DE2840156A1 - METHOD FOR PRODUCING A MIXED CATALYST - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 78 / F 187. 1978 Dr. DA / wö Process for the production of a mixed catalyst

The invention relates to the preparation of catalysts which allow a stereospecific polymerization of 1-olefins to polymers with a high isotactic content and a low fine grain content. 5

Processes for the selective polymerization of 1-olefins to give predominantly crystalline ones are described in numerous publications or amorphous polymers using certain supported catalysts.

Catalysts have been described which are prepared by grinding magnesium or manganese halides with titanium tetrahalide electron donor complexes and are used together with aluminum alkylene and electron donor compounds for the polymerization of propylene (cf. DE-OS 22 30 672). However, the stereospecificity of approx. 95 % (isotactic proportion in the polymer) is not yet sufficient and the yield of polymer products is still too low for the catalyst residues to remain in the

Allow 20 polymers.

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Furthermore, a catalyst system which enables the polymerization of propylene with particularly good yields, even when the polymerization is carried out in the presence of an inert hydrocarbon diluent, is known. The catalyst is prepared by grinding a magnesium halide with an electron donor. The millbase is then reacted with titanium tetrachloride and then washed several times with boiling heptane. An aluminum trialkyl together with an aromatic carboxylic acid ester (cf. DE-OS 26 43 1 ^ 3) is used as an activator. The decisive disadvantage of this catalyst system lies in the relatively large amounts of fines below 100 μm in the polypropylene.

Finally, a mixed catalyst is known for whose transition metal component a magnesium halide support is reacted with two different electron donors (cf. DE-OS 27 08 588). The catalyst produced on the basis of this modified carrier leads, in the polymerization of propylene, to a polypropylene with a smaller proportion of grain sizes . 100 µm, however, the reduction in fines is not sufficient.

It has now been found that the fines content can be effectively reduced and the polymer yield can also be increased can if you look after making the modified Catalyst carrier switches on a washing stage.

The subject matter of the invention is thus the method mentioned in claims 3.0 and the method produced by this method PCatalyst.

To produce the catalyst component A, a magnesium halide is first used with an electron donor and / or modified a cyclopolyene.

An anhydrous magnesium dichloride, which is commercially available, is preferably used as the magnesium halide.

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Such a magnesium chloride generally contains 0.05 to 1% by weight Water. Magnesium dibromide can also be used if desired.

As electron donor compounds, ethers, amides, Amines, esters, ketones, nitriles, phosphines, phosphinic acid esters, phosphoramides, thioethers or thioesters are used will. However, the electron donor compounds used should not be oxygen, nitrogen or Contain sulfur-bound hydrogen.

Suitable electron donor compounds are, for example, diethyl ether, dioxane, anisole, dimethylacetamide, tetramethylethylenediamine, Ethyl acetate, acetone, acetophenone, acetonitrile, benzonitrile, triethylphosphine, Triphenylphosphine, isobutyl methylethylphosphinate or hexamethylphosphoric trisamide.

However, preferred electron donor compounds are esters of aromatic carboxylic acids such as ethyl benzoate, Benzoic acid methyl ester, p-toluic acid ethyl ester, methyl p-toluate, ethyl anisate or methyl anisate are used.

Cyclopolyenes are also used to modify the magnesium halide such as cycloheptatriene (1,3,5) or cyclooctatetraene are suitable.

Modifying the magnesium halide with the electron donor and / or cyclopolyene may be carried out in manner known per se in the presence or absence of an inert solvent at a temperature of -20 ⁰ C to 100 C, for example by heating the magnesium halide in a solution of the reactant, Suspending the Mg halide in the liquid reactant or by grinding both components together, with higher temperatures also occurring due to the frictional heat during grinding

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can. In some cases it may also be necessary to cool the mill. The optimum temperature depends on the thermal stability of the electron donor or cyclopolyene used.
5

It is preferred to work in the absence of a solvent, for example by milling the magnesium halide with the pure electron donor compound and / or the cyclopolyene. The grinding is preferably done in a vibrating

10 tion mill carried out. The grinding time is 1-120

Hours or longer, preferably 30 to 100 hours. However, other comminution methods can also be used where sufficiently large shear forces act on the Regrind are exercised.

The molar ratio of the magnesium halide used to the electron donor compound and / or to the cyclopolyene is more than 2: 1, a molar ratio of 3 to 15: 1 is preferred, a molar ratio is particularly preferred

20 ratio from 4.5 to 8: 1.

The modified support used for the preparation of the catalyst component A should be specific

2
Surface area of more than 1 m / g, preferably one

2 25 have a specific surface area greater than 4 m / g.

It was found by X-ray spectral analysis that the preferred magnesium chloride used in? X-ray diagram of a halo with an intensity maximum 30 is between 2.44 and 2.97 Å.

The modified carrier is then mixed with a liquid Washed out hydrocarbon. As liquid hydrocarbons are e.g. suitable. Hexane, heptane, cyclohexane and especially diesel oil fractions, e.g. those with a

Boiling range from 135 to 170 ⁰ C. The washing temperature is

in the range from 50 to 150 ⁰ C, preferably from 70 to 120 ⁰ C, the

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Washing out is carried out until the washing liquid is in practically no electron donor or cyclopolyene can be detected. Through this washing out the excess reactant that is not bound to the magnesium halide is removed. That Washing is carried out by methods known per se, for example slurrying in liquid with stirring Hydrocarbon and subsequent suction through a filter or centrifugation, or settling and Decanting.

The modified support is then brought into contact with a trivalent or tetravalent titanium halide.

The III- or IV-valent titanium halides are preferred Titanium tetrachloride or titanium trichloride are possible. Both the products can be used as titanium trichloride are made by reducing titanium tetrachloride with metals such as aluminum or with organometallic Compounds are obtained such as one obtained by reducing titanium tetrachloride with aluminum Product of the composition 3 TiCl-, AlClo, that still can be activated by grinding (Stauffer AA).

Furthermore, a titanium trichloride is suitable, which is produced by reducing titanium tetrachloride with an organoaluminum Compound, e.g., of the formula AIR-, X, wherein R is an alkyl radical with 1-6 carbon atoms and X = R or halogen and η = O to 2, was obtained.

30 ·

The contacting can take place in various ways. In the case of titanium tetrachloride, this is undiluted In the form or in the form of a solution in a liquid hydrocarbon. The titanium trichloride can be used as pure solid or can be used in the form of a suspension in a liquid hydrocarbon. The touching the reactant can also be prepared by grinding in the absence or presence of a diluent

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by means of. This stage of the process according to the invention is carried out in a temperature range from approx. ⁰ ° C. to 150 ^° C., preferably from 20 ^° C. to 100 ^° C., over a period of from 10 to 600 min, preferably from 60 to 300 min. The liquid hydrocarbons already mentioned above are used.

In component A, the Mg / Ti ratio can be wide Boundaries fluctuate. In the case of the magnetic

10 silicon halide electron donor or cyclopolyene complex it is preferably in the range from 3 to 40: 1, particularly advantageously in the range from 10 to 30: 1. The ratio of moles of electron donor compound or cyclopolyene compound / Ti is usually in the range of 0.4

15 to 3: 1, preferably 1.2 to 3: 1.

When the modified support is reacted with titanium trichloride, for example the TiCl obtained by reducing TiCl ₁ with organic aluminum compounds, a

20 excess TiCl can be used. The relationship Mg / Ti can be 0.2 to 40: 1, preferably 0.3-30: 1. The electron donor or cyclopolyene / Ti ratio is also in the case of TiCl, in the range given above.

If component A by contacting the modified support with TiCl ₁ . was produced, the excess, unbound TiCl ₁ is now washed out with one of the hydrocarbons already mentioned.

Straight-chain and branched aluminum compounds are suitable as halogen-free organo-aluminum compounds (component B)

2 2
niumalkyle der AlR ,, where R is an alkyl radical with 1

- means 10 hydrocarbon atoms, such as aluminum trimethyl, Aluminum triethyl, aluminum triisobutyl; Aluminum tridiisobutyl. The reaction products of aluminum triisobutyl or aluminum diisobutyl hydride are also suitable and isoprene, which is sold under the name aluminum iso-

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prenyl are on the market. Aluminum triethyl and aluminum triisobutyl are particularly suitable. The molar ratio Catalyst component B to catalyst component A is in the range from 5 to 200: 1, preferably from 15 to 50: 1.

The mixed catalyst component C consists of a stereo regulator, which is selected from the group formed by cyclopolyenes and electron donors such as aromatic Carboxylic acid esters, phosphinic acid esters, hexamethylphosphoric acid trisamide and 1,2-dimethoxybenzene. Among the cyclopolyenes are to be emphasized cycloheptatriene- (1,3,5), Cyclooctatetraene, of the aromatic carboxylic acid esters, preference is given to using methyl benzoate, Ethyl benzoate, ethyl p-toluate, methyl p-toluate, Ethyl anisate and methyl anisate, of the phosphinic esters, isobutyl methylethylphosphinate. The compounds can be used alone or in a mixture, for example Cycloheptatriene (1,3-5) and aromatic carboxylic acid esters or cycloheptatriene (1,3,5) and methylphosphinic acid esters. Component C can mat the mixed catalyst component B can be reacted by mixing before the polymerization, it can also are introduced directly into the polymerization vessel. The dosage of components A, B and C can also be in in the sequence B-C-A, or in such a way that first B and C in a liquid Hydrocarbon are dissolved, part of this solution introduced into the polymerization reactor and added the remainder of the solution of component A and then the mixture is added to the reactor. The amount of catalyst component C depends on the amount Catalyst component B. The molar ratio of component B to component C should be greater than 1: 1, preferably 1.5: 1 up to 15: 1.

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AO

With the combination of the catalyst components according to the invention A, B and C a mixed catalyst system is obtained with which in the polymerization of 1-olefins not only a high activity but also a high stereospecificity is achieved.

The 1-olefins are those of the formula CH "= CHR, in which R ^{D is} an alkyl radical having 1 to 8 carbon atoms. Propylene, butene- (1), pentene- (I), 3-methyl-

butene (i), 4-methylpentene (1) and 3-methylpentene (1) are preferably polymerized with the aid of the catalyst according to the invention, but in particular propylene. In addition to the homopolymerization, the inventive Mixed catalyst also suitable for the polymerization of mixtures of these olefins with one another and / or with ethylene, the content of one of the said 1-0lefins in the mixture being 99.6 to 94% by weight? and the Ethylene content is 0.4 to 6 wt .- #, each time based on the total amount of monomers. Particularly Mixtures of propylene with small amounts of ethylene are preferred, the ethylene content being 0.5 to 5, is preferably 1.5 to 3 wt .- / S. Furthermore, the catalyst according to the invention for block copolymerization of these 1-0 olefins with one another and / or with ethylene

25 suitable, and the content of ethylene from 8 to 35 wt -.%

is, preferably for the production of block polymers from propylene and ethylene. These block polymers are characterized by high hardness and excellent impact strength at temperatures below 0 C.

30 off. .

The polymerization can be carried out continuously or batchwise in suspension or in the gas phase are at a pressure of 1 to 50 bar, preferably 1 to 40 bar.

The suspension polymerization is carried out in an inert solvent. A Low-olefin petroleum fraction with a boiling range of 60

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up to 250 ° C, which must be carefully freed from oxygen, sulfur compounds and moisture, or saturated aliphatic and cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane, Methylcyclohexane or in the case of catalysts containing TiCl ^ also aromatics such as benzene, toluene and xylene. The suspension polymerization can also be used advantageously the 1-olefin to be polymerized as a dispersant, for example in liquid propylene.

Another procedure is that the polymerization in the absence of a solvent in the gas phase, for example in a fluidized bed, is carried out.

The molecular weight is regulated, if necessary, by adding hydrogen.

The advantage of the method according to the invention is there in that when washing out the modified carrier unbound electron donor or cyclopolyene Will get removed. At the same time, the need for titanium halide is reduced, surprisingly by this measure greatly increased the activity of the catalyst, so that both during the polymerization A much higher polymer yield is achieved in suspension as well as in liquid monomers. The polymer is also characterized by a very low fine

30 share.

Implementation of the examples

For the examples according to the invention and the comparative examples games, the catalysts are prepared in the same V / eise with the difference that in the case of the invention Examples of the modified carrier is washed out and not in the comparative examples.

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Al

1. Milling

Anhydrous MgCl “(water content 0.05-1% by weight ) and ethyl benzoate are grounded in a vibration mill with a volume of 0.7 l or 5 l total volume with 2.1 kg or 15 kg of stainless steel balls mill to a diameter of 15 mm. The filling coefficient is 135 g / l of the total volume. The milling temperature adjusts itself is at 75 to 8O ⁰ C for the smaller mill, or at 150 to 175 ° C at the larger mill, the grinding time 100 hours. The filling of the mill with the products to be ground, the subsequent grinding and the removal of the modified carrier from the mill takes place under

15 nitrogen atmosphere.

2. Washing out (examples according to the invention)

100 g of the ground material are Inertgasatinosphäre in a glass cylinder riding frit filled thermometer, reflux condenser and stirrer, and with about 500 ml of a liquid hydrocarbon (boiling range 135-170 ⁰ C) for 15 minutes at 110 ⁰ C approx. The hydrocarbon is then filtered off while hot under nitrogen. This washing process is repeated until the washing liquid contains practically no more ethyl benzoate. Then it is suctioned off sharply and the moist millbase is dried in vacuo or in a stream of nitrogen.

The filtrate is separated into hydrocarbon and ethyl benzoate by distillation. Both Components can be reused.

By chromatographic investigations, the content of ethyl benzoate during the individual Steps of the preparation of the catalyst component A followed.

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/ 13

Ethyl benzoate wt. %

in the ground product
(Molar ratio 6.5 ί 1) 20 %

after washing with liquid hydrocarbon at 110 ⁰ C 12 %

in the finished component A 11 %

3. Treatment with TiCl ₁₁ 15

25 g of the washed or unwashed millbase are mixed with 375 mg of TiCl ₁ in the apparatus described under 2. above. stirred at 80 to 130 ⁰ C for 2 hours.

Then the excess TiCl ₁ , and the soluble in products by filtration at 80 to

130 ⁰ C withdrawn through the frit. _{The TiCl 1} adhering to the solid product is then deposited. washed several times by washing with an aliphatic hydrocarbon at 110 ° C., finally with boiling hexane. The hexane running off should not contain any titanium or chlorine.

Since the titanium tetrachloride only a little titanium tetrachloride-benzoic acid ethyl ester complex contains, the titanium tetrachloride can be recovered by distillation. The remaining as distillation residue small amount of complex is discarded.

¹ J. Polymerization in Liquid Monomers 35

A 16 l pressure autoclave is first flushed with propylene. A pressure lock is now used in metered in this order: the aluminum trialkyl and

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the stereo regulator, then the catalyst component A. The peak temperature is 60 C, the pressure approx. 26 bar, the polymerization time 4 hours. After the completion of the polymerization, the remaining propylene becomes evaporated and the polymer under a nitrogen atmosphere dried at 70 ° C.

5. Polymerization in the usual suspension process

The polymerization is carried out in a 1.5 l autoclave equipped with a stirrer and previously flushed out with nitrogen. The polymerization temperature is 60 ° C., the propylene pressure is 6 bar, and the polymerization time is 4 hours. As a suspending agent is an aliphatic hydrocarbon fraction having a boiling range of 135 - 170 ⁰ C used.

Aluminum triethyl and alurainium triisobutyl are used as aluminum alkyls, as a stereoregulator, ethyl 4-methylbenzoate used.

The autoclave is filled with 500 ml of the above-described aliphatic hydrocarbon under propylene, then with stirring the aluminum trialkyl and the stereo

25 regulator added. After about 10 minutes, the

Catalyst component A, previously in about 30 ml of solvent had been suspended, metered. The propylene pressure is adjusted to 6 bar and the autoclave initially cooled due to the heat of reaction occurring immediately to the polymerization temperature of 60 ° must be observed.

6. Determination of the fines by sieve analysis

To determine the fine fractions of the polymer, a sieve analysis with an ultrasonic sieve device is used F. Retsch (Kaen). With dry sieving there are difficulties when recording the fine

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problems, as the fines are a result of electrostatic Charging tends to aggregate grain and thus simulate a larger grain diameter. In the Sieving in aqueous alcohol, the aggregates are destroyed by the ultrasound, so that a real grain size distribution can be determined.

example 1

In a 16 l stirred autoclave, air and moisture are excluded at room temperature through a lock Activator and contact metered in in the order: 21.4 mmol aluminum triisobutyl (= 4.2 g) 8.2 mmol of 4-methylbenzoic acid ethyl ester (= 1.34 g) in 6.2 liters of liquid propylene;

then 216 mg of catalyst component A (= 0.073 mmol of titanium) in
6.2 liters of liquid propylene.

The polymerization starts after a few seconds. The temperature of the boiler jacket is raised to 60 ° by heating brought and optionally held by cooling at this temperature. The boiler pressure is 25 bar. After a The polymerization time of 4 hours is cooled to room temperature and the remaining propylene is evaporated. The polymer is dried in a vacuum cabinet at 70 °. The yield obtained is 3,243 g of polypropylene, which is a Contact yield of 926,000 g of polypropylene per 1 g of titanium. The polymer has a bulk density of 490 g / l and a ball indentation hardness, measured according to DIN 53

456, of 78 N / mm. The reduced specific viscosity (measured 0.1?> Ig in decahydronaphthalene at 135 °) is 6.9 dl / g.

To determine the atactic fraction of the polypropylene, 10 g of the polymer powder are in heptane for 10 hours Heated to reflux, filtered off, dried in a vacuum cabinet at 90 ° for 1 hour and reweighed. This becomes the

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percentage of the part that is soluble in boiling heptane is determined. The polymerization resulted in 3% by volume of soluble (atactic) polypropylene (= APF), based on the total polymer.
5

Comparison test A

In the same stirred autoclave under the same polymerization conditions As described in Example 1, the following comparative experiment was carried out:

The following are metered into the 16 l stirred autoclave according to Example 1:

21.4 mmol aluminum triisobutyl (= 4.2 g)

15 8.2 mmol of ethyl 4-kethylbenzoate (= 1.34 g) in 6.2 1 liquid propylene:

then 185 g of catalyst component A (= 0.073 mmol Titanium), produced according to comparative experiment A / B in Table 1 in 6.2 l of liquid propylene.

The results are summarized in Table 2.

Beis piel 2

16.15 mmoles of aluminum triethyl (= 1.9 g) and 5.18 mmoles 25 ethyl 4-methylbenzoate (= 0.85 g) are mixed with

6.2 l of liquid propylene pressed into a 16 l autoclave by means of a pressure lock. Box 10 Mituten stirring at 2O ⁰ C are metered 239.5 mg Katalysatorkoirponente A (= 0.081 mmol of titanium), suspended in 50 ml of heptane, with 6.2 1 of liquid propylene in the autoclave. The temperature is set to 60 ° C. The stirring speed is 180 rpm, the pressure is 25 bar and the polymerization time is 4 hours. Working up is carried out as described in Example 1. Test results can again be seen from Table 2.

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-> * ■ - 28A0156

Comparative experiment B

The 16 l autoclave is filled and the polymerization is carried out as described in Example 2. The following are used: 16.15 mmoles of aluminum triethyl (= -1.9 g) and 5.18 mmoles of 4-methylbenzoic acid ethyl ester (= 0.85 g) and 6.2 l of liquid propylene: then 203.5 mg of catalyst component A (= 0.080 mmol titanium) in 6.2 1 liquid propylene.
For the test results, see Table 2.

Example 3

A 1.5 l autoclave is flushed out with nitrogen, then filled with 500 ml of an aliphatic hydrocarbon fraction with a boiling range of 135 170 ^{° C. under propylene gas.} Then 6.02 mmoles of aluminum triisobutyl (= 1.19 g) and 2.31 mmoles (= 0.38 g) of ethyl 4-methylbenzoate are metered in one after the other. After stirring for about 10 minutes, 79.3 mg of catalyst component A (= 0.02 mmol of Ti) suspended in 30 ml of the abovementioned hydrocarbon fraction are added under nitrogen. The propylene pressure is adjusted to 6 bar, the temperature to 60 °, the stirring speed is 750 rpm and the polymerization time is 4 hours.

After the end of the polymerization, the pressure in the autoclave is released and the polymer is filtered off while hot. The polymer will dried in a vacuum cabinet at 70 ° and weighed. The yield is converted to g polypropylene per gram titanium, (g FP / g Ti). The filtrate is concentrated to dryness in a rotary evaporator and weighed out of the residue the atactic proportion of polypropylene (APP). Those obtained during suspension polymerization

35 results are shown in Table 4.

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Comparative experiment C

For comparison, under the same test conditions 6.02 mmoles of aluminum triisobutyl (= 1.19 g) and 2.31 mmoles of ethyl 4-methylbenzoate (= 0.38 g) and 47.9 mg (= 0.02 mmol) of catalyst component A, which had been prepared in accordance with Table 3 “Comparative Example”, was used.

The polymerization conditions and the work-up of the 10 polymer correspond to the example according to the invention 3. The results are shown in Table 4.

A comparison of Examples 1 and 2 with Comparative Experiments A and B clearly shows the advantage of the method according to the invention. In example 1, the contact yield is 2.6 times and in example 2 2.3 times that of the comparative experiment. The differences with regard to the undesirable fines in the polymer are also very clear. Fine fractions below 100 and ...

(m drove frequently

clogging of nozzles, valves and filters. Furthermore, they can lead to very dangerous dust explosions. By the inventive method, the fine particles of 19 wt .-% to 3 wt can -.% And x-Zith lowered of 15 wt .-% to 1 wt .-%.

The superiority of the process according to the invention is also evident in suspension polymerization. The contact yield is 1.3 times that of the comparative experiment. The fines (sieve fraction below 100 .mu.m) are

30 leg: comparative test 56% by weight , in the method according to the invention only 6 % by weight.

The bulk density in example 3 is 100 units higher than in the comparison experiment.

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Table 2
Polymerization in liquid propylene

Example salary Contact no. Titanium yield by weight g FP / g Ti

APP bulk weight g / l ball pressure RSV

hardness ₅ value

N / mnT dl / g

Sieve fraction

around
Weight %

1.62 926 GOO

490 78

8.9

Comparative experiment A 1.89

347,000

■

450 69

7.8

19th

1.62

900,000

470 71

9.4

Comparative experiment B 1.89

402,000

440 63

8.7

15th

Table 3

production of the supported catalyst component A for Example 3 and the

Comparative experiment C

according to the invention example 3

. Grinding process: _

Volume of the mill

Use of magnesium chloride

Use of ethyl benzoate

Molverh. MgClp / ethyl benzoate

Grinding time

660

157

6.6: 1

100

hours

2. Wash out with a liquid hydrocarbon

1 TO ⁰ C

_o 3rd treatment with titanium chloride :

KS amount of hollow product 750

(S = S titanium tetrachloride 4,

^ Treatment temperature 130

Filtration temperature 130

Wash out with aliphatic! Hydrocarbon 1 1 u ^l

Comparative experiment C

Specification of the catalyst component A

titanium

chlorine

Surface (BET)

1.2 wt. 58 wt .- i 170 πι / g

5 1

g g 6.6: 1

hours

no washing out

1

4.2 1

130 ° C

130 ° C

110 ° C

2.0 wt -.% 61 Cew .-% 150 nr / g

Table 4

Suspension polymerization in aliphatic hydrocarbons (Sp. 135 - 170 °)

Polymerization pressure Polymerization time Polymerization temperature

6 bar (propylene)

4 hours

■ Example salary contact APP bulk no. of Ti yield. weight (weight 50 (g PP / g Ti) (wt -.%) (g / l) sieve fraction RSV Kugeldruckum Value Hardness (wt ..-) (dl / g) (N / mnt)?

1.2

402,000

1.6

8.0

81

Comparative experiment C 2.0

298,000

2.3

56

9.1

75

Tabel

Preparation of the supported catalyst component A for the 'Examples 1 and 2 and the

Comparative versions A and B

according to the invention, comparative experiment A and B, Examples 1 and 2

Grinding process:

Volume of the mill Use of magnesium chloride Use of ethyl benzoate Molverh. MgCl ₂ / ethyl benzoate

Milling time 0.7 77.4 g 18.6 g 6.5: 1 100 hours

0.7 77.4 g 18.6 g 6.5:

100 hours

O U) O

2. Wash out with a liquid hydrocarbon

4th

S pezifikatio n of the titanium catalyst component A chlorine surface area (BET) at 110 ^u C

Treatment with titanium tetra chloride Amount of milled product Ti tantetrachlor id Treatment temperature Filtration temperature Washing out with aliphatic! Hydrocarbon 25 g 375 _o g

80 ⁰ C 8O ⁰ C 1 10 ⁰ C

1, 62 wt

67, 1 wt.

190 m / g

no washing out

25 g 375 g 8O ⁰ C 8O ⁰ C 110 ⁰ C

1.89 wt.

/ " rj OC ^

179'm ² / g

Claims (5)

Patent claims: Process for the production of a mixed catalyst for the polymerization of 1-olefins of the formula R-CH = CHp, 3
where R denotes an alkyl radical having 1 to 8 carbon atoms, by modifying a magnesium analogue with an electron donor and / or a cyelopolyene, bringing the modified support into contact with a titanium halide and mixing the thus obtained catalyst component A with an organoaluminum compound (component B) and a stereoregulator ( Component C), characterized in that the modified support prior to being brought into contact with the titanium halide with a liquid hydrocarbon at a temperature 15 temperature of 50 to 150 ⁰ C is washed out. 2. The method according to claim 1, characterized in that a modified carrier is used, which by Grinding the magnesium halide with the electron donor 20 tor and / or Cyelopolyen was produced. 3. Catalyst prepared by the process according to Claims 1 and 2. 4. Use of the catalyst according to claim 3 for polymerizing _{1-olefins of the formula R-CH = CH 9} , in which R is an alkyl radical having 1 to 8 carbon atoms, or for copolymerizing these 1-olefins with one another and / or with up to 6 wt £ .- ethylene or bulk polymerization of 1-olefins with one another / or with up to 35 wt -.% ethylene. 5. Process for polymerizing 1-0 olefins of the formula R-CH = CH ", wherein R * denotes an alkyl radical having 1 to 8 carbon-atoms or copolymerizing these 1-olefins with one another and / or with up to 6 wt -.% Ethylene or Blackpolymerisation these 1-olefins with one another and / or with up to 35 wt ..- ί ethylene, in 030013/0252 ORK3 / NAL IM Presence of a mixture catalyst that is produced was made by modifying a magnesium halide with an electron donor and / or a cyclopolyene, "bringing the modified support into contact with a Titanium halide and mixing of the catalyst component A obtained in this way with an organoaluminum compound (Component B) and a stereo regulator (component C), characterized in that the polymerization is carried out in the presence of a mixed catalyst, the raodfizierter carrier before being brought into contact with the titanium halide with a liquid hydrocarbon at a temperature of 50 to 150 C was washed out. 030013/0252