DE1770726B1 - PROCESS FOR THE POLYMERIZATION OF AETHYLENE - Google Patents

Description

questionable catalyst or carrier removal from the Polymer can not be dispensed with if you want to obtain a technically useful product.

In technology, polymerizations according to the Ziegler process with carrier contacts can only then be carried out easy to carry out when further processing of the polymers without removal of the catalyst and support is possible. However, the amounts of catalyst remaining in the polymer, in particular the chlorine content should only be very low, so that neither discoloration of the polymers nor signs of corrosion occur on the processing machines.

A process has now been found for the polymerization of ethylene or mixtures of ethylene x5 with up to 10 percent by weight of «-olefins of the general formula R - CH = CH ₂ , in which R is a branched or unbranched hydrocarbon radical with 1 to 13, preferably 1 to 8 carbon atoms means in suspension or in the gas phase at temperatures from 20 to 120 ⁰ C and at pressures up to 20 atm in the presence of mixed catalysts from (a) a solid titanium-containing reaction product which has been produced using a hydroxyl-containing magnesium compound and a halogen-containing titanium compound and (b) an organoaluminum compound, optionally with regulation of the molecular weight by hydrogen, which is characterized in that the polymerization is carried out in the presence of a mixed catalyst whose component (a) is made by reacting hydroxyl-containing magnesium compounds fixed on carrier solids with tetravalent magnesium compounds Titanium compounds containing halogen atoms and alkoxy or aralkoxy groups.

In the laid-out documents of Belgian patent 650 679 it is emphasized that when used of other divalent metal compounds containing hydroxyl groups instead of Me (OH) Cl as a carrier - such. B. Hydroxides - no active catalysts can be obtained.

It was therefore extremely surprising and by no means predictable for the person skilled in the art that the reaction products of magnesium compounds containing hydroxyl groups fixed on solids with halogen and titanium compounds containing alkoxy or aralkoxy groups, particularly active supported catalysts represent.

By fixing the magnesium compound containing hydroxyl groups on a solid, it is possible to after reaction with tetravalent titanium compounds containing halogen and alkoxy groups or aralkoxy groups Produce very active supported catalysts, so that at pressures of 4 to 8 at very high Polymer yields are obtained.

As tetravalent titanium compounds containing halogen atoms and alkoxy or aralkoxy groups, halo-titanic acid esters are suitable, advantageously halo-orthotitanic acid esters of the general formula

60 TiX "(OR) ₄ _"

in which η = 1 to 3, X = chlorine and bromine and R denotes identical or different hydrocarbon radicals, preferably alkyl radicals having 1 to 18, preferably 1 to 10 carbon atoms.

Alkoxy titanates of the formula mentioned, with η = 1 to 2, and in which R represents identical or different alkyl radicals with 2 to 8 carbon atoms, are advantageous. For example, are

Ti (OC ₂ H ₅ ) ^ Cl ₂ , Ti (OC ₈ Hi) ₈ Cl, Ti (OC ₃ H ₇ ) _- Cl ₂ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (O — iC ₄ H ₉ ) ₂ Cl ₂ ,
Ti (OiC ₄ H ₉ ) ₃ Cl

called. Ti (O - iC ₃ H ₇ ) ₂ Cl ₂ and Ti (O - iC ₃ H ₇ ) ₃ CL are particularly preferred

Temperatures of 0 to 200 ° C. are recommended for the reaction, the upper temperature limit being predetermined by the decomposition temperature of the titanium compound used in accordance with the invention. Temperatures from 20 to 120 ^° C. are advantageous.

If appropriate, the reaction takes place in inert solvents. Suitable inert solvents are aliphatic or cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane, Methylcyclohexane and aromatic hydrocarbons such as benzene and xylene; Hydrogenated ones are also useful Diesel oil fractions that have been carefully freed from oxygen, sulfur compounds and moisture are.

The reaction product, which is insoluble in hydrocarbons, is then obtained from the reaction product according to the invention used, fixed on the support magnesium compound and the titanium compound by repeated Wash with an inert solvent in which the titanium (IV) compound used dissolves easily from freed unreacted titanium compound.

As a carrier for the hydroxyl-containing magnesium compounds inert inorganic and organic solids can be used; these include B. natural, mineral substances or also defined, simply compound connections. For example:

Silicates or substances containing silicate, such as bentonite, pumice stone, kieselguhr, kaolin, aluminum silicate Talc,

Oxides such as MgO, Al ₂ O ₃ , TiO ₂ ,

Phosphates such as Ca ₃ (PO ₄ ) Sa, apatite,

Sulfates such as BaSO ₄ , CaSO ₄ ,

Carbonates such as BaCO ₃ ,

Activated carbon, silica gel.

Average carrier particle sizes of 0.1 to 300 microns are recommended, preferably 2 to 250 microns,

As magnesium compounds that can be used for fixation on these carriers are, for. B. Mg (OH) ₂ or those magnesium compounds which, in addition to the hydroxyl groups, for. B. contain sulfate, phosphate, carbonate, carboxylate, nitrate groups or halogen.

In the case of the use of magnesium compounds containing hydroxyl and carbonate groups, a Hydroxyl group content of 80 to 500 mg per gram of magnesium compound is recommended; is preferred a hydroxyl group content of 100 to 400 mg per gram of magnesium compound.

In the case of magnesium compounds containing hydroxyl groups and halogen, they are of the general formula

MgCl ₈ • ZMg (OH) ₂

where X ^ 3, preferably 3 to 10, or those corresponding to magnesia (Sorel) cement are preferred. The fixation on the carrier can be known per se

5 6

terWeisez. B. be done by the fact that the hydroxyl With addition ζ. B. of ZnCl ₂ is a carrier catalyst

group-containing magnesium compound obtained in the presence of a generator, which produces improved responsiveness of the wearer. towards H ₂ and therefore for the production of

So you can z. B. for fixing Mg (OH) ₂ polymers with lower molecular weight aqueous solutions of magnesium salts such as MgCl ₂ , 5 is suitable.

MgSO ₄ , Mg (NO ₃ ) ₂ in the presence of the carrier with the conversion of the tetravalent titanium compound

Add alkaline solutions, eg sodium hydroxide solution, to stirring; in component A into the polymerization-active one, then it is filtered off, washed and dried, the lower valence stage is expediently carried out. This may for example at temperatures of 180 to during the polymerization by the alu-300 ⁰ C, preferably from 200 up to 25O ⁰ C. io miniumorganische connection (component B) at

Analogously, in the fixation of hydroxyl- temperatures of 20 to 12O ⁰ C, preferably 60 to 100 ° C. undcarbonatgruppenhaltigenMagnesiumverbindungen

proceed on supports, where for the precipitation of this component (a) can, however, also before the

Compounds in the presence of the carrier Karbonatlö- polymerization with the organoaluminum compounds, such as. B. Soda solutions or mixtures of 15 bond at temperatures from -30 to 100 ⁰ C, pre-carbonate solutions and alkalis, such as. B. caustic soda, preferably 0 to 20 ° C, can be treated and connected. ßend be used in the polymerization. In case of

When fixing the magnesia (Sorel) cement to the support of chlorine-containing organoaluminum, it is expedient to proceed in such a way that compounds, however, it is expedient to add an aqueous _{reaction product containing about 3 to 5 N MgCl 2} solution containing 20% to wash. Then MgO in a ratio of 1: 3 to 1: 8, preferably 1: 3, is activated with organoaluminum verbs 1: 5, reacted in the presence of the carrier. The other compounds at temperatures of 20 to 120 ⁰ C, vorAufarbeitung can then again as in the Fixie- preferably 60 to 100 ⁰ C.

tion of Mg (OH) _{2 has been} described. As organoaluminum compounds, the

The weight ratio between the carrier and the hydro-reaction products of aluminum trialkyls or xyl-containing magnesium compounds can vary in aluminum dialkyl hydrides with hydrocarbon-wide limits: a residue with 1 to 16 carbon atoms, preferably 1: 0.01 to 1: 1, is recommended; preferably an Al (i-Bu) ₃ or Al (i-Bu) ₂ H and 4 to 20 carbon weight ratio of 1: 0.05 to 1: 0.6 is used. Atoms-containing diolefins, preferably isoprene, in order to obtain as finely dispersed precipitates as possible, can be used; for example, aluminum iso are the precipitations at room temperature and in prenyl.

concentrated solutions as possible. Also suitable as component (b) are chlorine-

Specifically with MgO as a carrier, organoaluminum compounds such as di-

supply of Mg (OH) ₂ also proceed in such a way that the alkylaluminum monochloride of the formula R ₂ AlCl or MaO is reacted with a calculated amount of water or water vapor of the formula R ₃ Al ₂ Cl ₃ . Expediently, where R, identical or different hydrocarbon 1 g of MgO is reacted with 0.2 to 10 mmol of water. residues, preferably alkyl residues with 1 to 16, preferably if other hydroxyl-containing magnex can be 2 to 12 carbon atoms. as

If you want to fix silicon compounds on MgO, it is advantageous examples are: (C ₂ H ₅ ) ₂ A1C1, (iC ₄ H ₉ ) ₂ AlCl, stick, the MgO with acids of the formula HX, where X 40 (C ₂ H ₅ ) ₃ A1 ₂ C1 ₃ .

a halogen, nitrate, (carbonate); ^ -, (TO ^) ₁ I ₃ -, (SuI- are advantageous as component (b) aluminum

fat): t / ₂ , carboxylate, preferably acetate, means trialkyl AlR ₃ or aluminum dialkyl hydrides to react. Appropriately, the formula AlR ₂ H is used, in which R uses 0.2 to 10 mmol of HX, the same or per gram of MgO. The different hydrocarbon radicals, preferably alkyl acids HX, can also be reacted in water-containing form with 45 radicals with 1 to 16, preferably 2 to 6, carbon-MgO. atom means like Al (C ₂ H ₅ ) ₃ , Al (C ₂ Hg) ₂ H, Al (C ₃ H ₇ ) 3,

The titanium content of component A is expediently A1 (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , Al (iC ₄ H ₉ ) ₂ H. moderately 0.01 to 10 mg-atom, preferably 0, 1 The organoaluminum activator can be used in

to 5 mg-atom per gram of component A. It allows concentrations of 0.5 to 10 Mmol, preferably 2 to by the reaction time, the reaction temperature 5 ° 4 m mol per liter of dispersant or per liter door and the concentration of the tetravalent reaction volumes used are used, gene, halogen-containing titanium compound affect. The polymerization can be in suspension or in the

Before the reaction with the titanium compound, the gas phase can continuously or discontinuously at the hydroxyl group-containing temperatures of 20 to 120 ⁰ C, preferably 60 to magnesium compounds with other inert ones, which are 55 100 ° C and particularly advantageously at 80 to 90 ⁰ C, by polymerization non-inhibiting inorganic led. The pressures are up to 20 at before solids are converted. As such, 1.5 to 8 at are preferably suitable.

Metal compounds such as oxides, hydroxyls, halogens are suitable for suspension polymerization

nides, sulfates, carbonates, phosphates, silicates; Examples which are common for the Ziegler low-pressure process include: alkaline earth oxides such as CaO, inert dispersants such as aliphatic or cyclo-Al (OH) ₃ , fluorides and chlorides such as MgF ₂ , AlCl ₃ , aliphatic hydrocarbons; as such, ZnCl ₂ , NiCl ₂ , alkaline earth metal carbonates such as BaCO ₃ , earth, for example butane, pentane, hexane, heptane, cycloalkali _{metal phosphates such as Ca 3} (PO _{4 I 2} or apatite, talc, hexane, methylcyclohexane) may be given Molar ratio between the magnesium compounds, aromatic hydrocarbons such as benzene, compounds on the carrier and inorganic solid 65 xylene or gasoline or hydrogenated material can vary within wide limits 1: 0.05 to 1: 0.9, preferred cellular compounds and moisture have been freed from 1: 0.08 to 1: 0.5, Ethylene or mixtures of

Ethylene with up to 10 percent by weight, preferably up to 5 percent by weight, of α-olefins of the general formula R - CH = CH ₂ , where R is a branched or unbranched hydrocarbon radical, preferably an alkyl radical having 1 to 13, preferably 1 to 8 carbon atoms , can be used. Propylene, butene (I), pentene (I), 4-methylpentene (I) are advantageously used as comonomers.

The molecular weights of the polymers can be determined in a known manner by molecular weight regulators, preferably hydrogen.

The great technical progress compared to the procedures of the laid out documents of the Belgian Patents 650 679 and French patent specification 1 448 320 results once in the simpler polymerization version, since with the aid of the supported catalysts used according to the invention already in a pressure range customary for Ziegler polymerization from 4 to 9 at high catalyst yields can be achieved, so that the supported catalyst is completely may remain in the polymer.

In the case of suspension polymerization, such complex operations as catalyst decomposition, Catalyst and support removal, etc. After filtration from the dispersant, drying is carried out and processed directly. The extremely small amounts of catalyst and carrier cause neither Discoloration of the polymers and corrosion damage to the processing machines.

So arise z. B. with 1 g of MgO, on which hydroxyl-containing magnesium compounds _{are fixed, after reaction with TiCl 2 (OiC 3} H ₇ ) ₂ in the ethylene polymerization 3 to 15 kg of polymer at pressures of 5 to 9 atm.

In contrast, one obtains z. B. according to French patent specification 1,448,320 with 1 gram of MgOH · Cl, on which TiCl _{4 is} fixed, at 20 at a maximum of 1.5 kg of polymer.

Another essential advantage of the method according to the invention is that when using the as preferred mentioned chloroalkoxytitanates (IV) of the formula

TiCl _K (OR) ₄ - "

in which κ 1 to 2 and R should be the same or different alkyl radicals with 2 to 8 carbon atoms, polymers with a very narrow molecular weight distribution and interesting application properties are formed, the - ~ ^ - values between 2 to 6 'Mn

lie.

The products obtained in this way have excellent color and corrosion properties and are particularly suitable for the production of injection molded articles.

60

example 1
I. Representation of the supported catalyst

a) 500 g of MgO, which was prepared by annealing of MgCO ₃ at 800 to 900 ⁰ C, are placed in a fluidized bed with hot nitrogen wasserdampfgesättigtem into contact. The MgO is allowed to react with the steam until an increase in weight of 20 g is reached. In this way, Mg (OH) ₂ fixed on MgO is produced.

b) 160 g of the carrier prepared according to I, a) are refluxed for _{8 hours with 1000 ml of an 1 molar TiCl 2} (O - iC ₃ H ₇ ) ₂ solution in cyclohexane with a nitrogen blanket and stirring. The precipitate is then washed by decanting and stirring 10 times with 500 ml of cyclohexane. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 1000 ml.

The titanium content of the suspension is determined colorimetrically with hydrogen peroxide (G. O. Müller, practical course in quantitative chemical analysis, 4th edition [1957], p. 243). 10 ml Suspension contain 3.6 mmol of titanium compound.

II. Polymerization of ethylene

In a boiler-150-1 1001 Diesel oil may be presented with a boiling range from 140 to 200 ⁰ C, the air is displaced by flushing with pure nitrogen and heated the reactor contents to 80 to 85 ⁰ C. A solution of 54 g (400 mmol) of aluminum triethyl in 500 ml of diesel oil and 60 ml of a suspension of the supported catalyst (prepared according to I, b) is then added. The polymerization is carried out at 85 ° C. There are kg of ethylene per hour and so much hydrogen introduced that the hydrogen content in the gas phase is percent by volume. The pressure rises to about 7 atm in the course of the polymerization.

After 7 hours, the resulting polyethylene is separated from the dispersant by filtration and dried. There are 42 kg of polyethylene with a Vspezjc-value = 2.1 (measured in 0, l% igerDekahydronaphthalinlösung at 135 ⁰ C).

Per gram of carrier - produced according to I, a) - about 4 kg of polyethylene are obtained.

It is a polyethylene with a very narrow MoIe-

kular weight distribution (ηττ— = 3.6) obtained. That Polymer also shows excellent color and corrosion values and can be injection molded process well.

45

Mw

In

Values were obtained from the fractionation data

the gel permeation chromatograph Waters (USA.) in 1,2,4-trichlorobenzene as a solvent and determined eluent at 130 ⁰ C.

Example 2
I. Representation of the supported catalyst

a) 500 g of MgO, which was prepared by annealing of _MgCO3 at 800 to 900 ° C, is added with intensive shaking with 25 ml of 2N HNO ₃ was added dropwise.

b) 100 g of the carrier prepared according to I, a) are refluxed for 7 hours with a nitrogen blanket _{and stirring with 1000 ml of an 1 molar TiCl 2} (O - IC ₃ H ₇ ) _{2 solution in cyclohexane.} The precipitate is then washed by decanting and stirring 10 times with 500 ml of cyclohexane. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 1000 ml.

The titanium content of the suspension is determined colorimetrically with hydrogen peroxide (G. O.

209 522/520

Müller, internship of quantitative chemical Analysis, 4th edition [1957], p. 243). 10 ml of suspension contain 2.8 mmol of titanium compound.

II. Polymerization of ethylene

100 liters of diesel oil with a boiling range of 140 to 200 ° C are placed in a 150-1 boiler and the air is displaced by flushing with pure nitrogen. A solution of 54 g (400 mmol) of aluminum triethyl in 500 ml of diesel oil and 80 ml of suspension of the supported catalyst (prepared according to I, b) is then added. The polymerization is carried out at 85 ° C. 6 kg of ethylene per hour and so much hydrogen are introduced that the hydrogen content in the gas phase is 30 percent by volume. The pressure rises to about 7 atm in the course of the polymerization. After 7 hours, the polyethylene formed is separated off from the dispersant by filtration and dried. About 42 kg of polyethylene with an ηspec. / C value = 1.9 (measured in 0.1% decahydronaphthalene solution at 135 ° C) are obtained.

A polyethylene with a very narrow mole-

weight distribution

= 3.4)

obtain. That

Polymer also shows excellent color and corrosion properties and can be injection molded process well.

'Example 3

(Gas phase polymerization)

I. Representation of the supported catalyst

a) 500 mg of MgO, which was produced by calcining MgCO ₃ at 800 to 900 ° C., is mixed with 40 ml of 3N hydrobromic acid with vigorous shaking.

b) 150 g of the carrier prepared according to I, a) are refluxed for 10 hours under a nitrogen blanket _{and stirring with 1500 ml of a 1} molar TiCl 2 (O - IC ₃ H ₇ ) _{2 solution in cyclohexane.} The precipitate is then washed by decanting and stirring 10 times with 500 ml of cyclohexane. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 1500 ml.

The titanium content of the suspension is colorimetric. The titanium content of the suspension is colorimetric determined with hydrogen peroxide (G. O. Müller, practical course in quantitative chemisehen Analysis, 4th edition [1957], p. 243). 10 ml of suspension contain 3.4 mmol of titanium compound.

■ II, gas phase polymerization

In a horizontal 10-1 reaction vessel with a wall-mounted stirrer, 500 g of polyethylene fyspec./c value = 1.8; Bulk density 430g / l). The reaction vessel is freed from air by evacuating it several times and rinsing it with an ethylene-hydrogen mixture for several hours and then heated to 83 ° C. _{5.7 gAl (C 2} H ₆ ) ₃ (50 mmol) and 12 ml suspension of the supported catalyst (prepared according to 3.1, b) are placed in the reaction vessel.

There are 400 g of ethylene per hour and so much Hydrogen initiated that the hydrogen content in the gas phase during the polymerization is always 20 percent by volume. The pressure increases in the course responding to about 9 at. The approach is terminated after 12 hours. It will be about 5.2 kg of polyethylene with a ^ spgz. / c value = 2.3 (measured in 0.1% strength decahydronaphthalene solution at 135 °).

Example 4

I. Representation of the supported catalyst

a) To a solution of 203 g of MgCl ₂ · 6H ₂ O in 500 ml of water is added 200gy-Al ₂ O ₃ with an average particle size of 50 microns. At 25 ° C., a solution of 80 g of NaOH in 500 ml of water is added dropwise with thorough stirring over the course of 20 minutes.

The precipitate is centrifuged and washed by decantation.

_{The Mg (OH) 2} fixed on aluminum oxide is then dried at 230 ° C. for 25 hours.

b) 80 g of the carrier prepared according to 4.1, a) are refluxed for 12 hours with a nitrogen blanket _{and stirring with 500 ml of a molar TiCl 2} (O - IC ₃ H ₇ ) _{2 solution in cyclohexane.} The precipitate is then washed by decanting and stirring 10 times with 500 ml of cyclohexane. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 500 ml.

The titanium content of the suspension is determined colorimetrically with hydrogen peroxide (G. O. M ü 1 Ie r, practical course in quantitative chemical analysis, 4th edition [1957], p. 243). 10 ml Suspension contain 3.6 mmol of titanium compound.

II. Polymerization of ethylene

In a 150-1 boiler, 1001 diesel oil are added submitted to a boiling range of 140 to 200 ° C, displaced the air by purging with pure nitrogen and the boiler contents are heated to 80 to 85 ° C. Then a solution of 54 g (400 mmol) of aluminum triethyl in 500 ml of diesel oil and 80 ml of suspension of the supported catalyst (prepared according to I, b) are added. the Polymerization is carried out at 85 ° C. Kg ethylene per hour and so much hydrogen are introduced that the hydrogen content in the gas phase is 30 percent by volume. The pressure increases in the course of the Polymerization to about 7 at. After 7 hours, the resulting polyethylene is filtered off from Separated dispersant and dried. There are kg of polyethylene with a ^ ez. / C value = 1.7 (measured obtained in 0.1% strength decahydronaphthalene solution at 135 ° C).

A polyethylene with a very narrow molecular weight distribution [-TT - = 3.7J is obtained. The polymer also shows excellent color and corrosion properties and can be processed well by injection molding.

Example5
I. Representation of the supported catalyst

a) 200 g of silica gel with an average particle size of 40 microns are added to a solution of 246.5 g of MgSO ₄ · 7H _{2 O in 500 ml of water.} At 25 °, a solution of 55 g of Na ₂ CO ₃ and 40 g of NaOH in 250 ml of water is added dropwise with thorough stirring over the course of 20 minutes. The precipitate is centrifuged and poured through

Washed decant. Subsequently, the immobilized on silica gel hydroxyl-containing magnesium compound at 23O ⁰ C was dried 25 hours.

b) 50 g of the carrier prepared according to I, a) are refluxed for 8 hours under a _{nitrogen blanket and stirring with 300 ml of an imolar solution of TiCl 2} (O - iC ₃ H ₇ ) _{2 in cyclohexane.} The precipitate is then washed by decanting and stirring 10 times with 300 ml of cyclohexane each time. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 300 ml.

The titanium content of the suspension is determined colorimetrically with hydrogen peroxide. 10 ml Suspension contain 2.8 mmol of titanium compound.

II. Copolymerization of ethylene-butene

In a boiler-150-1 1001 Diesel oil may be presented with a boiling range of 140 to 200 ° C, the air is displaced by flushing with pure nitrogen and heated the reactor contents to 80 to 85 ⁰ C. A solution of 79.2 g (400 mmol) of aluminum triisobutyl in 500 ml of diesel oil and 90 ml of a suspension of the supported catalyst (prepared according to 5.1, b) is then added. The polymerization is carried out at 85 ° C. 6 kg of ethylene and 180 g of butene- (l) per hour and so much hydrogen are introduced that the hydrogen content in the gas phase is 20 percent by volume. The pressure rises to about 7 atm in the course of the polymerization. After 7 hours, the resulting ethylene-butene copolymer is separated off from the dispersant by filtration and dried. There are about 43 kg of an ethylene-butene interpolymer with a ^ spec. / C value = 2.6 (measured in o, l ° / _O Dekahydronaphthalinlösung strength at 135 ° C) and a density of 0.932 g · cm ^"3 The product shows excellent color and corrosion values.

40 Example 6

I. Representation of the supported catalyst

a) 200 g of talc are added to a solution of 203 g of MgCl ₂ —OH _{2 O in 500 ml of water.} At 25 ° C., a solution of 80 g of NaOH in 500 ml of water is added dropwise with stirring over the course of 20 minutes. The precipitate is centrifuged and washed by decantation. Subsequently, the fixed onto talc Mg (OH) ₂ at 23O ⁰ C for 30 hours.

b) 50 g of the compound obtained under I, a) are refluxed for 12 hours with a nitrogen blanket _{and stirring with 500 ml of an 1 molar TiCl 2} (O - iC ₃ H ₇ ) _{3 solution in cyclohexane.} The precipitate is then washed by decanting and stirring 10 times with 250 ml of cyclohexane each time. The cyclohexane above the solid should be free of titanium compounds. The volume of the suspension is made up to 500 ml.

The titanium content of the suspension is determined colorimetrically with hydrogen peroxide. 10 ml Suspension contain 3.1 mmol of titanium compound.

c) Implementation of the supported catalyst with ethylaluminum sesquichloride.

_{A solution of 50 mmol of Al 2} (C ₂ Hs) ₃ Cl ₃ (= 12.4 g) in 250 ml of diesel oil is added to 100 ml of the supported catalyst suspension prepared under I, b) with the exclusion of air and moisture at 0 ° C. within added dropwise 2 hours and then stirred for 2 hours at 2O ⁰ C. A blue-black precipitate forms, which is washed out 4 times with 300 ml of diesel oil each time. The volume of the suspension is made up to 100 ml.

II. Polymerization of ethylene-propylene

In a boiler-150-1 1001 Diesel oil may be presented with a boiling range from 140 to 200 ⁰ C, the air is displaced by flushing with pure nitrogen and the reactor contents heated to 80 to 85 ° C. A solution of 54 g (400 mmol) of aluminum triethyl in 500 ml of diesel oil and 40 ml of suspension of the reduced supported catalyst (prepared according to I, c) is then added. The polymerization is carried out at 85 ⁰ C. There are 6 kg of ethylene and 150 g of propylene per hour and so much hydrogen introduced that the hydrogen content in the gas phase is 20 percent by volume.

The pressure rises to about 7 atm in the course of the polymerization.

After 7 hours, the resulting copolymer is separated off from the dispersant by filtration and dried. There are about 43 kg of an ethylene-propylene interpolymer with a Vspezjc value of 3.5 (measured in o, l% ig ^e r Dekahydronaphthalinlösung at 135 ⁰ C) and a density of 0.935 g ^cm-3 obtained.

The product shows excellent color and corrosion values.

Claims (6)

pe of the periodic table mixed with metallorga patent claims: niche compounds of the elements of I. to III. Main group of the periodic table and works in 1. Process for the polymerization of ethylene generally in suspension, in solution or in or of mixtures of ethylene with up to 5 of the gas phase. 10 percent by weight of a-olefins of the general There are also known processes in which the Formula R - CH = CH ₂ , in which R is a branched catalyst component in connection with one or unbranched hydrocarbon radical with 1 to carrier substance are used. 13 carbon atoms means in suspension. B. according to the procedure of the French or in the gas phase at temperatures from 20 to io sischen patent 1198 422 the compounds of 120 ° C and at pressures up to 20 at in the presence of IV. To VI. Subgroup of the periodic table with of mixed catalysts from (a) a solid titanium carrier such as bentonite, pumice stone, kieselguhr, calcium-containing Reaction product that is treated using phosphate or silica and then a magnesium compound containing hydroxyl groups is reduced with organoaluminum compounds, manure and a halogen-containing titanium compound 15 In this process, however, the polymerization takes place has been produced, and (b) an aluminum-independent of the composition of the organic carrier Connection, if necessary under materials; therefore only the regulation is of importance of the molecular weight by hydrogen, composition of the catalysis fixed on the carrier by this marked that one sators. The main disadvantage is that for further profit Polymerization in the presence of a mixed catalyst processing of the polymers a catalyst and lysators, whose component (a) is inevitable due to carrier removal. Implementation of fixed on carrier solids, In several other patents, however, hydroxyl-containing magnesium compounds highlighted that a certain composition with tetravalent titanium compounds, the halogen and nature of the carrier is required to atoms and alkoxy or aralkoxy groups to achieve sufficient activity, hold, was established. According to the documents laid out by the 2. The method according to claim 1, characterized in Belgian patent 609 261 alkaline earth phosphates recorded that as fixed on the carrier solids, the magnesium compound before the reaction with titanium or hydroxyl group-containing magnesium compound in vanadium compounds but only to 200 to 1000 ° C of the production Component (a) Mg (OH) ₂ must be heated so that sufficient activity has been used. vity for a polymerization is achieved. In doing so, 3. The method according to claim 1, characterized in that only very low polymer yields are obtained, that th as a carrier solid in the manufacture. 4 component (a) MgO has been used. In the documents accompanying the Belgian patent 4. The method according to claim 1, characterized in 35 650 679 and French patent specification 1 448 320 draws that in the manufacture of the component are hydroxychlorides of divalent metals (A) as halogen and alkoxy groups or aral general formula Me (OH) Cl, preferably Titanium compounds containing koxy groups, halogen-Mg (OH) Cl, as a carrier for Ziegler catalysts, titanium acid esters of the general formula. When implementing the carrier with the TiX (OR) ⁴ ° transition metal component should be a chemical ⁴ ~ ™ reaction take place, e.g. B. have been used, where η = 1 to 3, X = Cl or Br and R are identical or different _{carbons - Cl - Mg - OH + TiCl 4} -> ClMg - O-TiCl _{3 are} hydrogen radicals with 1 to 18 carbon atoms. 45 Higher polymerization yields are only 5. The method according to claim 1, characterized in that achieved when working at pressures of about 20 atü records that the component is manufactured. A further disadvantage is the rather cumbersome (a) the implementation of the method of manufacture of the magnesium compound containing hydroxyl groups, which is fixed on the solid, by very careful step-by-step dehydration of the titanium compound at temperatures of 50 MgCl ₂ · 6H ₂ O at 285 ° C and also the re-0 to 200 ⁰ C has been made. relatively high chlorine content of the carrier. 6. The method according to claim 1, characterized in that, in the production of the component 1 214 653, a method for the production of support a) the fixed on the support solid, hydroxyl catalysts have become known, after which one on group-containing magnesium compounds before the 55 pyrogenic metal or metalloid oxides, preferably reaction with the titanium compound with inert, pyrogenic alumina, pyrogenic titanium dioxide or pyrolyzation non-inhibiting metal genes Silica, which act as carriers and their oxides, hydroxides, halides, sulfates , -car surfaces contain hydroxyl groups, certain carbonates, phosphates or silicates have been converted into heavy metal compounds of the metals in the groups. 60 IVa ₃ Va, Via, VIIa and VIII of the Periodic Table can act. The average particle size - ■ the carrier material must be smaller than about 0.1 Mi be kron, and in addition, the hydroxyl group concentration should be so large that the hydroxyl groups It is known that implement a-olefins and their micro 65 with at least 1 x 10 ~ ⁴ equivalents of convexities over by the Ziegler low-pressure process transition metal per gram of the carrier, can polymerize. The catalysts used are but the polymerization yields are even at Compounds of the elements of IV. To VI. Subgroup pressures of 190 atmospheres are so low that a subsequent