NO152562B - PROCEDURE FOR POLYMERIZATION AND CO-POLYMERIZATION OF OLEFINES - Google Patents

Description

The present invention relates to a method for the polymerization and co-polymerization of olefins from the group consisting of ethylene, propylene, butadiene and isoprene, using a catalyst system consisting of a catalyst component consisting of titanium or vanadium trichloride-containing metal chloride mixtures obtained by Al, Mg, Cr, Mn or Fe has been evaporated under a vacuum of 10<->^ Torr and the vapors thus obtained have been reacted with TiCl^ or VCl^, and a co-catalyst component consisting of an aluminum alkyl compound

sharing, and the peculiarity of the method of progress according to the invention

the idea is that the reaction product from the reaction between the metal vapors and TiCl^ is used as a catalyst component

respectively VC14 carried out at low temperature from -80 to +20°C, preferably in the presence of an inert solvent.

These features of the invention appear in the patent claim.

By using a catalyst system with a catalyst component and a co-catalyst component as indicated, one can polymerize and co-polymerize ethylene and higher OC olefins with very good yields to high-density polyethylene or to isotactic polypropylene, and is likewise able to polymerize butadiene to 1,4-trans-polybutadiene, and isopropene to 1,4-cis-polyisoprene.

The aforementioned catalyst system offers significant advantages

for other catalysts suitable for the polymerization of ethylene with high yields and of ethylene with other higher OC -olefins.

More detailed is the activity (calculated as kg polymer per g

titanium produced during 1 hour with an atmosphere of ethylene under the conditions indicated in the examples) extremely high, of the order of 230 kg. The synthesis of the catalyst takes place from raw materials which are particularly simple and which can be standardized (unlike mangé carriers used in other catalyst compositions which can be difficult to characterize from a physico-chemical point of view) and thus give catalysts

with an activity that is both homogeneous and reproducible. The manufacturing technique for the catalyst is both simple and fast. The catalyst can be used as it has been prepared, in association with the co-catalyst, by dispersion polymerization of ethylene without any subsequent separations, filtrations or washing processes. More specifically, any transition metal that is reacted is converted into an active catalyst. The catalyst can be used after it has been dispersed on an inert support, the latter can even be the polyolefin as such, by polymerization of ethylene in a gaseous state and thus without any hydrocarbon dispersant being present. The adjustment of the molecular weight with hydrogen within wide molecular weight ranges (melting index MFI 0.1 to MFI 15) does not involve yield loss of polymer in relation to transition metal.

The invention relates to the use of a catalyst system with an above-mentioned composition which allows the above-mentioned disadvantages to be eliminated and which in use entails the following advantages: obtaining hcye polymer yields in relation to transition metal,

a morphologically homogeneous polymer,

an easy setting of the molecular weight of the polymer,

the polymerization takes place in the gas phase with the achievement of high

dividends.

As stated above, such a catalyst system comprises an alkyl compound and an aluminium-metal chloride mixture obtained by reaction between vapors of the aforementioned transition metals and without titanium or vanadium trichloride. Among other things, it is known that titanium trichlorides can be produced by reducing TiCl^ using the following methods: a) with hydrogen under drastic conditions (500°C to 700°C). The products obtained are due to the high temperatures which

have been used with little activity in the polymerization of olefins.

b) with metals such as e.g. aluminium, antimony and others, at temperatures of or higher than 200°C. In this case is

not all metals are suitable in that for many of them the reaction only takes place to a limited extent or does not take place at all. Admittedly, such a deficiency can be avoided by using polar solvents, such as e.g. DMF, THF, dimethoxyheptane, but in this case the final titanium trichloride is complexed with the polar solvent and is of no interest from a catalytic point of view. Also the use of a liquid amalgam can prevent this disadvantage (US patent no. 3,658,723) but all the metals have a very limited solubility in mercury so that this method requires the use of large quantities of this metal which can only be separated from titanium with difficulty -trichloride. Furthermore, these products are not particularly active during polymerisation.

c) with metal-alkyl compounds, a method that allows the use of moderate temperatures, but which uses relatively expensive ones

materials, and which are also extremely reactive and fraught with risk.

With this method, it is not possible to use transition metals as the alkyl derivatives do not have sufficient stability to be used in practice.

d) with carbonyl derivatives of transition metals with low valence, as described in the Norwegian patent application no. 75/1368 submitted

16.4.1975.

There is the advantage that reduction is achieved with metals that will not react as such, but the method is limited to the transition metals and among them only those that give stable carbonyl derivatives. The thus obtained titanium chlorides have a fairly good catalyst activity in the polymerization of unsaturated hydrocarbons, either alone or in a mixture. The basis of the present invention is thus that titanium chlorides or vanadium trichloride are provided for the polymerization without any of the disadvantages indicated above, obtained by a method with evaporation of transition metal under a high vacuum and condensation in MCl^ (whereas M

is either Ti or V), either pure or diluted in inert solvents, these being kept at a low temperature.

The main advantage of such a method is that it can be used quite generally and gives reproducible results.

In addition, the advantage of obtaining products that have

a controlled thermal history and thus differentiated physical properties, and consequently different catalytic effects, as several metals can be co-evaporated simultaneously in a controlled manner.

The products thus obtained can be used as catalysts for the polymerization and co-polymerization of ole-

veneers using aluminum alkyls as co-catalysts.

In the present invention, the trichlorides of Ti are obtained

or of V by reacting MC14 with a metal selected from Al,

Mg, Cr, Mn and Fe.

The evaporation is carried out under a very high vacuum, maintained

— 3 — 6

between 10 Torr and 10 Torr at temperatures that vary depending on the metal used, usually from 800°C

to 2500°C, as described by P.L. Timms, Angew. Chem., 14,

273 (1975).

The metal vapors are reacted with MC14 at a temperature in the range

from -80°C to +20°C, preferably between -60°C and -20°C.._

The reaction can take place with MCl^, either pure or diluted

with inert solvents selected from aliphatic or aromatic

saturated or unsaturated hydrocarbons and the halogenated hydrocarbons, such as chlorohexane and fluorobenzene.

The choice of solvent or solvent mixture is controlled

of the conditions of use (the temperatures for solidification and

steaming under the pressure used).

It has further been found that if by the above-mentioned

position, a high ratio between Mg and Ti is used and reaction

is carried out in the presence of a halogen donor, it becomes possible to obtain a composition which together with an aluminum alkyl compound gives extremely good results in high-yield polymerization of oC -olefins, especially of ethylene, as such or in admixture with one or several of its higher homologues.

More particularly, such a composition is obtained by evaporation of magnesium or an alloy thereof, and subsequent condensation

sering and in an inert diluent containing the titanium compound and the halogen donor.

The evaporation of magnesium is preferably carried out under a

vacuum of from 10~ Torr to IO<-4> Torr, at a variable temperature, in accordance with the applied pressure, of from 500°C

to 1200°C.

The metal vapors are condensed into a solution, which is kept stirred,

of the titanium compound and the halogen donor, at a temperature higher than the freezing point temperature and lower than the boiling point temperature of the solution.

As indicated above, useful results for high yield polymerization of CX/ -olefins are obtained if a high ratio of Mg to Ti is used, especially if such a ratio is 4

or more. At the same time, it is necessary to have a halogen donor, selected from organic or inorganic halogenated compounds, which is used in an excess in relation to magnesium.

It is preferred to use ratio between halogenated connecti-

se and magnesium of 2 or more. The condensation of the magnesium vapors is then carried out in an inert diluent, chosen from among aliphatic or aromatic hydrocarbons.

The halogenated compound, as indicated above, may be selected from organic or inorganic halides. In particular, the alkyl and aryl halides can be used. At the end of the reaction, a very fine dispersion is obtained which can be used as such in the polymerization.

The polymerization reaction, as indicated above, is carried out in the presence of a catalyst system composed of the suspension obtained in advance, together with an alkyl-aluminum compound, in a hydrocarbon solvent, which may optionally be the same as that used in the preparation described above.

The working temperatures can vary from 20 to 200°C, preferably between 50 and 200°C, under pressures of between 1 and 20 atmospheres. As an alternative, when it is desired to carry out the polymerization reaction in a gaseous state, it is sufficient to distribute the catalyst in a low-boiling solvent, so that the latter can be easily removed. In such a case, the catalyst can also be dispersed on an inert solid carrier, and this can even be made up of the polyolefin itself. The conditions that can be used for the polymerization in the gas phase are provided by a temperature range that is maintained below the melting point of the olefin and in the special case of polymerization of ethylene, the preferred temperature range is between 40 and 90° C. The pressures are preferably chosen between 1 and 40 atmospheres. Hydrogen can be used as a regulator for the molecular weight.

In the following, some examples of the production of catalyst components are given.

A. Preparation of mixture 3 TiCl^-AlCl^. A rotating flask is used in which a tungsten filament connected to a source of electrical energy is centrally arranged. A cooling bath is placed horizontally under the flask. In the upper part of the apparatus there are connections to a nitrogen supply and a vacuum source. Inside the spirally wound tungsten filament is placed 160 mg of pure aluminum in flakes. The flask is filled under nitrogen with 250 ml of anhydrous decane, containing TiCl^ corresponding to 30% of the solvent. The rotating flask is cooled with the bath which maintains -40°C and then the flask is exposed to a vacuum with a diffusion pump until a pressure of 10 -4 Torr is achieved. When these conditions are achieved, the filament is heated until the metal is evaporated. The evaporated metal reacts instantly with TiCl^ and gives a very fine dark brown precipitate.

After complete evaporation, the flask is put back under pressure and brought to the ambient temperature by supplying nitrogen, then the suspension is brought to 150°C over the course of 3 hours. After filtering and drying, the thus obtained violet product is analysed:

B. The same apparatus and method as under A is used. 190 mg of metallic pure Mg in wire form and 250 ml of octane, containing 2% TiCl4, are introduced. After cooling at -60°C and achieving a vacuum of 10-4 Torr, the evaporation of the metal is initiated and this takes 5 minutes. The formation leads to a fine brown-violet precipitate. The flask is brought back to ambient pressure and temperature. A sample is brought to 125°C during 4 hours, after which the dispersion is filtered and the violet precipitate is washed with n-heptane to completely remove TiCl^ and then the solid product is analyzed after drying in vacuum (2 g):

The two samples, the untreated and the treated, had an X-ray analysis. gamma structure.

C. The same apparatus and method as under B was used, adapting to a concentration of TiCl3 in n-octane of 14%. A brown-violet product was obtained which was filtered, washed with n-heptane to remove TiCl 2 and then resuspended in a heptane and analyzed. The analysis gave <M>^l<Ti>l.84<C1>4-D. The same apparatus and method as under A was used. 0.240 g of metallic magnesium in wire form and 300 ml of n-octane containing 0.07% TiCl 2 and 12% n-chlorohexane were introduced. After cooling to -60°C, a vacuum was established on

_4

10 Torr and magnesium evaporated within 7 min. It was

formed a solid light brown product which was collected on a filter, washed with n-heptane and kept at 100°C in this solvent for 2 hours.- The analysis shows the following molar composition: <M>^3,l<Ti>lC17, 8-

E. The same apparatus and method as described under A was used.

0.180 g of metallic Mn in flakes and 250 ml of octane containing 2% TiCl were introduced. After cooling to -60°C, a vacuum of . 10 -4 Torr and the evaporation of the metal is initiated, and this was completed within 3 min. A brown-violet precipitate was formed. The flask is brought back to ambient temperature and pressure and the suspension is filtered, washed with n-hexane, until complete removal of TiCl4. after which the product is dried under vacuum and analyzed.

The analysis gave:

F. The same apparatus and method as mentioned under A was used. 0.25 g of metallic Fe in the form of shavings and 250 ml of anhydrous n-octane containing 5% TiCl 2 were introduced. After cooling to -50°C, a vacuum of 10 ^ Torr was reached and the evaporation of the metal was started and this took 5 min. A solid red-brown product formed which was collected on a filter, washed with anhydrous hexane and dried under vacuum. 1.87 g of a product was obtained as the following analysis:

G. The same apparatus and method as mentioned under A was used. 0.120 g of Mg wire and 250 ml of n-octane containing 3 ml of VCl 2 were introduced. After cooling to -60°C, a vacuum of 10 Torr was reached and the evaporation of the metal began and proceeded within 5 min. A solid dark brown product was formed which was washed with n-heptane to remove excess VCl 2 and then reslurried in n-heptane. The analysis gives Mg^ V^ j^Cl^ gQ.

H. The same apparatus and method as mentioned under A was used. 1 g of metallic chromium in lumps and 250 ml of n-heptane, containing 10 ml of TiCl., were introduced. After cooling to -80 o C, a vacuum of about 10 -4 Torr was reached and was completed within 20 min. A solid greenish product formed which was collected on a filter and washed with heptane to remove excess TiCl 2 and then resuspended in heptane.

The analysis gave:

EXAMPLE 1 (POLYMERIZATION OF ETHYLENE)

A 5-liter autoclave is filled with 2 1 of anhydrous n-heptane, containing the catalyst as prepared under C in a concentration of 0.03 mg atoms of titanium and 4 mg atoms of Al(iso Eu). The mixture is brought to 85<0>C and then 5* kg/cm hydrogen and an equal amount of ethylene are introduced. The polymerization is carried out during 4 hours while the total pressure is kept constant by the addition of ethylene. After completion of polymerization, the slurry is centrifuged and the polymer is dried under vacuum at 50°C for 4 hours and then weighed. 400 g of a white polymer is obtained, equivalent to a specific yield of 6440 g of polymer per g Ten per hour and atmosphere C^, with a melting index = 0.60.

EXAMPLE 2 (POLYMERIZATION OF ETHYLENE)

The procedure is the same as in example 1, using the catalyst sample described under A, with a concentration of 0.06 mg atoms per 1 titanium and co-catalyst Al(iso Bu-| i

concentration 4 mg atoms per 1. 5 kg/cm 2 of hydrogen and 5 kg/cm 2 of ethylene are introduced. The polymerization is carried out under a constant pressure by introducing ethylene during 4 hours and 120 g of a white polymer is obtained, corresponding to a specific yield of 1030 g of polymer per g Ten per hour and per atmosphere C^, with melting index 2.16 = 1.5 (MFI^-^ 6/MFI2 16 = 49.4).

EXAMPLE 3 (POLYMERIZATION OF ETHYLENE)"

A 2 liter autoclave is filled with 2 1 of anhydrous and deaerated n-hexane, containing 20.8 mg of a catalyst prepared under F corresponding to 0.0941 mg atoms of titanium and 4 mg atoms of Al(i so Bu)., per 1. 20 kg/cm <2> hydrogen and 20 kg/cm <2> ethylene are introduced<.>

The temperature is raised to 85°C and the pressure is kept constant by continuous introduction of ethylene. After 2 hours of polymerization, the reaction mixture is cooled, the autoclave is vented and the polymer is centrifuged, dried under vacuum at 50°C and weighed. 320 g of a polymer with MF^ <=><0.>12 (MFI_, ,/MFI_ 44.7) is obtained. Dividend = 1750 per Ten per hour and Zl , D 2. , ±6

per atmosphere.

EXAMPLE 4 (POLYMERIZATION OF ETHYLENE)

The procedure is the same as in example 1, using the product described under E as catalyst, in a concentration of 0.10 mg atoms per 1 titanium. As a co-catalyst, Al(iso Bu) is used, in a concentration of 4 mg atoms per 1. Polymerization is carried out over 3 hours with 5 kg/cm<2 >hydrogen and 5 kg/cm 2 ethylene. 390 g of a polymer with MFI» .,= 0.35 and an MFI„, ,/MFI_ = 35 are obtained.

2.16 ^ 21.6 2.16

The yield was 2,700 g per g Ten per hour and per atmosphere.

EXAMPLE 5 (ETHYLENE POLYMERIZATION)

The procedure is the same as in example 1 using the sample described under 4 as catalyst in a concentration of 0.026 mg atoms per 1 titanium and 2 mg atoms per 1 Al(iso Ru)-.. 5 kg/cm 2 hydrogen and 5.5 kg/cm 2 ethylene are introduced. The temperature is raised to 85°C and the pressure is kept constant by continuous introduction of ethylene. After 2 hours of polymerization, the reaction mixture is cooled, the autoclave is vented and the polymer is collected on a filter and dried under vacuum at 50°C and weighed. 108 g of a polymer with MFI = 0.11 correspondingly are obtained

a yield of 3,900 g of polymer per g Ten per hour and per atmosphere ethylene.

The following Table 1 indicates the specific activities obtained by the polymerization of ethylene with the samples of TiCl 2 prepared as indicated under A to. 4.

EXAMPLE 6 (ISOPREN POLYMERIZATION)

A 100 ml two-necked flask that had previously been flushed with an inert gas is filled under an inert atmosphere with 30 ml of anhydrous n-hexane and then 0.1 millimol Ti according to example 3, 0.1 millimol (Al(iso C^Hg) 3 and then 7 g of anhydrous isoprene distilled twice over LiH. The mixture contained in the flask is stirred for 2 hours at a temperature of 20°C and then poured into 30 ml of methyl alcohol containing 1% of an antioxidant. The coagulated polymer is dried under vacuum at room temperature overnight. Under these conditions, the yield of solid polymer was 6.3 g, corresponding to 90% of the introduced monomer. NMR analysis shows the predominant presence of a 1,4-cis-type structure.

EXAMPLE 7 (BUTADIENE POLYMERIZATION)

A 200 ml stoppered flask, which had previously been purged with an inert gas, is filled under an inert atmosphere with 90 ml of anhydrous n-hexane and then 0.5 millimoles of V according to Example 7 and 1 millimoles of AlEt 2 . The flask is closed with a neon-pren plug and with a perforated "crown" stopper so that a hypodermic needle can be inserted. At this stage, 14 g of a monomer in liquid form are introduced by means of a hypodermic needle directly connected to a metal bottle containing butadiene. The plug bottle is placed in a rotating bath that is thermostatically maintained at a temperature of 20°C for 1 1/2 hours. After completion of the experiment, the bottle is opened and the contents emptied into 1/2 1 methanol containing 1% ionol. The coagulated polymer is dried under vacuum for 16 hours. Under these conditions, the yield of solid polymer is 1.8 g, corresponding to 13% introduced monomer. IR analysis shows a structure that was mainly integral 1,4-trans.

EXAMPLE 8 (POLYPROPYLENE)

A 2 liter autoclave is filled with 1 1 of anhydrous and deaerated n-hexane containing 340 mg of catalyst prepared according to example 8, corresponding to 1.66 mg atoms of titanium and 7 mg atoms of AlEt^ per 1. 8 kg/cm 2 propylene is introduced. The temperature is raised to 65°C and pressure is kept constant by supplying propylene for 6 hours. After cooling the autoclave, the polymer is collected on a filter and dried under vacuum at 50°C. 135 g of a polymer with a crystallinity (RX) of 42% and a residue of 85% after extraction with hexane are obtained.

EXAMPLE 9 (ETHYLENE POLYMERIZATION)

Preparation of catalyst component with a ratio Mg/Ti higher than 0.5. The same apparatus as described under A is used. The tungsten spiral is filled with 800 mg Mg in needle form. The 500 ml flask is filled under nitrogen with 130 ml of anhydrous and deaerated n-heptane, 20 ml of n-chlorohexane corresponding to 146 millimoles and 0.15 ml of TiCl^ corresponding to 1.35 millimoles. The flask is cooled to -70°C and a vacuum of 10<->^ Torr is applied, and then the spiral is heated so that the metal evaporates. A very fine grey-brown precipitate is obtained. After complete evaporation (approximately 15 minutes), nitrogen is introduced into the apparatus and the flask is brought back to ambient temperature, stirring not being continued.

Analysis of the dispersion gave the following molar ratio:

- Mg to Ti = 24; Cl to Ti = 45.

A 5-liter autoclave with an anchor stirrer is filled with 2 L of anhydrous and deaerated n-heptane, 4 millimoles (Al(iso Bu^) and an amount of catalyst, prepared as indicated above, corresponding to 0.01 mg atoms of elemental titanium. The temperature is raised to 85 o C and 5 kg/cm 2 of hydrogen and 3.5 kg/cm<2 >ethylene are introduced. The ethylene is introduced continuously so that the total pressure is kept constant for 1 hour. 350 g of polyethylene with MFI =9 is obtained, 8 g/10 min and d = 0.9690 g per cm The specific activity is 200,000 g polymer per g titanium per hour and per atmosphere ethylene.

EXAMPLE 10 (POLYETHYLENE)

The same synthesis method as stated in example 9 is carried out, using bromohexane as haloalkyl. A dispersion is obtained with the following analysis:

Ratio of Mg to Ti = 16.5; Ratio (Br + Cl) to Ti = 33

During the polymerization of ethylene, under the conditions of example 9, 165 g of a polymer with MFI = 4.18 g/10 minutes corresponding to a specific activity of 98,000 g per g Ten per hour and per atmosphere ethylene.

EXAMPLE 11 (POLYETHYLENE)

With the method indicated under 3 and the same reaction components, several catalysts were produced with different ratios between Mg and Ti, their activities during the polymerization of ethylene, carried out under the conditions in example 9, are reproduced in the following table 2.

EXAMPLE 12 (POLYETHYLENE)

The same synthesis method as in example 9 is used, with the following reaction components: Mg: 1,100 mg (46 mg atoms)

TiCl„(0. Pr)„ = 0.2 ml corresponding to 0.68 millimoles, and

2 in so z

C,H,,Br = 20 ml corresponding to 142 millimoles in 20 ml nor.octane.

6 16

After the reaction, the analysis of the suspension is:

Mg to Ti = 48; Ratio (Br + Cl) to Ti = 83.5.

When polymerizing ethylene during the processes in example 9

265 g of a polymer with MFI = 8.5 g per

10 minutes, corresponding to a specific activity of

157,000 g of polymer per g Ten per hour and per stmosphere ethylene.

EXAMPLE 13 (POLYETHYLENE)

The same synthesis method as in example 9 was used with the following reaction components:

Mg: 1,050 mg (43 mg atoms)

<C>6<H>13C1 15 ml (110 mg atoms)

Ti (0 iso Pr)4 0.2 ml (0.67 mg atoms) in 170 ml nor.octane.

P = 0.05 mmBg; t = -50°C.

After complete evaporation of the magnesium, the flask was filled with nitrogen and set aside overnight. The suspension gave on analysis:

Ratio of Mg to Ti = 52; Ratio cl to Ti = 90.

(i

In the polymerization of ethylene, which was carried out under the conditions described in example 9, 125 g of a polymer with MFI = 6.7 g per 10 minutes and a specific activity of 75,000 polymer per g Ten per hour and per atmosphere ethylene.

COMPARISON EXAMPLE 1

An apparatus similar to that described under A was used. 1.096 g of pure metallic magnesium wire was arranged in the tungsten filament, while 130 cm 3 of anhydrous ligroin containing 1 millimol of TiCl^ together with 66.7 millimoles of SnCl^ were added to the 1-liter flask. The magnesium was completely evaporated in 40 minutes under a vacuum of 0.09 Torr, by keeping the flask rotating at

-6<0>°c to -70°c. The flask is returned to ambient temperature and pressure and stirring is continued for about 1 hour. During this time, the color of the dispersion changes from dark brown to grey-white. Filtration is carried out using a porous G3 diaphragm and then washing is carried out with anhydrous neptane and the solid is resuspended in heptane.

Analysis of the dispersion gives the following results:

Ti =5.77 millimol per 1; Mg = 181 millimoles per 1;

Sn = 170 millimoles per 1; Cl = 731 millimol per 1.

COMPARISON EXAMPLE 2

1.0 g of pure magnesium wire is arranged in the tungsten filament. The flask is filled in the indicated order with 130 ml of anhydrous toluene and 1 millimol of TiCl^, which gives the solvent a yellow tint. 2 millimoles of diethyl phthalate are then added dropwise at -78°C. The solution changes color from yellow to light green. 66.7 millimoles of anhydrous SnCl^ are then added, which gives a yellow-orange hue and an orange-coloured oily substance is deposited on the bottom of the flask. Magnesium is evaporated during 40 minutes under a vacuum and 0.06 Torr by keeping the flask in rotation at -78°C. The flask is returned to ambient temperature and pressure and kept stirred for about 1 hour. During this time, the dispersion changes color from dark brown to yellow. The slurry is collected on a filter, washed with anhydrous heptane and resuspended in heptane.

Analysis of the dispersion gives the following results:

Ti = 7.74 millimol per 1; Mg = 235 millimoles per 1;

Sn = 190 millimoles per 1; Cl = 897 millimoles per 1.

COMPARISON EXAMPLE 3

809.5 mg of pure magnesium wire is arranged in the tungsten filament

while the flask is filled with 100 ml anhydrous toluene and 1

millimol TiCl4 which colors the solvent yellowish. 2 millimoles of diethyl phthalate are then added at room temperature and with stirring. The solution assumes a light green hue. 43.3 millimoles of SnCl^ n-But are further added, which gives a yellow-orange color tone and an oily substance is deposited on the bottom of the flask. Magnesium is evaporated during 40 minutes under a vacuum of 0.07 Torr by keeping the flask in rotation at -78°c. The flask is returned to ambient pressure and temperature and stirring is continued for approximately 2 hours at room temperature. The slurry passes from dark brown to light gray during this time. Filtration, washing with anhydrous heptane and renewed suspension in heptane are carried out. The analysis of the slurry gives the following results:

Ti = 7.18 millimol per 1 Mg = 66 millimoles per 1

Sn = 80 millimoles per 1 Cl = 349 millimoles per 1

COMPARISON EXAMPLE 4

970 mg of pure magnesium wire is placed on the tungsten filament.

In the flask containing 100 ml of anhydrous heptane and 1 millimol of TiCl^, 60 millimoles of freshly distilled SbCl^ are added at room temperature and with stirring. The solution remains clear. When the magnesium evaporates, the suspension turns yellow-brown. A white powder is then formed which gradually darkens to gray and finally to black. Filtration, washing with anhydrous heptane and renewed suspension in the aforementioned solvent are carried out. The analysis of the slurry gives the following results.

Ti = 4.60 millimol per 1 Mg = 226 millimoles per 1 Sb = 95 millimoles per 1 Cl = 1.058 millimol per l

COMPARISON EXAMPLE 5

IN

831.8 mg of pure magnesium wire is placed on the tungsten filament. In the bottle containing 100 ml anhydrous nor. hepane is added at room temperature and with stirring 51.3 millimoles of distilled P0C13 and 1 millimoles of TiCl4< A yellow precipitate is formed. Magnesium is evaporated while the flask is kept at -78°C. j The suspension is yellowish brown. The flask is returned to ambient temperature and pressure and stirring are continued

2 hours at room temperature. The suspension turns pale yellow. Filtration, washing with nor.heptane and renewed suspension in the latter solvent are carried out. Analysis of up-

the slander produces the following results:

Ti = 9.62 millimol per 1 Mg = 126 millimoles per 1 P = 390 millimoles per 1 Cl = 655 millimoles per 1 Ethylene polymerization experiments with the catalyst mixtures, prepared in comparative examples 1 and 4 were carried out 1 in accordance with example 9 with a polymerization time of 2 hours with a hydrogen pressure of 5 kg/cm 2 and an ethylene pressure of 5 kg/cm 2. The results obtained are reproduced in the subsequent table 3.

EXAMPLE II (POLYMERIZATION OF ETHYLENE)

A two-necked flask, flushed with nitrogen, is filled with 10 g of pulverized polyethylene, 50 ml of anhydrous and deaerated nor.hexane and 1.5 milligram atoms of Al(iso Bu)^-

After homogenization, the mixture is allowed to stand for 2 hours, after which 0.0075 milligram atoms of a catalyst such as e.g. the titanium catalyst prepared as described in Example 9 together with 1.5 milligram atoms of Al(iso Bu)^. Hexane is completely distilled off under vacuum at 60 C. The thus produced material is introduced under nitrogen into a well-dried 2 liter autoclave which has been vented and which is kept under a nitrogen atmosphere. The autoclave is evacuated to remove nitrogen after which ethylene is introduced until a manometer pressure of 1.5 kg/cm is reached and the temperature is raised to 80°C. During the course of the polymerization, ethylene is introduced so that the manometer pressure of 1.5 kg/cm 2 is kept constant. The absorption of ethylene is checked using a rotameter. The polymerization is interrupted after 5 hours. During this time, the absorption remains constant. 84 g of polyethylene is obtained, corresponding to a specific activity of 16,500 g of polymer per g Ten per hour and per atmosphere ethylene.

EXAMPLE 15 (POLYMERIZATION OF ETHYLENE)

The procedure referred to in the preceding example is followed exactly with 2 kg/cm 2 of hydrogen as molecular weight control agent. After 3 hours of polymerization, 56 g of a polymer with an MFI of 2.1 g per 10 minutes

EXAMPLE 16 (COPOLYMER OF ETHYLENE AND BUTENE-1)

Co-polymerization of ethylene with butene-1 is carried out using catalyst as described in example 9, with the same method, the same polymerization conditions and the same concentrations of catalyst as described in this example. The supply of butene-1 is carried out at the same time as the ethylene supply by introducing an amount of butene-1 corresponding to 5% of the ethylene, the gases being measured with calibrated flow meters. After 1 hour of polymerization, 290 g of a copolymer with an MFI of 10 g per 10 minutes and apparent specific weight, d = 0.9580 g/cm 3. The specific activity is 170,000 g of copolymer per g Ten per hour and per atmosphere ethylene.

EXAMPLE 17 (COPOLYMER OF ETHYLENE AND HEXENE-1)

i Co-polymerization of ethylene with hexene-1 is carried out by using the catalyst described in example 9 under the same conditions and concentrations as discussed in this example.

The procedure is as follows:

an autoclave is filled with 1.8 1 nor-heptane containing

8 g anhydrous and deaerated hexen-1-

the temperature is kept thermostatically controlled at 85°C.

the catalyst is introduced (4 millimol Al(iso Bu)3 and 0.01

mg atomic catalyst such as titanium diluted with 200 ml n-heptane. 5 kg/cm 2 of hydrogen and 3.5 kg/cm 2 of ethylene are introduced. During the supply of ethylene, which. is carried out continuously during the entire polymerization time

(1 hour) to keep the total pressure constant, introduce 8 g of hexene-1 diluted in 100 ml of nor-heptane using

of a metering pump. After 1 hour of polymerization, the gases are vented, the copolymer is collected on a filter and dried. j> 230 g of a copolymer with an MFI = 8.5 g/10 min and an apparent specific weight d = 0.9576 g per

cm"^. The specific activity obtained is 136,000 g of copolymer

per g Ten per hour and per atmosphere ethylene.

Claims (1)

Process for the polymerization and co-polymerization of olefins from the group consisting of ethylene, propylene, butadiene and isoprene, using a catalyst system consisting of a catalyst component consisting of titanium or vanadium trichloride-containing metal chloride mixtures obtained by Al, Mg, Cr, Mn or Fe has been evaporated under a vacuum of 10 ^ Torr and the thus obtained vapors have been reacted with TiCl^ or VCl^, and a co-catalyst component consisting of an aluminum-alkyl compound, characterized in that the reaction product from the reaction between the metal vapors is used as a catalyst component and TiCl^ respectively VCl^ carried out at low temperature from -80 to +20°C, preferably in the presence of an inert solvent.