DE2035943A1 - Process for the preparation of polymers of alpha olefins - Google Patents

Description

DR. ING. E. HOFFMANN · DIPL. ING. W. EITLE DR. RER. NAT. K. HOFFMANN

D-8000 MÖNCHEN 81. ARABELIASTRASSE 4 ■ TELEPHONE (0811) 911087

Chisso Corporation
Osaka / Japan

Method of manufacture vq
Polymers of 0 (-olefins

The invention relates to a process for the preparation of polymers of (X-olefins. It relates in particular to polymerization or copolymerization
of an O (-olefin in the presence of a catalyst which
by mixing a metal oxide with a halide
of a trivalent metal, reacting the mixture obtained with a transition metal compound in the presence of an aromatic compound and activating the solid reaction product obtained with an organoaluminum compound.

009887/2049

In the German patent application P 19 O4 815.8 a process for the polymerization of <λ -olefins in the presence of a catalyst is described, which has been obtained in that a halide of a trivalent metal with at least one type of compounds from the group of halide hydrates, sulfide -Hydrates, sulfate hydrates, hydroxides, hydroxide hydrates of metals of groups I to VIII of the periodic table has been subjected to a burning reaction, as a result of which active groups have formed on the surface of the product of the burning reaction obtained. The combustion reaction product was then reacted with a transition metal compound and the reaction product obtained was then activated with an organoaluminum compound.

The following advantages can be obtained with this procedure: The usable effectiveness of the transition metal compound is very high, the reduction resulting from hydrogen of the molecular weight is considerable, no polymer films etc. are formed on the wall of the polymerization vessel.

With the procedure described above, however, it is necessary to to carry out a burning reaction. However, the burning reaction is associated with a dehydrοChlorierung, sometimes in the reaction between the active groups on the surface of the solid combustion reaction product and the transition metal compound an additional dehydroChlorination takes place, whereby the corrosion the facilities used. In addition to this disadvantage, there is another shortcoming that the Bulk density of the polymer obtained depends on the temperature of the firing reaction.

009887 / 2-048

2035343

The invention is therefore based on the object of providing a process for the production of polymers of & -olefins available, in which a solid reaction product is used as a component forming the catalyst, which is obtained in that in the process according to the earlier application a metal compound hydrate or a metal hydroxide is replaced with a metal oxide, whereby the burning reaction becomes unnecessary in the reaction with the halide of the trivalent metal. In this way, the implementation becomes easier and there is no disadvantageous dehydrochlorination.

Another object of the invention is to provide a method to make available at which a higher effectiveness of the transition metal is present on the surfaces of the polymerization vessel in the course of the polymerization no polymer film is formed and the molecular weight of which is very well controlled by hydrogen can.

It ip'r Finally, another object of the invention to provide a """out to provide for disposal, wherein without further the dispersibility of the catalyst is maintained and wherein the polymers obtained with improved properties physikaiischen.

According to the method of the invention, a metal oxide is mixed r :: it is a halide of a trivalent metal the mixture obtained in the presence of an aromatic compound with a transition metal compound and activated see the received solid product with an aluminum organ! Link. In this way, a polymer of an o-olefin or a copolymer of o-olefins is catalytically produced here.

009887/2049

Examples of metal oxides which can be used in the process of the invention are: CUgO, CuO, Ag ₂ O, Ag ₃ O ^, MgO, CaO, SrO, BaO, ZnO, CdO, B ₂ O ₅ , Al ₂ O ₅ , Ga ₃ O ₅ , SiO ₂ , SnO, SnO ₃ , PbO, Pb _p 0 ,, Pb O ₂ ,, TiO, TiO _p , TipO ,, ZrOp, \ BipO ,, VpO ,, V ₃ O ^, CrO, Cr ₃ O ₅ , MoO ₃ , MoO ₅ , WO ₅ , MnO, Mn ₃ O ₅ , Mn ₅ O ₄ , FeO, Fe ₃ O ₅ , Fe ₅ O ₄ , CoO, Co ₅ O ₄ , NiO, NaAlO ₂ , CaAl ₂ O ₄ , MgAl ₂ O ₄ , FeTiO Mg ₃ SiO ₄ , CaTiO ₅ , MgWO ₄ , MggMnOg and the like.

As the halide of a trivalent metal which can be used in the process of the invention, for example, anhydrous AlCl-- ,, AlBr- ,, FeCl-, and the like can be named.

The metal oxides and the halides of the trivalent metal are prepared using suitable means, e.g. a ball mill, mixed. There is no particular limitation on the mixing ratio, however about 0.01 to 2 moles of the halide of the trivalent metal per 1 mole of the metal oxide suffice.

As aromatic compounds that are present in the reaction of the mixture of the metal oxide with the halide of the trivalent metal with the transition metal compound The following compounds can be mentioned, for example: benzene, naphthalene, pyridine and the like Compounds, as well as alkyl-substituted benzenes, such as toluene, Xylene, mesitylene, durol, ethylbenzene, isopropylbenzene and the like, polynuclear aromatic ring derivatives, such as ■ 2-ethyl-naphthalene, 1-phenyl-naphthalene and the like, Aniline derivatives that do not have active hydrogen, such as dimethylaniline, aromatic amines that do not have an active Own hydrogen, such as N-methyl-diphenylamine, triphenylamine, Nitro and nitroso derivatives, such as nitrobenzene, nitrosobenzene, p-nitrosotoluene, halides such as monochlorobenzene,

009887/2049

ortho-chlorotoluene, alkoxide derivatives such as anisole, ether derivatives, such as phenyl ethers, phenols such as xylenol, 2,6-di-t-butyl-4-methyl-phenol and the same.

The above aromatic compounds can preferably be used alone. However, they can also be used in a mixture with a saturated aliphatic hydrocarbon, such as n-heptane, octane and the like. -

As transition metal compounds which can be used, halides and oxyhalides of the transition metals of the groups IVa and Va of the periodic table, such as titanium, vanadium "

etc., whereby titanium tetrachloride, vanadium tetrachloride., vanadium oxytrichloride and similar compounds to be favoured.

The reaction mechanism by 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 reacts with the transition metal compound has not yet been fully elucidated. However, it is it has become known that an aromatic compound and a transition metal compound form a charge transfer complex form and that such a complex is also formed between a halide of a trivalent metal and an aromatic Connection trains. It has also become known that a metal oxide with a halide is a converts trivalent metal. It can therefore be assumed that the transition metal compound is in a combination of these reactions with the solid reaction product of the metal oxide and the halide of the trivalent metal is reacted and fixed thereon. In fact, the

009387/2049

Transition metal compound after the reactions of the The surface of the solid cannot be removed by physical measures, e.g. washing.

In the method of the invention, the metal oxide, the Trivalent metal halide, aromatic compound and transition metal compound are indispensable Components. If only one of these components is missing, the polymerization catalyst cannot be used with the High activity specified here come * If in the absence of an organic compound a reaction between a mixture of. a metal oxide and a halide of a trivalent metal with a transition metal compound is carried out, a solid catalyst with high activity is not obtained. When the reaction. "Between a metal oxide and a transition metal compound carried out in the presence of an aromatic compound, but without the use of a halide of a trivalent metal is, then only a catalyst is obtained which has a considerably lower activity than one catalyst made according to the process of the invention.

In the reaction between a transition metal compound and a mixture of a metal oxide and a halide of a trivalent metal in the presence of an aromatic compound, too low a temperature is not advisable, since the attachment of the transition metal compound cannot be carried out effectively in this case =, and vice versa Working at temperatures that are too high is not practical because it makes the implementation difficult to operate. The reaction is therefore preferably carried out gewöhnileherireise at temperatures ranging from room temperature to 300 ⁰ C ₃ of 50 to 200 ⁰ C.

There is no particular limitation on the Reaction time, but from 20 minutes to several hours is usually preferred.

The reaction between a mixture of a metal oxide and a halide of a trivalent metal and a Transition metal compound in the presence of an aromatic compound can be carried out by any known method come.

It can be carried out, for example, in such a way that a mixture of a metal oxide and a halide of a trivalent metal is suspended in a solvent of an aromatic compound or in a solvent mixture of aromatic and aliphatic hydrocarbons and that the suspension obtained is used to effect the reaction the transition metal compound is added. ' The reaction can also be carried out by mixing a transition metal compound and the solvent and mixing the resulting mixture with a mixture of a metal oxide and a halide of a trivalent metal to initiate the reaction, and the solid product formed by these methods becomes filtered off, gently washed with an anhydrous hydrocarbon solvent until the washing g liquid no trace amounts of transition metal place and used zxxr preparing the catalyst. in the other case, a slurry in which the four components indicated above have completely reacted and in which no free transition metal element remains as such without filtration being used.

It can also be a mixture of a metal oxide and a · Halide of a trivalent metal, which with a

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ÖAD

aromatic solvent or its vapor has been treated, reacted with a transition metal compound will.

The solid product must be activated by bringing it into contact with an aluminum-organic compound. Compounds particularly suitable for such activators are trialkylaluminum compounds, such as trimethylaluminum, Triethylaluminum and the like, and alkylaluminum halides (Dialkyl aluminum monohalides, alkyl aluminum sesquihalides and alkyl aluminum dihalides) such as diethyl aluminum monochloride, Ethylaluminum sesqui chloride, monoethylaluminum dichloride and the like.

The catalysts used according to the invention exert their excellent catalytic activity in the homopolymerization of? -Olefins and in the copolymerization of (A-olefins with each other.

The Gt olefins used include those commonly known as (λ, olefins: straight chain monoolefins such as ethylene, propylene, butene> -1, hexene-1, octene-1, decene-1, branched monoolefins such as 3 Methyl-1-butene, 4-methyl-1-pentene, styrene and the like.

The polymerization reaction is usually carried out in an inert hydrocarbon solvent, with better Results generally at temperatures from -50 ° C to about 150 ° C and at pressures from atmospheric to 40 kg / cm can be obtained.

Performing the process of the present invention enables the titanium alkoxide to be added to the polymerization system

009887/2049

the control of the density of the products, in particular in the polymerization of ethylene. This also significantly increases the physical properties of the polymers obtained is improved, in particular cracking and stress. The addition of the titanium alkoxide also ensures better dispersibility of the catalyst, prevents the aggregation of polymer particles and results in a polymer having uniform and fine particles. Furthermore, this can increase the activity of the catalyst, so that the polymer yield per catalyst unit is increased significantly, whereby due to the reduced amount of catalyst that is used, after the polymerization, the removal of the remaining catalyst, for example by deactivation, washing. ■ and drying, is simplified. Since still in 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. Titanium tetraalkoxides, more precisely titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetramethoxide and the like.

The amount of titanium alkoxide used is generally "

mean in the range of 0.1 to 5 * 0 millimoles per gram of solid Product, if the amount of titanium used is lower, then the effectiveness is lower, while vice versa with the larger the amount the soluble part of the polymerization product becomes larger.

A large one obtainable in the preparation of the polymerization catalyst as carried out according to the invention

009887/2019

The advantage is that the reaction of the metal oxide and the halide of the trivalent metal and further the reaction of the product obtained with the transition metal compound in the presence of the aromatic compound is not accompanied by any dehydrochlorination what is on the Use of a metal oxide that does not contain a hydroxyl group can be attributed to the surface of the pesticide. Accordingly there is no corrosion of the device and it can be quantitatively a stable solid catalyst with good reproducibility and manufactured in shorter stages.

Another advantage of the method of the invention is that the effectiveness of the transition metal compound ' is extremely high. This can be seen, for example, from the fact that the polymer yield is per gram of used per hour Transition metal is 10 g polymers / Ti-g / h.

A further advantage of the process of the invention should be mentioned that there is no on the wall of the polymerization vessel Polymer film is formed. This is very often observed in catalysts that contain a liquid transition metal compound, such as titanium tetrachloride and an organoaluminum compound. This polymer film will the cause of serious malfunctions, e.g. difficult polymerization control as well as deterioration ■ tion of product quality.

Another advantage of the method of the invention is that the control of the molecular weight of the Polyr merging can be done very well when an appropriate amount of hydrogen is added to the polymerization system which contains the new catalyst used according to the invention.

009887/2041

The invention is illustrated in the examples.

The Mi values (melting indices) were determined 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:

10 g of magnesium oxide and 4 g of anhydrous aluminum chloride were mixed and pulverized. 10 g of this mixture was placed in a 200 ml flask. 15 ml of xylene and 1 ml of titanium tetrachloride were added to this. The mixture was reacted with stirring in a nitrogen atmosphere at 120 ^° C. for 1 hour. After the reaction had ended, the product obtained was filtered into a dry receiver in which the air had been replaced by nitrogen. It was washed four times with 10 ml of η-hexane each time in order to completely remove the unreacted titanium tetrachloride and dried for 1 hour under reduced pressure. A solid product (i) was thereby obtained. This solid product (i) contained 11.8 mg of titanium per g.

b) Polymerization of ethylene:

In a 1 liter stainless steel reaction vessel that is equipped with was provided 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 are added. The reaction vessel was locked. The mixture was under a hydrogen pressure of 1.0 kg / cm and

009887/2049

an ethylene overpressure of 3.0 kg / cm 1 hour at a
Polymerization temperature of 80 ° C for the polymerization
subject. The obtained polymer fell 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 38 [? g / g / h. The yield of the polymer
per g of the titanium obtained in the solid product (I) was 32,600 g / tig / h of polymer. As a result, the yield was very high. MI = 0.18.

Example 2

In a manner similar to Example 1, a solid product was obtained (II) obtained, with the exception that the .15 ml of xylene were replaced by 15 ml of benzene. The solid product (II) contained 805 mg of titanium in 1 g.

The polymerization of ethylene was carried out in a similar manner
as in Example 1, using the solid product (il). The results obtained are in Table 1
compiled.

Example 3

In a manner similar to Example 1, a solid product (ill) was obtained, except that the 15 ml of xylene were replaced by 15 ml of monochlorobenzene. The firm pro

009887/2049

duct (III) contained 6.8 mg of titanium in 1 g.

The results of the polymerization of ethylene, which under Use of the solid product (ill) in a similar way as carried out in Example 1 are summarized in Table 1.

example

In a manner similar to Example 1, a solid product (IV) was obtained except that the 15 ml of xylene were replaced by 15 ml of anisole. The solid product (IV) contained 18.5 mg titanium in 1 g.

The polymerization of ethylene was carried out in a manner similar to that in Example 1 using the solid product (IV) carried out. The results obtained are shown in Table "1 compiled.

Example 5

■ ■ ■ i

In a manner similar to Example 1, a. solid product (V) obtained, with the exception that the 15 m ^ xylene were replaced by a liquid mixture of 15 -föl n-heptane and 5 ml of dimethyl aniline. The solid product (v) contained 1 g k, 9 mg titanium,

ι ■ ■■ - ■■■

The polymerization of ethylene was carried out in a similar manner as in Ileisplel 1 using the solid product (V) carried out. The results obtained are in Table 1 compiled.

009887 / 20A9

ORIGINAL iMSPECTED

Comparative example 1

In a manner similar to Example 1, a solid product (VI) was obtained except that the 15 ml of xylene were replaced by 15 ml of n-heptane. That. received solid 1 g of product contained 8.7 mg of titanium.

The polymerization of ethylene was carried out in a manner similar to Example 1 using the solid product (Vl) carried out. The results obtained are shown in Table 1.

Comparative example 2

In a manner similar to Example 1, a solid pro ^ product (VII) except that the 15 ml of xylene was omitted and that no solvent was used and that instead of 1 ml of titanium tetrachloride, 5 ml was used became. The solid product (VII) contained 2.8 mg of titanium in 1 g.

The polymerization of ethylene was carried out in a manner similar to that in Example 1 using the solid product (VII) P carried out. The results obtained are in Table 1 compiled.

Comparative example 3

48 hours at 150 ⁰ C dried- j

Addition of aluminum chloride finely powderedWg öea er.: The powder held was placed in a 200 »liter flask. ; 15 ml of xylene and 1 ml of titanium tetrachloride were added to this.

ORIGiNAL INSPECTED

0-09 * 87/204 *

In a manner similar to Example 1, a solid product was obtained (VIII) obtained. The solid product (VIII) contained 5.7 mg titanium in 1 g.

The polymerization of ethylene .wurde in a similar manner as in Example 1 using 162 mg of the solid Product (VIII) and carried out from 280 mg of triethylaluminum. The amount of the polymer obtained was 6.2 g. The yield of the polymer was 38 g / g / ii. From this it follows found that the activity was considerably lower than in Example 1, which in the presence of γοη aluminum chloride had been carried out.

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

1 Tabel 2 - 1 Po 1 y m e r e Schütt
density 2 Educational
speed
age 3E MI 0.213 3 385 0.18 0.218 4th solvent 249 0.25 0.189 Ex. 5 Xylene 197 0.19 0.219 Il benzene 258 0.30 0.222 Il Monochlorobenzene I89 0.28 0.200 ti Anisole 52 not
measurable 0.169 It Mixture of
n-heptane and
Dirnethylaniline 34 Comparative
ex. 1 n-heptane Il

M polymer g / solid product g / h

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Example 6

In a manner similar to Example 1, a solid product (IX) was obtained except for "that" 10 g of magnesium oxide were replaced by 10 g of zinc oxide. The solid product (IX) contained 5.7 mg titanium in 1 g »

The polymerization of the ethylene was carried out in a manner similar to Example 1 using the solid product (IX) carried out. The results obtained are in Table 2 compiled.

Example 7

10 g of alumina and 4 g of anhydrous aluminum chloride were mixed up 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 Ig.

In a manner similar to Example 1, the polymerization of ethylene was carried out using the solid product (X) carried out. The results obtained are shown in Table 2.

009887/2049

Example 8

10 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. For this purpose, 15 ml were o-Chlortqluol and 1 ml of titanium tetrachloride and reacted for 1 hour at 15O ⁰ C with stirring in a nitrogen atmosphere. The following operations were carried out in a manner similar to that 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 a similar manner as in Example 1 using the solid product (Xl) carried out. The results obtained are shown in Table 2.

Example 9

In a manner similar to Example 1, a solid product (XII) containing 3.6 mg of titanium in 1 g was prepared, except that 10 g of zirconia was used.

The polymerization of ethylene was carried out in a manner similar to that in Example 1 using the solid product (XIl). The results obtained are shown in Table 2.

Example 10

In a manner similar to Example 1, a solid product (XEII) containing 8.6 mg of titanium in 1 g was prepared, with the exception that 10 g of vanadium oxide (VgOc) is used became.

009887/2040

The polymerization of ethylene was carried out in a manner similar to Example 1 using the solid product (XIII) carried out. The results obtained are shown in Table 2

Example 11

In a manner similar to Example 1, a solid product (XIV) containing 10.5 mg of titanium in 1 g was prepared, with the exception that 10 g of chromium oxide (CrO) was used.

The polymerization of ethylene was carried out in a similar manner carried out as in Example 1 using the solid product (XIV). The results obtained are in Table 2 compiled.

Example 12

In a similar manner to Example 1, a solid product (XV) containing 8.9 mg of titanium in 1 g was prepared, with the exception that 10 g of MrwOh was used.

The polymerization of ethylene was carried out in a manner similar to Example 1 using the solid product (XV) carried out. The results obtained are in Table 2 compiled.

example \ J

In a manner similar to Example X , a solid product (XVI) containing 6.8 mg of titanium in 1 g was prepared, except that 10 g of Pe, 0 ^ was used.

009887/2048

The polymerization of ethylene was carried out in a manner similar to Example 1 using the solid product (XVl) carried out. The results are in Table 2 compiled.

Example l4 ■

In a manner similar to "Example 1", a solid product was obtained (XVII) containing 6.7 mg of titanium in 1 g, with the exception that 10 g of Co, CK was used.

The polymerization of ethylene was carried out in a similar manner as in example 1 using the solid product ' (XVII) carried out. The results obtained are shown in Table 2.

Example 15

In a similar manner to Example 1, a solid product (XVII) containing 3.5 mg of titanium in 1 g was prepared, except that 10 g of nickel oxide was used.

The polymerization of ethylene was carried out in a similar manner as in Example 1 using the solid product (XVIII) carried out. The results obtained are shown in Table 2.

The results of Examples 6 to 15 are in Table 2 compiled.

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L type of Tabel 2 P 0 I y m e r e Schütt Oxide Educational MT density Example] Solution swiftly. MJ. 0.256 No. ZnO middle 198 0.19 0.245 Al ₂ O ₅ I85 0.20 0.269 6th . SiO ₂ Xylene 168 0.20 0.218 7th ZrO ₂ Monochlorobenzene 145 0.17 0.245 8th V ₂ O ₅ o-chlorotoluene 205 0.21 0.215 9 • CrO Xylene 169 0.18 0.222 10 ■ Mn ₃ O ₄ Xylene 269 0.45 0.250 11 Fe ₃ O ₄ Xylene 158 0.15 0.245 12th Co ₃ O ₄ Xylene 129 0.18 0.215 15th NOK Xylene 148 0.17 14th Example ΐβ Xylene 15th Xylene

10 g magnesium oxide and 4 g anhydrous iron trichloride were mixed and pulverized. 10 g of the mixture obtained was placed in a 200 ml flask. For this 15 ml and 1 ml of titanium tetrachloride were added and the whole was stirred for 1 hour under a nitrogen atmosphere and implemented with stirring. The following operations were carried out in a manner similar to that in Example 1. To this Way became a solid product (XIX), which in 1 g 4.8 mg Contained titanium.

The polymerization of the ethylene was in a manner similar to Example 1 using 158 mg of the solid

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Product (XIX) and 290 mg of triethylaluminum carried out. In this way 35 * 6 S polymer was obtained. the The rate of formation of the polymer was 225 g / g / h. It follows that the activity is considerably higher than was as in Comparative Example 3 in which the iron trichloride was absent. MI = 0.35.

Example 17

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

The following measures were carried out in a similar way as carried out in Example 1. As a result, a solid product (XX) containing 8.5 mg of vanadium in 1 g was obtained.

The polymerization of ethylene was carried out in a similar manner carried out as in Example 1, with I58 mg of the solid Product (XX) and 300 mg of triethylaluminum were used. In this way 28.9 g of polymers were obtained. The education speed of the polymer was 183 g / g / hr · MI = 0.95

Example l8

10 g of magnesium aluminate (spinel) and ig anhydrous aluminum trichloride were mixed and pulverized. 15 ml of benzene and 1 ml of tetrachloride were added to this and ^{reacted at 120 °} C. for 1 hour in a nitrogen atmosphere.

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The following actions were taken in a manner similar to carried out in Example 1, a solid product (XXl) incurred, which contained 6.9 mg of titanium in 1 g.

The polymerization of the ethylene was carried out in a manner similar to that in Example 1 using 1Ö9 mg of the solid Product (XXI) and 280 mg of triethylaluminum carried out. In this way 48.3 g of polymer was obtained. The rate of formation of the polymer was 286 g / g / h. MT = 0.25.

Example 19

The polymerization of the ethylene was carried out in a similar manner v / ie in Example 1, with 215 mg of the solid Product (I) of Example 1 and 350 mg of diethyl aluminum monochloride were used. This tit got 23.5 Obtain polymer. The rate of formation of the polymer was 109 g / g / h.

Example 20

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

Propylene was injected for 1 hour under a gauge pressure of 7 kg / cm using I83 mg of the solid product (I) according to Example 1, polymerized from 300 mg of triethylaluminum and 500 ml of n-hexane. After completion of the polymerization were obtained by the usual treatment 21 ", 8 g of a white polymer. The rate of formation of the polymer was 119 g / g / h. The obtained polypropylene was as follows Characteristics:

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(Viscosity in tetralin at 135 ° C): 2.15 Fractions insoluble in n-heptane: 53 #

Example 21

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

Ea 205 mg of the solid product (i) of Example 1, 290 mg of triethy aluminum and 500 ml of η-hexane were used.

48 g of butene-1 were fed in ^{and 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-1 was 69 %.

/ 7} J (in tetralin at 130 ⁰ C): 1.84

Example 22

The copolymerization of ethylene and propylene was carried out in carried out in a similar manner as in Example 1. For this purpose, 185 mg of the solid product (i) of Example 1, 280 mg of triethylaluminum and 500 ml of η-hexane are used. The propylene was 10 minutes and under positive pressure polymerized by 7 kg / cm at 80 C. After rinsing out of the unreacted propylene was 1 hour under a hydrogen overpressure of 1 kg / cm and an ethylene over-

pressure of 4 kg / cm carried out a further polymerization.

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After the end of the polymerization, 38 g of a white polymer were obtained by the usual treatment «, It was confirmed that the polymer was a copolymer ". This copolymer had the following physical properties:

Density (25 ° C) ϊ 0.9 ^ 36 g / cm? / JhJ (in tetralin at 130 ⁰ C): 1.91

Example 23

The copolymerization of ethylene and butene-1 was carried out in a manner similar to Example 1. 195 mg of the solid product (1) of Example 1, 280 mg of triethylaluminum and 50 ml of η-hexane were used. After the addition, 0.8 g of butene-1 was heated ^{to 80 ° C. at room temperature.} The polymerization reaction lasted for 1 hour

under a hydrogen pressure of 0.5 kg / cm and

2 carried out an ethylene overpressure of 4.0 kg / cm. To Completion of the polymerization, 21.6 g of a white polymer was obtained by the usual treatment. It it was confirmed that this polymer was a copolymer. The copolymer had the following properties:

Density: 0.9330 g / cnr

/ JLJ ^(ln tetralin at 130 ⁰ C); 1.97

Example 24

In the similar way .As in Example 1 carried out Polymerization of ethylene was added as titanium tetra-butoxide added.

009887/2049

-as- 20359A3

Using I85 mg of the solid product (I) des Example 1, 0.20 millimoles of titanium tetra-n-butoxide, 2.5 millimoles Triethylaluminum and 500 ml of η-hexane was the polymerization 1 hour at 80 ° C under a hydrogen over-

pressure of 1.0 kg / cm and an ethylene overpressure of J.0 kg / cm.

After completion of the polymerization, the usual Treatment 64, J5 S of a white polymer obtained. The speed of education of the polymer was 348 g / g / h. MI = 0.45. According to ASTM D-169> -6OT, the cracking of the Polymers carried out under tension, with a period ^ of more than 1,000 hours for a 50 $ break solid- ™ was asked. It thus turned out that the Polymer possesses superior physical properties. For comparison purposes, a polymer was made in this way which was similarly obtained except that no tetra-n-butoxide was added was. The equivalent time for a $ 50 break was 69 hours.

Example 25

For the polymerization of ethylene carried out in a manner similar to Example 1, titanium tetra-n-butoxide was added given.

Using 185 mg of the solid product (XV) of Example 12, 0.15 millimoles of titanium tetra-n-butoxide, ZO millimoles of triethylaluminum and 500 ml of η-hexane, the polymerization was carried out for 1 hour at 80 ° C. and a hydrogen pressure of 1 , 0 kg / cm and an ethylene pressure of 3.0 kg /

2
cm carried out.

009887/2049

After the completion of the polymerization, 68.0 of a white polymer was obtained by the usual treatment. The rate of formation of the polymer obtained in this way was 367 g / g / h · MI = 0 * 25 "The corresponding measurement according to the ASTM Ό ~ Ιβ9 ^ -6θΤ gave a period of time for a 50% fracture of more than 1,500 hours" prove that the polymer has superior physical properties. The polymer had the other physical properties;

Density: 0.9320 g / cnr
Tensile strenght? 196 kg / cm

Example 26

The copolymerization of ethylene and styrene was carried out in a manner similar to that in Example 1. 158 mg of the solid product (I) of Example 1, 280 mg of triethylaluminum and 500 ml of η-hexane were used. After 10 ml of styrene had been fed in, the polymerization was carried out for 1 hour at 80 ^° C. and an excess hydrogen pressure of 0.5 kg / cm and an excess ethylene pressure of I ₃ O kg / cm.

After the completion of the polymerization, 16.9 g of a white polymer was obtained by the usual treatment. It was confirms that this polymer was a copolymer having the following property '

(in tetralin at 130 ^° C.); 3.24

009887/2049

Claims (1)

Pat ent claims Ti Process for the preparation of polymers of o (-olefins, characterized in that an o (-olefin is polymerized or an o (-olefin is copolymerized with another olefin in the presence of a catalyst which has been obtained by combining a metal oxide with a is a trivalent metal halide has been mixed, the resulting mixture in the presence of an aromatic compound with an excess' ■ transition metal compound has been reacted and organ aluminum, the obtained solid reaction product with a λ! see compound activated. 2. The method according to claim 1, characterized in that the polymerization or the " Copolymerization carried out together with a titanium alkoxide. 5. The method according to claim 1, characterized in that one et -olefin ethylene, propylene and / or butene-1 and the other <* - olefin ethylene, propylene, butene-1, hexene-1, octene-1, Decene-1, 3-methyl-1-butene, ² J-methyl-1-pentene and / or styrene. -. 4. The method according to claim 1, characterized in that the metal oxide MgO, ZnO, CaO, AlgOw SiO ₂ , ZrO ₂ , V ₂ O ₁ -, CrO, Mn., 0 ^, Pe ^ O ^, Co, 0 ^, KiO and / or 5 · The method according to claim 1, characterized in that the halide of the trivalent Metal is aluminum trichloride or iron trichloride. - 009887/2049 ο. Process according to Claim 1, characterized in that the transition metal compound Titanium tetrachloride, vanadium tetrachloride and / or vanadium oxytrichloride is. 7. The method according to claim 1, characterized in that g e k e η η, that the aromatic compound from the group Benaol, naphthalene, or their alkyl-substituted Derivatives, their aromatic amine derivatives without active hydrogens, their nitro and nitroso derivatives, their Halides, the alkoxides and / or phenols of which is selected. 3. The method according to claim 1, characterized in that the aromatic compound benzene, Toluene, xylene, anisole, dimethylaniline, monochlorobenzene and / or ortho-chlorotoluene. 9. The method according to claim 1, characterized in that the organoaluminum compound a trialkyl aluminum, a dialkyl aluminum monohalide, an alkyl aluminum sesquihalide and / or a monoalkyl aluminum halide is. 10. A method for producing according to claim 2, characterized ge kennsei cn η et that the titanium alkoxide Titanfeetran-butoxide, Titanium tetraethoxide and / or titanium tetramethoxide is. 009887/2049