DE1924709A1 - Process for the production of alkylene polymers - Google Patents

Description

. . 19247Q9

License plate 2079 _ \

_β Dr. F. Zumsfein - Dr. E Assmann

Dr. R. Koenigsberger
Dipl. Phys. R. Holzbauer

Patent attorneys
Mönchen 2, Bräuhausstralje 4 / III

STAMIGARBON N.V., HEERLEN (the Netherlands) Process for the production of alkylene polymers

The invention relates to a process for the production of alkylene polymers by polymerizing one or more alkylenes in a liquid Distributing agent with the aid of a mixture of an aluminum halogen compound, a titanium compound and an organomagnesium compound.

As is known, a mixture of an alkyl aluminum dihalide, a Titanium halide and a magnesium hydrocarbon are a more effective catalyst for the polymerization of .Alkylenes as a mixture of a titanium halide with only an alkyl aluminum dihalide or a magnesium hydrocarbon (French Patent 1,174,286).

From the Dutch patent application 6.414.992 it is known, alkylenes to polymerize in the presence of a catalyst obtained by adding a organic aluminum compound to a mixture of a titanium compound and one by reacting an organohalide with magnesium in the absence of ether compounds produced organomagnesium complex. According to this patent application is also the presence of moisture, air and substances that interact with the Avoid catalyst reacting, such as alcohols, ketones, etc.

It has now been found that in the polymerization of alkylenes .with one by mixing an aluminum halogen compound, a titanium compound and an organomagnesium compound produced a larger catalyst

00 9823/1787

- O _

Yield achieved if one during and / or after the preparation and / or the Mixture of the catalyst components one of an alkanol, alkenol, alkanolate, Alkenolate, a carboxylic acid, an ester or a salt thereof, an aldehyde or ketone existing activator is added and the polymerization is carried out at a temperature above 110 C, in such a way that a solution of the polymer forms.

An aluminum trihalide, e.g. Aluminum trichloride or alurainium tribromide, or an organoaluminum halide Find application. Mixtures of aluminum compounds can also be used. Suitable organoaluminum halides contain on average a minimum of one and a maximum of two halogen atoms per aluminum atom and a minimum of one directly with one Carbon atom attached to aluminum. The hydrocarbon radical can be an alkyl, cycloalkyl, alkaryl, aryl, or aralkyl group be. Examples are diethylaluminum chloride, monoethylaluminum chloride, Diisobutyl aluminum chloride, diisobutyl aluminum bromide, aluminum ethyl sesquichloride and monohexyl aluminum dichloride.

The titanium compound used is preferably a halide, in particular a chloride, of tri- or discarded titanium or a compound derived therefrom by replacing one or more halogenated and an alkoxy group, such as tetrabutoxytitanium, diethyltitanium dibromide, dibutoxytitanium dichloride and monoethoxytitanium trichloride. In addition to the titanium compound, compounds of other transition metals, for example vanadium, molybdenum, zirconium or chromium, such as VCl., VOCl ₃ , MoCl ₅ , ZrCl. and chromium acetylacetonate be present. If one starts out from a compound of a transition metal which cannot dissolve in the dispersant in which the polymerization takes place, then this compound can often be made soluble by first adding it to one of the activators used according to the invention, preferably in an alcohol or a Acid,: 'dissolves.

The organomagnesium compound has the formula MgR X ₀ ; R is an alkyl, cycloalkyl, alkaryl, aryl or aralky group, X is an activator radical or halogen and 1 <η <2. Examples include: diphenyl, diethyl and dibutyl magnesium, butyl isopropoxy, isopropyl ethosyl and phenyl decoxymagnesium and butyl magnesium bromide. A dissolved organomagnesium compound is preferably used, in particular an alkylmagnesium compound, for example dialkylmagnesium such as dibutylmagnesium and diethylmagnesium. The magnesium compound can be produced in the presence of ether if desired. . .-. ·.

009823/1707

The activators to be used according to the invention can be applied to aluminum or replace magnesium-bound hydrocarbon radicals; doing so will likely the activator residue through an oxygen atom on aluminum or magnesium bound. This replacement can optionally be carried out during or after the production of the aluminum and / or the magnesium compound. This can ■ the activator can be added in various ways. For example, you can use the total amount of activator during the production of one of the catalyst components to add. It is also possible to use part of the activator during the preparation of one of the catalyst components and the remaining part during to be included in the manufacture of the other or one of the other components. Furthermore, part of the activator can be added during the preparation of one or more of the catalyst components and the remaining part can be added afterwards. It is also possible to use one or more of the catalyst components to mix together before adding the activator. Preferably, the activator is allowed to react with the aluminum halogen compound and mixed - you then the reaction product with the other catalyst components.

Because the distribution agent and the alkylenes to be polymerized usually contain small amounts of impurities that react with the catalyst and have the same effect as the activator take into account the presence of these impurities when adding the activator. The same applies to any activator residues bound to titanium, such as alkoxy groups, the hydrocarbon bonded to aluminum or magnesium able to replace radicals.

According to the invention, both aliphatic and aromatic, as well as aliphatic-aromatic activators are used. The activators can one or more than one alkenol, alkenol, alkanolate, alkenolate, carboxylic acid, Contain ester, salt, aldehyde or ketone group. Suitable activators are for example: methanol, ethanol, propanol, decanol, dihydrocarveol, butenol, glycol, Aluminum isopropylate, magnesium ethanolate, triethyl borate, magnesium stearate, calcium oleate, Acetic acid, propionic acid, stearic acid, benzoic acid, ethyl acetate, Butyl acrylate, acetaldehyde, benzaldehyde, acetone and cyclohexanone. Preferably Activators are soluble in hydrocarbons, especially saturated aliphatic ones Alcohols with 1-20 carbon atoms are used.

The aluminum and titanium compounds are preferably used in one Molar ratio of over 1 applied; 2-50 moles of Al are preferably used Mol Ti. Larger ratios, however, up to 200 or more, can also be used can be used with success.

00 9823/1767

The molar ratio between the magnesium and the titanium compound .., can also be varied widely. In general, the activity of the catalyst initially increases as the Mg / Ti ratio rises and is then reached a maximum and then decreases again. The Mg / Ti ratio at which the Activity peaking is generally lower, as the case may be. Al / Ti ratio is lower. The Mg / Ti ratio is usually between 0.1 and 200, preferably between 0.3 and 50, more in particular between 0.5 and 10, ..... "

The molar ratio between the. Aluminum and magnesium connections is mostly between 0.25 and 50, preferably between 0.5 and 30.

Even a small amount of activator increases the effectiveness of the catalyst. This effectiveness increases and reaches with increasing addition of activator finally a maximum value. It should be noted, however, that at most one; such an amount of activator is added that on average per magnesium atom at least one carbon directly bonded to it with a carbon atom * hydrogen radical remains. When adding a larger amount of activator, the activity slows down pretty quickly. The to achieve the maximum Effectiveness required Aktivatox amount can easily be based on experimental Determine ways. When using a dialkyl aluminum halide or aluminum sesquihalide the highest is usually achieved as the catalyst component. Effectiveness if you add such an amount of activator that average per aluminum and magnesium atom at least 1 and preferably 1.1-1.6 directly with a carbon atom attached thereto, there remain hydrocarbon radicals.

The addition of activator also has the advantage that the The effectiveness of the catalyst in the range of the maximum value is much less dependent on the mutual ratio of the catalyst components than in the absence of the activator. In the latter case, the composition of the catalyst must usually be very precisely constant in order to achieve a maximum yield of polymers because the yield, entered as a function of the catalyst composition, shows a maximum with a sharp tip. By adding the activator however, this maximum becomes not only higher but also much wider. The yield is thus far less due to fluctuations in the added amounts of catalyst components and due to old catalyst components reacting, present in the distributing agent and the alkylenes to be polymerized Impurities affected. ·

The inventive method is suitable for the production of crystalline homo- and copolymers of α-alkylenes such as polyethylene, polypropylene, Polybutylene and poly-4-methylpentene-l, also copolymers and block copolymers,

009823/1767

ti% t te · Ilk «. _ ¹ IM * tt,

t f. t

which mainly consist of such a ct-alkylene and only small amounts - e.g. up to 15 mol% - of one or more other alkylenes are built up. Preferably is ethylene or a mixture of ethylene with a maximum of 15 mol .-% of one other alkenic unsaturated monomers are used.

The process according to the invention is also suitable for the polymerization unsaturated compounds, which cannot be achieved with normal Ziegler catalysts are to be polymerized, e.g. vinyl chloride and acrylic acid,

The polymerization can take place at very high pressure, up to 5000 at or more, be carried out, but preferably takes place at relatively low Pressure, more especially at 1-200 at, takes place and can be intermittent, semi-continuous or continuously, if desired, in one or more stages. The polymerization is preferably carried out in a completely liquid-filled one Reactor carried out. As "distributing agents" for the polymerization common distribution agents are used with Ziegler catalysts, e.g. hexane, Jieptane, pentamethylheptane, gasoline, kerosene, benzene and cyclohexane. Mixtures are also applicable. The alkylene itself can also be used as a distribution agent use by working at temperature and pressure ratios, under where this alkylene is liquid. Another means of distribution is unnecessary in this case. '

The polymerization temperature can be above or below the melting point of the Polymers lie. The polymerization is preferably carried out at one temperature from 110-180 C; However, there are also higher temperatures, e.g. up to 240 C, possible. This gives a solution of the polymer in the distribution medium in which the catalyst can easily be distributed homogeneously over the polymer. Man can the catalyst components at a temperature above 100 C with each other. mix by placing them in a dispersing agent in which an alkylene is dissolved is, brings together. In this way a very fine distribution of the active catalyst in the distribution medium is obtained, which has a favorable effect on the effectiveness will. The catalyst is preferably left for some time after the catalyst components have been mixed, e.g. from a few seconds to less than 10

* ο ο

Minutes, preferably below 0 C, e.g. at -40 C. With the inventive The catalyst system has the advantage that the catalyst is so active that the polymerization can take place in such a way that the polymer solution has a residence time in the polymerization zone of not more than 10 "minutes and especially a residence time of not more than 5 minutes. Longer Dwell times, e.g. of a few hours, are also possible.

008823 / 1-787

With the method according to the invention, such a high level is usually achieved Yield of polymers *, calculated per g of catalyst, obtained that you do not need to remove the catalyst residues from the polymers, because they are in an amount are present, which is below the permissible value. This is an important benefit because removing catalyst residues from the polymer is an expensive and time consuming undertaking *

example 1

101 experiments were carried out; were different Catalyst components and activators used in different proportions « The tests were carried out as follows:

In a double-walled glass reactor, which was provided with a stirrer, a thermometer, a gas inlet pipe and a gas outlet pipe, \ liter of pentamethylene / heptane was introduced; this pentamethylheptane was then heated to the desired reaction temperature and then saturated with ethylene. The activator, the aluminum, the magnesium and the titanium coraponents, all dissolved in pentajsieihy! Heptane, were then introduced into the reactor one after the other. While stirring vigorously and passing Athylea through, the polymerization was continued for the desired period of time. The polymer was then eliminated from the reaction mixture.

The test results are compiled in Table 1 below. Unless otherwise stated, the polymerization temperature was 140 ° C and the Polymerization time 30 minutes and was used as a titanium component TiCl. used and although in a concentration of 0.1 mmol per liter of pentamethylheptane.

The symbols At and 0 used in the table represent ethyl and phenyl, respectively

represents. i;

j table 1 '

attempt
No. Catalyst components, which with TiCl ^
the effective, cat
(in mmol per liter of pentamethylheptane) Mg component Activator Yield of polymer ^! ·
(in g polymes per mmol Ti) 1
2
3 ·
4th
5
6th Al component 009823/1 747 0.5
9
.34
- '27
20th
ί.
14th AlAt ₂ Cl 0.2
0.5
¹¹ 1.0
2.0
4.0
8.0

t f f I

(f ί
rt τ

t t

<I.

t ft

192A709

Continuation of Table 1 - 0.2 Ng co-component 0.05 Activator 0.1 Yield of polymers
(in g Polym, per mmol Ti) - o, a ^ ₂ mg 0, Io - 0.1 attempt
No. - 0 _# 2 Il 0.2 - 0.1 0.2 7th - -. 0.2 Il 0.4 - 0.1 2 8th Catalyst components, which with TiCl.
the effective. Form cat
(in oHol per liter of pentaethylheptane) AlAt ₂ Cl 1.0 * Il. 0.6 - 0.1 14th 9 Al component Il 1.0 ti ' 0.05 - 0.5 108 10 • ti 1.0 If 0.1 - 0.5 78 11th ti 1.0 Il O, 2 - 0.5 64 12th . it 2.0 •1 0.4 0.5 144 13th Il 2.0 ti 0.05 - 0.5 74 14th Il ti 0.1 - 1.0 34 15th ti 2.0 M.
ti 0.2 - 1.0 86 16 ti 0.2 Il 0.4 1.0 138 17th Il 0.2 It 0.05 - 1.0 56 18th ti 0.2 ti 0.1 - 1.0 _f 30 19th ti 0.2 ti 0.2 1.0
1.0 68 20th ti 0.2 Il 0.4 - 68 21 Il Il 0.075 - 57 22nd Il 1.0 It 0.1 Oecanol 37 23 ti 1.0 It 0.2 150 24 Il 1.0 • 1 0.3 dd 204 25th Il 1.0 ti 0.4 It 183 26th • 1 2.0 •1 0.06 ti 125 27 Il 2.0 ti 0.1 Il 73 28 • 1 2.0 ti 0.2 dd 210 29 Il 2.0 Il 0.4 ti 216 30th ι · < 2.0 Il 0.6 Il 271 31 Il 2.0
2.0 Il 0.05 It 231 32 Il • I 0.1 It 73 33 ■ 1 •1 0.2 It 167 34 Il It 0.4 Il 221 35, Il
♦ i. ti 0.6 dd 224 36 ■ 1 0.8
1.0 dd 306 37 It
Il It
It 274 38 138
70 39
40

009823/1767

Table 1 continued

attempt
No, Catalyst components that work with TiCl-.
. educate ■
(in mmol per liter of pentamethylheptane) 1.0 ^C 4 ^H 9 Mg component 0.2 Cat. Decanol 0.1 Yield of,
Polymer
(in g Polym. 41 Al component 1.0 (C ₁₀ H ₂₁ O) Mg 0.2 0.2 Activator It 0.3 per mmol Ti) ' 42 AlAt ₀ Cl 1.0 Il 0.2 Decanol Il 0.5 197 43 Il 1.0 It 0.2 It ti 0.7 258 44 If 1.0 dd 0.4 ti It 0.8 304 45 Il 2.0 It 0.4 ■ «ti If .1.6 292 46 Il 2.0 ti 0.4 tf It 1.8 252, 47 If 2.0 ti 0.2 dd dd 2.0 355 ' 48 ■ 1 2.0 ti 0.2 Il
i If 1.6 301 49 ff 2.0 Il 0.2 r
If ft 1 * 7 61 50 It 2.0 It 0.2 If If 2.05 279 51 ff 1.0 I ₂ mg dd 0.2 ti dd 0.2 145 52 Tf 1.0 dd 0.2 dd 0.4 - 8th 53 dd 1.0 dd 0.2 Cyclohexanone 0.6 . 153 - 54 ff 1.0 Il 0.2 dd 0.8 208 55 dd 1.0 ti 0.2 Il 1.2 220 56. ft 1.0 ff . 0.2 »T 0.5 200 " 57 It 1.0 ft 0.2 dd 0.1 7th 58 Il 1.0 Il 0.2 Benzoic acid '0.5 191 ' 59 It s ² ' ⁰ Il 0.4 Butyl acrylate 159 60 It 2.0 Il 0.6 Benzaldehyde 196 61 AlAt- -CL
X ₉ ο ι, 2.0 dd 0.2 - 158, 62 If 2.0 If 0.4 - 1.0 202 63 It 2.0 Il 0.6 1.0 96 64 If 2.0 If 0.8 1.0 261 65 It 2.0 If 1.0 1.0 350 66 If 2.0 ti 0.4 1.0 400 67 If 2.0 ft 0.4 0.8 472 68 Il 2.0 Il 0.4 1.2 411 69 Il 2.0 dd 0.2 1.6 264 ' 70 It 1.0 0.4 0.5 304 71 If 20th (C ₄ Hg) ₂ mg 2.0 17th 114 72 AlAt ₂ Cl 20th ^ ₂ mg 4.0 17th • 99 ^y) 73 ff 20th ti 009823/176 ' 17th 277 74 If Il 440 It 420

t • ·

Oll

Continuation.Table

Attempt • no.

Catalyst components, which with TiCl. the effective. Cat.

bijden (in mmol per liter of pentamethy! heptane)

Al component

Mg component activator

Yield to

Polymers »

(in g Polym.

per miBOl Ti)

AlAt ₀ Eq

, 5

AlCl

^Α1Αΐ 15 ⁰¹

20 1 1 1 1 1 2.46 1 1 1

2.0 2.0 2.0 2.0 2.0 2.0 2.0

1.5 ^ 1.5 '2.0

AlAt ₂ Al

Il Il

A1 (C ₄ H ₉ ) ₃

• 2.0 1.0 1.0 1.0

0.2 0.2 0.2 2.0

C ₄ H _9- (C ₃ H ₇ O) Mg

g 8.0

0.2 0.2 0.2 0.2 0.2 0.62 Q,

C ₄ H ₉ (C ₃ H ₇ O) Mg 0.2 C.HJHgCl.2 (C HJ ₉ O 0.2 0.4 0.6 0.6 0.6 0.8 2.4 2.4 0 , 6 '0.6 0.6 0.2 0.2 0.2

0.1

0.1 2.0

At ₂ Zn decanol

Decanol
Al (OAt),

Magnesium stearate

Decanol

17th

0.2

0.4

0.85

0.5

0.6i

0.5

0.5

0.5

1.2

0.4

0.8

i; .2

1.2 1.0 1.2

0.6 1.0 2.0 0.05

0.1 1.0

238

96

219

232

10

477

45

30th

243

106

185

2)

2) ·, 2) 2)

3) 4) '6)

V D 1) 2)

205 264 261

1) 2) 1) 2) 1) 2) 1) 2), 1) 2)

, 1) 2)

85 129

D D

59 97 86

7) 7) 7) 7)

009 82 3/1767

1) Polymerization time 10 minutes

2) Tetrabutoxy titanium was used instead of TiCl ₄

3) Instead of 0.1 fflMol TiCl ₄ , 0.05 mmol TiCl ₄ + 0.05 mmol VOCl ₃

. 4) Propylene was polymerized instead of ethylene (Teap. 120 ° C, polymerization time 2 hours); instead of 0.1 mmol TiCl ₄ , 1.23 aMol TiCl ₃

5) polymerization temperature 200 ° C; Distribution agent paraffin oil; Polymerization time 1 hour

6) Instead of TiCl. TiBr. used

4 4

7) Polymerization time 30 minutes.

The results of the first 40 attempts are in the enclosed, three-dimensional . Diagram shown.

Example 2

Ethylene was continuously polymerized in a 5-liter metal reactor at a temperature of 120 C and a pressure of 20 atm. 30 liters of hexane, in which 1000 liters of gaseous ethylene had been dissolved at room temperature, were passed through the reactor per hour. A solution of diphenylmagnesium in benzene and a solution of TiCl ₄ in hexane were separately fed directly into the reactor. Before entering the reactor, the reaction product of diethylaluminum chloride and decanol (molar ratio 3: 1) dissolved in hexane was dissolved in hexane via a solution of ethylene in hexane , added.

Four experiments were carried out with different amounts of the aforementioned catalyst components. The results are shown in Table 2 below. ₍

Table 2. I.

attempt
No. Al component
(mmol / h) Mg component
(mMbl / h) Ti component
(mmol / h): Polyethylene
(g / h) , j-—
Ti content of the *
Polyethylene
(p _e pm) 1
2
3
4th '23.2
16.3
12.0
5.2 2.4
1.6
1.25
1.6 0.81
0.54
0.39
0.54 1030
920
820
930 38 /
28
23
28

Example 3

In the reactor described in Example 1 were 0.4 liters of pentamethylheptane brought in; this pentamethylheptane was heated to 140 ° C and at

009823/17 67

saturated with ethylene at this temperature. Thereafter, 2 mmol of diethylaluminum chloride and 0.8 mmol of phenylisopropoxyiragnesium, both dissolved in pentamethylheptane, were introduced into the reactor in sequence. Then 10 ml of a solution, obtained by dissolving 1 mmol of TiCi ₃ in 10 mmol of decanol and diluting to 100 ml with pentamethylheptane. The total volume of the liquid in the. Reactor was 0.5 liters. Polymerization was carried out at 140 ° C. for 30 minutes; then the polyethylene formed was eliminated from the reaction mixture. The yield was 45 g.

Example 4 In the reactor described in Example 1, 0.40 liters of Pentamethy1-

heptane introduced; this pentamethylheptane was heated to 140 C and at saturated with ethylene at this temperature. Thereafter, 1 mmole of dietary aluminum chloride and 0.2 mmole of butylisopropoxymagnesium, both dissolved in pentane ethyl heptane, were introduced into the reactor in sequence. Then 0.05 mmol of TiCl ₄ and 50 ml of a solution obtained by dissolving 1 mmol of TiCl ₃ in 10 mmol of benzoic acid and diluting it to 1 liter with pentamethylheptane were added. The total volume of the liquid in the reactor was 0.5 liters. Polymerization was carried out at 140 ° C. for 30 minutes. The yield of polyethylene was 331 g per mmol of titanium compound *

Example 5

Example 3 was repeated, but with the difference that the series The following were added: 1 amole of dietary aluminum chloride, 0.2 mmole of butylisopropoxymagnesium, both dissolved in pentamethylheptane, and 50 ml of a solution were obtained by dissolving 1- »moles of MoCl. in 5 «moles of decanol and diluting the solution with Pentamethylheptane to 1 liter with the addition of 1 mmol TiCl .. After 30 minutes Polymerization at 140 ° C was the yield .624 g of polyethylene per mmol of the titanium compound

The previous attempt was modified as follows. After the magnesium compound, 0.25 mmol of decanol was introduced into the reactor, and only TiCl _{4 was used} as the transition metal compound in an amount of 0.05 mmol. 370 g of polyethylene were formed per mmole of titanium.

Example 6

In the first of two double-walled glass reactors connected in series according to Example 1, which contained 50 ml of optionally ethylene-saturated pentamethylheptane at the temperature indicated in the table, were sequentially

00 98 23/1767

0.3 mmoles of decanol, 1 mmoles of AlAt ₁ -Cl ₁ , 0.3 mmoles of dibutylmagnesium and 0.05 mmoles of tetrabutyl titanate were introduced. After stirring for 5 minutes, the mixture was passed into the second reactor, where 450 ml of ethylene-saturated pentamethylheptane was added of 155 C. While stirring vigorously and passing ethylene through, the. Polymerization continued for 10 minutes, after which the polyethylene formed was recovered from the solution. The yield mentioned in the table is given in g of polyethylene per mmol of titanium compound.

Premix temperature Mix
in attendance
of ethylene yield -20 ⁰ C Yes 285 ' -15 ° C no 254 0 ° C Yes 205 +10 ° C no 180 '

·. With direct introduction of the catalyst components into the second Reactor, a yield of 135 g of polymer per mmol of titanium compound was achieved under the same polymerization conditions.

00 9 823/1767

Claims (13)

I til • PATENT CLAIMS 1. A process for the preparation of alkylene polymers by polymerizing one or more alkylenes in a liquid distribution agent with the aid of a catalyst obtained by wiping an aluminum halogen compound, a titanium compound and an organomagnesium compound, characterized in that during and / or after the preparation and / or the mixture the catalyst constituents an activator consisting of an alkanol, alkenol, alkanolate, alkenolate, a carboxylic acid, an ester or a salt thereof, an aldehyde or ketone, and the polymerization is carried out at a temperature above HO C in such a way that a Solution of the alkylene polymer is formed. -: ■ 2. The method according to claim 1, characterized in that at most one such The amount of activator contributes to the fact that on average per magnesium atom there is at least one immediately hydrocarbon radical bonded to it with a carbon atom remains. 3. The method according to claim 1 or 2, characterized in that one in Hydrocarbons soluble, saturated aliphatic alcohol with 1-20 Adding carbon atoms. . , 4. The method according to claim 1, characterized in that when using Dialkyl aluminum halide or aluminum alkyl sesquihalide adds a maximum amount of activator that on average per aluminum and magnesium atom at least one hydrocarbon directly attached to it with a carbon atom radical remains. 5. The method according to claim 4, characterized in that such an amount of activator adds that an average of 1.1-1.6 per aluminum and per magnesium atom is a hydrocarbon directly bonded to it with a carbon atom radicals remain. 6. The method according to claim 1, characterized in that the activator with the aluminum halogen compound is allowed to react and the reaction mixture is then mixed with the other catalyst components. 7. The method according to claim 1, characterized in that the catalyst 2-50 Moles of the aluminum compound per mole of the titanium compound, and 0.5-10 moles of the magnesium compound contains per mole of titanium compound, 8. The method according to claim 1, characterized in that a dissolved organomagnesium compound is used as a catalyst component. 9. The method according to claim 1, characterized in that an alkylmagnesium ■ compound is used as a catalyst component. 0 0 9 8 2 3/1767 192A7Q9 10. The method according to claim 1, characterized in that there is ethylene or a Mixture of ethylene with a maximum of 15 mol% of another alkene, unsaturated Monomers used. 11. The method according to claim 1, characterized in that the polymerization in takes place in such a way that the residence time of the polymer solution in the polymerization zone does not exceed 10 minutes, 12. The method according to claim 11, characterized in that the residence time is not is more than 5 minutes. 13. The method according to claim 1, characterized in that the polymerization in takes place in a reactor completely filled with liquid. 009823/176 7