SK59494A3 - High-active catalyst for polymerization of olefins, method of its preparation and use - Google Patents

Abstract

Highly active olefin-polymerisation catalysts comprising organometallic Ti, Zr or Hf compounds and partially hydroxylated metal oxides from group IIa, IIIa, IVa or IVb of the Periodic Table which are essentially free from byproducts.

Description

Technical field

The invention relates to high-activity catalysts for the polymerization of olefins and to a process for the polymerization using these catalysts.

BACKGROUND OF THE INVENTION

US 3,932,307, US 3,950,269, US 4,228,263 and US 4,335,225 disclose olefin homopolymerization and copolymerization catalysts, such as ethylene, propylene, butene-1 and higher olefins, obtained by reacting organometallic compounds Ti, Zr or Hf with partially hydroxylated metal oxide surfaces. , for example Al2O3, T1O2, S1O2. MgO. The polyolefins obtained on these catalysts are characterized by improved properties and, in particular, polyolefins having elastomeric properties can be obtained, in particular, by the stereoregular arrangement of the blocks in the chain structure. For example, elastomeric polypropylenes, such as those described in US 4,335,225, consist essentially of blocks of isotactic and atactic propylene sequences that are alternately arranged in a polymer chain, and additional comonomers may also be incorporated into the polymer chain. Elastomeric polyolefins are characterized in particular by high elasticity and good toughness and impact toughness properties. The elastomeric polyolefins are prepared according to a conventional method by polymerizing olefins, optionally together with other comonomers in organic reaction media such as hexane, cyclohexane or in liquid or gaseous monomers.

A disadvantage of the known catalysts used for the preparation of the elastomeric polyolefins is, in particular, that their activity is not very high, so that relatively large amounts of catalyst are required for polymerization. For example, US 4,228,263 yields from 30,000 to 1 million g of polymer per g of Zr atom, but the yields actually achieved by 575,000 g of polymer / g Zr atom are well below this value. In addition to the high consumption of catalyst, it also proves to be very unfavorable that relatively large amounts of catalyst residues are present in the finished polymer, which constitute contamination of the polymer, which entails a deterioration in the properties of the polymer, in particular mechanical and optical properties. The catalyst residues in the polymer are, for example, according to a preferred process type in the sense of US 4,228,263 in Example 3A · about 0.63% by weight. Al 2 O 3 and 217 ppm Zr.

SUMMARY OF THE INVENTION

It is an object of the present invention to overcome these disadvantages and, in particular, to find catalysts of higher activity with which higher polymer yields can be achieved. Such improved catalysts can be obtained according to the invention in such a way that the catalyst by-products and by-products produced during the catalyst production are also partially or completely separated

Accordingly, the present invention provides a highly active catalyst for the polymerization of olefins, predominantly consisting of a reaction product and / or organometallic compounds of the formula (R-CH3), wherein R is an aryl, aralkyl, tertiary alkyl or trialkylsilyl radical, wherein RCH2 is there is no hydrogen bonded to the beta atom, and M represents Ti, Zr or Hf, with b / metal oxides from the group IIa, IIIa, IVa, IVb of the periodic system with a partially hydroxylated surface or mixtures thereof in a hydrocarbon reaction medium, the catalyst obtained is optionally hydrogenated and is characterized in that it contains no or very small amounts of by-products resulting from the reaction.

R is understood in particular to be those described in US 3,932,307 and US 3,950,269, wherein the alkyl radicals may have 1 to 12 C atoms. Preferably, these are benzyl, neopentyl and neopyl radicals. Examples of organometallic compounds include tetraneophyllzirconium, tetraneopentylzirconium, tetrabenzyltitanium, tetrabenzylzirconium, tetraneopentylhafnium, tetrabenzylhafnium, tetrakis (trimethylsilylmethyl) zirconium, tetranofuranitane. Particularly suitable metal oxide components of the catalyst are those described in US 3,932,307 and US 3,950,269. Preferred metal oxides are Al2O4, TiO2, SiO2 or MgO. Hydroxylation of the metal oxide surfaces takes place, for example, in a water vapor atmosphere and subsequently at 300 to 500 ° C:

Both catalyst components generally react in a ratio of about 0.01 to 1 mMol of organometallic compound per gram of metal oxide. Preferred catalysts are those produced by reacting an organozirconium compound (RC 1 O 2 Zr, in particular tetraneophylzirconium (TNZ), with hydroxylated Al 2 O 3. The most preferred ratio of TNZ and Al 2 O 3 is about 0.1 to 1 mMol organozirconium compound per gram Al 2 O 3. catalysts in known low activity form are described, for example, in US 3,932,307, US 4,335,225, optionally in their hydrogenated form in US 3,950,269 and US 3,971,269.

The process for producing the catalysts in their highly active form is a further object of the invention. Essentially, the a / organometallic compounds of the formula (R-Cl → M), in which R represents an aryl, aralkyl, tertiary alkyl or trialkylsilyl radical, are reacted, with no hydrogen atom bonded to the beta and M atom in the RCH2 group. means Ti, Zr or Hf, with b / metal oxides from the group IIa, IIIa, IVa, IVb of the periodic system with a partially hydroxylated surface or mixtures thereof in a hydrocarbon reaction medium, the catalysts obtained optionally being subsequently hydrogenated. the by-products subsequently wholly or partially from the obtained catalyst

- 4 plugs removed.

Conventional hydrocarbons, such as alkanes, for example butane, pentane, hexane, cycloalkanes, for example cyclohexane, or mineral oils, are used as reaction medium in the olefin polymerization.

It is believed that the reaction of the organometallic compounds with the partially hydroxylated metal oxide, for example the partially hydroxylated Al 2 O 3, proceeds preferably according to the following equation:

O-A1-O-A1-O

I!

-OH OH '

O-Al-O-Al-O

II oo (r - ch ₂ Ti m

2rch.

Zr (CH ₂ - R) ₂

The reaction to a catalyst containing Al and Zr is followed by separation of the by-products of the invention, for example by scrubbing with, for example, a liquid, inert hydrocarbon to be used as reaction medium, by mechanical separation such as filtration, centrifugation or decanting together with the reaction medium and / or evaporation preferably under vacuum. .

In the post-purification of the reaction according to the invention, preferably RCH 3 is formed, which is formed alongside the catalyst as a by-product according to the above reaction equation. Other by-products which may be used are, for example, those which are formed when the catalyst is aging or hydrogenated and which are formed largely in liquid or soluble form, for example R-C1-radicals or, if appropriate, hydrogenation of compounds such as ethylcyclohexane.

(1-methylethyl) cyclohexane and (1,1-dimethylethyl) cyclohexane. Compared to the activities of the known catalysts, considerable improvements are already shown when by-products are separated, for example in the case of tetraneophylzirconium tert. butylbenzene according to the invention, for example by filtration or centrifugation together with a liquid hydrocarbon used as reaction medium. Furthermore, it has proved to be advantageous to recrystallize the organometallic compound (RCH ₂ ) ₄ M used for the production of the catalyst prior to reaction with the metal oxide from the liquid hydrocarbon, and preferably to dissolve it at the lowest possible temperature.

A further object of the invention is a process for the polymerization of olefins using the catalysts according to the invention which achieve particularly high polymer yields based on the amount of catalysts used as olefins, in particular ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1,4-hexadiene or 1,5-hexadiene, whereby homopolymers as well as copolymers can be produced. Preference is given to using catalysts for the homopolymerization or copolymerization of ethylene, propylene, butene-1, pentene-1 and 4-methylpentene-1, particularly preferably with propylene or ethylene as a comonomer. The polymer yields in the case of propylene are about 2.6.10 µg per mole of transition metal M used. The catalysts can be used in the polymerization mixture, both as a powder and as a slurry in a hydrocarbon such as butane, pentane, hexane , cyclohexane or mineral oils.

With the aid of the catalysts according to the invention, the molar masses of the polymers can be controlled to a large extent by the addition of hydrogen during the polymerization. The catalysts can be used in all known polymerization processes, such as continuous and discontinuous solution, gas phase or bulk polymerization processes. They are characterized by increased stability even at higher polymerization temperatures, as a result of which they exhibit increased efficiency and can also be used in processes with longer residence times.

DETAILED DESCRIPTION OF THE INVENTION

A Catalyst production

Example 1: Catalyst A

44.22 g of gray-brown tetraneophylzirconium (TNZ; Tm - 66 ° C, Du Pont) was dissolved at 20 ° C in a shielding gas flask under pure nitrogen in 620 ml of n-hexane, which was purified using Cu-catalyst (BASF) catalyst R 3-11 at 70 ° C) to remove oxygen and a 4 or 10A molecular sieve to remove water and polar impurities. After settling most of the insoluble residue after 15 minutes, the resulting suspension was filtered through a glass frit into a glass flask with stirring gas, cooled to -40 ° C (heated in an oven to above 150 ° C and purged with pure nitrogen (below 2 ppm O2) ) · The flask was kept at -40 ° C for 15 minutes with stirring to complete the TNZ as much as possible after stirring (about 140 min.) With stirring. The remaining TNZ was dissolved in an additional 350 ml of n-hexane at about 5-10 ° C for 15 minutes and re-precipitated after cooling to -34 ° C.

After the TNT precipitate had settled, the solution was again filtered through a filter candle to a cooled shielding gas flask containing the first mother liquor via N ₂ pressure. Subsequently, the TNZ was dried by connecting the vacuum of an oil pump (below 1.10 ~ 3 mPa) through a liquid nitrogen cooled freezer. The purified TNZ had a melting point of 68 ° C and was white to cream. The mother liquors were collected. concentrated by evaporation to about 200 ml and the dissolved TNZ was precipitated by cooling to -40 ° C. After re-filtration through a filter plug, TNZ was redissolved in 100 mL hexane, reprecipitated at -40 ° C, filtered and dried under vacuum as described above. The overall yield of this purification process was 82.2%. All operations were conducted under pure nitrogen.

A 6 L four-necked shielding gas flask was weighed with 266.7 g of conditioned Al 2 O 3 (Alumina C DEGUSSA, conditioned at about 800 to 1000 ° C in a stream of N and after storage at 50% relative humidity and 23 ° C for 16 hours and re-drying to set the optimum hydroxyl concentration on the surface of about 1 mmol / g alumina (at 400 ° C under a stream of nitrogen) and mixed with 5035 ml of n-hexane, purified with BASF catalyst R 3-11 and 4 or 10Λ molecular sieve. The suspension was stirred for about 1 hour at 300 rpm. Thereafter, 33.23 g of TNZ (free from mother liquor) were previously dissolved in 465 ml of n-hexane (purified as previously described) and this TNZ solution was first added dropwise to the Al 2 O 3 slurry with stirring over 50 minutes. after addition of a few ml of TNZ solution, the viscosity was significantly reduced. After the addition of the TNZ solution, the revolutions were reduced to 120 rpm and stirring was continued for an additional 12.5 hours with protection from light. In order to accelerate filtration, the obtained catalyst solid was allowed to settle for 1 hour and finally the solution was separated by pressure filtration through a glass frit (duration 3 hours). Then, the catalyst solid was applying a reduced pressure below 1.1 () ^J mPa.s (oil diffusion pump with two with intermediate circuit, liquid nitrogen-cooled trap, with stirring, dried to constant weight of 292 g (duration about 5 hours). All operations were carried out under extra pure nitrogen. The obtained TNZ / Al 2 O 3 catalyst was a beige to pale brown color and was a free-flowing powder that formed small beads of about 1 mm diameter.

1.66% by weight.

The Zr content was

Example 2; Catalyst B

Catalyst production was analogous to Example 1, but proceeded with the parameters shown in Table 1, except that tetraneophysirconone (TNZ) was recrystallized again from n-hexane for a second time. Melting point 68.2 ° C, Zr content 1.69 wt%.

Examples 3-6: Catalyst C-F

Catalysts were prepared analogously to Example 1, but in accordance with the parameters in Table 1.

Example V7: Comparative Catalyst G

The catalyst was produced analogously to Example 2 in accordance with the parameters of Table 1, but without separation of the reaction medium.

Example 8: Catalyst H

30.79 g of the catalyst obtained according to Example 2 were charged into a 250 ml 3-neck shielding gas flask with a thermometer and a manometer of 1.2 bar of hydrogen and stirred at 30 ° C for 105 minutes at 100 rpm. After the pressure dropped to 0.2 bar, the flask was again pressurized with hydrogen to 1.2 bar and heated to 47 ° C in an air bath. After 3 hours, the pressure in the shielding gas bank dropped to 0.6.10 $ Pa. The shielding gas flask was evacuated (below ^{10 5} mPa) via an oil pump through two liquid nitrogen-cooled freezers to separate the reaction products. 0.57 g of a mixture, consisting mainly of alkylcyclohexanes, were separated.

The partially hydrogenated TNT / Al 2 O 3 catalyst obtained was in the form of a free-flowing beige to light brown powder with a Zr content of 1.72% by weight.

Example 9: Catalyst 1

11.2 g of the catalyst produced according to Example 8 were

- 9 are placed in a 250 ml 3-necked shielding flask fitted with a thermometer and a pressure gauge of 1,2.10 bar of hydrogen. The flask was heated in a water bath heated to 80 ° C for 94 minutes while the catalyst was stirred at 100 rpm. The internal gas temperature rose to 44 ° C, the pressure dropped to 1.08 bar. Subsequently, the flask was cooled to room temperature and evacuated as in case 8. The hydrogenation loss (94 minutes) was less than 0.1 g. The obtained TNZ / Al 2 O 3 catalyst was hydrogenated to more than 90%.

B / Polymerization:

Example 10:

At 160 ° C and 0.1.10 µmPa, a heated 20 L double jacket reactor with a wall mounted stirrer with polished surfaces, a thermostat jacket, temperature, speed and torque measurements was charged 7.15 after three propy / vacuum purge cycles. kg of propene at 25 ° C. After acceleration to the mixer 400 οΐ / min was injected 11.24 g of the catalyst prepared in Example 1 Λ of 300 ml of liquid propene (about 20 ^e C), and the speed was reduced to 2 minutes at 260 οΐ / min. Subsequently, the temperature of the propene was raised to 60 ° C over about 10 minutes and this temperature was maintained for 67 minutes after the addition of the catalyst. Subsequently, the stirrer speed was reduced to 200 ΐΐ / min and 4000 g of acetone preheated to 40-50 ° C were added to the reactor using nitrogen overpressure over three minutes. After increasing the stirrer speed to 400 rpm for about 2 minutes and then reducing it to 100 rpm, the unused propene was distilled off within 20 minutes. The remaining ELPP (elastomeric polypropylene) -acetone suspension was miscible and could be drained through the bottom outlet. To stabilize the ELPP, an appropriate amount of stabilizer mixture XONOL ® (Shell) and IRGAFOS ® PEPQ (Fa Ciba-Geigy) was added to the acetone slurry at a 2: 1 weight ratio, which was about

0.3% by weight. in a dried polymer.

The reactor walls and the stirrer were mostly polymer-free. After filtering the ELPP and drying under a stream of nitrogen at 50 ° C, we obtained 1.39 kg of a powder-friable non-sticky ELPP with a melting point (Tm) of 141.7 ° C (measured by Du Pont Differential Svanning Calorimeter 910/20 / Thermal Analyst 2100). /), corresponding to a balanced Zr content of 135 ppm and an Al2O3 content of 0.74% by weight.

Example 11:

The procedure was analogous to Example 10 in accordance with the parameters set forth in Table 2, except that 6.6 kg of propene at 29 ° C were additionally charged when the reactor was charged ^! dosed with 8.25 1 H2

The resulting ELPP-acetone slurry was miscible and could be drained through the bottom of the reactor. After filtration and vacuum drying, 1.07 kg of ELPP powder capable of flowing in a thin stream with an inherent viscosity of 5.42 dL / g, measured based on DIN ISO 1628, was obtained at a concentration of 1 g / l and a melting point of 149.1 ° C. , measured with a Du Pont Differential Scanning Calorimeter 910/20 (Thermal Analyst 2100).

Example 12:

The procedure was analogous to Example 10 in accordance with the parameters given in Table 2, except that the polymerization time was 120 minutes instead of 67 minutes.

The resulting ELPP-acetone slurry was miscible and could be drained through the bottom of the reactor. After filtration and vacuum drying, 1.88 kg of ELPP powder capable of flowing in a thin stream with a melting point of 148.1 ° C was obtained, measured with a Du Pont Differential Scanning Calorimeter 910/20 (Thermal Analyst 2100). The balance zirconium content was 89 ppm, the Al 2 O 3 content was 0.49%.

Example 13:

After 120 minutes of polymerization, analogous to Example 11 and with the polymerization parameters shown in Table 2, about 40-50 ° C of preheated methanol was charged into the reactor in place of acetone with preheated methanol at a nitrogen pressure of 40.10 Pa for 2 minutes at 200 rpm. . Subsequently, the reactor jacket was thermostatized to 60 ° C and unused propylene was distilled off over 15 min. The methanol suspension obtained was miscible and could be discharged through a ball valve at the bottom of the reactor. The reactor walls, stirrer and thermocouple sleeve were largely polymer free: 0.3% by weight added. (based on the dried polymer) of a corresponding amount of stabilizer mixture consisting of IONOL ^R (Shell) and IRGAFOS ^R PEPQ (Ciba-Geigy), in a 2: 1 ratio by weight to suspension and drying in a stream of air followed by vacuum at 50 ' C, we obtained 1.93 kg of pulverulent, non-sticky, and suitable ELPP dispensing machines with an inherent viscosity of 10.1 dl / g, measured based on DIN ISO 1628 at a concentration of 1 g / l and a melting point of 147 ° C, measured with Du Pont Differential Seanning Calorimeter 910/20 (Thermal Annals).

Examples 14 and 15:

The procedure was analogous to Example 12 in accordance with the parameters given in Table 2, except that the polymerization time was extended. Balanced contents of zirconium and Al 2 O-j show that the activity of the catalyst was maintained at a polymerization temperature of 60 ° C for more than 4 hours.

Example 16:

The procedure was analogous to Example 10 in accordance with the parameters given in Table 2 except that the polymerization temperature was raised to 70 ° C.

The obtained acetone slurry was flowable and drained through a valve at the bottom of the reactor. After stabilization with 0.3% by weight. Ionol / Irgafos PEPQ (w / w = 2: 1) based on the polymer and dried in a stream of air and vacuum at 50 ° C we obtained a transportable and dispensable, friable-powdered elastomeric polypropylene. Balanced content of Zr or Al 2 O 3 111 ppm or 0.61 wt%, respectively. corresponds to an activity increase of about 34% when the polymerization temperature rises from 60 ° C to 70 ° C.

Example 17:

The procedure was analogous to Example 13 in accordance with the parameters given in Table 2 except that the polymerization temperature was 70 ° C and 2800 g of acetone were metered in instead of methanol. After separation of the acetone, the obtained crumb-powdered elastomeric polypropylene with a Zr or Al2 O3 content of 69 ppm or 0.38% by weight, respectively, is obtained. exhibited an inherent viscosity of 10.35 dl / g, measured according to DIN ISO 1628 at a concentration of 1 g / l and an inherent viscosity of 10.22 dl / g, measured according to DIN ISO 1628 at a concentration of 0.55 g / l.

Example 18:

The procedure was analogous to Example 17 in accordance with the parameters in Table 2, using catalyst B according to Example 2 (TNZ twice recrystallized) and a polymerization time of 4 hours. After precipitation with acetone, the obtained ELPP suspension was liquid and could be drained through the bottom valve. Addition of 0.3% stabilizer, based on ELPP (Ionol / Irgaf os) PEPQ (weight ratio - 2: 1) or drying in air stream and then under vacuum at 50 ° C, gave a crumb-powdered, elastomeric polypropylene with a balanced content Zr or Al 2 O 3 41 ppm or 0.22 wt%, respectively. and an inherent viscosity of 9.6 dl / g, measured based on DIN ISO 1628 at a concentration of 1 g / l.

Comparative example V19:

The procedure was analogous to Example 18 in accordance with the parameters given in Table 2, except that catalyst G produced in the reaction medium of n-hexane and not according to the invention of Example V7 was used without separation of the reaction medium and other reaction products. After precipitation with acetone, the obtained ELPP suspension was liquid and could be drained through the bottom valve. After adding about 0.3 wt.%. Ionol / Irgafos PEPQ stabilizer mixture (weight ratio = 2: 1) relative to the dry polymer and air dried and then vacuum dried at 50 ° C to obtain a friable-powdery elastomeric polypropylene having a Zr 60 ppm balance and ΑΙ ^ Οβ 0, 33% with an inherent viscosity of 9.8 dl / g, measured based on DIN ISO 1628 at a concentration of 1 g / l. By way of example, it is evident that much larger catalyst residues remain in the polymer when using a catalyst not according to the invention.

Example 20:

The procedure was analogous to Example 17 in accordance with the parameters in Table 2 except that the polymerization temperature was 80 ° C.

polypropylene 0.30% by weight. temperature increase after separation of acetone, the elastomer obtained obtained showed a Zr content of 54 ppm or Al 2 O 3, in accordance with an increase in activity of 28% at a lot from 70 to 80 ° C.

Example 21:

The procedure was analogous to Example 17 in accordance with the parameters in Table 2 except that the polymerization temperature was 80 ° C and the polymerization time was 4 hours. The ELPP obtained after acetone separation showed a Zr content of 35 ppm and an Al2O3 content of 0.19%.

Example 22:

The procedure was analogous to Example 12 in accordance with the parameters in Table 2, except that after a polymerization time of 15 min. after catalyst loading, the total reactor pressure was increased from 22.7 bar to 23.7 by ethylene feed. 10 bar and this pressure was maintained by adding ethylene until precipitation with acetone after 60 minutes. The total ethylene feed rate was about 270 g.

The obtained acetone suspension of the elastomeric copolymer was miscible and fluid and could be discharged through a bottom valve. The Zr content optionally in the air-dried elastomeric copolymer and subsequently under vacuum at 50 ° C was 58 ppm or 0.33% by weight.

Example 23:

The procedure was analogous to Example 12 in accordance with the parameters given in Table 2, except that after a polymerization time of 15 minutes and after the catalyst was metered in, ethylene with a constant gas flow was metered to precipitation with acetone. The feed rate of ethylene was about 610 g.

The acetone suspension of the elastomeric copolymer obtained was miscible and fluid and could be discharged through a valve at the bottom of the reactor. The Zr or Al2O4 content of the elastomeric copolymer dried in the air stream and subsequently under vacuum at 50 [deg.] C. was 42 ppm and 0.23% by weight, respectively.

Example 24:

The procedure was analogous to Example 12 in accordance with the parameters set out in Table 2, except that the hydrogenated catalyst H produced according to Example 8 was used.

The obtained acetone suspension of elastomeric polypropylene was miscible and fluid and could be discharged through a bottom valve. The content of Zr and / or Al2O4 in the finely powdered, transportable (pumpable) elastomeric polypropylene, dried in a stream of air, optionally subsequently under vacuum at 50 DEG C., was 89 ppm and 0.49% by weight, respectively.

Example 25:

The procedure was analogous to Example 18 in accordance with the parameters given in Table 2 except that the hydrogenated catalyst I produced according to Example 9 was used.

The resulting elastomeric polypropylene acetone slurry was miscible and fluid and could be drained through the bottom valve. Balancing of the Zr content, or Α1 ₂ 0β of fine powder, and carried, the elastomeric polypropylene, dried in a stream of air and then in vacuo at 50 ° C was 50 ppm, or 0.27 wt.%

Table 1: Production of catalysts

Ex. catalytic Zator surový- TNZ * [G] hexane [Ml] filtering [Min] temperature precipitation [° C] extracts TNZ * [%] 1 A 44.22 620 140 -40 82,2 2 B 39.95 475 80 -40 80.2 3 C 28.77 380 120 -35 84.6 4 D 12.02 158 50 -39 73.2 5 E 24.2 340 50 -40 83.8 6 F 31.71 380 64 -45 83.9 V7 G 39.95 475 80 -40 80.2

Table 1 - continued: production of catalysts

Pr. ^A1 2 ° 3 con. [G] n-hexane for AlqOq [Ml] TNZ * [G] n-hexane for TNZ [Ml] Insertion eTNZ catalysis. dried stirrer. r / min el. ml / min 1 266.7 5035 33.23 465 350 10 292 2 232.8 4410 29.1 404 350 10 251.52 3 144.44 3000 17.35 270 500 10 154,62 4 71.04 1462 8.8 136 450 6 76,69 5 148.25 2800 18.46 260 450 10 162.31 6 203.3 3850 25.27 356 400 10 215,75 V7 4 76 0.5 10 350 0.5

♦ Tetraneophyllzirconium

Table 2: Polymerization

Pr. catalytic Zator [G] propene [Kg] temperature polymer [° C] duration polymer [H] addition of acetone (ac) and methanol (me) _ evaporation. [° C] [Kg] [° C] 10 11.24 7.3 60 1.1 4 ac 40-50 60-50 11 6.17F 6.6 60 1 2,5 ac 40 40-35 12 10.02 7.6 60 2 1,88 ac 50 60-46 13 10.82D 7.6 60 2 1,7 me 40-50 60-46 14 11.26 .7,6 60 4 2,5 ac 40-50 56-32 15 8.55 7.6 60 6 2,5 ac 40-50 55-32 16 11,46F 7.6 70 1 2,5 ac 40-50 67-36 17 6.02 7.6 70 2 2.8 ac 50 65-22 18 4,4-bis 7 70 4 2,5 ac 40-50 56-25 V19 4.5g 7 70 4 2,5 ac 40-50 56-25 20 5.4E 6.5 80 2 2,5 ac 50 69-40 21 4,26F 7.4 80 4 2,5 ac 40-50 70-40 22 11.12C 7.6 + ethene 60 1 2,5 ac 25 50-25 23 7,26Λ 7.6 + ethene 60 2 2,5 ac 40-50 55-35 24 8,25H 7.2 60 2.1 2.7 ac 25 53-13 25 5,421 7.1 70 4 3 ac 50 53-25

Table 2 - continued: polymerization

Pr. polymer [Kg] Zr [Ppm] ^A1 2 ° 2 [%] dark (melting point) [° C] inherent viscosity [Dl / g] 10 1.39 135 0.74 147.1 11 1.07 99 0.54 149.1 5.42 12 1.88 89 0.49 148.1 13 1.93 94 0.52 147 10.1 14 2.72 69 0.38 147.2 15 2.46 58 0.32 147.9 16 1.76 111 0.61 17 1.45 69 0.38 10.35 18 1.82 41 0.22 9.6 VI9 1.22 60 0.33 20 1.67 54 0.30 147.2 21 2.11 35 0.19 22 3.13 58 0.33 23 2.91 42 0.23 24 1.59 89 0.49 25 1.89 50 0.27

Claims (9)

PATENT CLAIMS A high activity olefin polymerization catalyst comprising Ti, Zr and / or Hf, consisting essentially of a reaction product (a) organometallic compounds of the formula (R-CF3-M) where there is an aryl, aralkyl, tertiary alkyl or trialkylsilyl radical, wherein no R bond is present in the RCH2 group, and M represents Ti, Zr or Hf with (b) metal oxides of Group IIIa, IIIa, IVa, IVb having a partially hydroxylated surface or mixtures thereof in a hydrocarbon reaction medium, the catalyst obtained optionally being hydrogenated, characterized in that the catalyst thus obtained contains no or only minor amounts of by-products; formed in the reaction. Catalyst according to claim 1, characterized in that the residue R of the organometallic compound is a benzyl, neopentyl or neophyll residue. Catalyst according to claim 1 or 2, characterized in that the metal oxides are selected from the group of ^ ^ ^Ο, T1OO, S SOO and MgO. Catalyst according to one of Claims 1 to 3, characterized in that it consists essentially of a reaction product of tetraneophylzirconium and hydroxylated Al 2 O 3. Catalyst according to one of Claims 1 to 4, characterized in that it is suitable for the homopolymerization or copolymerization of ethylene, propylene, 1-butene, 1-pentene or 4-methyl-1-pentene. 6. A process for producing high-activity olefin polymerization catalysts in which they react (a) substantially organometallic compounds of formula (RCl 2), wherein R is an aryl, aralkyl, tert-alkyl or trialkylsilyl radical, wherein the RCH ₂ group contains no beta bond to M, and wherein M is Ti, Zr or (b) with oxides of the group IIa, IIIa, IVa, IVb having a partially hydroxylated surface or mixtures thereof in a hydrocarbon as reaction medium, the catalysts obtained are subsequently optionally hydrogenated, characterized in that the by-products forming are wholly or partially removed from the catalyst obtained. The process for producing catalysts according to claim 6, characterized in that the organometallic compound of formula (RCF? M) is recrystallized from a liquid hydrocarbon prior to reaction with the metal oxide. 8. A method for the production of polyolefins by catalytic homopolymers or _t rizáciou kopolymerizáeiou olefins wherein U * C is characterized r that is used in the polymerization catalyst according to any one of claims 1 to 7th Process according to claim 8, characterized in that propylene is used as olefin, optionally with ethylene as a comonomer.