DE1545070C3 - Process for the polymerization of monounsaturated alpha-olefins - Google Patents

Description

- Al —O -

contains, in which R stands for an alkyl radical with 1 to 12 carbon atoms or an aryl radical, a compound of transition metals of the formula MX », where M stands for the transition metal and η stands for its valency and X stands for a halogen atom or an organic radical and optionally one Compound of the metals of groups IA, IIA and III B of the formula MeR'a, where Me is the metal and χ is its valence and R 'is a hydrogen atom, an alkyl radical having 1 to 12 carbon atoms or an aryl radical, in an inert diluent has been received.

2. The method according to claim 1, characterized in that a catalyst is used which 0.2 to 20 millimoles of the polymerized organoaluminum oxide, 0.001 to 0.05 millimoles of the transition metal compound and from 0 to 2 millimoles of the Group IA, HA and III B metal compound per liter of the inert diluent contains.

3. The method according to claim 1, characterized in that that polyisobutylaluminum oxide is used as polymerized organoaluminum oxide will.

4. The method according to claim 1, characterized in that the transition metal compound Chromium (III) -2-ethylhexanoate, chromium (III) acetate, chromium (II) -2-ethylhexanoate, vanadium tetrachloride, Titanium (IV) -2-ethylhexanoate, zirconyl acetate or uranyl butyrate is used.

5. The method according to claim 1, characterized in that the metal compound of the groups IA, HA and III B triisobutyl aluminum is used.

6. The method according to claim 1, characterized in that as »-olefin ethylene, 4-methyl-1-pentene, Butene-1 or mixtures thereof can be used.

7. The method according to claim 1, characterized in that the polymerization is carried out at a temperature of -10 to 100 ⁰ C and a pressure of 5 to 30 atmospheres.

8. The method according to claim 1 to 7, characterized in that during the polymerization Hydrogen is present.

It is known that mono-unsaturated -olefins with one of a mixture of two components existing catalyst preparation can be polymerized. In these known catalyst preparations the two components consist of a compound of a transition metal of groups IVA, VA and VIA and a compound of a metal from Groups IA, IIA and III B of the Periodic Table of the elements. The compounds of the metals of

ίο Groups IA, HA and IIIB can be the organometallic Compounds, the organo-metallic halide compounds, the organo-metallic hydrides or the metal hydrides. The Periodic Table of the Elements mentioned above is that of the

W. M. Welch Manufacturing Company, Chicago, 111th, 1956 edition.

The inventive method for the polymerization of monounsaturated α-olefins, in which a catalyst system made of an organic aluminum compound

ao generation and a compound of a transition metal of groups IVA, VA and VIA used and the polymerization is carried out at temperatures from -10 to 100 ° C, is now characterized by that a catalyst is used which is produced by reacting a polymerized organoaluminum oxide, the units of the formula

Al-C

contains, in which R stands for an alkyl radical with 1 to 12 carbon atoms or an aryl radical, a compound of transition metals of the formula MX _n ,

where M is the transition metal and η is its valence and X is a halogen atom or an organic radical and optionally a compound of the metals of groups IA, IIA and IIIB of the formula MeR'z, where Me is the metal and χ is its valence and R 'represents a hydrogen atom, an alkyl radical having 1 to 12 carbon atoms or an aryl radical, has been obtained in an inert diluent.
The polymerized organoaluminum oxide used as a component for the catalyst complex according to the invention consists of units of the general formula:

- Al —O -

in which R stands for an alkyl radical with 1 to 12 carbon atoms or an aryl radical, phenyl, benzyl, Tolyl or naphthyl radical. The ones represented by R. Alkyl radicals can, for. B. be the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, Nonyl, decyl, isodecyl, undecyl and dodecyl radical.

These are produced by the reaction of water with an organo-aluminum compound, which contains at least one Contains hydrocarbon radical of the type indicated above bonded to the aluminum atom. The reaction of water with the organoaluminum compound is preferably carried out by adding the Water to a solution of the aluminum compound

3 4

in an anhydrous, inert, organic solution tungsten. Thorium and uranium. Suitable fasteners. The concentration of the aluminum compound fertilize can be represented by the formula MX _n in the solvent can vary between 5 up to 75 percent by weight, in which M for the transition metal atom. Suitable organic solvent X for a halogen atom or an organic medium include the saturated aliphatic radical, e.g. B. an alkoxy or ester radical, and η for compounds, e.g. B. hexane, heptane, pentane, isooctane are the valence of the transition metal. Such and purified kerosene; the cycloaliphatic transition metal compounds are, for example, vanadium bonds, e.g. B. cyclopentane, cyclohexane, methyl dichloride, vanadium trichloride, vanadium tetrachloride, cyclopentane and dimethylcyclopentane; the aromatic vanadium trifluoride, vanadium tetrafluoride, vanadium solvents, e.g. B. benzene, toluene and xylene. io pentafluoride, vanadium triiodide, titanium dibromide, titanium - The inert, organic solvent only has to be liquid in the case of tribromide, titanium tetrabromide, titanium dichloride, titanium reaction temperature and must not be trichloride, titanium tetrachloride, titanium trifluoride, titanium with water or the introduced hydrocarbons - titanium tetrafluoride Zirconium substance-aluminum compound react or interfere with react dibromide, zirconium tribromide, zirconium tetrabrotion in any way. 15 mid, zirconium dichloride, zirconium trichloride, zir-die for use as starting materials in conium tetrachloride, zirconium tetrafluoride, zircon or production of polymerized organoaluminum tetraiodide, niobium pentabromide, niobium pentanium oxides, suitable aluminum compounds, tantalum pentabromidium oxides, speak of the general formula: tantalum pentabromidium fluoride, tantalum pentachloride, tantalum pentachloride fluoro, tantalum pentachloride, speak of the general formula, niobium pentalofluoride , Chromobro

20 mid, chromium bromide, chromochloride, chromium dichloride,

R - Al - R ' ₂ chromofluoride, chromifluoride, molybdenum dibromide,

Molybdenum tribromide, molybdenum tetrabromide, molyb-

in which R has the above meaning and R 'stands for a dene-dichloride, molybdenum trichloride, molybdenum tetra-alkyl radical with 1 to 12 carbon atoms, an aryl chloride, molybdenum pentachloride and molybdenum hexarest or represents a hydrogen atom. 25 fluoride. The organic compounds of the

The metals used in the reaction with water for the purpose of production include z. B. chromium acetate, chromium (III) lung the polymerized organo-aluminum oxy - 2 - ethylhexanoate, chromium (III) - 2 - ethylhexanoate, Usable hydrocarbons - aluminum compounds - ChromCII ^ -dichlsrähylhexanoat, Chrom (II) -2-äthyldungen have a carbon-aluminum bond. Hexanoate, titanium (IV) -2-ethylhexanoate, chromium (III) - suitable Compounds are e.g. the trialkyl isobutoxide, zirconyl acetate, uranyl butyrate and chromium aluminum compounds, the triaryl aluminum compound acetylacetonate.

fertilize, the dialkylaluminum hydrides and the mono- The third component of the catalyst complex

alkyl aluminum dihydrides, e.g. B. Trimethylaluminum, is a compound of the formula:
Triethylaluminum, tripropylaluminum, tri-n-butyl-

aluminum, triisobutyl aluminum, trihexyl aluminum, 35 MeR'z

Trioctyl aluminum, tridodecyl aluminum, triphenyl

aluminum, trinaphthylaluminum, tritoylaluminum, in which R 'has the meaning given above, dimethylaluminum hydride, diisobutylaluminumhy- Me for a metal from groups IA, IIA and III B drid, dihexylaluminum hydride, diphenylaluminum and χ for the valency of the metal,
hydride, monoethylaluminum dihydride, monobutyl 40 The inventive polymerization catalyst aluminum dihydride and monooctylaluminum dihydride can be added in a known manner by adding drid. of the three components to an inert, organic

The polymerized organoaluminum oxides can be prepared from polymerization solvents. In a preferred method, by slowly adding the required water, the amount of catalyst to the hydrocarbon-aluminum compound 45 mixture is prepared by first preparing the polymerized one. The addition of water is carried out at organo-aluminum oxide in a concentrated Löeiner temperature between 0 to 100 ⁰ C, preferably prepared solution, a portion of this reaction mixture is between 10 to 65 ° C. removed and this part with a thinner

The amount of water added can be diluted from 0.25 to medium to this diluted mixture 1.25 moles of water per mole of the aluminum compound 50 are added to the transition metal compound and then can be varied. The preferred range, however, is this mixture to a solution of the third component 0.85 to 1.05 mol of water per mol of aluminum, namely the organometallic compound nium compound. Despite this preferred range of metals from Groups IA, IIA and III B added larger quantities can also be used; will.

However, it has been found that the inert organic with an outside The amount of water lying in this range see solvents are the same as in the Asked polymerized organo-alumina itself manufacture of polymerized organo-aluminum not be used to this extent for use as catalyst oxides. The polymerization of the component is suitable. It was also found that "mono-unsaturated" olefins takes place by the when using an amount of water over 1 mole, about 60 α-olefin with the mixture of the catalyst complex Alumina is formed either from solution in contact with an inert diluent precipitates or forms a gel. is brought.

To the transition metal compounds of metals The composition of the catalyst complex

from group IVA, VA and VIA, which as the second grain is such that it 0.001 to 0.05 millimoles of the transition _{component in the catalyst prepa- 65 metal compound MX n} according to the invention, 0.2 to 20 millimoles of the rate can be used, belong to Verbin - polymerized organo-aluminum oxide and 0 to fertilize the metals titanium, zirconium, hafnium, Ce 2 millimoles of the compound of the metals vonGruppelA, rium, vanadium, niobium, tantalum, chromium, molybdenum, IIA or IIIB per liter of the inert diluent

means contains. The molar ratio of the transition metal in the transition metal compound to aluminum in the polymerized organo-aluminum oxide can be varied from 1:30 to 1: 800, but is expediently between 1:40 and 1: 200. The amount of the compound of the metals from group IA, IIA or III B, when used, is kept as low as possible. This third component is present, any traces of impurities that may be present in the reactants or diluents to remove; and it is not necessary when using highly purified reactants will. Small amounts of water, carbon dioxide, carbon monoxide and oxygen poison the catalyst preparation, by reacting with the components and forming insoluble complexes. These will removed or inactivated by the third component. Therefore, if there are no impurities, then is the third component is not required.

The purity of the polymerization process according to the invention usable ethylene is of great importance. Commercially available ethylene with a purity of 95 percent by weight, the main impurity of which is ethane and the minor one Containing amounts of carbon monoxide, carbon dioxide, water and oxygen requires use a catalytic converter system made up of three components. However, if the ethylene is cleaned beforehand, it can a two-component catalyst system can be used. The impurities can be easily removed remove the known procedure. The presence of inert hydrocarbons, such as methane, or ethane Propane, does not interfere with the polymerization.

The properties of the polyolefin produced can be varied by varying the ratio of the three Components in the manufacture of the catalyst complex, by varying the components themselves and changed by varying the reaction temperature, pressure and time.

The polymerization can be carried out at temperatures from -10 to ^100.degree. C., preferably between 40 to 80.degree. The pressure can be varied from subatmospheric pressure using an inert gas as a diluent to superatmospheric pressures of up to 100 atm. However, the reaction is expediently carried out at a pressure of 5 to 30 atm.

It has been found that a small amount of hydrogen present during the polymerization influences the average molecular weight of the polymer produced. The presence of hydrogen during the polymerization serves in particular to reduce the average Molecular weight of? formed polymer.

The materials that can be polymerized according to the invention include the mono-unsaturated -olefins with 2 to 10 carbon atoms, such as. B. ethylene, propylene, butene-1, pentene-1., 3-methylbutene-1, He-

xen-1, 4-methylpentene-1, 3-ethylbutene-1, heptene-1, Octene-1, decene-1, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene and 3,4-dimethyl-1-hexene.

The density of the polyolefins is determined according to that of E. Hunter and W. G. Oaks, Trans. Faraday Society, 41, 49; definitely; the melt index was determined according to the ASTM method D-1238-52T; and the flow rate was used after that used to determine the melt index Method determined, but being either 4.7 times or 10 times that in the ASTM method specified weight was used. The following examples illustrate the invention Proceedings.

B e i s ρ i e 1 1

A clean, dry reaction flask was purged with dry, oxygen-free nitrogen and provided with a serum stopper. In this flask were 90 ecm dry, oxygen-free Heptane, which is passed through a column of dry silica gel and mixed with dry, oxygen-free Nitrogen had been purged, introduced with a hypodermic needle. Similarly, 8 g (40 millimoles) triisobutylaluminum added. A hypodermic needle tied with a mineral oil bubble counter Connected to a nitrogen line, the serum stopper was inserted to relieve the pressure Relieve the reason for the development of isobutane during the reaction. With constant shaking were at 45 ° C within 25 minutes, slowly pass 0.71 ecm of water (about 40 millimoles) through an injection needle introduced. The product of the reaction was polyisobutylaluminum oxide receive.

In the manner described above, a series of reactions to produce further polymerized organo-aluminum oxide compounds carried out. These attempts are - inclusive the one described above - shown in the table below.

attempt Alkyl volume Weight Millimoles Solution
medium
volume Added
water Maximum
Temperature ¹ ) ecm G in ecm Millimoles A. Triisobutyl aluminum 10 8th 40 90 40 B. Triisobutyl aluminum 10 8th 40 90 40 C. Triisobutyl aluminum 5 4th 20th 15th 17th D. Triisobutyl aluminum 10 8th 40 10 34 E. Triisobutyl aluminum 50 40 200 150 170 80 F. Triethylaluminum 10 - 75 65 75 65 G Triisobutyl aluminum 50 40 200 150 170 75 to 78 ² ) H Triisobutyl aluminum 27.5 22nd 110 75 93 75 I. Triisobutyl aluminum 25th 20th 100 75 85 75 to 80 ² ) J Triisobutyl aluminum 25th 20th 100 75 100 65

*) Room temperature was assumed and the temperature was allowed to rise with the heat of reaction. ² ) It was started at 75 ⁰ C; observed temperature range.

7 8

Example 2 Polyisobutylaluminum oxide from Experiment G of Example 1 containing portion and 0.006 g chromium (HI) -

A 1-1 polymerization vessel was filled with a 2-ethylhexanoate. The dried polyethylene had a high-speed stirrer, a gas supply line, a melt index of 12.2 dg / min, a flow gas outlet line, a thermocouple probe, a speed of 229 (determination with the opening closed with a serum stopper, a 4.7-fold amount) and a density of 0.9617 g / ccm. Liquid supply line and a liquid discharge '_. .
outlet pipe that reached to the bottom of the vessel, _<# examples
Mistake. The system was thoroughly cleaned and ethylene was dried in the manner described in Example 4 and then polymerized in a dry, oxygen-free manner, with toluene being flushed through as the solution nitrogen. Medium was used in the polymerization flask. The catalyst preparation was 500 ecm of pure, dry n-heptane, which consisted of 0.24 g of triisobutylaluminum, one passed through a silica gel column and - after 12 millimoles of polyisobutylaluminum oxide from Experiment I, flushing with enough nitrogen for the purpose of removing the portion containing Example 1 and 0.006 g removal of any included acidic 15 chromium (III) -2-ethylhexanoate. The ethylene was given substance - over sodium. Introduced into the reaction mixture for 48 minutes. The heptane was heated to 6O ⁰ C and by means of the polyethylene obtained was a stringy injection needle through the serum stopper was g 0.35 iso solid high molecular weight,
butyl aluminum dichloride introduced. Then were. .
4 millimoles of the polyiso obtained from experiment IC 20 __ ΰ egg game /
butylaluminum oxide and 0.47 g of titanium tetrachloride, ethylene, were introduced through the serum stopper in that described in Example 4. The stirring was polymerized in a manner. The catalyst preparation was interrupted and the system was ^{flushed through with 0.057 m 3 of} pure 0.4 g of triisobutyl aluminum, a 12 millimole of ethylene. Then polyisobutylaluminum oxide from Experiment G was stirred again for example and ethylene passed through the reaction mixture containing 25 game 1 and 0.006 g of chromium (III) mixture for 86 minutes. Then 50 ecm of isopropanol were 2-ethylhexanoate. The ethylene was added for 117 minutes and the polymer suspension was filtered and passed through the catalyst mixture. The solid filter cake washed once with isopropanol and polyethylene WOg ₁ 31.3 g after drying,
dried. The yield was 17.7 g of a poly.
ethylene with a melt index of 0.93 dg / min 30 _. Example »
and a flow rate of 12.2 (the ethylene was determined in the mung described in Example 4 was carried out with 4.7 times the amount). Way polymerized. The catalyst preparation passed

. . from 0.5 g of tridodecylaluminum, a 12 millimole Example 3 polyisobutylaluminum oxide from Experiment G by Beiätthylen was polymerized in the proportion described in Example 2 containing 35 game 1 and 0.006 g of chromium (III). The catalyst preparation consisted of 2-ethylhexanoate. The dried polyethylene weighed 0.24 g of triisobutylaluminum, a 12 millimole 14.7 g and had a melt index of 0.37 dg / min polyisobutylaluminum oxide from Experiment G and a flow rate of 30 (determination game 1 containing portion and 0.006 g Chromium (III) - 4.7 times the amount).
2-ethylhexanoate. Before adding the monomeric 4 ° _R. . ..
Ethylene was the catalyst mixture for 1 hour at _ B e 1 s ρ 1 e 1 y
60 ° C under an atmosphere of dry nitrogen ethylene was allowed to age in the material described in Example 4 in the reaction flask. Way polymerized. The catalyst preparation consisted of. The ethylene was passed through the 0.24 g triisobutylaluminum, a 12 millimole catalyst, for a total of 76 minutes. The dried polyethylene weighed 45 polyisobutylaluminum oxide from experiment G of at-21.6 g and had a melt index of 0.69 dg / min containing 1 portion and 0.006 g of chromium (II) - and a flow rate of 56 (determination of 2-ethylhexanoate. The dried polyethylene weighed 4.7 times the amount). 30.7 g and had a melt index of 2.37 dg / min

. . and a flow rate of 105 (determination

Example 4 50 with 4.7 times the amount).

Ethylene was described in Example 2 in _R. . ^

Way polymerized with the exception that the heptane example U

solution after adding the triisobutylaluminum to a stainless steel autoclave equipped with a

4O ⁰ C and sealed after addition of the other Katalysatorkompo- means of a serum stopper gas line

nente to 6O ⁰ C was heated. The catalyst was provided with dry nitrogen.

preparation consisted of 0.08 g of triisobutyl aluminum, rinsed and then 250 ecm of dry n-heptane added

a 12 millimole polyisobutyl aluminum oxide adds. Through the serum stopper, 0.56 g of triiso

Experiment G of Example 1 containing portion and butylaluminum introduced with a hypodermic needle.

0.006 g chromium (III) -2-ethylhexanoate. The ethylene triisobutylaluminum was found with a low

was passed through for 60 minutes. The dried 60 parts of dry heptane were washed in. In the same way

Polyethylene had a melt index of 0.61 dg / min. 3.2 millimoles of polyisobutylaluminum

and a flow rate of 48 (determination of oxide from Experiment A of Example 1 added and in

with 4.7 times the amount). flushed into the autoclave. Then the content

. of the autoclave stirred for 1 minute, followed by a mixture

^{ß e 1 s} P ^{1 e l 5} 65 from 0.25 g chromium (III) -oxy-2-ethylhexanoate in n-Hep-

Ethylene was added in the tan described in Example 4 and with as much n-heptane in the autoclave

Way polymerized. The catalyst preparation was flushed in that had a total volume of

from 0.24 g of triisobutylaluminum, a 12 millimole of 500 ecm of n-heptane. The mixture was taking

Heated with stirring to 60 to 70 ⁰ C, the pressure was released and then the system is brought again to 28 atm ethylene pressure. Ethylene was then passed for 5 minutes through the catalyst preparation suspended in the solvent at a temperature of 82 to 103 ^° C., the contents were cooled to room temperature and isopropanol was added to quench the catalyst complex. The slurry was

10

filtered and the polyethylene filter cake once with Washed isopropanol. The dried polyethylene weighed 39.8 g.

A series of tests were carried out in the same way, but with the composition of the catalyst complex, the temperature and the time were varied. These attempts are in the listed in the following table.

attempt Triisobutyl
aluminum
G Polyisobutyl
aluminum-
oxide
Millimoles chrome
connection
G temperature
⁰ C time
min yield
G Melt index
dg / min Flow
swiftly
ability *) A. 0.56 3.2a) 0.25 82 to 103 5 39.8 B. 0.4 1.6a) 0.05 65 to 101 7.5 36.5 2.35 56.0 C. 0.32 0.8 ") 0.03 62 to 70 12.5 13.5 0.054 1.08 D. 0.24 0.6b) 0.02 80 to 87 20th 20.0 0.23 4.8 E. 0.2 1.0 ") 0.011 71 20th 21.5 0.037 0.90 F. 0.56 1.6 ·) 0.03 ^d ) 64 to 97 10 31.5 1.44 34.0 G 0.28 1 °) 0.016 66 to 103 4th 34.6

( ^a ) From Experiment A of Example 1.
( ¹ O from Verasch B of Example 1.

( ^c ) From Experiment C of Example 1.

( ^d ) Chromium chloride acetate was used in this experiment.
*) The determination with the 4.7-fold amount.

EXAMPLE 11

Ethylene was polymerized in the manner described in Example 10 at a pressure of 7 atmospheres. The catalyst preparation consisted of a 4 cc portion of the polyisobutylaluminum oxide from Experiment J. of Example 1 and 3.6 g of vanadium tetrachloride. After a reaction time of 5 minutes, 7.3 g of polyethylene were obtained receive.

Example 12

Ethylene was polymerized in the manner described in Example 11. The catalyst preparation consisted of 0.24 g of triisobutylaluminum, 5 mg of titanium (IV) -2-ethylhexanoate and 4 ecm of the polyisobutylaluminum oxide from Experiment J of Example 1. After a ^{reaction time of 1 and} ₂ hours, a solid polyethylene was obtained.

Example 13

Ethylene was in the manner described in Example 10 at a temperature of 73 to 80 ° C and polymerized at a pressure of 28 atmospheres. The catalyst preparation consisted of 0.05 g of zirconyl acetate, 0.4 g of triisobutyl aluminum and 5 ecm of the polyisobutyl aluminum oxide from Experiment B of Example 1. After a reaction time of 25 minutes, 5.7 g of a solid polyethylene were obtained.

Example 14

Ethylene was in the manner described in Example 10 at a temperature of 74 ° C and a Polymerized at a pressure of 28 atm. The catalyst preparation consisted of 0.8 g of triisobutylaluminum, 0.05 g of uranyl butyrate and 3 ecm of the polyisobutylaluminum oxide from Experiment A from Example 1. According to A reaction time of 20 minutes gave 11 g of polyethylene.

Example 15

A 15 cc pressure vessel was cleaned, dried, flushed with nitrogen and fitted with a serum stopper locked. The following ingredients were then added in the order shown: 2 ecm of polyisobutyl aluminum oxide from Experiment E of Example 1, 0.02 millimoles of chromium (II) -2-ethylhexanoate in 1 ecm heptane and 10 ecm 4-methyl-1-pentene. The addition was made in each case by means of an injection needle. The reaction mixture was at for 16 days Allowed to stand at room temperature, then poured the contents into isopropanol, filtered and dried. The drier poly-4-methyl-1-pentane weighed 1.8 g.

Similarly, butene-1 became polybutene-1 polymerized.

B e i s ρ i e 1 16

A 1-1 stainless steel autoclave was purged with nitrogen and then 500 cc of anhydrous heptane, 0.16 g of triisobutylaluminum, 0.8 millimole of polyisobutylaluminum oxide, and 500 cc of gaseous hydrogen were introduced. The autoclave was closed, heated to 70 ° C. and brought to a pressure of 7 atmospheres with ethylene. A solution of 2 mg of chromium (III) -2-ethylhexanoate in 20 ecm of heptane was added to start the reaction. After 29 minutes at 70 ° C. and 7 atmospheres ethylene pressure, the autoclave was cooled and vented. The contents were filtered and the polyethylene washed with isopropanol and dried. The polymer had a melt index of 6.5 dg / min, a flow rate of 500 (determination with the 10-fold amount), a rigidity of 10 710 kg / cm ² , a density of 0.9638 g / cm and a wax content of 15, 8th%.

II. If the reaction was repeated in the absence of hydrogen, after 47 minutes 44 g of polyethylene were obtained. This polymer had a melt index of 1.2 dg / min, a flow

from 153,

speed of 153, a stiffness of 10 430 kg / cm ² , a density of 0.9614 g / ccm and a wax content of 16.9%

Example 17

Ethylene was in the manner described in Example 10 at a temperature of 70 to 75 ° C and polymerized at a pressure of 7 atmospheres. The catalyst consisted of 0.064 g triisobutyl aluminum, 0.2 millimoles Polyisobutyl aluminum oxide and 4 mg chromium (III) -2-ethylhexanoate. Before heating and before Addition of the chromium (III) -2-ethyl-hexanoate were

800 ecm of hydrogen (gaseous) introduced. After 32 minutes, 26 g of solid polyethylene were with a Melt index of 1.1 dg / min, a flow rate

: speed of 67 (determination with 10 times the amount), a stiffness of 9,240 kg / cm ² , a density of 0.9527 g / ccm and a wax content of 2.3%.

Example 1 18

ίο Ethylene was described in Example 10 Polymerized manner, but the pressure in the autoclave was kept at 7 atmospheres. The trials are listed in the table below.

attempt Triisobutyl
aluminum Polyisobutyl
aluminum-
oxide • chrome
connection temperature time yield Enamel
index Flow
swiftly
ability *) G Millimoles G ⁰ C min G dg / min A. 0.24 4.0 *) ^£ 0.002) 66 to 72 30th 28.8 1.52 44 B. 0.24 4.0 «) 0.0040 70 to 76 32 14.9 C. 0.12 ^a ) 4.0o) 0.002 ') 66 to 68 18th 1 D. 0.24 1.0 «) 0.0020 68 to 72 35 11.5 E. 0.24 2.0 «) 0.0020 74 to 76 31 18th F. 0.24 5.0 ^) 0.0020 64 to 76 48 27 G 0.24 4.01) 0.0020 68 to 86 30th 41 H 0.2 2.0 *) 0.002 «) 68 to 83 20th 34 1.88 40 I. 0.08 2.0 «) 0.002ε) 70 to 92 16 25th J 2.0 «) 0.002ε) 70 to 80 30th 12.5 0.052 0.99 K 0.24 3.0b) ο, οοιό 66 to 74 38 20.3

( ^a ) Triethylaluminum.

( ^b ) From experiment E of example 1.

( ^c ) From experiment G of example 1

( ^d ) From Experiment H of Example 1.
( ^c ) From Experiment C of Example 1.

Example 19

In the manner described in Example 16 (I), a copolymer was prepared from ethylene and butene-1. The catalyst preparation consisted of 0.08 g of triisobutyl aluminum, 0.4 millimole of polyisobutyl aluminum oxide and 4 mg of chromium (III) -2-ethylhexanoate. The monomer mixture contains 3 mol percent butene-1. After 63 minutes of reaction at 70 to 74 ° C. and a pressure of 7 atmospheres, 44 g of a copolymer with a melt index of 0.19 dg / min, a flow rate of 37.1 (determination with 10 times the amount), a density of 0.9497 g / ccm, a stiffness of 7700 kg / cm ² and a wax content of 27.1%. As in all other cases, the wax could be removed by dissolving it in boiling cyclohexane.

B e i s ρ i e 1 20

55

Into a 1–1 autoclave purged with nitrogen 500 ecm of anhydrous heptane and 0.08 g of triisobutylaluminum were added from stainless steel. The autoclave was sealed, heated to 70 ° C and treated with a 3 mole percent butene-1 containing Ethylene mixture brought to a pressure of 7 atm. A mixture of 4 mg of chromium (III) -2-ethylhexanoate was then added and 0.2 millimoles of polyisobutylaluminum oxide which had been aged overnight, pressurized into the autoclave. After 21 minutes at 70 to 74 ° C. and a pressure of 7 atmospheres, 21 g of a copolymer were obtained

(f) Chromium (III) oxy-2-ethylhexoate.

(g) Chromium (II) -2-ethylhexoate.
(h) Chromium (III) acetate.

*) The determination was carried out with 4.7 times the amount.

Ethylene and butene-1 with a melt index of 0.01 dg / min, a flow rate of 4.8 (determination was made with 10 times the amount), a density of 0.9483 g / ccm, a stiffness of 7700 kg / cm ² and obtained a wax content of 5%.

As is known, the melt index of a polymer is a measure of the molecular weight of the Resin and inversely proportional to the same. The melt indices of the produced according to the invention Polyolefins can vary widely from as little as 0 to 1000 dg / min or more. Also the density the polyolefins can be varied, e.g. B. the density of polyethylene between 0.93 and 0.975 g / ccm. the However, polyethylene polymers prepared according to the invention preferably have a density im Range from 0.94 to 0.96 g / cc.

The amount of polymer formed! Material that is soluble in boiling cyclohexane is made by the excess present of compounds of the metals of Group IA, IIA or IHB; of the Total concentration of the catalyst complex, from the presence of small amounts of other olefinic Compounds and the presence of other impurities in the starting materials. Therefore, constant monitoring of these factors is necessary to determine the level of cyclohexane to keep soluble materials as low as possible.

The melt index of the polyolefins produced with the catalyst preparations according to the invention can can be adjusted by controlling the polymerization temperature since it was found to be easy is influenced by temperature changes. So

13 14

became ζ. B. found that the melt index rates used hydrocarbon-aluminum compounds

is influenced by polyethylene from 0.2 dg / min to 2.0 dg / min bond. An optimal polymerisation

increased when the polymerization temperature of 67 tion rate can be achieved when the

is increased to 74 ° C. Molar ratio of water to hydrocarbon

It has also been found that the polymerization aluminum compound is 1: 1. So were

speed due to the molar ratio of water. Polymerization speeds up to 90,000 g of poly-

to that in the production of polymerized organo-ethylene per millimole of transition metal per hour

Aluminum oxide component of the catalyst preparation achieved.

Claims (1)

Patent claims: 1. Process for the polymerization of monounsaturated α-olefins, in which a catalyst system consists of an organic aluminum compound and a compound of a transition metal of the groups IVA, VA and VIA are used and the polymerization is carried out at temperatures from -10 to 100 ° C is, characterized in that a catalyst is used which is obtained by reacting a polymerized organoaluminum oxide, the units of the formula