mmol of titanium was introduced into the reactor as a suspension diluted with diesel oil. The reactor was charged with H ₂ (hydrogen) to 8 bar or less and then decomposed again, and this operation was repeated several times to completely remove nitrogen from the reactor (this method is observed by measuring the H ₂ concentration in the reactor gas space, Finally 95% by volume). The ethylene inlet was opened to initiate polymerization. Over the entire polymerization time, ethylene was fed in an amount of 8.0 kg / hour, with the pressure in the reactor slowly increasing. The hydrogen content in the gas space of the reactor was constantly measured, and the volume ratio was kept constant by metering hydrogen accordingly (H ₂ vol% = 40).

The polymerization was terminated after 225 minutes (30 kg of ethylene gas injection) and the total pressure was read. The reactor contents were drained onto the filter. The polymer to which the diesel oil adhered was dried in the nitrogen stream for several hours. The polymerization results are summarized in Table 1.

Polymerization experiment 200dm ³ reactor, 50mmol of triethylene, 2.0mmol of Ti (catalyst solid), diesel oil 100dm ³ , 8.0kg / hour of ethylene, polymerization temperature of 85 ° C, polymerization time of 225 minutes, 40 vol% of hydrogen in gas space Polymerization experiment Catalyst component (a) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Final pressure [bar] 5.156 5.376 4.278 4.014 6.426 4.528 Polyethylene Yield [kg] 29.7 29.9 30.0 30.0 30.0 30.0 MFR 190/5 [dg / min] 6.53 5.77 7.68 9.94 6.98 8.56 Bulk Density [g / ℓ] 344 330 366 358 345 325 d ₅₀ [μm] 344 299 298 275 310 300 S value [In (d ₅₀ / d ₁₆ )] 0.24 0.34 0.26 0.31 0.39 0.39

It can be clearly seen from the values in Table 1 that the particle size distribution of the polymer, expressed in S values according to DIN 66 144, is advantageously narrower in the method according to the invention compared to the comparative examples. However, the narrowest possible particle size distribution is very important for producing products with the highest possible quality. Furthermore, in Comparative Example 1, where the suspension of milled magnesium alkoxide in inert hydrocarbon was not converted to the gelatinous magnesium alkoxide dispersion via the dispersion step according to the invention before reacting with the transition metal compound, expressed in final pressure (bar). The catalytic activity produced is relatively low. Higher final pressures indicate that higher ethylene partial pressures are produced, resulting in the same amount of polymer under the same experimental conditions using the same catalyst amount. L.L. Boehm, Chem. Ing. Techn. 56 (1984) 674, Eq. (2)].

In addition, in Comparative Example 2 corresponding to the prior art such as EP-A-0 532 551, although the catalytic activity is acceptable, the gelatinous dispersion in the comparative example was prepared using ice. It can be seen that it must be made with a constant externally cooled, high performance disperser, which is a very energy intensive method of avoiding according to the invention.

Claims (14)

A catalyst consisting of a reaction product [component (a)] of a magnesium alkoxide and a transition metal compound and an organometallic compound [component (b)], wherein component (a) comprises a transition metal compound of titanium, zirconium, vanadium or chromium in an inert hydrocarbon. in the magnesium alkoxide of the gelatinous dispersion and by the reaction formula in the temperature range and pressure range of 0.5 to 50bar in the presence of are Preparation 20 to 200 ℃ R ⁴ CH = 1- olefins CH ₂ (wherein, R ⁴ is hydrogen or A method of preparing poly-1-olefin by suspension polymerization, solution polymerization or gas phase polymerization of an alkyl radical having 1 to 10 carbon atoms, Gelatinous dispersion of magnesium alkoxide is obtained by anhydrous grinding of magnesium alkoxide powder having an average particle size [d ₅₀ ] in the range of 15 µm or more in an inert hydrocarbon in which magnesium alkoxide particles are not dissolved in an inert grinder. A process for producing a poly-1-olefin, characterized in that a suspension of magnesium alkoxide powder having a size [d ₅₀ ] of less than 15 μm is obtained by stirring using a stirring device or shearing using a high performance shear device. The method according to claim 1, characterized in that the stirring using a stirring device of pulverized magnesium alkoxide powder or shearing using a high performance shearing device is performed in an inert hydrocarbon for a time ranging from 1 to 24 hours in a temperature range of 10 to 150 ° C. , Poly-1-olefin production method. The aliphatic or cycloaliphatic hydrocarbon according to claim 1 or 2, wherein the inert hydrocarbon used is butane, pentane, hexane, heptane, isooctane, cyclohexane or methylcyclohexane, or an aromatic hydrocarbon comprising toluene or xylene, Or hydrogenated diesel oil or gasoline fractions carefully removed from oxygen, sulfur compounds and water. The gelatinous dispersion according to claim 1 or 2, wherein the gelatinous dispersion comprises a titanium compound comprising TiCl ₄ or Ti (OR) ₄ , a zirconium compound comprising ZrCl ₄ or Zr (OR) ₄ , VCl ₄ or VOCl ₃ . Method for producing a poly-1-olefin, characterized in that the reaction with a vanadium compound or a chromium compound containing CrO ₂ Cl ₂ in one or a multi-step. The method according to claim 1 or 2, wherein the magnesium alkoxide is reacted with a transition metal compound in the presence of an inert hydrocarbon in the temperature range of 20 to 100 ° C, wherein the transition metal compound is 0.05 to 5 moles per mole of magnesium alkoxide. Used in amounts). The method of claim 5, wherein the reaction time is 0.5 to 8 hours. The organoaluminum compound of formula R ³ ₃ Al comprising (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, according to claim 1 or ₂ chlorine-containing organoaluminum _{compound, (iC 4 H 9) 2} AlCl formula R ³ ₂ AlCl dialkylaluminum monochloride, containing _{(C 2 H 5) 3 Al} 2 formula containing Cl _³ R _{3 3} Al ₂ Cl ₃ alkyl aluminum sesquichloride, or mixtures of such compounds of formula (wherein, R ³ is a C 1 -C 16 alkyl radicals) the process for producing a poly-1-olefin, characterized in that. The method according to claim 1 or 2, wherein component (a) and component (b) are mixed in a temperature range of -30 to + 150 ° C before polymerizing in a stirred tank reactor, or component (a) and component (b) Is directly mixed in the polymerization reactor in the temperature range of 20 to 200 ° C., or pre-activation of component (a) using a first fraction of component (b) in the temperature range of -30 to + 150 ° C. before the polymerization reaction and , Wherein the additional fraction of component (b), which is the same as or different from the first fraction, is added to the polymerization reactor at a temperature of 20 to 200 ° C., in a two step. The process for producing poly-1-olefin according to claim 1 or 2, wherein the catalyst is added to the polymerization reaction in a prepolymerized state. The process according to claim 1 or 2, characterized in that it is used for the polymerization of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene, the molecular weight of the polymer being controlled by hydrogen. A method for producing a poly-1-olefin, characterized in that. The process according to claim 1 or 2, wherein the polymerization is carried out in a solution, in a suspension or in a gas phase, continuously or discontinuously, in a single or multistage, in a temperature range of 20 to 200 ° C. and a pressure of 0.5 To 50bar, characterized in that the method for producing a poly-1-olefin. The method according to claim 1 or 2, wherein component (a) or the reaction product of component (a) and component (b) is used at a concentration of 0.0001 to 1 mmol of transition metal per dm ^{3 of} dispersion medium, based on the transition metal. The polymerization is carried out from a group consisting of aliphatic or cycloaliphatic hydrocarbons including butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane, and gasoline or hydrogenated diesel oil fractions carefully removed from oxygen, sulfur compounds and water. A process for the preparation of poly-1-olefins, characterized in that it is carried out in a selected inert dispersion medium. A catalyst consisting of a reaction product [component (a)] of a magnesium alkoxide and a transition metal compound and an organometallic compound [component (b)], wherein component (a) comprises a transition metal compound of titanium, zirconium, vanadium or chromium in an inert hydrocarbon. Prepared by reacting with a gelatinous dispersion of magnesium alkoxide in the genus], An average particle size [obtained by gelatinous dispersion of magnesium alkoxide obtained by anhydrous grinding of magnesium alkoxide powder having an average particle size [d ₅₀ ] of 15 μm or more in an inert hydrocarbon in which magnesium alkoxide particles are not dissolved in an inert grinder [ 1-olefin of the formula R ⁴ CH = CH ₂ as that obtained characterized by d _50] is stirred using 15㎛ under stirring a suspension of a magnesium alkoxide powder device or shear, using a high-performance shearing device (here, R ⁴ Is hydrogen or an alkyl radical having 1 to 10 carbon atoms). The method according to claim 10, which is used for the homopolymerization of ethylene or at least 50% by weight of ethylene and at most 50% by weight of another 1-olefin of the formula R ⁴ -CH = CH ₂ , wherein R ⁴ is hydrogen or 1 to 10 carbon atoms. Method for producing a poly-1-olefin.