DE2035943B2 - Process for the homopolymerization of ethylene, propylene or butene - <1) and for their interpolymerization with one another or with 3-methyl-1-butene, 4-methyl-1-pentene, hexene (1), octene (1), decene - (l) and / or styrene - Google Patents

Description

From I SPS 32 85 890 is a process for olefin polymerization by means of a catalyst system known that from the reaction product of a metal oxide carrier treated with an aromatic TiCI ι and an organometallic activator.

Furthermore, from AT-PS 2 40 043 a process for olefin polymerization by means of a catalyst system is known which consists of a metal oxide carrier, such as Al> O | or SiO ₂ , Al (Halogcn) i and TiCIi, inter alia, in the presence of an aromatic component (A) and an organosilicon component (B) as an activator has been obtained.

However, these known processes leave something to be desired with regard to the catalyst activity.

The invention is therefore based on the object Process for the preparation of polymers from vOlcfincn to make available, in which there is a higher effectiveness of the transition cell, on the Surfaces of the polymerization vessel in the course of the polymerization no polymer film is formed and at which the molecular weight can be controlled very well by hydrogen.

It is a broad object of the invention. to provide a method in which without further du · dispersibility of the catalyst system is maintained and by which polymers with better physical properties are obtained.

The subject of the invention is! thus the claimed method.

The metal oxides and the I lalogenidc of the trivalent metal are using suitable equipment, z. B. a ball mill mixed.

The aromatic compounds mentioned are benzene, napththstlin, pyridine, toluene,
Xylene, mesitylene, durol, ethylbenzene,
Isopropylbenzene ^ -ethyl-naphthalene,
1-phenyl-naphthalene, dimethylaniline,
N-methyl-dipheiiylamine, triphenylamine,
Nitrobenzene, nit rosobenzene,
p-nitrosotulol, anisole,
Phenyl ether, xylenol,
2,6-di-tert-butyl-4-methyl-phenol,
Monochlorobenzene or o-chlorotoluene

and optionally a saturated aliphatic Hydrocarbon, or initially with one of the aromatic compounds, optionally im Mixture with a saturated aliphatic hydrocarbon, and then with the component 3 was received and the, so ^ rn they still contains unreacted component 3, aofiltered and Carefully washed with anhydrous hydrocarbon solvent until the No trace amounts of the transition metal were found in washing liquid, which was used as a catalyst component (B) a trialkylaluminum, a dialkylaluminum monohalide, an alkyl aluminum sesquihalide and / or a monoalkyl aluminum dihalide used and that the polymerization optionally with the addition of 0.1 to 5 millimoles of a Titanium tetraalkoxide per gram of the catalyst component (A) as the catalyst component (C).

preferably used al'vin. However, you can too mixed with a saturated aliphatic Hydrocarbon. such as n-heptane or octane are used will.

The reaction mechanism according to which the mixture of the metal oxide and the halide of the trivalent metal in the presence of an aromatic hydrocarbon and / or its derivative with the transition metal bond has not yet been fully elucidated. However, it has become known that an aromatic compound and a transition rivet compound form a charge transfer complex and that such a complex is also between a halide of a trivalent metal and an aromatic compound. It is further became known that a metal oxide reacts with a halide of a third metal. It can therefore it is assumed that the transition melallverbimliinjr in a combination of these reactions with the solid reaction product of the metal oxide and the halide of the trivalent metal is converted and attached to it. Indeed, the transition metal connection can after the introduction of the surface of the solid by physical measures, z. B. by washing, are not removed.

In the process of the invention, the metal oxide, the trivalent metal halide, the aromatic compound, and the transition metal compound indispensable components. If only one of these components is missing, the polymerization catalyst used does not achieve the high levels given here Activities. If the preparation of the catalyst components used in the process according to the invention

component (A) in the absence of an organic compound by reaction between a mixture of the Metal oxide and the halide of the trivalent metal (2) with the transition metal compound (3) is carried out, a solid catalyst with high activity is not obtained. When the manufacture of the Catalyst component (A) by reaction between the metal oxide and the transition metal compound (3) although in the presence of an aromatic compound, but without the use of a halide trivalent metal is carried out, then only a catalyst is obtained which has a significant has lower activity than a catalyst used in accordance with the process of the invention.

In the reaction between the transition metal compound and a mixture of the metal oxide and the halide of the trivalent metal in the presence of an aromatic compound, too low a temperature is not appropriate because the attachment of the transition metal compound cannot be carried out well in this case. Conversely, it is also not advisable to work at excessively high temperatures because the implementation of the reaction is then difficult. The reaction is therefore preferably carried out at temperatures ranging from room temperature to 300 ⁰ C, of 50 to 200 ° C.

There is no particular limitation on the reaction time, but that of 20 Minutes to several hours are preferred.

The reaction between a mixture of the metal oxide and the halide of the trivalent Metal and the transition metal compound in the presence of an aromatic Vvrbindu.ig can in the way take place that the mixture of the metal oxide and the halide of the trivalent metal; .. the aromatic Compound or in a solvent mixture of aromatic and aliphatic hydrocarbons is suspended and that to the suspension obtained the transition metal compound is added to effect the reaction. The reaction can also be in the Be carried out in a manner that a transition metal compound and the aromatic compound are mixed and that the mixture obtained to initiate the reaction with the mixture of the metal oxide and is mixed with the halide of a trivalent metal. The solid formed by these methods The product is filtered off, carefully washed with an anhydrous hydrocarbon solvent, until there are no trace amounts of the transition metal in the washing liquid, and for production of the catalyst system used in the process of the invention. Otherwise it will a slurry in which the four components indicated above are fully implemented and in which no free transition metal element remains, other than those without filtration to the Use.

It can also be the mixture of the metal oxide and the halide of the trivalent metal, which with the aromatic compound or its vapor has been treated. with the transition metal compound implemented.

The solid product (catalyst component (A)) must be activated by reacting with the organoaluminum Component (B) is brought into contact. Such activators are trialkylakiminium compounds, such as trimethylaluminum or triethylaluminum and dialkyl aluminum monohalides, alkyl aluminum sesquihalides and alkyl aluminum dihalides such as diethyl aluminum monochloride, ethyl aluminum sesquichloride or monoethyl aluminum dichloride.

When carrying out the method according to the invention allows the addition of the titanium tetraalkoxide to the polymerization system to control the density of the products, especially during the polymerization of ethylene. Furthermore, this considerably increases the physical properties of the polymers obtained improves, especially stress cracking. The addition of the titanium alkoxide ensures also better dispersibility of the catalyst system, prevents the aggregation of polymer particles and leads to a polymer with uniform and

π fine particles. Furthermore, the activity of the Catalyst system are increased, so that the polymer yield per catalyst unit is increased significantly which, due to the reduced amount of catalyst, which is used, after the polymerization, the removal of the remaining catalyst, for example by deactivating, washing and drying, is simplified. Since continuing to control the molecular weight of the polymer can be done very simply and effectively by adding the titanium alkoxide, the Production of polymers with the same molecular weight at lower polymerization pressures and thus using smaller devices enables. Preferred titanium tetraalkoxides are titanium tetra-n-butoxide, titanium tetraethoxide and titanium tetra-

j <i called methoxide.

The amount of titanium alkoxide used is in the range of 0.1 to 5.0 millimoles per gram of the catalyst component (A). If the amount of titanium used is lower, then the effectiveness is lower,

Γ) while conversely with a larger amount the soluble one Part of the polymerization product becomes larger.

A great advantage in the preparation of the polymerization catalyst used in the process according to the invention is that r ^l; .e implementation of the

M) the metal oxide and the halide of the trivalent metal and furthermore the reaction of the product obtained with the transition metal compound in the presence of the aromatic compound is not accompanied by dehydrochlorination. what to use

r, a metal oxide that does not contain a hydroxyl group, is due to the surface of the solid. Accordingly, the device does not corrode and quantitatively a stable solid catalyst can be obtained with good reproducibility and in shorter stages

-, (ι be produced.

Another advantage of the method of the invention is that the effectiveness of the transition metal compound is extremely high. This is z. B. from the fact that the polymer yield per g of the

Vi per hour of transition metal used IO ⁴ g of polymeric Ti - g / h.

Another advantage of the method of the invention should be mentioned that on the wall of the polishing vessel no polymer film is formed. This one gets very often

Wi observed in catalysts that comprise a liquid transition metal compound such as titanium tetrachloride and an organoaluminum compound. This polymer film becomes the cause of serious troubles, e.g. B. for difficult polymerization control as well

h> for a deterioration in product quality.

Another advantage of the method of the invention is that the control of the molecular weight of the Polymers can be done very well, though

an appropriate amount of hydrogen is added to the polymerization system, which is the new, in which Contains catalyst used in the process of the invention.

In the following examples, the MI values were (Melting index) in a device for determining the melting index at: 190 ° C, a load of 500 g and a unit of g / 10 minutes.

example 1
a) Preparation of the catalyst component (A)

10 g of magnesium oxide and 4 g of anhydrous aluminum chloride were mixed and pulverized. 10 g this mixture was placed in a 200 ml flask. For this purpose, 15 ml of xylene and ImI Titanium tetrachloride added. The mixture was stirred in a nitrogen atmosphere for 1 hour 120 ° C implemented. After the reaction had ended, the product obtained was placed in a dry receiver Filtered in which the air was replaced with nitrogen. It was four times each with 10 ml Washed η-hexane to completely remove the unreacted titanium tetrachloride, and 1 hour at dried under reduced pressure. A solid product (I) was thereby obtained. This solid product (I) contained 11.8 mg titanium per g.

b) Polymerization of ethylene

In a 1 liter stainless steel reaction vessel equipped with a stirrer, after purging with nitrogen gas, 500 ml of n-hexane, 179 mg of the above solid product and 280 mg of triethylaluminum were charged. The reaction vessel was locked. The mixture was subjected to polymerization under a hydrogen pressure of 1.0 kg / cm ² and an ethylene pressure of 3.0 kg / cm ^{2 for} 1 hour at a polymerization temperature of 80 ° C. The polymer obtained was obtained in the form of a fine powder. No adhesion of the polymer was observed on the surface of the polymerization vessel. After the reaction had ended, the catalyst was deactivated according to the usual procedure. After washing, filtering and drying, 69 g of a white powder were obtained. The rate of formation of the polymer per g of the solid product (I) was 385 g / g / hr. The yield of the polymer per g of the titanium contained in the solid product (I) was 32,600 g / Ti / hr of polymer. As a result, the yield was very high. Ml = 0.18.

Example 2

In the same manner as in Example 1, a solid Product (II) was prepared except that the 15 ml of xylene was replaced with 15 ml of benzene. The solid Product (II) contained 8.5 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same way as in Example 1, but using the solid product (II). The results obtained are shown in Table I.

Example 3

In the same manner as in Example I, a solid Product (III) prepared, with the exception that the 15 ml of xylene was replaced by 15 ml of monochlorobenzene became. The solid product (III) contained 6.8 mg of titanium in 1 g.

The results of the polymerization of ethylene obtained using the solid product (UI) in the same Manner as carried out in Example 1 are summarized in Table I.

Example 4

A solid product (IV) was prepared in the same manner as in Example 1 except that the 15 ml of xylene were replaced with 15 ml of anisole. The solid product (IV) contained 18.5 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid Product (IV) carried out. The results obtained are shown in Table I.

Example 5

In the same manner as in Example 1, a solid

Product (V) manufactured, with the exception that the 15 m! Xylene by a liquid mixture of 15 ml

2 (> n-heptane and 5 ml Dimethylarr.-n were replaced. The solid product (V) contained in 1 g43 n-.gTitan.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid Product (V) carried out. The results obtained 2Ί sin 'are compiled in Table I.

Comparative experiment A

In the same manner as in Example 1, a solid Product (VI) produced, with the exception that those in 15 ml of xylene were replaced by 15 ml of n-heptane. That solid product obtained contained 8.7 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid Product (Vl) carried out. The results η obtained are summarized in Table I.

Comparative experiment B

In the same way as in Example 1, - became a solid Product (VII) produced, with the exception that the

4Ii 15 ml of xylene have been omitted and that no Solvent was used and that 5 ml was used in place of the 1 ml of titanium tetrachloride. That solid product (VII) contained 2.8 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same

4 ") way as in example I using the solid Product (VlI) carried out. The results obtained are shown in Table I.

Comparative experiment C

Vi 48 hours hei 15O ⁰ C dried magnesium oxide was pulverized fen without the addition of aluminum chloride. 10 g de ^r obtained powder was placed in a 700 ml flask. 15 ml of xylene and 1 ml of titanium tetrachloride were added to this.

>> In the same way as in Example I, a solid Product (VIII) obtained. The solid product (VIII) contained 5.7 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same manner as in Example I using 162 mg

Wi of the fesien product (VIII) and of 280 mg of triethylaluminum carried out. The amount of the polymer obtained was 6.2 g. The yield of the polymer was 38 g / g of catalyst component A / h. It follows that the activity was considerably lower than in

ι »Example 1, which in the presence of aluminum chloride had been carried out.

The results of Examples 1 to 5 and the comparative experiments are shown in Table 1.

Tabel

solvent Polymers Ml Bulk density educational windy wedge ") Ex. 0.18 0.213 1 Xylene 385 0.25 0.218 2 benzene 249 0.19 0.189 J Monochlorobenzene N7 0.30 0.219 4th Anisole 258 0.28 0.222 5 Mixture of n-heptane and Dimcthvlamlm 189 Comparative attempt not measurable 0.200 A. n-heptane 52 0.169 FJ 34

") i'oiymcrc". jj'KnumsntniKonippnente \ g π

Example 6

A solid product (IX) was prepared in the same manner as in Example I, except that the 10 g Magnesium oxide was replaced by 10g zinc oxide. The solid product (IX) contained 5.7 mg of titanium in 1 g.

The polymerization of ethylene was carried out in a manner similar to Example I using the solid product (IX). The results obtained are summarized in Table II .

Example 7

10 g of aluminum oxide and 4 g of anhydrous aluminum chloride were mixed and pulverized. 10 g of the mixture obtained was placed in a 200 ml flask. 15 ml of monochlorobenzene and 1 ml of titanium tetrachloride were added to this and reacted for ^{1 hour in a nitrogen atmosphere at 150 ° C. with stirring.}

Then, in the same manner as in Example 1, a solid product (X) was obtained. The solid product (X) contained 36 mg of titanium in 1 g.

In the same manner as in Example 1, polymerization of ethylene was carried out using the solid product (X). The results obtained are summarized in Table II.

Example 8

! 0 g of quartz sand (silicon dioxide) and 4 g of anhydrous aluminum chloride were mixed and pulverized. 10 g of the resulting mixture was then placed in a 200 ml flask. 15 ml of o-chlorotoluene and 1 ml of titanium tetrachloride were added to this and ^{reacted at 150 °} C. for 1 hour in a nitrogen atmosphere with stirring. The following operations were carried out in the same manner as in Example 1. There was thus obtained a solid product (XI) containing 4.2 mg of titanium in 1 g.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid Product (XI) carried out. The results obtained are shown in Table II.

Example 9

In the same manner as in Example 1, a solid product (XII) was obtained. which contained 3.6 mg titanium in Ig. produced, with the exception that 10 g / irkondumd use; became.

The polymerization of ethylene was carried out in the same Carried out as in Example I using the solid product, (II). The results obtained are compiled in Table 11.

Example 10

In the same manner as in Example 1, a solid product (XIII) was obtained. which contained 8.6 mg titanium in Ig, with the exception that 10 g vanadium oxide (VjO,) were used.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid product (XIII). The results obtained are summarized in Table II.

Example 11

In the same manner as in Example 1, a solid Product (XIV). which contained 10.5 mg titanium in Ig, except that 10 g of chromium oxide (CrO) was used.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid product (XIV). The results obtained are shown in Table II .

Example 12

In the same manner as in Example 1, a solid product (XV) containing 8.9 mg of titanium in 1 g was prepared except that 10 g of Mn ₃ O _{4 was} used.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid Product (XV) carried out. The results obtained are shown in Table II.

Example 13

In the same manner as in Example 1, a solid product (XVI) containing 6.8 mg of titanium in 1 g was prepared except that 10 g of Fe ₃ O ₄ was used.

The polymerization of ethylene was carried out in the same manner as in Example 1 using the solid

Product (XVI) carried out. The results are summarized in Table II.

Example 14

In the same manner as in Example I, a solid product (XVII) containing 6.7 mg of titanium in 1 g was prepared, except that 10 g of CO3O4 were used.

The polymerization of ethylene was carried out in the same manner as in Example I using the solid Product 1 (XVII) carried out. The obtained results are compiled ir, Pabelle Il.

10

Example 15

A solid product (XVII) containing 3.5 mg of titanium in Ig was prepared in the same manner as in Example 1, except that 10 g of nickel oxide was used.

The polymerization of ethylene was carried out in the same manner as in Example I using the solid product (XVIII) . The results obtained are summarized in Table II.

The results of Examples 6 to 15 are shown in Table II compiled.

Table Il Type of (l \ i (ls I .oMitiL'SMnnel l'nl \ niere Ml Schuiulichi lieisriiel Hiklinijiv No. eesihuiiul. 0.19 0.256 ZnO Xylene 198 0.20 0.245 6th AhO-, Monochlorobenzene 185 0.20 0.269 7th SiO: 0 chlorotoluene 168 0.17 0.218 8th ZrO, Xylene 145 0.21 0.245 9 V.O-, Xylene 205 0.1 ö 0.215 10 CrO Xylene 169 0.15 0.222 Il Mn ₁ O, Xylene 269 0.15 0.250 12th Fe ₁ O ₁ Xylene 138 0.18 0245 I j Co ₁ O, Xylene 129 0.17 0.215 14th NOK Xylene 148 15th

Example 16

10 g of magnesium oxide and 4 g of anhydrous iron trichloride were mixed and pulverized. 10 g des The resulting mixture was placed in a 200 ml flask brought in. Thereto, 15 ml of benzene and 1 ml of titanium tetrachloride were added and the whole was 1 hour under a nitrogen atmosphere and under Stirring implemented. The following procedures were carried out in the same manner as in Example I. carried out. In this way, a solid product (XIX) containing 4.8 mg of titanium in 1 g was obtained.

The polymerization of ethylene was carried out in the same manner as in Example 1 using 158 mg of the solid product (XIX) and 290 mg of triethylaluminum carried out. In this way 35.6 g of polymer was obtained. The speed of formation of the Polymer was 225 g / g / h. It follows that the activity is considerably higher than in Comparative Experiment C was, in which the F. trichloride was missing. Ml = 0.35.

Example 17

10 g of calcium oxide and 4 g of anhydrous aluminum trichloride were mixed and pulverized. To this, 15 ml of monochlorobenzene and ImI vanadium tetrachloride were added and reacted for 1 hour with stirring in a nitrogen atmosphere.

The following operations were carried out in the same manner as in Example 1. This became a solid product (XX) containing 8.5 mg of vanadium in 1 g was obtained.

The polymerization of ethylene was carried out in the same manner as in Example 1 using 158 mg of the solid product (XX) and 300 mg of triethylaluminum. In this way 28.9 g of polymer was obtained. The rate of formation of the polymer was 183 g / g / h. MI = 0.95

B ei ν ρ ie I 18

10 g of magnesiurialuminite and 4 g of anhydrous aluminum trichloride were mixed and pulverized. For this purpose, 15 ml of benzene and ImI of titanium tetrachloride were added and reacted for 1 hour in a nitrogen atmosphere at 120 ⁰ C.

The following operations were carried out in the same manner as in Example 1, with one solid Product (XXI) was obtained which contained III g 6.9 mg titanium.

The polymerization of ethylene was carried out in the same manner as in Example 1 using 169 mg of the solid product (XXI) and 280 mg of triethylaluminum. In this way, 48.3 g Obtained polymer. The rate of formation of the polymer was 286 g / g.'hr. Ml = 0.25.

Hatchet, pi el 19

The polymerization of ethylene was carried out in the same manner as in Example I using 215 mg of the solid product (I) of Example 1 and 350 mg of diethylaluminum monochloride. In this way 23.5 g of polymer was obtained. The rate of formation of the polymer was 109 g / g / h.

Be is pie! 20th

The polymerization of propylene was carried out in a manner similar to that in Example 1 as follows :

Propylene was polymerized for 1 hour under a pressure of 7 kg / cm ² using 183 mg of the solid product (1) according to Example I _1, 300 mg of triethylaluminum and 500 ml of η-hexane. After the completion of the polymerization, 21.8 g of a white polymer was obtained by the usual treatment. The rate of formation of the polymer

was 119 g / g / h. The polypropylene obtained had the following properties:

/>; 7 (viscosity in tetrahydronaphthalene at 135 ° C):

2.15

Fraction insoluble in n-heptane: 53%

Example 21

The polymerization of butene- (I) was carried out in a similar manner to Example 1.

There were 205 mg of the solid product (I) of Example 1, 290 mg of triethylaluminum and 500 ml n-hexane is used.

After addition, 48 g of butene- (t) were heated to 70 ° C. at room temperature and polymerized for 2 hours. After the completion of the polymerization, 33 g of a white polymer was obtained by the usual treatment. The conversion of butene- (I) was 69%.
/> / 7 (in tetrahydronaphthalene at 130'C): 1.84

Example 22

The copolymerization of ethylene and propylene was carried out in a manner similar to that in Example 1. To this end, 185 mg of the solid product (I) of Example 1, 280 mg of triethylaluminum and 500 ml of n-hexane were used. The propylene was polymerized for 10 minutes and under a pressure of 7 kg / cm- at 80 ° C. After the unreacted propylene had been rinsed out, a further polymerization was carried out for 1 hour under a hydrogen pressure of 1 kg / cm ² and an ethylene pressure of 4 kg / cm ^2.

After the completion of the polymerization, 38 g of a white polymer was obtained by the usual treatment. It was confirmed that the polymer was a copolymer. This copolymer had the following physical properties:
Density (25 ° C): 0.9436 g / cm>
[η] (\ η tetrahydronaphthalene at 130 ^° C.): 1.91

Example 23

The copolymerization of ethylene and butene- (I) was carried out in a manner similar to Example 1. 195 mg of the solid product (I) of Example I, 280 mg of triethylaluminum and 50 ml of n-hexane were used. 0.8 g of butene (l) were heated after supplying at room temperature to 80 ⁰ C. The polymerization reaction was carried out for 1 hour under a hydrogen pressure of 0.5 kg / cm ² and an ethylene pressure of 4.0 kg / cm ² . After the completion of the polymerization, 21.6 g of a white polymer was obtained by the usual treatment. It was confirmed that this polymer was a copolymer. The copolymer had the following properties:

Density: 03330 g / cm '

[η] (\ η tetrahydronaphthalene at 130 ° C): 1.97

Example 24

In the similar manner as in Example 1 carried out polymerization of ethylene was as Addition of titanium tetra-n-butoxide added.

Using 185 mg of the solid product (I) of Example 1, 0.20 millimoles of titanium tetra-n-butoxtd, 2.5 millimoles of triethyaluminum and 500 ml of η-hexane, the polymerization was carried out for 1 hour at 80 ° C under a hydrogen Overpressure of 1.0 kg / cm ² and an ethylene overpressure of 3.0 kg / cm ² carried out.

After the completion of the polymerization, 64.3 g of a white polymer were obtained by the usual treatment

ίο received. The rate of formation of the polymer was 348 g / g / h. MI-0.45. According to ASTM D-1693-60 T, the cracking of the polymer was carried out under tension, with a period of more found than 1000 hours for 50% breakage

I would. It was thus found that the polymer possesses superior physical properties. For comparison purposes, a polymer was applied to these Examined manner, which was obtained in the same way u / rirrlpn with rlrr inclusion, rlnß no Tetra-n-bit-

.'Ii oxide had been added. The corresponding Time to break 50% was 69 hours.

Example 25

The polymerization of ethylene carried out in a manner similar to that in Example I. ') Was obtained Given titanium tetra-n-butoxide.

Using 185 mg of the solid product (XV) of Example 12, 0.15 millimoles of titanium tetra-n-butoxide, 20 millimoles of triethylaluminum and 500 ml of n-hexane, the polymerization was carried out for 1 hour at 80 ° C. and under hydrogen pressure of 1.0 kg / cm and an ethylene overpressure of 3.0 kg / cm ² .

After the completion of the polymerization, the usual treatment gave 68.0% of a white polymer r, received. The rate of formation of the polymer thus obtained was 367 g / g / h. Ml = 0.25. the Corresponding measurement according to ASTM D-1693-60T showed a period of time for a 50% break of more than 1500 hours. As a result, the polymer has excellent physical properties owns. The polymer had the following physical properties:

Density: 0.9320 g / cm ^J
Tensile strength: 196 kg / cm ²

Example I 26

In a manner similar to Example 1, the copolymerization of ethylene and styrene was carried out. 158 mg of the solid product (I) of Example 1, 280 mg of triethylaluminum and 500 ml of n-hexane were used. After 10 ml of styrene had been fed in, the polymerization was carried out for 1 hour at 80 ° C. and a hydrogen excess pressure of 0.5 kg / cm ² and an ethylene excess pressure of 3.0 kg / cm ²

After the completion of the polymerization, 16.9 g of a white polymer was obtained by the usual treatment. It was confirmed that this polymer was a copolymer having the following property:
[η] (\ η tetrahydronaphthalene at 130 ° C): 3.24

Claims (3)

Claim: Process for the homopolymerization of ethylene, propylene or butene- (l) and for their interpolymerization with one another or with 3-methyl-l-butene, 4-methyl-l-pentene, hexene (l), octene (l), decene - (l) and / or styrene in an inert hydrocarbon solvent, at temperatures from -50 ° to 150 ⁰ C, and a pressure from atmospheric pressure to 40 kg / cm ² , in the presence of a catalyst system, which by activating one of 1. a carrier , 2. anhydrous aluminum trichloride, aluminum tribromide or ferric chloride, 3. Titanium tetrachloride, vanadium tetrachloride and / or vanadium oxychloride, in the presence of 4. an aromatic compound prepared catalyst component (A) with an organometallic catalyst component (B), characterized in that a catalyst conipuiicnic (A) is used, which by Rcakücn one made of MgO, CaO, ZnO, Al ₂ Oj, SiO ₂ , ZrO ₂ , V ₂ O ₅ , CrO, MnjO ,, Fe ₁ O ₄ , COiO ₄ , NiO or MgAl ₂ O ₄ as a carrier, whereby this does not contain any hydroxyl groups, and component 2 in amounts of 0.01 to 2 moles per mole of component 1 mixture produced by grinding at a temperature in the range from room temperature to 30O ⁰ C either with a mixture of component 3 and one of the aromatic compounds