DE1934677B2 - POLYMERIZATION CATALYST, PROCESS FOR ITS MANUFACTURING AND ITS USE IN A PROCESS FOR POLYMERIZATION OF ALPHA-OLEFINS - Google Patents

Description

The invention relates to a polymerization catalyst which separates the starting materials and activates it, a process for its production by reacting with an organoaluminum compound of a vanadium, titanium and organoaluminum formula AlRnXä'-n. ^{R eme} carbon minium compound in an inert solvent hydrogen group having 1 to 14 carbon atoms, and its use in a process for X 'a halogen atom or an alkoxy group and polymerization of α-olefins. η is a number from 1 to 3, contacted.

It is known that catalysts, the main subject of the invention is also a process

mainly from compounds of transition metals 50 for the polymerization of α-olefins, which thereby of groups IVa to VIa of the Periodic Table is characterized in that the above gekennder Polymerization catalyst signed with elements and organometallic compounds is used, of metals of groups Ia to IHa of the Peri- The polymerization catalyst according to the invention

Odic system of elements exist in which has opposite the known Polymerisationskata-Polymerisation of olefins at low temperatures, especially compared to those from the USA and pressing can be used. Such polymerizations are known in patent specification 3,218,266 For example, from the USA patent specification catalysts, the advantage that it has a higher poly-218 266 catalysts for the polymerization of merization activity, which over a prolonged α-olefins known that can be sustained from a mixture of period of time, so a titanium compound and a vanadium compound 60 that when used in a process applies with an organoaluminum compound at 0 to polymerization of α-olefins a constant poly-300 ° C. merization rate during the polymerization

These known catalysts are not, however, capable of being sustained leading to poly-free of disadvantages, especially when they merisate with a high bulk density in the large-scale production of polyolefins 65 (cf. in this regard those described below can be used. Although many of them have a comparative experiment 1 to 3).

extraordinarily high catalytic activity and that the first component of the invention

do not need cocrystallized to form polymerization catalyst after the end of the polymerization;

3 ₄

Product can easily vary by reducing a mixture of minium component depending on the kind of a titanium compound and a vanadium compound used as a reducing agent with an organoaluminum compound with an organoaluminum compound, the reduction will be made. The ratio of titanium compound treatment treatment usually with sufficient to vanadium compound in the stirring to be reduced in the presence of an inert gas in the case of a mixture can vary within wide limits, temperature from -50 to 30O ⁰ C, preferably from 0, according to the one limit value to 120 ⁰ C, for a period of 1 minute or titanium compound only with a sense of vanadium carried out for a longer period of time. For this compound is mixed, while according to the other treatment, an inert solution limit value is expediently used, the vanadium compound only with a 10 .mittel in order to achieve a complete reduction trace of a titanium compound is mixed, that is, regardless of whether the to ratio can be liquid or solid within the range of 0.01 reducing mixture.
up to 99, expressed as V: Ti. In particular, the reduction treatment is carried out, preferably in the range from 0.01 to 10, expressed the valence of both transition metals as V: li. The lithium compound can be reduced beforehand with a _{maximum value of 15} to lower values of the vanadium compound or at the same time together, that is, mostly to its trivalent state with the vanadium compound and the organoaluminum state.

minium compound are mixed. _After t _he reducing the resulting cokristalli-To prepare the coknstaUisierten ProdukteSj catalyzed product in the presence of an inert gas which is one component of the poly _zo invention from the solvent and the unreacted substances mensationskataFysators, the comparable can suitably z. B. by filtration, centrifugal bonding of titanium and vanadium compounds or in a similar way, separated. After being turned. These are preferably in the form of the separation of the cocrystallized product from liquids which are miscible with one another, the unreacted substances and the substances contained therein. J or are soluble in inert solvents, 25 contained solvents essentially completely, which will be explained in detail below. removed. In order to remove the unreacted substances, tetrahalides are usually used, such as titanium tetrachloride, titanium tetrabromide, vanadium tetra under heat and reduced pressure, a scrubbing chloride and vanadium tetrabromide; Alcoholates, such as treatment with an inert solvent in titanium tetraethylate, titanium tetraisopropylate, titanium tetra- 30 in the presence of an inert gas or similar verpentylate, vanadium tetraethylate and vanadium tetra-n-bu- used. If the solvent has a tylat; Acetylacetonate, such as titanium acetylacetonate and having a relatively low boiling point, is vanadium acetylacetonate; Oxyhalides such as vanadyl - a distillation treatment in the presence of a trichloride and vanadyl dichloride; Oxy alcoholates, such as inert gas applied. If the solvent has vanadyl triethoxide and vanadyl triisopropoxide, and has a high boiling point, this is preferably used with halogen alcohols such as vanadyl monochloride prop- with the use of heat and reduced oxide and vanadyl dichloromonoethoxide. Pressure distilled off in the presence of an inert gas. Of these compounds are the tetrahalides. It is expedient to provide unreacted substances, which are particularly preferred in the product, since they contain particularly good results, in particular nits. _{4Ö completely remove} the titanium and vanadium compounds to reduce a mixture of the aforementioned, since incomplete removal of these titanium compounds and vanadium compounds with unreacted substances can lead to the formation of the cocrystallized product, a catalytic activity being low.
Organoaluminum compound of the general formula I, _n the majority of cases, the co-crystallized AlR _n X ₃ - * used, a _{hydrocarbon-45} product is a obtained in the R usually in the form of a solid mass hydrocarbon group having 1 to 14 carbon atoms, X. This product will therefore suitably denote a halogen atom and η a number from 1 to 3. suitable for further use. Examples of the hydrocarbon group are small. This comminution is usually carried out in alkyl groups, such as methyl, ethyl, propyl, butyl, in the presence of an inert gas according to customary ver-octyl, decyl and dodecyl; Aryl groups, such as phenyl, are carried out, for example by stirring, tolyl, xylyl and naphthyl; Aralkyl groups such as in a ball mill and the like.

Benzyl; and cycloalkyl groups, such as cyclopentyl. The reason that the cocrystalline thus obtained and cyclohexyl. In general, it is used as a product in the polymerization of olefins of alkylaluminum compounds, such as triethylalu- has a high activity, is not yet known, minium, triisobutylaluminum, diethylaluminum 55 However, from comparative experiments it can be seen that monohalide, dibutylaluminum monohalide - the product thus obtained is actually a cocrystallid, Ethyl aluminum sesquihalides and similar sated product is. This is particularly evident Connections, recommended. The halogen atom from that obtained according to the invention Be chlorine, bromine or iodine. drawn effects cannot be obtained Titanium compound and the vanadium compound product of a titanium compound and a reduc are used Organoaluminum compound is used in a vanadium compound ion product usually in the range of 0.01 to 10 (see U.S. Patent 3,218,266), and as a molar ratio, based on the above mentioned, that the process of the present metal compounds. Preferably, the amount of cocrystallized product obtained is in the range of 0.5 to 5. It is colored but completely discolored when it is Even if the conditions of reduction are exposed to air. It is believed that it Using such an amount of the organoaluminum results in a new cocrystallized product

ιοσΑ

is that of the cations Ti, V and Al and pressure up to 100 atmospheres is sufficient to the Anions, such as Cl, are where Ti and V achieve trivalent polymerization.

are or have a lesser valence and the process of the invention can be hydrogen

Ratio V / Ti can vary within wide limits. be present in the polymerization reaction system By X-ray analysis and elemental analysis, the average molecular weight is 5 µm in fact it has been confirmed that the obtained by Reduk- other physical properties tion of a mixture of a titanium tetrahalide and polymer not only in the high temperature polyeines Vanadium tetrahalide with an aluminum merization, but also with the low temperature sesquihalide produced product to control a cocrystalline polymerization. Because the hydrogen ized product, which is mainly of the formula io amount that should be present, of the polymers

sationsbedingungen and the desired molecular «[(Ti ^ OOi-pXn] · AlX _m , weight of the polymer depends, the amount

be adjusted appropriately.

where ρ is a number from 0.01 to 0.99, X is a halogen- The polymerization of «-olefins is carried out in dei

atom, α a number from 1 to 100 and m and η each * 5 white described above. Since the füj mean a number from 0 to 3, corresponds to. Catalysts useful in the process of the invention

In this case the vanadium compound can be easily deactivated by moisture and oxygen and reduced to its divalent state. Therefore, if the number η is added to the polymerization system, in most cases a number of starting products, such as the olefins, hydrogen, and between 2 and 3, and since the catalyst obtained is also a solvent, it is advisable to use those that have previously been highly active . have been adequately cleaned .

As a second component, an organoaluminum die is produced according to the method of the invention

Minium compound of the general formula AlR "X ₃ '-", polymers are colorless, crystalline polymers in which R is a hydrocarbon grape with 1 to with a high bulk density and a narrow 14 carbon atoms, X' a halogen atom or 25 molecular weight distribution.

an alkoxy group and η a number from 1 to 3. As can be seen from the above explanations,

interpret, used, which together with the first, the 1 ? r catalyst component according to the process of the invention, the catalyst according to the invention forms an excellent, high catalytic converter. As a hydrocarbon group with lyric activity. If the polymerization of 1 to 4 carbon atoms is carried out, for example, 30 «-olefins using the alkyl groups, aralkyl groups, aryl groups and aryl groups according to the invention, this catalyst shows a cyclic group in question. extremely high polymerization activity not only at

The catalyst according to the invention is made of these high temperatures, but also with ratio-catalyst components manufactured. The ratio of moderately low temperatures, and the average between of the first catalyst component and the 35K molecular weight of the polymers obtained Second catalyst component is usually can be easily controlled by the fact that water in the Range from 0.1 to 500, preferably from 1 to substance is introduced into the polymerization system. 50, expressed as Al transition metal molar ratio, if olefins according to the process of the invention

nis. It is possible to polymerize the catalyst immediately from the removal step Mixture of the titanium and vanadium compounds 40 tion of the catalyst omitted. This is another one to produce by a large excess of organotechnical advantage. Also allows education Aluminum compounds is applied to both of polymers with a high bulk density to achieve the reduction as well as the activation. an increase in the production of polymers,

The polymerization of α-olefins is carried out using, in particular, the emulsion polymerization using the catalyst obtained in this way. This leads to the method of the invention. Suitable «olefins are, for example, ethylene; the polyethylene obtained is suitable for the production of propylene, butene-1 and similar compounds. It is of various types of molded bodies, which is also possible, to subject a mixture of such ^ -olefins, for example by the injection process, to the extrusion of a copolymerization. The polishing process and the like can be produced
The polymerization reaction can be carried out in the absence of a solvent. The following examples illustrate the invention. However, she will

usually carried out so that the catalyst Example 1

dispersed in an inert solvent, the olefin

introduced and the mixture on a specific In a 500 ml four-necked flask equipped with a

Temperature and a certain pressure kept 55 stirrer, an inlet pipe for an organo becomes. metallic connection, a gas inlet pipe

As inert solvents, ali- and a thermometer are preferred, phatic hydrocarbons such as pentane, hexane, after removing the air with argon, 100 ml of ge-heptane, octane and isooctane; cycloaliphatic carbon-purified cyclohexane, 27 mmol of titanium tetrachloride and hydrogens such as cyclopentane and cyclohexane; 60 added 18 mmol vanadium tetrachloride. The ge and aromatic hydrocarbons such as benzene and mix are stirred and the temperature is set to toluene. However, any 25 ^° C. can also be maintained. To this mixture, different solvents were added dropwise, which in the way 34 mmol of ethylaluminum sesquichloride were used in a rule for the polymerization reaction at a rate of 1.4 mmol per minute. 65 given.

In general, temperatures are in the range after the addition of the aluminum compound

between room temperature and 200 ⁰ C and is complete proportionate, the mixture is stirred for 30 minutes at ately low pressures in the range of normal 25 ° C continuously to the reduction

I 934 677

end reaction. The unreacted substances and the solvent were removed from the reaction product by decanting. The temperature was increased to 40 ^° C. and the remaining cyclohexane was distilled off under reduced pressure. After the temperature had been increased to 60 ^° C., unreacted substances were distilled off over a period of 2 hours under a pressure reduced to less than 1 mm Hg, and the cocrystallized product remaining as a residue was dried.

The cocrystallized product obtained was a brown solid. She was in a stream of argon crushed. This product was a new substance largely of the formula:

(Ti-V- A1) C1 ₂ , ₈ , (Ti + V) Al = 3.0 V / Ti = 2/3.

is equivalent to.

In a 1 liter autoclave equipped with a magnetic stirrer, after displacing the air contained therein with nitrogen, 500 ml of purified n-heptane, 5.0 mg of the cocrystallized product obtained as described above and 0.16 mmol of triisobutylaluminum were placed . After the autoclave ^{had been heated to 80 °} C., hydrogen was introduced with stirring up to a pressure of 25 kg / cm ² and then ethylene until the total pressure was 40 kg / cm ² .

Heat was evolved during the introduction of the ethylene and the polymerization of the ethylene was observed. The temperature was set at 80 ^° C. and the polymerization was carried out under constant pressure for 90 minutes with the total pressure being kept at 40 kg / cm ² by introducing ethylene alone. This gave 232 g of white powdery polyethylene with an average molecular weight of 98,000.

The polyethylene obtained had a bulk density of 0.35 g / ml (according to ASTM-D-392-37) and a Density of 0.965 (according to ASTM-D-12488). It was accordingly a high density polyethylene.

In this polymerization reaction, the rate of polymerization was calculated on the cocrystallized product and the first catalyst component, 31 kg polymer / g cat. Hour, and the catalyst efficiency was 46.5 kg polymer / g cat.

Comparative experiment 1

The polymerization of ethylene was completely analogous to the procedure described in Example 1 carried out, however, the cocrystallized product used in Example 1 by 5.0 mg of commercially available titanium trichloride was replaced. As a result, there was obtained 34.5 g of a white powdery Obtained polyethylene with an average molecular weight of 121,000. That so The polyethylene obtained had a bulk density of 0.30 g / ml.

In this polymerization reaction, the rate of polymerization was calculated on the titanium trichloride, 4.6 kg polymer / g KaL Std., and the catalyst efficiency was 6.9 kg polymer / g KaL

This comparison point shows in a more obvious way Way that the polymerization reaction according to the method of the present invention with an about ten times faster than the polymerization reaction using of the commercially available titanium trichloride as the first catalyst component and that according to of the invention, the molecular weight can be easily adjusted by hydrogen and polymers with a high bulk density can be obtained.

Comparative experiment 2

The polymerization of ethylene went crazy. Example 1 described carried out, with each the following changes were made in place of 5 mg of the cocrystallized product:

(V / Ti = 5 = 2/3) from Example 1 were 3 mg of titanium tetrachloride and 2 mg vanadium tetrachloride (V / Ti = 2/3; used together with 18.8 mg triisobutylaluminum. The polymerization was set in motion by shaking a triisobutyl aluminum-filled ampoule was destroyed.

The ethylene uptake was initially 4.0 g _; Minutes, but quickly decreased. About 5 minutes later, the ethylene uptake had fallen to ¹ I _{7 of} the original value immediately after the start of the polymerization. Then the return of the recording was a little slower. 90 minutes later, when the polymerization had ended, the ethylene uptake was only Vxo of the initial value. 59 g of polyethylene were obtained compared to 232 j according to Example 1 according to the invention. The polyethylene had an average molecular weight of 8.5 · 10 ⁴ . It was white and fibrous.

In this polymerization reaction, the polymerization rate was 7.9 kg polymer / g cat. Hour per unit TiCl ₄ + VCI ₄ , and the catalyst efficiency was 11.9 kg polymer / g cat. (Compared to 31.0 kg polymer / g cat Hour or 46.5 kg polymer / g cat. According to example 1 according to the invention)

Comparative experiment 3

The polymerization was carried out as in Example 1 of the U SA. -Patent specification 3,218,266 described through leads. The result thereby obtained became the result obtained according to Example 1 of the invention compared. The results obtained are compiled in the following table:

Vanadium compound

Titanium compound

Polymerization time

Ethylene intake
(Polymerization rate)

Initial city mm

Final stage ..........

Absorption of ethylene units *)

Initial stage

Terminal stage

example 1 of USA.Patent

3,218,266

3μΜο1
45μΜθ1
150 min.

5ϋ ml / min.
5 ml / min.

1.3 - ΙΟ- ³

eat ■ 10- ⁴

example 1

according to invention

ΙΟμΜοΙ 15 μΜοΙ 90 min.

2.5 g / mm.

7.7 · 10- »

g-polymer

*) μΜοΙ (Ti + V) Min. - kg / cm * (ethylene partial pressure)

309529/4 «

t 934

From the table it can be seen that when using the catalyst according to the invention a constant polymerization rate achieved during the entire polymerization reaction and the initial high activity over a long period of time 5 sation.

can be sustained. In contrast, "tüe-polymerization activity increases with use of the catalysts according to the prior art remarkably with the progress of the polymer

Tabel

III

IV

V-Ti mixing ratio

Polymerization rate (kg polymer / g

Cat. *) / Hour)

Catalyst efficiency (kg polymer / g cat.)

average molecular weight · 10 ~ ⁴

Bulk weight (g / ml)

3.0 4.5 11.9 0.30 0.10

28.6
42.9
10.2
0.32

0.67

31.0
46.5
9.8
0.35

9.0

15.8
23.7
10.8
0.28

2.0
3.0
11.5
0.29

*) Cat. - the first catalyst component (cocrystallized product).

Example 2

The reduction treatment was carried out analogously to that described in Example 1, with however, the ratio between titanium tetrachloride and vanadium tetrachloride was varied. There were Obtain cocrystallized products of various compositions. Using this like that Products obtained in combination with triisobutylaluminum was the polymerization of ethylene carried out completely analogously to that described in Example 1. In doing so, those listed in Table 1 were used Get results.

Comparative experiment

The polymerization of ethylene was carried out analogously to that described in Example 2, wherein however, instead of the cocrystallized products prepared according to Example 2, those with the compositions V / Ti = 0 and Ti / V = 0 in amounts of 3 mg and 2 mg, respectively. As a result were 16.5 g of white powdery polyethylene with an average molecular weight of 118,000 received. In this reaction the rate of polymerization was calculated on the cocrystallized product, 2.2 kg polymer / g cat. hour, and the catalyst efficiency was 3.3 kg polymer / g Cat.

The comparative experiment shows in an obvious way that according to the invention by reduction cocrystallized product made of a mixture of a titanium compound and a vanadium compound has a polymerization activity very different from that of a mixture of each separately reduced solid products.

Example 3

The production of the cocrystallized products was carried out analogously to the case of Example 1, however, the type of reducing agent, the reducing temperature and the reducing time have been modified.

Using the products obtained in each case, the polymerization of ethylene was carried out analogously to carried out in Example 1, the results compiled in Table 2 being obtained.

Tabel

ΙΠ

IV

Catalyst preparation:

Reducing agent

Reduction ^{temperature (0} C)

Reduction time (min.)

Catalyst Composition:
Ratio of Cl / (Ti + V + Al).

Result of the polymerization:

Rate of polymerization

(kg polymer / g KatStd.)

Catalyst efficiency (kg polymer / g cat)
Average Molecular Weight · 10 ~ ⁴ ...

AlAt ₃ *) 0 30

2.7

30.4

45.6

9.0 Al (OCt) ₈
0
30th

2.5

32.8

49.2

9.1

*) The amount required for reduction: 68 mMol At ₁ -C ₂ H ,.

Example 4

AlAt ₈ Cl *)
15th
30th

Al ₂ At ₃ Cl ₃
25th
30th

29.8

44.7

9.4

31.0

46.5

9.8

Al ₂ At ₃ Cl ₃ 75
30th

2.7

32.1
48.2
10.4

The polymerization of ethylene was carried out in the same way as in Example 1, but the type of the organoaluminum compound at the time of polymerization and the amount thereof were changed. the The results are shown in Table 3.

Tabel

πι

IV

Organoaluminum compound

Amount (mmol)

Rate of polymerization

(kg polymer / g KatStd.)

Catalyst efficiency (kg polymer / g cat.) Average molecular weight · 10 " ⁴ ... bulk density (g / ml) Et = - C ₂ H ₅

AlAt ₃ 0.16

28.8 43.2 9.7 0.35 Al (I-Bu) ₃
0.16

31.0

46.5
9.8
0.35

Al (I-Bu) ₃
0.32

32.2

48.3
9.6
0.35

AlAt ₂ Cl
0.32

15.6
23.4
10.5
0.33

AlAt ₂ OAt 0.16

22.8
34.2
10.2
0.36

Example 5

The polymerization of ethylene was carried out in the same way as in Example 1, but the polymerization temperature, the amount of hydrogen and the total pressure changed at the time of polymerization became. The results are summarized in Table 4.

Tabel

III

IV

Polymerization ^{temperature (0} C)

Amount of H ₈ (kg / cm *)

Total pressure during polymerization (kg / cm *) rate of polymerization

(kg polymer / g KatStd

Catalyst efficiency (kg polymer / g cat. Average molecular weight · 10 ~ ⁴ ..

80

10

8.6

12.9

9.5 80
25th
40

31.0

46.5

9.8

80 42 70

51.2

76.8

9.6

90
18th
40

37.7

56.6

6.7

90
22nd
40

30.6

45.9

5.1

Example 6

The polymerization of ethylene was carried out in the same way as in Example 1, but not n-heptane was used at the time of polymerization. As a result, 220 g of white powdery became Polyethylene with an average molecular weight of 95,000, a bulk density of 0.39 g / ml and a density of 0.965.

Table 5

35

Polymerization conditions

Temperature ( ⁰ C)

Total pressure (kg / cm ⁸ )
Partial pressure of H ₂

fcg / cm ² )

Polymerization time

Results:
Rate of polymerization
(kg polymer / g cat /

Hours.)

Catalyst efficiency
(kg polymer / g cat)
Average
Molecular weight IQ- *

130 10

1.5 30

23

12th

4.5

130 10

3.0 60

22nd

22nd

2.5

160 20

0.5 30

30th

15th

3.0

Example 7

The polymerization of ethylene was carried out in the same way as in Example 1, but using cyclohexane was used in place of the n-heptane and the temperature, reaction time, amount of hydrogen and the total pressure were changed during the polymerization. The results are in Table 5 compiled

Example 8

In a four-necked flask as used in Example 1, after displacing the air with argon, 100 ml of purified cyclohexane, 38 μΜο! Titanium tetraisopropoxide and 38μΜο1 vanadium tetrachloride are given. The mixture was heated for 2 hours with stirring at 6O ⁰ C To this mixture was then added dropwise 17.2 ml of A1 ₂ (C _S H _{S) 3} C1. ₃ After the addition of the aluminum compound was completed, the mixture was continuously stirred at 25 ° C. for 20 minutes to complete the reduction reaction. The treatment was then carried out as described in Example 1, a coconutized product of O / Ti + V + Al = 1.8 being obtained.

34 mg of the cocrystallized product thus obtained and 46 mg of triethylaluminum were placed in a 1 liter autoclave. After the autoclave had been heated to 90 ⁰ C, -were hydrogen and ethylene with stirring guided up to a total pressure of 10 kg / cm ^2, wherein the ratio of the partial pressure of hydrogen was kept to the partial pressure of ethylene to 1.4. The polymerization was carried out for 30 minutes at 90 ° C under icon

13 14

constant pressure, the total pressure being 215 g of crystalline polypropylene

hold at 10 kg / cm ² by just introducing.

Ethylene was maintained. 126 g of example were
white powdered polyethylene with an MI

received from 6. In this reaction, the poly was 5 in a 500 ml four-necked flask fitted with a

merization rate, calculated on the co-stirrer, an inlet pipe for an organometal-

crystallized product, 7.3 kg polymer / g cat./h, liquid compound, a gas inlet tube and

and the catalyst efficiency was 3.7 kg poly- a thermometer was fitted according to

mer / g cat. Removal of air by argon 100 ml purified

B e 's ο' e 1 9 ¹⁰ cyclohexane, 18 mmol titanium tetrachloride and 17 mmol

Given tri-n-butoxyvanadyl. The mixture became

The same amounts of the catalyst components erliitzl and with stirring for 2 hours at 60 ⁰ C on

and the solvent used in Example 1 is refluxed. Then the reaction liquid

were placed in a 1 liter autoclave. drop by drop of 26 mmoles of ethylaluminum sesqui-

The temperature was raised to 80 "C, and below 15 chloride added, keeping the temperature at 25 ° C

Stirring was carried out in the autoclave until hydrogen was kept.

initiated a pressure of 25 kg / cm ^2. A mixture After the addition was complete, the liquid of ethylene and a small proportion of propylene was stirred for a further hour at 25 ° C., and was then passed in so that the total pressure finally ^{reached 40 kg / cm 2 of} unreacted starting materials. 20 and the solvent Then, 300 ml of purified cyclohexane was added to the residue under constant pressure at 80 ° C. The mixture obtained was stirred for 10 minutes and then stirred for about 15 minutes Keep total pressure at 40 kg / cm ^8. As left standing, the supernatant cyclohexane was as a result, 209 g of white powdery ethylene-25 was removed by decantation. After obtaining the addition of copolymer, an IR absorption spectrum cyclohexane and decanting in the above analysis of the copolymer obtained, which was repeated four times in a written manner had been recovered, thin plate had been pressed, showed that the residue was ^{distilled at 6O 0} C under a reduced pressure of an ethylene-propylene copolymer, an ethylene-propylene copolymer reduced pressure of less than 1 mm Hg, with 2.6 branched methyl groups per 1000 Carbon was about 6 g of a powdery co-crystallized pro-substance atom. product during a period of 2 hours

Keep the result of the analysis of the vapor phase gases.

in the autoclave before and after the polymerization showed a mixture of 5.0 mg of the thus obtained co-

an average composition as follows: crystallized product, 500 ml of purified n-hexane

Ethylene 40 mol percent 35 and 0.1 mmol triisobutylaluminum was in one

Propylene 3 mole percent 1 liter autoclave with a magnetic stirrer

Hydrogen '.'. '.'. '.'. '.'. '.'. '.'. '. Υ. 57 Molprozem is equipped, given. The autoclave was before

sufficiently rinsed out with dry nitrogen

Till r> ie 1 10. After the autoclave has been heated ^{to 90 r C}

40 was added while stirring the mixture

The reduction treatment was carried out in the same way as hydrogen up to a pressure of 5.0 kg / cm ² , and as described in Example 1, but ethylene then introduced the ratio of titanium tetrachloride to vanadium ^{up to a total pressure of 10 kg / cm 2.} Subsequently, the mixture was 130 mitetrachloride 9: 1 to polymerize a cocrystallized groove to prepare polymerization products. The temperature was controlled at 90 ° C and the total in a 500 ml flask was 390 mg of the pressure on JO kg / cm ^{2 was} obtained by introducing endured product, 250 ml of n-heptane and 2.5 mmol of ethylene. in this case diethylaluminum monochloride was added. the tem- 155 g of a white powdery polyethylene having temperature was raised with stirring to 70 ⁰ C and an average molecular weight of 52000 propylene was introduced until the pressure 800 mm Hg 50 obtained. This amount corresponded to a catalyst achieved. the The polymerization reaction was carried out for 2 hours at an efficiency of 31.0 kg polymer / g catalyst, which was carried out under constant pressure, the polyethylene thus obtained having a bulk density of propylene being introduced during the reaction of 0.30 g / ml (according to ASTM-D -392-38).

Claims (3)

to be removed from the polymeric product, claims: when used for the production of olefin polymers by polymerisation in suspension, 1. Polymerization catalyst, obtained by the fact that generally at low temperatures that a Vam dium, titanium and an organo 5 is carried out, their catalytic activity aluminum compound in an inert solution is not sufficient to produce polymers with the medium brings to reaction, whereby one leads to a desired high bulk density
mixed solution of the vanadium and the titanium man has therefore been looking for a long time for a compound at -50 to 300 ⁰ C with the organo- a polymerization catalyst that reacts in the Heraluminiamverbindungen, the resulting co- ίο position of polymers of olefins, A specially crystallized product from the solvent and those from -olefins, used successfully, separates unreacted starting materials and cannot and does not have the disadvantages of the previously known catalysts for activation with an organoaluminum analyzer. bond of the general formula AlR _n X ₃ '- *, the object of the invention is to provide a new, for where R is a hydrocarbon group with 1 to 15 production of polyolefins with a high debris 14 carbon atoms, X 'is a halogen atom or weight suitable polymerization catalyst and an alkoxy group and η a ZaW from 1 to 3 to indicate a process for its production,
mean contacted. The subject matter of the invention is therefore a poly 2. A process for the preparation of a polymerization catalyst, which has been prepared by sationskatalysators, in which a vanadium, 20 is that a vanadium, titanium and an organo-titanium and an organoaluminum compound in an inert aluminum compound in an inert solvent Reacting solvent brought to reaction, being a mixed one, characterized in that a solution of the vanadium and titanium compound at -50 mixed solution of the vanadium and titanium compound to 300 ⁰ C with the organoaluminum compound at -50 to 300 ⁰ C reacts with the organo-25, converts the resulting cocrystallized product of aluminum compound, separates the obtained cosolvent and unreacted starting crystallized product from the solvent and non-substances and separates them for activation with a converted starting materials and to the organoaluminum compound of the general formula activation with an organoaluminum connecting AlR _n X ₃ '- ,,, in which R is a hydrocarbon group of the general formula AlRnX ₃ ' -n, in which 30 with 1 to 14 carbon atoms, X 'is a halogen-R is a hydrocarbon group with 1 to 14 atoms or an alkoxy group and η is a number of carbon atoms, X 'is a halogen atom or 1 to 3. an alkoxy group and η a number from 1 to 3 The invention also relates to a process mean contacted. for the production of the above 3. Process for the polymerization of α-oils 35 polymerization catalyst in which a vanadium, finer ,, characterized in that the cata-titanium and an organoaluminum compound in lysator according to claim 1 is used. reacted with an inert solvent be, which is characterized in that a mixed solution of the vanadium and titanium compounds 40 bond at -50 to 300 ⁰ C reacts with the organoaluminum compound, the cocrystallized product obtained from solvent and not vice versa