HUT76719A - Catalysts for ethylene polymers production, method for preparation of said catalyst - Google Patents

Abstract

The invention relates to a process for the purification of an impure phosphoric acid prepared by the wet process. The acid to be purified is concentrated to 58-68 % P2O5 acid by heating. The impurities are removed from the acid by crystallization, as a compound M<2+> (H2PO4)2.n.H3PO4, where M<2+> is a bivalent metal ion impurity and n may vary within 2-5.

Description

Catalyst for the preparation of ethylene polymers, process for the preparation of the catalyst and its use

The present invention relates to a catalyst component of a Ziegler-Natta catalyst composition for the preparation of ethylene polymers. The preparation consists of a mixture which is a compound of formula III. contains metals (13), chloride, magnesium and titanium on a particulate, inorganic support. The invention also relates to the preparation and use thereof.

Ethylene, alone or in combination with other olefinically unsaturated monomers, is often polymerized in the presence of a catalyst composition containing two essential components: the periodic table (Hubbard,

IUPAC 1970) Groups 4 and 6 of the transition metal, often referred to as catalysts, and are described in Tables 1-3 of the Periodic Table. which is a so-called cocatalyst.

This type of Ziegler-Natta catalyst has been improved by applying the catalyst to a more inert, particulate support and adding various additives, including electron donor compounds, to the catalyst composition during its preparation. These compounds improved the polymerization activity of the catalyst, the catalyst life and the other properties of the catalyst composition, and in particular the catalyst composition. properties of the resulting polymers.

When ethylene polymers, as well as other polymers, are produced, the polymer molecules formed are not uniform in molecular weight, but form a mixture with a narrower or wider molecular weight distribution. To characterize the most occurring molecular weight by providing the highest standard deviation, different average molecular weights can be determined in a polymer blend. In addition, various indices have been developed to characterize the spread width. Substances known as chain transfer agents can be added to the polymerization reaction to control the molecular weight. In order to obtain polymer products of different molecular weights, various amounts of such materials must be added to the polymerization reaction to control the molecular weight. The most commonly used and most preferred chain transfer agent is hydrogen because there are no foreign atoms or groups of atoms remaining in the growing molecule that would cause discomfort in the polymerization reaction or disadvantageous properties of the resulting polymer.

The molecular weight of the polymer produced varies with the amount of hydrogen, but the change in hydrogen sensitivity is strongly dependent on the catalyst preparation.

ménytöl. Generally, the problem is that some catalyst compositions used in the production of high molecular weight polyethylene have higher polymerization activity, often several times, sometimes up to ten times higher, than that used in low molecular weight polymer production.

The imbalance in the activity of this catalyst is a frequent disadvantage of prior art catalysts. In the use of the state-of-the-art catalyst, an imbalance occurs when the productivity of the catalysts drastically decreases to convert from high molecular weight (low melt flow) polymerization conditions to low molecular weight (high melt flow) polymerization conditions. Even if the common catalyst has a fairly good productivity with a polymer melt flow index 1 (MFR - Melt Flow Rate as defined by ISO 1133), often only 10% of the productivity remains within a 500. flow index polymer. Thus, it would be desirable to have a high activity catalyst system independent of the molecular weight of the polymer formed.

• • · * * * <<<<_ _ _ _ _ _ _ _ _ _

SUMMARY OF THE INVENTION The present invention provides a novel catalyst for the preparation of low molecular weight and high molecular weight ethylene homopolymers or copolymers with uniform high activity. Irrespective of the amount of hydrogen gas introduced into the polymerization reactor, 1.

In each case, the activity of the catalyst composition according to claim 1 is balanced.

Special feature of the catalyst used herein, the good activity balance between the very broad molecular weight limits, controlled hydrogenation _was used in the polymerization of n partial pressure. As a result, the use of the new catalyst allows the polymerization of ethylene to be carried out with the same high productivity in both high and low melt flow polymer products. This flow index / activity balance provides the catalyst with universal applicability for most types of PE resins in all polymerization processes using a heterogeneous catalyst system.

It is an object of the present invention to provide maximum catalyst activity and, at the same time, catalyst activity independent of the polymerization hydrogen pressure, i.e. the polymer flow index. Accordingly, activity equilibrium (AB) can be defined as follows:

A '+ A

AB and • · ·

-6log MFR / - hangs MFR ₂ AB »A '- which implies that * A' + A AB =, MFR ', hangs ~

MFR,

A-A 'where

AB = activity balance

A = activity in [kg PE / g cat.h]

MFR ₂ = polymer melt according to ISO-1133

Flow index [g / min] measured at 2.16 kg load without superscript '= high MFR ₂ process superscript' = high. MFR ₂ procedure

In another embodiment of the invention, the catalyst comprises an inorganic support to which is added a chlorine compound, a magnesium compound and a titanium compound. It was prepared by the following steps:

a) an inorganic support with an alkyl metal chloride of the formula (R _n MeCl _{3 - n} ) _m (1) wherein R is a C 1 -C 4 alkyl group, Me is a metal of group 111 (13) of the periodic table; contacting n = 1 or 2 and m = 1 or 2 to obtain the first reaction product,

-Ί-

b) contacting the first reaction product with a compound or mixture containing hydrocarbons, hydrocarbyl oxide and magnesium to obtain a second reaction product,

c) the second reaction product a

Cl _x Ti (OR ^iv ) _{4 to x} (2) is a chlorine-containing titanium compound wherein R ^IV is a C ₂ -C ₂₀ hydrocarbon group and x is 3 or 4. This yields the catalyst.

Accordingly, the catalyst described in the present application comprises a metal alkyl chloride, a sufficiently low viscosity soluble magnesium compound or a mixture thereof (hereinafter referred to as a magnesium complex) and a titanium compound containing chlorine as an internal soluble chlorinating agent having a cocatalytic effect. Solubility of soluble compounds refers to solubility in a non-polar hydrocarbon solvent. The catalyst components are applied to a suitable catalyst support.

A good morphology can be achieved for the catalyst and, accordingly, for the polymer when used in combination with a sufficiently low viscosity soluble catalyst component.

The carrier material should have an appropriate particle size distribution, high porosity and a large specific surface area. Good results are obtained when the specific surface area of the carrier is between 100 and 500 m ² / g of carrier and the pore volume is between 1 and 3 ml / g of carrier. The carrier may be chemically pretreated, such as silanized, or treated with aluminum alkyl, etc.

Various metal oxides are suitable, but oxides of silicon, aluminum, titanium, chromium and zirconium or mixtures of oxides are preferred. Silica or silica is most suitable.

Prior to impregnation with another catalyst component, it is desirable to dry the support. Good results can be obtained if the support is heated at a temperature of 100 ° C to 900 ° C for a suitable period of time, which results in the surface hydroxyl groups, in the case of silica, falling below 2 mmol / g SiO ₂ .

The internal cocatalyst and chlorinating agent must be a chlorine-containing metal compound which is soluble in non-polar hydrocarbon solvents. A good result is obtained when this compound is an alkyl metal chloride of formula (1):

R _n MeCl _{3 - n} ) _m (1) wherein R is a C _x -C ₂₀ alkyl group, Me is a metal from group III (13) of the periodic table, preferably aluminum, k = 1 or 2 and m is one or two. The alkyl group R may be straight chain, branched, or cyclic. · ·· carbocyclic or a mixture thereof, preferably C ₂ -C ₂ o alkyl group.

Mixtures of different chlorinating agents may also be used. Good results are obtained when alkylaluminum chloride, preferably lower alkylaluminum chloride, more preferably ethylaluminum chloride, is used.

The magnesium complex used in this catalyst synthesis must be completely soluble in a non-polar hydrocarbon solution. The Mg complex (compound, mixture) is a compound of the following general formula:

Mg _a (OR ') _b R' _c X _d (3) wherein X is halogen, preferably chlorine, R 'is a hydrocarbon group, preferably C ₂ -C ₂₀ hydrocarbon group and in the formula' a '>1,' b '> 0, 'c'> 0 and 'd'>

0, and the molar ratio c / b <1.

Preferred alternatives to Mg complexes are the following compounds of formula (4), (5) or (6), or mixtures thereof:

Mg (OR ') _p (R'') ₂ - _p (4)

Mg (OCOR ') _p (R) _{2 - P} (5)

Mg (O-CH ₂ -OR ') _p (R) ₂ - _p (6)

In the formulas (4), (5) and (6), R 'and R' 'may be different or identical hydrocarbon groups. Preferably straight or branched aliphatic or aromatic groups, most preferably R 'is an alkyl group and p is 1 <p <2, most preferably 1.2 <p <2.0. OCO means in a carboxylic acid

-10 existing carboxyl group. It is essential that the p value of the formulation should be less than 2.

Compounds (3) through (6) are defined below as magnesium complexes. It is desirable to have a small amount of alkyl in each compound from (3) to (6). One way to prepare magnesium complexes is to react a soluble alkyl magnesium with alcohol. In order to achieve a good balance of reaction with hydrogen and polymerization activity, the charge ratio MgR ₂ / ROH should be higher

It should be less than 1: 2 and less than 1: 1, preferably

1: 1.75 to 1: 1.99, but most preferably 1: 1.80 to

It is between 1.98. This ratio may not necessarily be required during the preparation of the magnesium complex, but may be achieved later, for example, after the magnesium compound has been impregnated into the support to add sufficient MgR ₂ to form the appropriate MgR ₂ / ROH charge ratio. The relationship between the charge ratio and the complex can be easily obtained from the stoichiometry of the following reaction equation:

MgR ₂ + pR '''OH-> Mg (OR') _p R _{2 - p} + pRH where p is the number of R '''OH molecules per mole of MgR ₂ .

Preferably, the magnesium complex is a di (C 1 -C 10, _o ) alkyl magnesium, more preferably dibutyl magnesium, ethyl · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · butyl octane magnesium or butyl octyl magnesium and the reaction product of an alcohol. Preferably, the magnesium complex is a dialkyl magnesium and a branched alcohol, more preferably a 2-alkyl alkanol, more preferably

2-ethylhexanol or 2-propylpentanol.

The titanium compound may be a chlorinated alcohol such as Ti ₃ * OR or a unique chloride containing compound such as TiCl ₄ . The compound has the general formula (2):

Cl _x Ti (0R ^(IV1 ) ₄ _ _x (2)

In complex (2), R ^IV is a C ₂ -C ₂₀ hydrocarbon group and X is 3 or 4, preferably 4. The Ti compound must be completely soluble in non-polar hydrocarbons at the temperature employed. If pure TiCl ₄ is used, there is no additional hydrocarbon after this compound is a liquid.

Alkyl metal chloride, which also has a cocatalytic action, can be the first compound to be deposited on the support in this catalyst synthesis. It is preferred that the mole ratio of alkyl metal chloride to inorganic oxide is> 1, preferably 1 to 1.5. A uniform sedimentation is achieved if the viscosity of the material or solution is less than 10 mPa.s at the temperature employed. To achieve this low viscosity, the alkyl metal chloride may be diluted with a non-polar hydrocarbon. The best sedimentation is achieved if the total amount of alkylated metal chloride to be deposited does not exceed the pore volume of the support, or if the excess hydrocarbon solvent is evaporated after the alkyl metal chloride has been evaporated. Use of a 5-25% solution of ethyl aluminum dichloride in hydrocarbon is preferred. The settling can be carried out over a wide temperature range, preferably from 0 ° C to 110 ° C. The multiplication of the chemical addition and the addition techniques must be chosen so as to give some distribution of the chemical in the carrier.

Good sedimentation of the solution of the magnesium complex is achieved when the volume of the magnesium complex is twice the pore volume of the carrier. This, in turn, is achieved when the concentration of the complex in the hydrocarbon is between 5 and 60% by weight. The ratio of magnesium to chlorine in the alkyl metal chloride is between 1: 1.5 and 1: 2.0.

When the magnesium complex is settled on the support material, the viscosity at the temperature used should be less than 10 mPa.s. The viscosity of the solution of the magnesium complex can be adjusted, for example, in the formulas (3) to (6) by appropriate choice of the R 'group, by appropriate choice of the concentration of the hydrocarbon solution, between alkyl magnesium and alcohol.

Or by using a viscosity reducing agent.

The titanium compound may be added to the support material by pre-drying the catalyst to remove the volatile hydrocarbons or may be added without drying. The TiCl ₄ or titanium compound thereof is added in a molar amount such that the Ti / Mg is greater than 0.1 and less than one, preferably 1: 5 to 1: 1.43.

A good result is obtained when the Ti / Mg molar ratio is 0.2 to

0.7. The reaction components are allowed to react with one another for a specified temperature for a suitable period of time.

The remaining hydrocarbons, under mild vacuum, at elevated temperature or by nitrogen purge.

The catalyst is prepared as follows:

If a carrier is used, it is first dried as described above. The support is then treated with an alkyl metal chloride (1), preferably ethyl Al dichloride (EADC), which binds to the surface of the support particles by reaction with surface hydroxyl groups. Accordingly, carrier particles are formed to which the so-called internal cocatalyst with chlorinating activity is chemically bonded to form the -O-Al-Xj groups. Any free alkyl Al chloride remains between the carrier particles.

The next step involves applying Mg atoms to the carrier particles. Most commonly, magnesium is precipitated from its solution onto the particles. The most readily available Mg compounds, such as Mg halides, especially MgCl ₂ , are insoluble in liquid non-polar hydrocarbons, only in polar solvents.

Thus, short aliphatic alcohols such as methanol or ethanol can be used to prepare magnesium alcoholates. The Mg alcoholates thus formed are not completely miscible with the hydrocarbon solvents, and their mixture will form separate layers. Mg-alcoholates precipitated directly onto a support such as silica have no polymerization activity. On the other hand, a branched-chain alcohol such as 2-ethylhexanol or 2-propylpentanol, which is spherically inhibited from binding the molecule to the Mg-0 bond in the Mg alcoholate, does not readily form a coordination bond and consequently insoluble compounds. form. A solution of Mg alcoholate is formed which is completely miscible with the liquid hydrocarbons. This type of hydrocarbon solution is designed to impregnate the carrier particles so that the Mg atoms are fixed as much as possible on the carrier particles and as much as they can penetrate the particle when the hydrocarbon is evaporated.

-15A from the above-mentioned branched alcohol and dialkyl-Mg. Alcohol contains a spherically large hydrocarbon group which prevents close coordination. The dialkyl-Mg is the alkyl group

It has from 2 to 10 carbon atoms and may be straight or branched. Examples include dibutyl-Mg (DBM), ethyl-butyl-Mg (BEM), butyl-octyl-Mg (BOMAG), and the like. When the Mg alcoholate is prepared, the solution of the monoalcohol and dialkyl-Mg has a very high viscosity near the stoichiometric equivalent point, which makes the reaction difficult. The viscosity of the solution may be reduced by addition of Ti-tetraalkoxide, preferably Ti-butoxide.

When impregnating the carrier particles with a solution of Mg alcoholate in a small amount of dialkyl Mg (1-20 mol%, preferably about 10 mol%),

The -O-Al-X ₂ groups are converted to the supersaturated-u-Al-OR (OR) -R groups on the carrier particles, and MgX ₂ molecules are precipitated on the surface of the particles, presumably from the reaction between Mg compounds and the internal cocatalyst. In the surface groups, the alkyl groups R attached to the Al atom are formed from dialkyl Mg, which reacts readily with the internal cocatalyst.

Finally, in order to achieve an active catalyst, the support treated as described above is a quadrivalent support.

Titaniumize with -16Ti-halide. Preferred Ti halide a

TiCl ₄ . In the titanated catalyst, a small amount of alkoxy and alkyl groups in the backbone containing Al are exchanged for halogens and a small amount of TiCl ₄ is reduced to trivalent.

Examples

The following non-limiting examples illustrate the invention in comparison with the prior art. First, the preparation of the Mg compound complex is described, followed by the synthesis of the catalyst from this complex and other reagents, and finally polymerization of ethylene using the catalyst of the present invention and comparative examples using the prior art catalyst.

1. Complex preparation

9.5 ml of toluene (0.0899 mol) and 68.6 ml (0.060 mol) of BOMAG-A by weight were added to a flask. 16.65 mL (0.1065 mol) of 2-ethyl-1-hexanol was slowly added to the reactor. The temperature was kept below 40 ° C. The molar ratio of BOMAG-A to 3: 2-ethyl-1-hexanol was 1: 1.775.

Complex Preparation 2 kg of toluene (65.12 mol) and 27.8 kg (33.21 mol) of BOMAG-A (19.9% w / w) were added to the multipurpose reactor · The reactor was cooled to below 0 ° C. 7.89 kg (60.45 mmol / g Si)

2-ethyl-1-hexanol was added at a rate of 10-30 g / min.

-17- ............

reactor. The temperature was kept below 20 ° C. THE

The molar ratio of BOMAG-A to 2-ethyl-1-hexanol was 1: 1.8. 25.6 kg of this complex were collected in a container and used in Example 1 of catalyst preparation in an aliquot.

3. complex preparation

In Example 2 of Complex Preparation, another 0.887 kg (6.795 mol) of 2-ethyl-1-hexanol was added to the complex left in the multi-purpose reactor. Finally, 0.34 kg (1 mmol) of tetraisobutoxy titanium was added. The molar ratio of BOMAG-A to 2-ethyl-1-hexanol was 1: 2.03. The Mg: Ti molar ratio was 30: 1.

4. complex preparation

1.53 ml of 2-ethyl-1-hexanol were added to the complex of Example 3. The molar ratio of BOMAG-A to 2-ethyl-1-hexanol was changed to 1: 2.19.

Complex Preparation 5 kg of toluene was added to the reactor. Then 45.5 kg

BOMAG-A dissolved in 20.3% w / w heptane was also added to the reactor. 161 kg of 99.8% 2-ethyl-1-hexanol

The reactor was fed at a rate of 24-40 kg / hr. THE

The molar ratio of BOMAG-A to 2-ethyl-1-hexanol was 1: 1.83.

• · * «·« »· ·« ·· * · · * 4 * • · · ·

....... "· ··

catalyst Preparation

Example 1

54.9 mL (2 mmol / g Si) of 20% EADC was added slowly to 30 g of silica (Crosfield ES70X activated at 600 ° C) at 25 ° C. The mixture was stirred at 20 ° C for 2.5 hours. 72.1 g (2 mmol Mg / g Si) of the complexing compound of Example 1 were added and stirred at 20-45 ° C for 3.5 hours. The catalyst was dried at 45-75 ° C for two hours. The catalyst was cooled to 46 DEG C. and TiCl ₄ (3.33 mL, 1 mmol / g Si) diluted with 10 mL of toluene was added to the precursor. The catalyst was stirred at 45 ° C overnight. The catalyst was dried at 45-70 ° C for 2.5 hours. The catalyst composition contained 3.2% Ti, 2.0% Mg, 14.6% Cl and 2.5% Al.

The polymerization results are shown in Table 1.

Example 2

54.9 mL (2 mmol / g Si) of 20% EADC was added slowly to 30 g of silica (Crosfield ES70X activated at 600 ° C) at 25 ° C. The mixture was stirred at 20 ° C for 2.0 h. 81.0 g (2 mmol Mg / g Si), the complex of Example 2 of complexing was added and stirred at 20-45 ° C for 3.5 hours. The catalyst was dried at 45-75 ° C for two hours. The catalyst was cooled to 46 ° C · 9 · _ · *** ···· ··· ··· and 3.33 mL (1 mmol / g Si) of TiCl ₄ diluted with 10 mL of toluene was added to the precursor. The catalyst was stirred at 45 ° C overnight. The catalyst was dried at 45-70 ° C for 2.5 hours. The catalyst composition

2.6 wt% Ti, 3.0 wt% Mg, 14.3 wt% Cl and

It contained 2.4% by weight of Al.

The polymerization results are shown in Table 1.

Example 3

275 kg of activated silica at 600 ° C (Grace 955) was charged to a reactor. 411 kg of EADC (2.0 mmol / g Si) in 20% w / w 555 dm ³ (1) pentane was added to the reactor at room temperature for 1 hour. The temperature was raised to 35 ° C. The treated silica was stirred for 1 hour.

The treated silica was dried at 50 ° C for 8.5 hours. 655 kg (2 mmol Mg / g Si) of the complex prepared in Example 5 of complexing was added at 23 ° C for 10 minutes. 86 kg of pentane was added to the reactor at 22 ° C for 10 minutes. The mixture was stirred at 50 ° C for 8 hours. Finally, 52 kg of TiCl ₄ was added at 45 ° C for 0.5 hour. The suspension was stirred at 45 ° C for 5 hours. The catalyst was dried under nitrogen. The composition contained 2.4% Ti, 2.3% Mg, 14.1% Cl and 2.9% Al.

-20 * ··· «» »» · »♦ · · · ············•

• · · · • ·· ···· ··· (·

The polymerization results are shown in Table 1.

Example 4

54.9 mL (2 mmol / g Si) of 20 wt.% EADC was added slowly to 30 g of silica (ES70X activated at 600 ° C) at 25 ° C. The mixture was stirred at 20 ° C for 2.0 h. 76.6 g (2 mmol Mg / g Si), complex formation 3.

The complex of Example 1b was added and stirred at 20-45 ° C for 3 hours. The catalyst was dried at 45-75 ° C for two hours. The catalyst was cooled to 46 ° C and TiCl ₄ (3.33 mL, 1 mmol / g Si) diluted with 10 mL of toluene was added to the precursor. The catalyst was stirred at 45 ° C overnight. The catalyst was dried at 45-70 ° C for 2.0 hours. The catalyst composition contained 2.8 wt% Ti, 2.0 wt% Mg, 14.6 wt% Cl and 2.5 wt%

It contained Al.

The polymerization results are shown in Table 1.

Example 5

54.9 mL (2 mmol / g Si) of 20% EADC was added slowly to 30 g of silica (ES70X activated at 600 'C) at 25 ° C. The mixture was stirred at 20 ° C for 2.0 h. 76.7 g (2 mmol Mg / g Si), complex formation 4.

The complex of Example 1A was added and stirred at 20-45 ° C for 3 hours. The catalyst was heated to 45-70 ° C

We dried it for two hours. The catalyst was cooled to 46 ° C and TiCl ₄ (3.33 mL, 1 mmol / g Si) diluted with 10 mL of toluene was added to the precursor. The catalyst was stirred at 45 ° C overnight. The catalyst was dried at 45-70 ° C for 2.0 hours. The catalyst composition was 3.0% by weight.

Ti, 2.1% by weight Mg, 14.4% by weight Cl and 2.7% by weight

It contained Al.

The polymerization results are shown in Table 1.

Polymerization

Ethylene was polymerized under suspension conditions providing products of different molecular weights or melt indexes as follows. 1.8 L of purified n-pentane was fed to a 3 L reactor. The mixture was heated to 90 ° C. Meanwhile, a 500 mL vessel was pressurized with hydrogen at 500 kPa when polymerized under low flow index (LMFR) conditions and

1750 kPa when polymerized under high flow index (HMFR) conditions. When the temperature reached 90 ° C, the pressure in the reactor was about 420 kPa. The catalyst and the triethyl aluminum (TEA) cocatalyst were then fed into the reactor. The ethylene stream was then introduced into the reactor through a hydrogen containing vessel. The total pressure was raised to 1440 kPa and maintained by continuous ethylene supply. A po-

-22limerization lasted one hour. The Al / Ti molar ratio was 15.

The polymerization results are shown in Table 1. The results are shown in Figure 1 in the form of a graph where the polymerization activity is plotted against the average molecular weight plotted as a flow index (as determined by ISO 1133).

The BC-200 catalyst was compared with the old catalysts NC-20 (FI916192), FI886056,

FI906281 + FI895526 ', a common catalyst and US40354009.

1.8 L of purified isobutane was fed into a 3 L reactor. The contents were heated to 95 ° C. Meanwhile, one

A 500 mL vessel was pressurized with hydrogen to a pressure of 6.2 bar (6.2 * 10 ⁵ Pa) when polymerization was performed under low flow index (LMFR) conditions and to a pressure of 18.7 bar when polymerization was carried out under high flow index conditions . When the temperature of the catalyst in question and the triethylaluminum (TEA) cocatalyst were fed into the reactor. Subsequently, ethylene was fed through said hydrogen-containing vessel, thereby raising the total pressure to 28.5 bar and keeping it constant with the ethylene feed. The Al / Ti molar ratio was 30. The results are shown in Table 2. The BC-200 according to the present invention.

The AB index of catalyst -23 is clearly higher than that of the old catalysts.

Table 1

1-4. The results of the polymerization described in Examples 1 to 8

eg BOMAG: MFR ₂ g / min activity (A) k A = (A + A ' 2 AB = K FRR BD f ino pany APS 2-EH mfr ₂ MFR ' ₂ kg PE / g hour 21/2 kg / m M gold THE THE' > 0, 1 mm mm 1 1: 1,775 1.3 5.4 30 340 0, 5 1, 25 1 ' 1: 1,775 114 2.5 0, 670 3, 95 2, 64 260 0, 6 0, 93 2 1: 1,820 1.9 3, 8 29 360 0.4 1, 04 2 ' 1: 1,820 132 3, 3 3, 683 3.55 13.0 280 1.0 1, 07 3 1: 1,830 1.9 4.1 31 390 000 0, 82 3 ' 1: 1,830 135 4.1 OO 4.10 OO 290 0, 3 0, 85 4 1: 2.02 1.7 4.8 28 350 0, 6 1.14 4 ' 1: 2.02 140 1, 9 0, 660 3, 35 2.21 280 0, 8 0, 85 5 1: 2.19 1, 6 4, 9 28 340 0, 7 1, 14 5 ' 1: 2.19 130 1.7 0, 596 3, 30 1, 96 290 2.6 0, 74

BOMAG = butyl octyl magnesium

2EH = 2-ethylhexanol

EADC = ethyl aluminum dichloride

LMFR = low melt flow polymerization conditions

HMFR = High melt flow polymerization conditions

MFR2 = melt flow index according to ISO 1133 with a load of 2.16 kg

FRR = melt flow rate ratio MFR21 / MFR2 ISO 1133

-24 ·· ···· ···· • • · · · · · · · · · · · · · · • · · · ····

BD = melt density

APS = average particle size

The Al: Mg: Ti molar ratio is each. . ,. _Z1 (A + A ')

AB = activity equation = 2: 2: 1 log (MFR ' ₂ -MFR ₂ ) AA' in the example.

MFR ' ₍ log ^ £ ± A) _: ( _A- A') MFR, Table

sample activity (A) MFR ₂ g / min k A = AB = kg PE / g cat * h mfr ₂ MFR ' ₂ (A + A '): 2 K THE THE' results. 6, 0 4.2 2.0 140 1.03 5.1 5.25 FI906281 + 9.0 1, 1 2, 0 200 0.25 5, 1 1.2 8 FI895526 FI886056 6, 6 3.4 0, 3 32 0, 63 5, 0 3, 15 ordinary 3.7 1.0 0.4 40 0, 741 2.4 1.78 NesteNC20 2.3 1.2 1.2 110 1,784 1.75 3, 12 US4354009 1.7 0.2 9.0 25 0.296 1.0 0, 30

Claims (39)

claims Catalyst for the preparation of ethylene polymers, which catalyst is an inorganic support, a supported chlorine compound, a supported magnesium compound, a supported titanium compound, whereby the chlorine compound may be different from the magnesium compound and / or the titanium compound, under polymerization conditions AB activity balance AB> 3.2 where AB = [(A + A '): 2] · | log (MFR' ₂ : MFR ₂ ) :( A - A ') |, A represents the polymerization activity [kg PE / g cat * h ], MFR ₂ is the melt flow index determined in accordance with ISO 1133 at a load of 2.16 kg / min, the absence of the superscript 'means low melt index polymerization and the presence of the superscript' means high melt index polymerization. Catalyst according to claim 1, characterized in that AB> 5. The catalyst according to claim 1 or 2, characterized in that the polymerization conditions are as follows: 1.8 L of purified n-pentane was fed to a 3 L reactor and heated to 90 ° C. A separate 500 ml vessel is pressurized with hydrogen at 500 kPa, · · · · · · · · · -26- ............ when polymerization is carried out under low melt index conditions and at 1750 kPa when polymerization is carried out under high melt index conditions. When the reactor temperature reaches 90 ° C, the pressure is approximately 420 kPa. The catalyst and the triethylaluminum cocatalyst were then fed to the reactor at a Al: Ti ratio of 15: 1 mol. The ethylene stream is fed through said vessel to the reactor. The total pressure reaches 1440 kPa and is kept constant with ethylene feed. Polymerization is continued for 1 hour, and the ethylene polymer is recovered and analyzed for yield, MFR ₂ , and the yield and the amount of catalyst used. 4. A catalyst for the preparation of ethylene polymers comprising an inorganic support, a supported chlorine compound, a supported magnesium compound, a supported titanium compound, characterized in that it is prepared by a process comprising the following steps: a) an inorganic carrier, (R _n MeCl _{third n) m} (1) metal alkyl chloride of the formula: wherein R is C, _{L-C 20} alkyl group, Me is a metal of III (13) group of the Periodic Table , n = l ···· ······· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · -27- ............ or 2 and m = 1 or 2, contacting to form the first reaction product, b) contacting the first reaction product with a compound or mixture containing hydrocarbons, hydrocarbyl oxide and magnesium to produce a second reaction product, c) the second reaction product a Cl _x Ti (OR 1 ^V ) _{4 - x} (2) containing a chlorine-containing titanium compound to form a catalyst wherein R ⁴ is C ₂ -C ₂₀ hydrocarbon and x is 3 or 4. 5. The catalyst according to claim 4, wherein the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium has the following general formula or composition: Mg _a (OR ') _b R _c X _D ' (3) wherein R 'is a C ₂ -C ₂₀ hydrocarbon group, whether or not containing a hetero element, R is C ₂ -C ₂₀ hydrocarbon group, X is halogen, preferably chlorine, a> 1, b> 0, c> 0, d> 0, a = 1/2 (b + c + d) and c / b <1. 6. The catalyst according to claim 5, wherein the c / b molar ratio is between 0.05 and 0.1 and d is 0. -28 · · · «« «* * * * · * * * 7. A catalyst according to claim 5 or 6, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium has the following general formula or composition: MgOR ') _p (R) ₂ _ _p (4) Mg (OCOR ') p (R) ₂ - _p (5) Mg _(O-CH2 -OR ') p (R) 2-p (6) wherein R' is C ₂ -C ₂₀ hydrocarbyl, preferably linear or branched aliphatic or aromatic C ₂ -C ₂₀ group, R is C ₂ -C ₂₀ alkyl group and 1 <p <2, preferably 1.78 <p <1.99, most preferably 1.80 <p <1.98. A catalyst according to claim 5, 6 or 7, characterized in that the group R 'or R' is a branched C ₂ -C ₂₀ aliphatic group, preferably an aliphatic group. C ₄ -C ₂₀ , which is branched at the 2-position relative to oxygen, most preferably 2- (short alkyl) -C ₃ -C ₁₉ -alkyl than 2-ethylhexyl or 2-propyl-pentyl. 9. A catalyst according to any one of claims 1 to 5, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a product of dialkyl magnesium and an alcohol. • · · · · * * · · · · ··· ··· -29- —..... ' 10. Catalyst according to any one of claims 1 to 3, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a di (C ₂ -C ₁₀ alkyl) magnesium, preferably dibutyl magnesium, ethyl butyl magnesium or butyl. octylmagnesium and a product of an alcohol. 11. A catalyst according to any one of claims 1 to 5, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a dialkyl magnesium and a branched alcohol, preferably 2-alkylalkanol, most preferably 2-ethylhexanol or 2-propylpentanol. 12. A 4-11. A catalyst according to any one of claims 1 to 3, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a dialkylmagnesium to alcohol product, dialkylmagnesium and alcohol 1: 1.78 to 1: 1, 99 molar, preferably 1: 1.80 to 1: 1.98 molar. 13. A 4-12. Catalyst according to any one of claims 1 to 3, characterized in that in step b) the compound or mixture containing the hydrocarbon, hydrocarbyl oxide and magnesium is contacted with the first reaction product so that the compound or mixture containing the hydrocarbon, hydrocarbyl oxide and magnesium is in a hydrocarbon solution. in a hydrocarbon solution having a viscosity of less than 10 mPa * s. 14. A 4-13. A catalyst according to any one of claims 1 to 3, characterized in that it is prepared by a process wherein in step a) the inorganic support is an inorganic oxide, preferably a silica having hydroxyl groups on its surface. The catalyst according to claim 14, characterized in that the inorganic support is an inorganic support, preferably a silica having a portion of its surface hydroxyl group removed, preferably a silica having up to 2.0 mmol of surface hydroxyl group per g. 16. The catalyst of claim 14 or 15, wherein in step a) the inorganic oxide containing the surface hydroxyl groups is contacted with an alkyl metal chloride such that the molar ratio of the surface hydroxyl groups of the alkyl metal chloride to the inorganic oxide is at least 1, preferably 1 to 1.5. 17. A 4-16. Catalyst according to any one of claims 1 to 3, characterized in that it is prepared by a process in which the inorganic oxide is contacted with an alkyl metal chloride in step a) and the alkyl metal chloride is an alkylaluminum chloride, preferably a short -31 alkyl alkyl dichloride, most preferably ethyl aluminum dichloride. 18. A 4-17. Catalyst according to any one of claims 1 to 3, characterized in that it is prepared by a process comprising contacting the inorganic oxide with an alkyl metal chloride in step a), wherein the alkyl metal chloride is in a 5 to 25% by weight hydrocarbon solution, and its viscosity is preferably below 10 mPa * s. 19. Catalyst according to any one of claims 1 to 3, characterized in that the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium and the alkyl metal chloride of step a) are in a ratio such that the magnesium and the chloride of the alkyl metal chloride the atomic ratio is from 1: 1.0 to 1: 2.5, preferably from 1: 1.5 to 1: 2.0. 20. A catalyst according to any one of claims 1 to 3, characterized in that the titanium compound of step c) is titanium tetrachloride. 21. Catalyst according to any one of claims 1 to 3, characterized in that the ratio between the titanium compound of step c) and the compound or mixture containing b) hydrocarbon, hydrocarbyl oxide and magnesium is such that the atomic ratio of titanium to magnesium is 0.1 <Ti / Mg <1, preferably between 0.1 and 0.7. -32 • · * · · · · · ··· ···· ··· A process for the preparation of ethylene polymers for use in the preparation of a catalyst comprising an inorganic support catalyst, a chlorine compound applied to the catalyst, a magnesium compound applied to the catalyst, and a titanium compound applied to the catalyst comprising the steps of: a) contacting the inorganic support with an alkyl metal chloride of the formula (R _n MeCl _{3 - n} ) _m (1) R is C ₁ -C ₂₀ alkyl, Me is a metal of group 111 (13) of the periodic table, n = 1 or 2 and m = 1 or 2, to give the first reaction product, b) contacting the first reaction product with a compound or mixture containing hydrocarbons, hydrocarbyl oxide and magnesium to obtain a second reaction product, c) the second reaction product a Cl _x Ti (OR ^1V) ₄ _ a titanium compound of formula _X with chlorine (2) is contacted with the catalyst is prepared, wherein R ^IV is C ₂ -C ₂₀ hydrocarbyl group and x is 3 or 4. 23. The process of claim 22, wherein step b) is a hydrocarbon, hydrocarbyl oxide, ·········· * · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · -33- ............ and a magnesium compound or mixture thereof, having the following general formula or composition Mg _a (OR ') _b R _c X _D (3) wherein R' is a C ₂ -C ₂₀ hydrocarbon group, whether or not containing a hetero element, R is C ₂ -C ₂₀ hydrocarbon group, X is halogen, preferably chlorine, a> 1, b> 0, c> 0, d> 0, a = 1/2 (b + c + d) and c / b <1st 24. The process of claim 23 wherein the c / b molar ratio is between 0.05 and 0.1 and d is 0. 25. A process according to claim 23 or 24, wherein the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium has the following general formula or composition: MgOR ') _p (R) ₂ _ _p ' (4) Mg (OCOR ') p (R) _{2 - p} (5) Mg _(O-CH2 -OR ') p (R) ₂ _ _p (6) wherein R' is C ₂ -C ₂₀ hydrocarbyl, preferably linear or branched aliphatic or aromatic C ₂ -C ₂₀ group, R is a C ₂ - C ₂₀ alkyl group and 1 <p <2, preferably 1.78 <p <1.99, most preferably 1.80 <p <1.98. 26. The method of claim 23, 24, or 25, wherein the group R 'or R' is branched. · «• · · · _34- ............ chain C ₂ -C ₂₀ aliphatic group, preferably an aliphatic C ₄ -C ₂₀ , which is branched at the 2-position relative to oxygen, most preferably 2- (short alkyl) -C ₃ -C ₁₉ -alkyl than 2-ethylhexyl or 2-propyl-pentyl. 27. A 22-26. A process according to any one of claims 1 to 3, wherein the compound or mixture of step b) containing hydrocarbon, hydrocarbyl oxide and magnesium is a dialkyl magnesium and an alcohol product. The process according to claim 27, wherein the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a di (C ₂ -C ₁₀ alkyl) magnesium, preferably dibutyl magnesium, ethyl butyl magnesium or butyl octyl magnesium and a product of an alcohol. A process according to claim 27 or 28, wherein the compound or mixture of step b) containing hydrocarbons, hydrocarbyloxide and magnesium is a dialkylmagnesium and a branched alcohol, preferably 2-alkylalkanol, most preferably 2-ethylhexanol. or 2-propylpentanol. 30. A 27-29. A process according to any one of claims 1 to 3, wherein the compound or mixture of step b) containing hydrocarbons, hydrocarbyl oxide and magnesium is a product of dialkylmagnesium and an alcohol, dialkylmagnesium and alcohol 1: 1.78 to 1: 1, 99 molar, preferably 1: 1.80 to 1: 1.98 molar. 31. A 22-30. A process according to any one of claims 1 to 6, wherein in step b) the compound or mixture containing the hydrocarbon, hydrocarbyl oxide and magnesium is contacted with the first reaction product so that the compound or mixture containing the hydrocarbon, hydrocarbyloxide and magnesium is in a hydrocarbon solution. in a hydrocarbon solution having a viscosity of less than 10 mPa · s. 32. A 22-31. A process according to any one of claims 1 to 3, characterized in that in step a) the inorganic carrier is an inorganic oxide, preferably a silica having hydroxyl groups on its surface. 33. The process of claim 32, wherein the inorganic carrier is an inorganic carrier, preferably silica, having a portion of its surface hydroxyl group removed, preferably a silica having a surface hydroxyl group of up to 2.0 mmol. 34. A catalyst according to claim 32 or 33, characterized in that in step a) the surface bridging agent · · -36- ............ contacting the inorganic oxide containing roxyl groups with alkyl metal chloride so that the molar ratio of the surface hydroxyl groups of the alkyl metal chloride to the inorganic oxide is at least 1, preferably 1 to 1.5. 35. A 22-34. Process according to any one of claims 1 to 3, characterized in that in step a) the inorganic oxide is contacted with an alkyl metal chloride and the alkyl metal chloride is an alkylaluminum chloride, preferably a lower alkylaluminum chloride, most preferably ethylene chloride. aluminum dichloride. 36. A 22-35. Process according to any one of claims 1 to 3, characterized in that in step a) the inorganic oxide is contacted with an alkyl metal chloride and the alkyl metal chloride is present in a 5 to 25 wt% hydrocarbon solution and the solution has a viscosity preferably below 10 mPa · s. it is. 37. A 22-36. A process according to any one of claims 1 to 3, wherein the compound or mixture of step b) containing hydrocarbon, hydrocarbyl oxide and magnesium and the alkyl metal chloride of step a) are in a ratio such that the magnesium and the chloride of the alkyl metal chloride the atomic ratio is from 1: 1.0 to 1: 2.5, preferably from 1: 1.5 to 1: 2.0. 38. A 22-37. A process according to any one of claims 1 to 5, characterized in that the titanium compound of step c) is titanium tetrachloride. -37 • · · · · · · ··· 39. A 22-38. Process according to any one of claims 1 to 3, characterized in that the ratio of the titanium compound of step c) to the compound or mixture of b) containing hydrocarbons, hydrocarbyl oxide and magnesium is such that the atomic ratio of titanium to magnesium is 0, 1 <Ti / Mg <1, preferably between 0.1 and 0.7.