DE2352154A1 - PROCESS FOR THE POLYMERIZATION OF ALPHAOLEFINS - Google Patents

Description

Process for the polymerization of alpha-olefins

The invention relates to an improved process for low pressure polymerization of olefins.

It is already known for the low pressure polymerization of Olefins catalytic ^ systems to use, which are a transition metal compound and an organometallic compound.

It is also known to use the transition metal compound on oxide supports with a large pore volume, such as Belgian aluminum oxides Applicant's patent 768,271 - and halogenated Aluminum oxides - Belgian patent 775 227 of the applicant - to bind.

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ORIGINAL INSPECTED

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The catalytic systems obtained in this way are very active when compared with those in which the transition metal compound is used as such. They lead to polymers, which are characterized by a broad Characteristic molecular weight distribution and which are free of long-chain branches, which makes them particularly too be suitable for further processing by blow molding.

However, these previously known catalytic systems have a significant disadvantage. You will mostly be at Polymerization process of olefins applied, which in the presence of a molecular weight regulator, which is almost exclusively Is hydrogen. These systems have also been found to catalyze the hydrogenation of olefins. A non-negligible part of the olefin to be polymerized is therefore in the corresponding, saturated Hydrocarbon converted, whereby the economics of the process is jeopardized. On the other hand, these generate catalytic systems polymers with a very high average molecular weight. To reduce this average molecular weight one is therefore forced to increase the hydrogen concentration in the polymerization medium and / or the polymerization to be carried out at a higher temperature. However, these two measures have the detrimental consequence that the degree of hydrogenation of the olefin to be polymerized is further increased.

The object of the invention is an improved process for low-pressure polymerization of olefins, which does not have these disadvantages.

It has now been found that the use of a new, improved type of catalytic complexes overcomes the disadvantages associated with the use of the prior art catalytic systems

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are connected, and in particular avoids hydrogenation, however, it is possible to use a broad range of olefin polymers Produce molecular weight distribution with even better activity, whose average molecular weight is regulated more easily can be.

The inventive method for solving this problem, namely for Kxederdruckpolymerisierung of alpha-olefins, carried out in the presence of a catalytic system, which is an organometallic compound of a metal of groups Ia, Ha, lib, IHb and IVb of the periodic table and a solid, catalytic Contains complex, is characterized in that the solid, catalytic ^ complex was produced by a Compound of a metal of groups IVa, Va and VIa of the periodic table with a porous aluminum oxide on which when an oxygen-containing or halogenated compound is deposited as the magnesium compound, was allowed to react.

The solid, catalytic complexes used in the process according to the invention are coated with a porous aluminum oxide produced as a raw material on which a magnesium compound is deposited.

Porous oxide is to be understood as any oxide which has a substantial internal porosity, ie in which the pore volume represents a substantial proportion of the volume of the particles. The internal porosity is generally characterized by the ratio of the pore volume to the weight of the material. The internal porosity of the oxides which can be used according to the invention, measured by the procedure known under the name BET method, see S. Brunauer, P. Emmett and E. Teller in J. Am. Chem. Soc, 60 (1938), pp. 309-319 - is above 0.3 cm / g and preferably above 0.7 cm / g. Excellent results are obtained with porous oxides whose internal porosity is above Λ cmvg.

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ORIGINAL IMSPECTED

In general, they have within the scope of the present invention used, porous oxides a specific surface above 100 m / g, more often of the order of

200 to 400 πι / g. These specific surface areas are measured according to the BET method described above, using the standardized method described in British Standards BS 4359, Part 1 (1969).

The grain size of the porous oxides used influences the Productivity of the catalyst is not. For reasons of easier handling, however, the use of particles is avoided "preferred, the mean diameter of which is between 1 and 500 microns and preferably between 40 and 200 microns. The morphology of the polymer and its flowability are, however, improved if porous oxides with regular particle shapes are used and a narrow grain size distribution is used. Excellent results are obtained with porous oxides, their average Particle diameter is close to 100 microns and whose diameter distribution is narrow «

Me exact chemical structure and manufacturing method of the Porous oxides used in accordance with the invention are not critical provided they contain aluminum, the is bound to oxygen in its molecule. This porous Cxids are among the simple aluminum oxides and the ItOiH) I exen oxides of aluminum and at least one other Metal selected »

Me aluminum oxides can be produced by all known methods, examples are;
- aur-ch pyrolysis of aluminum oxides, aluminum hydroxides

o & sr aluminum salts fcei elevated temperature;

<= ■ by precipitation voa. soluble aluminum salt dissolved in water. / Ji3 the helper and dsm chloride in the presence of an alkaline Te2 * bi3icLu2ig "sris ammonia _s as well as pyrolysis of the so

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iHAL IhSPcCTED

_ = 5 -

Aluminum oxides which are particularly suitable for carrying out the process according to the invention are the activated aluminum oxides which have been produced by pyrolysis of aluminum oxide hydrates at elevated temperature, see Belgian patent specification 768 271 of the applicant. Excellent results are obtained with activated aluminas having an internal porosity greater than 1 cm7g and out of the alpha-monohydrate by heating at 700 - 800 were prepared ⁰ C for 4 to 24 hours, "

The complex oxides used according to the invention are natural or synthetic complex oxides of aluminum and any one or more metals, which are generally composed of metals from groups Ia, Ib ₉ Ha ₁ Hb, IHb, IVa, ITb, Ta ₉ Tb ₉ TIa, VIIa and Till of the periodic table, preferably from lithium, sodium, potassium, magnesium ₉ calcium, barium, zinc, manganese, strontium, iron, nickel, cobalt, tin and silicon. Particularly preferred are the aluminum silicates % z _e B ₀ sillimanite Al ₀ O _x “SiO ₀ and mullite

2 5 2

aluminates and the silico-aluminates of lithium, potassium and sodium, for example, _e Eukriptit LIPQ. Al ₀ O ₅ ,, 2SiO ₂ , hepheline Wa ₂ O ₄₁ AlpO 2SiO ₂ and leucite K ₂ O ₀ Al ₂ O ₅₀ ^ SiO ₂ J

the aluminates and silico-aluminates of magnesium and calcium z _o B * spinel MgO ₀ Al ₂ O ₅ and anornite CaO ₀ Al ₂ O ₅ .2SiO ₂ ; the aluminates and silico-aluminates of strontium, barium, and zinc; z. B. Automolit

The synthetic, complex oxides can be produced by known methods. For example, this results in mixed precipitation working technique always gives satisfactory results. It consists in the soluble salts of aluminum and the dissolve other metals in solution in water in amounts that the soaked ratio for the complex oxide

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ir », the solution is reached» As soluble salts one uses usually the nitrates, chlorides and acetates. “Then an alkaline substance such as ammonia or sodium carbonate in aqueous solution is gradually added to the solution. In this way, the formation of a solid bodice is brought about, which after the pyrolysis, finally, according to the invention usable complex oxides results in »

Complex oxides which are particularly suitable for carrying out the process according to the invention are those in which the amount of aluminum is such that the ratio between this amount and the total amount of the other metals present, expressed in at-g / at-g, is generally between 0 , 1 and 10 and preferably between 0.25 and 5 «, Excellent results are obtained with complex oxides of aluminum and Hagnesiam with an internal porosity above 1 cin-Vg, the ratio of which, as defined above, is approximately 2 and the general formula MgOeAl ₂ O-, corresponds to «,

All oxides described above, porous can advantageously a Halogenierimgsbehandlung prior to deposition of Kagnesiumhalogenverbindung "out among the detail in Belgian Patent 773,227 described by the applicant conditions This Halogenierungsbehandjung improves the productivity of the catalysts produced from the porous oxides according to the invention _o is _f is the porous aluminas exposure to subject a EaIοgenierungsrnittels. The latter is preferably a fluorinating agent. It is preferably selected from solid compounds which can be decomposed into volatile products without leaving a residue, such as, for. B. Ammonium fluoride This treatment can be carried out so that the halogenated aluminum oxides or aluminum oxide complexes obtained have a halogen / aluminum atomic ratio between 0.01 and 1. The best. Results are obtained when this ratio is .06 to .30 and more preferably between 0 and 10 _t 0.15.

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ORIGINAL INSPECTED

Di-e-porous aluminas can target their Inb eriihrungbr ing en with the magnesium compound is advantageously a thermal treatment are subjected, especially when their production xrorden not completed by a pyrolysis is "Such a treatment preferably at a temperature between 100 and 1000 ⁰ C ₅ ■ between 300 and 800 ⁰ C carried out. In the case of porous oxides which have been subjected to a halogenation treatment, such a thermal treatment can be combined with or followed by the halogenation treatment *. It is therefore carried out under such conditions that one. Obtained porous oxides, which have the atomic ratio halogen / aluminum given above = The pressure under which such a treatment is carried out and the atmosphere in which one works are not critical = For the sake of simplicity, however, it is preferred, under atmospheric pressure and to work in an inert atmosphere »The duration of the thermal treatment is also not critical and is generally between 1 and 24 hours»

According to the invention, the porous aluminum oxides described above be treated with a magnesium compound in such a way that a deposition of this compound on the surface of the porous oxide is produced »

Magnesium compounds are to be understood as meaning all oxygen-containing compounds and all halogenated compounds of this metal, that is _, all magnesium compounds that have at least one magnesium-oxygen bond or at least one magnesium-halogen bond in their molecule ".

A first class of those suitable for performing the method Magnesium compounds itfird through the magnesium compounds formed, which xif at least a magnesium-oxygen bond exhibit*.

It can be oxygenated, inorganic magnesium compounds act, in the molecule of which the magnesium is only oxygen

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INSPECTED

23b2 1

is bound. These include:

- the hydroxide Mg (OH) ₂ ;

- the salts of inorganic oxy acids: e.g. E.g., MgCO 1, MgSO ₄ , Mg (NO ₃ ) ₂ , Mg ₂ (PO ₄ ) ₃ , Mg ₃ (BO ₃ ) _2, and Mg (ClO ₄ ) ₂ ;

- basic, optionally hydrated magnesium salts: e.g. B. 4MgC0 .MG _z (OH) ₀ O ₀ .5H and 3MgCO _x Mg (OH) ₅ .3H ₉ O;

^ / cL C- J ^ C-

- basic, optionally hydrated salts of magnesium and another metal: z. B.

It can also be organic, oxygen-containing compounds of magnesium, i. H. Connections, which any, have organic residues bound to the magnesium via oxygen.

The organic ones bound to the magnesium via oxygen Leftovers can be anything.

They are preferably selected from radicals which 1 to Carbon atoms and especially 1 to 6 carbon atoms own. These radicals can be saturated or unsaturated, straight-chain, branched or cyclic. Also can they can be substituted and / or have heteroatoms such as 0, S, N, P etc. in their chain. Preferably they are made from hydrocarbon radicals and in particular of alkyl, alkenyl, aryl, cycloalkyl, arylalkyl, alkylaryl, acyl radicals and their substituted derivatives selected.

Such compounds can be named:

- Magnesium alkoxides such as B. the methylate, ethylate, isopropylate, Decanolate, cyclohexanolate and benzylate;

- Magnesium phenoxides such as B. the phenolate, uaphthenate, anthracenate, Phenantrenate and cresolate

- optionally hydrated magnesium carboxylates such as e.g. B. the acetate, stearate, benzoate, phenyl acetate, adipate, sebacate, Phthalate, acrylate or oleate j

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- »organic magnesium compounds containing oxygen and nitrogen, d. H. Compounds which bond sequences magnesium-oxygen-nitrogen-organic Contain the remainder like the oximate, in particular the butyloximate, dimethylglyoximate, Cyclohexyloximate, hydroxamic acid salts and hydroxylamine salts, in particular the derivative of H-nitroso-IT-pheny / hydroxylamine;

- magnesium chelates, d. H. oxygen-containing organic compounds, in which the magnesium has at least one normal bond sequence of the magnesium-oxygen-organic radical type and has at least one coordination bond such that a heterocyclic radical is formed in which the Magnesium is included, such as. B. the enolates and especially acetylacetonate and the complexes, which from Phenol derivatives, which have an electron donating group in of the ortho position based on the hydroxyl radical, and in particular the 8-hydroxyquinoline derivative.

Of course, this series also includes the following organic, oxygen-containing compounds;

- Compounds5 which have several different organic residues, such as z «, B _e magnesium methoxyethylate;

- alkoxide and Phenoxidkomplexe of magnesium and another metal, such as _e Mg [Al (OR) ₄ I ₂ and Mg ₃ [Al (OR) ₆ J _2;

- Mixtures of two or more, organic, oxygen-containing Magnesium compounds according to the definitions given above,

Finally, the oxygen-containing magnesium compounds include the complex compounds, which have several types of residues, which are bound to the magnesium via oxygen.

For example, the oxygen-containing magnesium compounds also optionally organic and inorganic, oxygen-containing Carry leftovers "

They can also include organic residues which are bonded directly to the magnesium via carbon. Among these

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INSPECTED

Connections are ζ. B. Magnesiumhydroxymethylat and Magnesiumäthyläthylat to call.

Among all of the above-mentioned oxygen-containing magnesium compounds becomes the use of organic, oxygen-containing compounds of this metal and in particular of those preferred, which only binding sequences of magnesium-oxygen organic Bear rest. Among the latter compounds, the best results will be with the alkoxides and phenoxides of this metal.

A second class of magnesium compounds which are used to carry out of the method according to the invention are suitable, is formed by magnesium compounds, which at least one Have magnesium-halogen bond. The halogen bound to the magnesium can be fluorine, chlorine, bromine or iodine. Preferably the halogen is chlorine. As such connections can to be named:

- Commercially available magnesium dihalides, which are usually may be referred to as "anhydrous" which, however, are actually hydrated dihalides which are one mole or less Contain water per molecule of dihalide; "Anhydrous, commercially available" magnesium dichlorides are a typical example of such connections!

- Magnesium dihalides, which are complexed with various electron donors, e.g. B. the complexes with ammonia such as MgCl ₂ .6EH ₅ , MgCl ₂ .2HH ₅ and the complexes with alcohols such as MgCl ₂ .6CH ₅ OH, MgCl ₂ ^ C ₂ H ₅ OH and MgCl ₂ ^ C ₅ H ₇ GH;

- hydrated magnesium dihalides which contain more than one molecule of water per molecule of the dihalide, such as e.g. B. MgCl ₂ .6H ₂ O, MgCl ₂ .4H ₂ O and MgCl ₂ .2E ₂ O.

Among the magnesite mire dung belonging to this second class the dihalides are preferred for practicing the invention, with best results with the hydrated »

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ORIGINAL! NSFiCTED

Magnesium dichlorides are obtained. The use of two or more different compounds from the above specified compounds is also within the scope of the invention. A third and final class of magnesium compounds, which is suitable for carrying out the invention is formed by the compounds of this metal, which at the same time Have magnesium-halogen bonds and magnesium-oxygen bonds in their molecule. As examples of such connections can be named:

- Compounds which, in addition to the magnesium-halogen bond, preferably the magnesium-chlorine bond, have an inorganic residue bound to the magnesium via oxygen, such as, for. B. have a hydroxyl radical as in Mg (OH) Cl and Mg (OH) Br;

Compounds which, in addition to the magnesium-halogen bond, preferably the magnesium-chlorine bond, contain any organic radical bonded to the magnesium via oxygen. Such an organic radical is preferably one of the radicals already defined above, the best results with the chloroalkoxides and chlorophenoxides of magnesium such as z.-B. Mg (OCH ₃ ) Cl, Mg (OC ₂ H ₅ ) Cl, and Mg (OC ₆ H ₅ ) Cl, are obtained;

- hydrolysis products of hydrated halides, preferably chlorides, of magnesium, as long as these products still have magnesium-halogen bonds;

- mixed compositions comprising halogenated and oxygenated magnesium compounds. Typical examples of such compositions are the basic halides, preferably the chlorides of magnesium such as MgClp.MgO.HpO, MgCl ₂ .3MgO.7H ₂ O and MgBr ₃ .3MgO.6H ₃ O.

Finally, it should be noted that the use of two or more connections which lead to one of the three above Classes listed belong, also within the scope of the invention.

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ORIGINAL INSPECTED

The amount of magnesium compound to be deposited on the porous alumina is an essential feature of the invention. Expressed in the weight of the magnesium, based on the surface of the porous oxide, it must be between 10 "" and 10 "" mat-g (milliatomgrams) of this metal per m specific surface (BET) of the porous oxide 1.10 and 5.10 ^J mat-g Mg / m of the specific surface.

The results are within the limits given above optimal. However, it has been observed that the optimum amount of the magnesium compound is weak depending on the kind of Connection varies.

The best results are obtained with porous oxides, which have a specific surface between 200 and 4-00 m / g "own on which have been deposited:

- from 1.10 "to 2.5 · 10 ^J mat-g Mg / m of the specific surface area of an organic, oxygen-containing magnesium compound, which only has a magnesium-oxygen-organic residue in its molecule;

- from 2.10 "· ^ to 4.10" - 'mat-g Mg / m' "on a specific surface of a magnesium compound which has at least one bond Has magnesium-halogen and no magnesium-oxygen bond in its molecule.

The deposition of the magnesium compound on the surface of the porous aluminum oxide can be carried out in any known manner Method to be carried out »In particular, the required amount of magnetic core compound can be deposited on the porous oxide will:

= - in the form of solids, e.g. B, in suspension in an inert Diluents;

- is the form of steam or gas;

= in a liquid medium, be it in the form of a solution in water or in an organic solvent that is capable of dissolving the magnesium compound, be it in the presence of an oxygen-containing organic compound (H) _? as

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is defined in more detail below.

The temperature "at which the deposition of the magnesium compound performed on the porous alumina is not critical. Preference is given to "at one temperature worked below the decomposition temperature of the magnesium compound »In the case of the use of the magnesium compound in In the form of a solution, one usually works in the vicinity of the temperature, which is the maximum solubility of the magnesium compound is equivalent to. The pressure is also not essential; generally one works in the vicinity of atmospheric pressure.

It is preferred to use the magnesium compound in a liquid medium. It has surprisingly been found that in the Deposition of the magnesium compound on the porous oxide according to this method always contains part of this compound chemically remains irreversibly bound to the porous aluminum oxide. This bond is practically quantitative, if the one used Amount of magnesium compound, expressed in terms of weight

Metal, below 5 »10 ^ mat-g Mg / m at specific surface of the porous oxide.

The use of the magnesium compound in a liquid medium can be carried out according to several methods, with further details being described below «,

A first mode of operation is to use the magnesium compound in the form of a solution in a solvent, which Is water or an organic diluent due to dissolve the magnesium compound. All usually in the Organic chemistry applied diluents can be used. However, the alkanes and cycloalkanes are preferably used, whose molecule contains 4 to 20 carbon atoms ^ z. B. Isobutane, n-pentane, pentamethylpentane, η-hexane, n-heptane,

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Cyplohexane, methylcyclohexane and the dodecanes. Also can you use alcohols whose molecule has 1 to 12 carbon atoms per hydroxyl radical, such as methanol, ethanol, butanol, Decanol and cyclohexanol, as well as a mixture of the aforementioned alcohols, alkanes and Gyelοalkanes »

It is also possible to use solvents which have a strong ability to form complexes, such as. B. tetrahydrofuran. The magnesium dihalides are used in the form of an aqueous solution preferred.

A particularly simple way of bringing about the deposition of the magnesium compound on the porous aluminum oxide accordingly this procedure consists in treating the oxide with the aid of a volume of the solution so that the mixture has the properties of a powder, this volume containing an amount of magnesium compound which is at least the The amount that can be chemically fixed or bonded to the oxide is equal to that of the contact, preferably at ambient temperature and maintained while moving for a period of time is generally varied between about 1 minute and 1 hour. The excess, if any can using a solvent for the magnesium compound removed. As such a solvent, it is preferable to select a solvent which is the same as that used to perform the impregnation or impregnation of the porous aluminum oxide used is identical.

Make the deposition of the magnesium compound on the porous Alumina after this procedure, the solid obtained in this way is generally subjected to an activation treatment, whereby the removal of the solvent is easily possible. Such activation treatment is general essential if the solvent used was water.

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Preferably it is "at a temperature below the Decomposition temperature of the magnesium compound carried out, however, this condition is by no means essential, and one Decomposition of the magnesium compound is harmless to the properties of the catalyst, "as long as the magnesium content of the porous oxide remains within the limits given above »The other operating conditions of the activation treatments are 'depending on the type of used Solvent selected, and they are generally the same as the above-described thermal Treatment.

For certain magnesium compounds which are insoluble in water or in one of the above-mentioned organic diluents, it is also possible to use them in a liquid medium in accordance with a two-fold procedure, with an oxygen-containing, organic compound (M) of a metal from groups Ia, Hb, HIb , IVa ,. IVb ₉ Va, Via, VIIa and VIII of the Periodic Table, optionally in the presence of a diluent, are mixed _o This definition of an oxygen-containing organic compound (M) is understood to mean all compounds in which an organic radical is bonded to the metal via oxygen is «, compounds which also contain metal-oxygen bonds and condensed compounds which have" metal-oxygen-metal bond sequences can also be used, provided they also have at least one metal-oxygen-organic radical bond sequence per molecule "

The organic bound to the metal via the oxygen Residues can be any radicals »They preferably x-ize selected from the same radicals, which is possible in the composition of the oxygen-containing, organic magnesium compounds are, and preferably from hydrocarbon radicals and especially

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preferably from straight-chain or branched alkyl radicals, Cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups.

As metals of the aforementioned groups, for. B. can be named: lithium, sodium, potassium, zinc, boron, aluminum, Silicon, tin, titanium, zirconium, vanadium, chromium, manganese, Iron, cobalt and nickel, but the use of oxygen-containing organic compounds of aluminum, silicon, Titanium, zirconium, vanadium and chromium are preferred. The best results will be with oxygenated, organic titanium compounds obtain.

These oxygen-containing, organic compounds (M) can be represented by the general formula freO (OR) 1 , in which (Me) is a metal from the above-mentioned groups, E is an organic Eest, as defined above, χ and y any number from χ > _ 0 and y> O ₅ which are compatible with the valence of the metal (Me), and m is an integer. The use of oxygen-containing, organic compounds (M) in which zz 0 <χ < 1 and m Λ <_ m <_ 6 is preferred. As oxygen-containing, organic compounds (M), which are intended to come into contact with the magnesium compound, the following can be mentioned:

- Alkoxides like Li (OiC ₃ H ₇ ), Al (OiC ₅ H ₇ ) ^ ₅ B (OiC ₅ H ₇ ) SiCOC ^) ^, Ti (OiC ₅ H ₇ ) ₄ , Ti (OiC ₄ H _g ) ₄ , V (OiC ₃ H _? ) ₄ and ZrCOiC ^) ^;

- phenoxides such as Ti (OC ₆ H ₅ ) ^;

- oxyalkoxides such as VO (OiC ₅ H ₇ );

- Condensed alkoxides such as TIpO (OiC ^ H ₇ ), -;

- Snolates such as titanium acetylacetonate.

The use of oxygen-containing organic compounds (M) ₅ which contain several different organic radicals is also within the scope of the invention. The same applies to the use of several different, oxygen-containing,

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ORJGiN INSPECTED

235 15A

organic compounds of one and the same metal and the use of several oxygen-containing organic compounds different metals.

The working conditions for the mixture of the magnesium compound with the oxygen-containing organic compound (M) can be selected depending on the physical state of each of these compounds so that a liquid Mixture or solution is formed whose magnesium concentration sufficient to deposit the desired amount of magnesium on the surface of the porous alumina. At the Working in the absence of a diluent, the temperature and pressure conditions are selected so that at least one of the compounds and preferably the oxygen-containing, organic compound (M) is liquid. Often such a compound can be kept in a liquid state will dissolve the magnesium compound. A second oxygen-containing organic compound (M) can also be used, which is liquid and able to dissolve the magnesium compound.

Nevertheless, it can happen that the oxygen-containing, organic Compound (M) decomposes by heating, so that the mixture of this compound and the magnesium compound passes through Cooling becomes solid or that one does not have any of these compounds can use in the liquid state. In this case, however, the deposition of the magnesium compound on the porous Bring oxide in liquid medium using a diluent, which is preferably from among the above mentioned, organic diluents is selected and for at least partial dissolution of the oxygen-containing, organic compound (M) or the product of its mixture with the magnesium compound is capable.

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The use of such a diluent for this purpose represents the preferred embodiment of the use of the magnesium compound according to this second procedure. It should be pointed out that this second procedure, and in particular the variant described above, generally applies to the majority of the water-soluble magnesium compounds and is particularly applicable to the dihalides of this metal. It has the essential advantage that in this case the level of activation mentioned in the description of the first mode of operation is suppressed. When preparing the deposit of the magnesium compound on the surface of the porous alumina according to this second embodiment or procedure, the amount of oxygen-containing organic compound (M), which is liquid or dissolved in the diluent, must at least ensure the dissolution of the required amount Magnesium compound is sufficient. In general, the respective amounts of these compounds to be used are such that the atomic ratio between the metal (Me) of the oxygen-containing organic compound and the magnesium is between 0.5 "and 1GQ at-g / at-g and preferably between 0.5 and 2 at-g / at-g varies. When using the variant of this second procedure, which consists in adding "a diluent to the oxygen-containing organic compound (M) or to the mixture of this compound with the magnesium compound, it is preferred when the total concentration of the dissolved compound or compounds is above 5% by weight and preferably above 20% by weight, based on the diluent. The other conditions for the preparation of the solution or the liquid mixture are not critical. For reasons of simplicity, it is ^{preferred to work between 20 and 300 °} C. and preferably between 50 and 200 ^° C. and at approximately atmospheric pressure. The liquid mixture or the solution can be homogenized by stirring.

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A very simple way of precipitating the magnesium compound To get on the porous alumina according to this second embodiment is to first use a Solution of the mixture of magnesium compound and oxygen-containing organic compound (M) in the diluent manufacture and the porous oxide with a fixed volume of this solution according to the description of the first Embodiment mentioned method to treat Also can the porous oxide be converted into suspension in this solution, maintaining contact between the oxide and the solution under the conditions mentioned above, the excess the solution z, B «, remove by filtration or decanting and win the thus obtained solid, which then as such in the continuation of the production of the invention catalytic complexes is used »

As one of the essential characteristics of the porous Aluminum03ri.de, it is necessary to produce the catalytic complexes according to the Invention used, which lies in their surface content of magnesium, must be the chemical reactions whose Mechanism is not yet known, not considered xferden, which between the magnesium compound and the oxygen-containing, organic compound (M) in the preparation of the molten mixture or the solution, with the aid thereof the deposition of the magnesium compound on the porous oxide can occur =

The last stage of the production of the solid, catalytic Complex according to the invention consists in the porous Aluainium-

-, -,. »" ·, ·,, Is deposited, oxide, on which the magnesium compound / «- welcSe in the following referred to as "solid" - with a compound one. Metal of groups IVa, Va lader VIa of the periodic table x-jelches hereinafter referred to as transition metal. This latter connection is preferred

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ORiGiNAL INSPECTED

selected from compounds of titanium, zirconium, vanadium and chromium. When the solid is with the assistance of an oxygen containing organic compound (M) whose metal (Me) belongs to one of the groups IVa, Va or VIa, a transition metal compound is preferably selected, whose metal is identical to the metal (Me). The best results are obtained with titanium compounds.

As the compounds, halides, oxyhalides, alkoxyhalides, oxyalkoxides and alkoxides can be used. When using ha Io, we use brominated and chlorinated compounds such as TiCl ₄ , TiBr ₄ , VCl ₄ , VOCl-, VOBr ₅ , CrO ₂ Cl ₂ , Ti (OC ₂ H ₅ ) jCl, Ti (OiC ₃ H ₇ ) ^ Cl, Ti (OC ₂ H ₅ ) ₂ C1 ₂ , Ti (OiCJIr ₇ ) Cl ^ and ZrOCl _{2 are} preferred. When using compounds containing alkoxide radicals, these are preferably selected from compounds whose straight-chain or branched alkoxide radicals each have 1 to 20 carbon atoms and particularly preferably 1 to 10 carbon atoms each, such as Ti (OiC ₄ HQ) ₄ , Ti (OiC ₃ H ₇ ) ₅ C1 and VO (OiC ₃ H ₇ ) ₃ . It is also possible to use condensed alkoxides such as Ti ₂ O (OiC ^ H ₇ ) ^.

If the magnesium compound used to prepare the solid belongs to the class of compounds of this metal which have at least one magnesium-oxygen bond and no magnesium-halogen bond in their molecule, the use of halogenated transition metal compounds is preferred. In all of these cases the best results are obtained with TiCl ₄ . The use of several different transition metal compounds is also within the scope of the invention.

The transition metal compound is preferably selected in such a way that that they are in the form of vapor or gas, optionally diluted with an inert gas, in liquid form or in the form of a solution

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is used. The solvents used are generally those customarily used in the low-pressure polymerization of olefins used diluent. However, it is preferred to mix the solid directly with a large amount of the pure, in liquid To bring the maintained transition metal compound into contact, e.g. B. by simply transferring it into suspension. The reaction can also be brought about by adding the pest with the transition metal compound, if it is liquid under the reaction conditions, washes, or else by the Solid with successive fresh batches of the transition metal compound in a continuously operating extraction apparatus of the Soxhlet or Eumayawa type in Eontakt is brought. This latter working technique is particularly recommended when the solid is according to the preferred Variant of the previously described second embodiment or mode of operation has been produced.

The temperature at which the reaction is carried out is not critical. In general, one works between 0 and 300 ^° C. When working at atmospheric pressure, the temperature is selected between the ambient temperature and the normal boiling point of the transition metal compound. It is therefore preferable to work between 20 and 140 C.

Contact with the transition metal compound is maintained for a period of time sufficient to allow a chemical bonding or fixation of the transition metal compound on the solid takes place. Generally one will Binding or fixation achieved after 30 minutes to 1 hour.

After the reaction, the catalytic complex obtained can with the same transition metal compound that was used for the reaction. In general, it will then washed with the aid of an inert hydrocarbon solvent

409824/0959

ORIGINAL INSPECTED

235 7 15 4

such as isobutane, n-pentane, n-kexane, cyclohexane and the Dodecanese, in order to remove the excess of transition metal compound which is not chemically fixed on the support. at a transition metal content is measured before the elemental analysis of the catalytic complex treated in this way is carried out, which is generally above 10 g / kg and very often is above 15 g / kg, as well as a magnesium content that is equal to or slightly below the magnesium content of the solid that is used to produce the catalytic complex was used.

The catalytic systems according to the invention also comprise an organometallic compound of a metal from groups Ia, Ha, Hb, IHb and IVb of the periodic table such as organometallic compounds of lithium, magnesium, zinc, aluminum or tin. The best results are obtained with organoaluminum compounds ".

Completely alkylated compounds can be used, the alkyl chains of which contain 1 to 20 carbon atoms and are straight-chain or are branched such. B. n-buty! Lithium, dietary! Magnesium, Diethyl zinc, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Tri-n-butyl aluminum, tri-n-decy! Aluminum, tetraethyltin and tetrabutyl tin. However, the use of Trialkylaluminum compounds whose alkyl chains contain 1 to 10 carbon atoms and are straight-chain or branched are preferred.

You can also use hydrides of metal alkyls, their Alkyl groups also contain 1 to 20 carbon atoms, such as diisobutyl aluminum hydride and trimethyl tin hydride. Likewise metal alkyl halides in which the alkyl radicals also contain 1 to 20 carbon atoms, such as ethylaluminum sesquichloride, are suitable, Diethyl aluminum chloride and diisobutyl aluminum chloride.

409824/0959

ORIGINAL INSPECTED

Finally, you can also use organoaluminum compounds use obtained by trialkylaluminum compounds or dialkylaluminum hydrides whose Eeste i "to Contains 20 carbon atoms, with 4 "to 20 carbon atoms containing diolefins, and in particular the substances called isoprenaluminum compounds.

The inventive method is applicable to the polymerization of olefins with terminal unsaturation, the molecule of which Has 2 to 20 and preferably 2 to 6 carbon atoms, such as on ethylene, propylene, butene- (1), 4-iiethylpentene- (i) and Witch- (i). It is also suitable for the copolymerization of such olefins with one another and with diolefins, which is preferred Have 4 to 20 carbon atoms. Such diolefins aliphatic, non-conjugated diolefins such as hexadiene (1,4), monocyclic ^ diolefins such as 4-vinylcyclohexene, 1,3-vinylcyclohexane, Cyclopentadiene (1,3) or cyclooctadiene (1,5) alicyclic Diolefins with an endocyclic bridge such as dicyclopentadiene or norbornadiene and aliphatic, conjugated diolefins such as butadiene and isoprene.

The method according to the invention is particularly good for manufacture of ethylene homopolymers and copolymers which contain at least 90 Γ1ο1 .-% and preferably 95 mol .-% ethylene, suitable. .

The polymerization can be carried out by any known method in solution or in suspension in a hydrocarbon solvent or diluents or in the gas phase. In solution procedures or in suspension one uses solvents or diluents which are used for washing the catalytic complex used analogs are: these are preferably alkanes or cycloalkanes

4098 24 / .0.959

ORJGtNAL INSPECTED

such as butane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or their mixtures. Polymerization can also be used in the monomer or one of the monomers which is kept in the liquid state.

The polymerization pressure is generally between atmospheric

2 2

chemical pressure and 100 kg / cm, preferably 50 kg / cm. the

Temperature is generally selected between 20 and 200 ⁰ C and preferably between 60 and 120 ⁰ C. The polymerization can be carried out continuously or batchwise.

The organic compound and the catalytic complex can be added separately to the polymerization medium. They can also be brought into contact at a temperature between -40 and 80 ^° C. before being introduced into the polymerisation reaction vessel for a period of time which extends up to 2 hours. Furthermore, they can be brought into contact with one another in several stages, or part of the organic compound can be added before the reaction, or several different organometallic compounds can be added.

The total amount of the organic compound used is not critical. It is generally between 0.02 and 50 mmoles / dm ^ of solvent, diluent or volume of the reaction vessel, and preferably between 0.2 and 5 mmoles / dm. The amount of catalytic complex used is determined as a function of the transition metal content of the complex. In general, it is selected such that the concentration is between 0.001 and 2.5 and preferably between 0.01 and 0.25 mat.-g of the metal per aar of the solvent, diluent or the volume of the reaction vessel.

The ratio of the amounts of organic compound and catalytic Complex is also not critical. In general, it is selected so that the ratio of organic compound /

409824/0959

Transition metal, expressed in mol / at-g above 1 and is preferably above 10.

The average molecular weight and in particular the melt index of those produced by the process according to the invention Polymers can be obtained by adding one or more molecular weights s regulators such as hydrogen, zinc or cadmium diethyl, Alcohols or carbon dioxide can be regulated to the polymerization medium.

The specific gravity of the method according to the invention Homopolymers produced can also by adding an alkoxide of a metal of groups IVa and Va of the periodic table to be regulated to the polymerization medium. To this We can produce polyethylene with specific weights, which between those of the high pressure polyethylene produced and those of classic High density polyethylenes lie.

Among the alkoxides which are particularly suitable for such a regulation, those of titanium and vanadium, the residues of which each contain 1 to 20 carbon atoms, are particularly effective. These include: Ti (OCH,) ₄ , Ti (OC ₂ H ₅ ) ^, Ti [OCH ₂ CH (CH ₅ ) ^ and Ti (OC _i6 H ₃₃ ) ₄ .

The inventive method enables the production of Polyolefins with productivities which are comparable or also very often superior to those with known catalysts have been achieved in which the transition metal compound is based on an activated alumina or halogenated Aluminum oxide is fixed. Thus the productivity, expressed in grams of polyethylene per gram of the catalytic complex, exceeds in the homopolymerization of ethylene regularly 1000 and it can even amount to 2000 in the pail of catalytic complexes

409824/0959

ORIGINAL INSPECTED

23F7154

made from porous oxides that have received a prior fluorination treatment. Since furthermore the transition metal content of the catalytic complexes see very much is low, the concentration of disruptive, catalytic Residues when using the polymers are negligible. The polymers therefore do not have to be purified further. This becomes the most difficult and costly operation for the final preparation of the polymers avoided.

In addition, the catalytic complexes prepared according to the invention have a number of completely surprising Features on:

First of all, they enable the production of polymers with melt indices, measured under normal load according to the standard ASTM D Ί238-57 T, at much less high concentrations Molecular weight regulators which are comparable to those which are used with catalysts of the above-mentioned prior art Technique were obtained. This property is in the case of the Use of hydrogen as regulator or modifier "particularly advantageous, since the hydrogenation of the polymer to be polymerized Olefin is reduced which obviously improves the yield of the process.

Furthermore, they enable the production of polymers with a factor ü which is very much higher than that of polymers obtained in the presence of known catalysts.
The factor U is calculated using the following formula:

Ti

wherein:

- IT is the weight average molecular weight, defined by the ratio

409824/09 5 9

IWSPECTED

ι χ

is where N. represents the number of molecules with molecular weight H ₁ ;

H is the average molecular weight "z" defined by The relationship

i i

H ₂ . -

where U- and M. have the meaning given above.

The ratio H / H is by gel permeation chromatography of a solution of 1 g / kg of the values of the fractionation of the polymer in 1,2,4-trichlorobenzene at 130 ⁰ C determined.

A high factor U is extremely weight-distributed for a broad molecule.

V »

development in the zone of very high molecular weights.

It is therefore possible with the catalysts of the invention to prepare polymers with very low melting indices and a very high factor U, as defined above, under particularly advantageous polymerization conditions. The combination of these properties enables the production of polyolefins, which are particularly easy to use in shaping processing by extrusion or blow molding. In particular, the deformed articles have no surface ^{imperfections} and the deformation cracking phenomenon, commonly referred to as "3I melt cracking", does not occur even at very high extrusion speeds.

The invention is illustrated in more detail by means of the following examples. .; ■ -

40982A / 0959

ORIGINAL INSPECTED

Examples 1 to 8 and comparative example R9

A - Production of the catalvtic_complexes

Under a nitrogen atmosphere is maintained for 5 hours "at 700 ⁰ C a alpha alumina monohydrate of the type (boehmite) (commercially available under the trade designation Grade chains B). We

receives an activated aluminum oxide, its pore volume

1.1 cmvg and its specific surface area is 360 m / g.

Fixed amounts of this activated aluminum oxide are ^{treated at ambient temperature (25 °} C.) with fixed volumes of aqueous solutions of increasing concentrations of hydrated magnesium chloride. The hydrated magnesium chloride used is a commercially available product which corresponds to the formula MgC ^ .4HpO (product of the Bhone-Poulenc company). The treatment is carried out in such a way that the reaction mixture retains its powdery properties. The solids obtained are then kept for 16 hours at 250 ^° C. under a nitrogen atmosphere. Then 5 S of each of the solids obtained are suspended in 25 cm ^ TiCl. transferred, and the mixture is ^{brought to 120 0} C for 30 minutes with vigorous stirring. The solid reaction product is separated off and washed with hexane until chlorine ions disappear from the washing liquid. It is then dried under a stream of dry nitrogen. The particular conditions of each of these preparations, the analyzes of each catalytic complex and the magnesium content of each solid are summarized in Table I below:

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14th 12th 12th 28 24 ' 24 72 90 108 20th 25th 30th

20th 25th 40 50 144 180 40 50 - ι ro

Table I.

Example 1 2 3 4 5 6 7 8 R9

amount used

on activated 14 13 14 12 12

Aluminum oxide (g)

applied volume of the solution 28 26 28 24 '24 ■ "of MgCl ₀ .4H _o 0 (ml)

C. C-

j ^ concentration of

ο MgCl ₀ .4H ₀ O solution 36 54 72 90 108.

cr> ^dd (g / l)

^ inserted magnets

^ sium amount (g / kg 10 15 20 25 30

-v. on aluminum oxide)

Mg content of the

οη keep i solids.,, _ _, _, _,

cd fes (mat-g / m ² ) 1.10 " ⁵ 1.6.10" * 2.10 "" * 3-1O ^- ^ 3.3.10 "^ 3.3.10" ^ 3.5.10 "* 4.4.10" ° -

Ti content of the catalytic complex (mg / g) 18 18 18 19 18 22 22 21 'V /

Cl content of the catalytic complex (mg / g) 80 89 96 101 111 123 130 149.

Mg content of the cataglytic complex 8.7 14 17 25 28 28 30 38 nj

ο xes (mg / g) "co

"Z- pw)

>. *) Content, expressed per m of the specific surface area of the aluminum oxide (V

: - before treatment at 250 ⁰ C ■ - *

Interestingly, the fixation or binding of the magnesium on the surface of the aluminum oxide is practically quantitative, taking into account the amount of magnesium used.

Two series of polymerization experiments were carried out with the catalytic complexes described above under the following common conditions: A certain amount (see Tables II and III) of the catalytic complex was in 500 ml of hexane in a 1500 ml autoclave made of stainless steel, which was equipped with a Was equipped with a paddle stirrer, transferred into suspension. 100 mg of triisobutylaluminum were added to this. The temperature was brought to 85 ° C. and ethylene and hydrogen were introduced under the partial pressures indicated below. The polymerization was carried out for 1 hour while maintaining a constant ethylene pressure by continuously adding ethylene. After the autoclave had been blown off, the amounts of polyethylene indicated in Tables II and III were obtained.

The first series of polymerization attempts (Examples 1 to R9) was under identical partial pressures of ethylene and Hydrogen carried out. The results of these tests are shown in Table II.

The second set of polymerization runs (Examples 10 to R18) was carried out with the same set of catalytic complexes carried out under different partial pressures of ethylene and hydrogen, the ratio of these partial pressures was selected within the limits that a polymer was obtained whose melt index was between about 0.15 and about 0.20. the The results of these tests are shown in Table III.

409824 / .0 959

ORIGINAL IHSPECTEu

Table II (*)

co 00 ro

co cn co

catalytic ^ complexes prepared in the examples

Weight of the used
Complex (mg) 150 125 125 100 75 50 41 37 75 Weight gained
Polyethylene (PÄ), (g) 78 89 89 97 63 70 70 78 51 catalytic ^ producti
vity (g PÄ / g catalyti
great complex) 500 7OO 700 950 850 1400 I7OO 2100 680

specific activity , (g PA / h χ g Ti χ kg / cm *

Melt Index (MI) (g / 10 min)

Melt index under heavy load (HLMI) (g / 10 min) (* ♦♦ »)

HLMI / MI ratio

2900 39OO 3900 5100 4600 6400 77OO 10000 3990

(**) (**) (* ·) 0.04 0.06 0.26 0.28 0.53 (**)

0.27 2.14 3.2 4.36 5.44 15.95 13.67 23.2 0.65

- · - ■ - 109 91 61 49 44

*) Partial pressures of ethylene (10 kg / cm) and hydrogen (4 kg / cm), which

all attempts were the same.

**) not measurable ' ,

***) measured under normal load, 2.16 kg according to the ASTM standard ****) measured under heavy load, 21.6 kg according to standard ASTM 1238-57 ^

at

Table II clearly shows that the specific activity and the catalytic. Productivity of the invention according to s, catalytic systems under identical polymerization conditions are better than those of catalysts of the prior art based on activated alumina (the experiment FJ) was carried out with a catalytic complex, which in the same way as the catalytic complexes of Examples 1 up to 8 was produced, but without treating the activated aluminum oxide with magnesium chloride) as soon as the Magnesiusi content of the solid exceeds 2.10 mat-g / m in specific surface area. It was also found that the melt index of the polymers obtained increased in proportion to the magnesium content of the catalytic complexes while all other polymerization conditions were kept constant.

Examples

10

Table III

11 12 13 14 15 16 17 E18

cataly tisclier

Complex, her- 12 3 ^ 5

placed after

example

Weight of

used, 250 159 157 105 108

catalytic Complex (mg)

Partial pressure

of ethylene 8 10 (kg / cm ² ) (1)

Partial pressure of water _o * c.

Fabric (kg / cm ^) ^IP

7 8 R9

10

50 39 36 210

10 10 10 10 10 8

2 15

1.9

67

83 550

8 5 3 3

0.8 0.5 0.3 0.3 0.2 1.9

110 111 94- 78 98 96

700 1000 1900 2000 2700

Ratio (2) / (1)

Weight of

extracted polyethylene

catalytic

Productivity 270 (g PA / g catalytic complex)

Melt index _ ._

(g / 10 min) (3) 0.10 0.15 0.20 0.18 0.20 0.18 0.15 0.14 0.17

Schmelζ index

under strong 9.02 14.42 18.67 16.27 12.01 10.93 9.28 8.22 14.8

load

(g / 10 min) (4)

relationship

(4) / (3) 90 96 94 90 60 61 62 59 87

Factor U

15 13 21 28 26 16 11 13 11

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2357154

The tests compiled in Table III show that the production of polyethylene with melt indices in the same order of magnitude as the melt indices of using Polyethylenes produced by catalysts of the prior art (R9) in the presence of the catalytic ones according to the invention Complexes are possible, but where much less molecular weight regulator (hydrogen) is used and where nevertheless, the catalytic productivity is increased.

Fig. 1 of the drawing shows that the catalytic complexes obtained from solids, their magnesium content from about 1.10 to 5.10 "^ mat-g / m on a specific surface varies, make it possible to lower the ratio of the partial pressures of hydrogen and ethylene by a factor of about 10, whereby polyethylenes with comparable melt indices are obtained. Furthermore, Examples 10 to 17 and FIG. 2 show the drawing that with the same change in the magnesium content, the U factor of the polyethylene obtained is always higher

VV

is than the factor U of polyethylene, which is in the presence of the comparative catalytic complex K9 was obtained, and that there is an optimum for the magnesium content of the solids, which corresponds to a maximum of the values for the U factor.

Examples 19 and 20 and comparative example R21

A - Preparation of the catalytic complexes

Mixing alumina monohydrate alpha-type (boehmite; commercially available under the trade name Ketjen Grade B) with about 4 wt .-% EEL ·] ?, t) _n i _r gt mixture to a temperature of ⁰ C. and this 7OO Maintain temperature for 1 hour. The fluorinated aluminum oxide obtained in this way is subjected to a “thermal treatment, which is carried out at 700 ^° C. for 5 hours under a nitrogen atmosphere

specific surface is 250 m / g and its pore volume 1 cm ^ / g.

409824/0959

ORIGINAL SUSPECTED

Fixed amounts of this fluorinated alumina are treated with aqueous solutions of MgC ^. ^ - H ^ O in the same manner as for the preparation of the catalytic complexes of Examples 1-8. The Peststoffe obtained are then atmosphere for 16 hours at 250 ⁰ C under a nitrogen maintained. Eventually they will be with TiCl. treated in the same manner as in-Examples 1 to 8, except that the treatment temperature is I30 ⁰ C and the reaction product is subjected to five extractions with boiling TiCl ^.

The washed and dried products are used as catalytic complexes in polymerization experiments which were carried out under the same conditions that are detailed in Section B of Examples 1 to 8. The particular conditions for the production of these catalytic elements, the results of their analysis, the particular conditions and results of the polymerization, and the properties of the polyethylenes obtained are summarized in the following table TV , which also lists the results, i-those with a catalytic comparative complex R 21 were obtained, which had been prepared in the same way as the catalytic complexes described above, but omitting the treatment step of the fluorinated alumina with magnesium chloride «

409824/0959

INSPECTED

2352754

2,3.10 " -5 ₃ , 7.1O- ⁵ - 13th 14th 7.7 23 22nd 35 61 87 24 14th 23

Table IV

Special conditions e.g. 19 e.g. 20 e.g. R21

Amount of magnesium used
Cs Mg / kg fluorinated aluminum oxide) 15 25

Mg content of the solid obtained (mat-g / m ^) (before treatment at 250 C)

Ti content of the catalytic

Complex (mg / g)

F content of the catalytic complex (mg / g)

Cl content of the catalytic Complex (mg / s)

Mg content of the catalytic

Complex (mg / g)

Weight of the used, cat-

lytic complex (mg) 107 51 140

Amount of triiso used

butyl aluminum (mg) 100, 100 200

Partial pressure of ethylene (1) '

(kg / cm ² ) 10 10 8

Partial pressure of hydrogen (2) (kg / cm2)

Ratio (2) / (i)

Weight of polyethylene recovered (PÄ) (g)

catalytic productivity

(g PA / g catalytic complex)

Melt index (g / 10 min) (3)

Melt index under heavy load (g / 10 min) (4)

Ratio (4) / (3) factor U _w

10 5 15th 1 0.5 1.9 80 99 103 750 2000 736 0.10 0.11 0.23 7.98 10.15 11.5 80 92 50 12th 13th 10

A09824 / 0959

23 5 7154

From Table IV it can be seen, again, that it is an optimum for the magnesium content of the solids with the help of which the catalytic complexes according to the invention are prepared be, which corresponds to a maximum of the catalytic productivity and the production of a polyethylene at a allows a much lower ratio of the partial pressures of hydrogen and ethylene, which has a comparable melt index and a higher factor U compared to polyethylene

which was obtained in the presence of the comparative catalytic complex R21.

Example 22

A complex oxide of the general formula MgO. A ^ O ^ (spinel) was subjected to a ^{thermal treatment carried out under a stream of dry nitrogen at 900 °} C. for 5 hours. A complex oxide was obtained, which

2 was characterized by a specific surface area of 290 m / g and an internal porosity of 1.5 cni./g. This complex oxide was treated with an aqueous solution of MgClp.4 ^ 0 in the same manner as in Examples 1 to 8, the amount of magnesium used being equal to 15 g of magnesium / kg of complex oxide. The magnesium content of the solid obtained, which is only a fixation of the magnesium chloride to-write ', was therefore 4,6.10 ^J mat-g Mg / m of specific surface area. After an ^{activation treatment carried out at 250 °} C. for 16 hours and after the reaction with TiCl ^, which was carried out as indicated in Examples 2 to 8, the catalytic complex obtained contains 19 nig of titanium and 111 mg of chlorine per g. One with 4-1 mg of this complex under the same conditions specified in paragraph B of Examples 1 to 8 and under partial pressures of ethylene

and hydrogen of 10 and 2 kg / cm, respectively, the polymerization test carried out resulted in 68 g of polyethylene, its melt index 0.16 g / 10 min and its melt index under heavy load g / 10 min. The catalytic productivity was

409824/0959

ORIGINAL INSPECTED

23V -U

1650 g PA / g catalytic complex, and the specific activity 8700 g PA / h-g Ti χ kg / cm ² C ₉ tbsp. The U factor of the polyethylene was 6.

For comparison, it should be stated that a polymerization test carried out under the conditions given above with 60 mg of a catalytic complex, which was prepared in the same way but without treatment of the complex oxide with a magnesium halogen compound (Ti content = 13 mg / g), was carried out made it possible to obtain 25 g of polyethylene with a non-measurable melt index and a melt index under heavy loads of 0.61 g / 10 min. The catalytic activity and the specific activity amounted to 420 g PA / g catalytic complex and 3200 g PA / h χ g Ti χ kg / cn ^{2, respectively}

Example 23

To prepare the catalytic complex used in this experiment, 12.4 g of magnesium ethylate Hg (OCpHc) P, (product of dynamite Ibbelj to 17 g of titanium tetrabutylate Ti (OC ^ Hq) ^, (product of the titanium company) were added, and the mixture was stirred heated for 6 hours at 13O ⁰ C was observed almost complete dissolution of the Kagnesiumätiiylats In the mixture the atomic ratio Ti / frg at-0.5 g / ai was;.. -g - 10% error as iolge of impurities which contained compounds never used

O ⁷ I.

and the mixture previously cooled to 90 ° C. became 60 cm ^ hexane added, and the whole was stirred at this temperature for 1 hour. The solution thus obtained was made by adding Eexan brought to a volume of 120 cnr.

13.5 cm ^ of this solution, d. H. an etv / a containing 0.4 g of magnesium Volume, became gradually, in 100 cn * of a suspension introduced, which 21 g of a ilaoriortei prepared according to paragraph A of Examples 19'-iiid 20. AluGiiniunioxicls contained. The Jeniisch '/ zi-ie 15 ivinutexi b ^ i ambient temperature formed in this way stirred, · then decanting was geiasst;.! and

4 0 9 8 "L A / 0 9 5 9

ORIGINAL INSPECTED

235 "Μ 54

then the supernatant liquid is removed. The analysis showed a content of magnesium fixed or bound on the solid obtained in this way of 2.2.10 mat-g / m 2 on the specific surface. The solid obtained in this way was initially measured at 140 cm; TiCl ^ transferred under stirring for 2 hours at ambient temperature in suspension, then after removal of the first TiCl ^ -Charge in the same volume of TiCl ^ for 50 Hinuten bei.120 ⁰ C. Finally, the obtained was catalytically e separated complex with hexane until the disappearance of chlorine ions, washed in the washing liquid and dried under a stream of dry nitrogen. It contained 18 g titanium, 21 g fluorine, 65 g chlorine and 14 g magnesium per kg. A polymerisation experiment carried out under the same conditions as the first series of polymerisation experiments (Examples 1 to R9) with 55 mg of the catalytic complex enabled the production of 117 6 polyethylene, its melt index 0.14 g / 10 min and its melt index under heavy load 11.05 g / 10 min. Their ratio was therefore about 79 »and the factor U _{w of} the polyethylene was 11. The catalytic productivity was 21Q0 g PA / g catalytic complex and the specific activity 11700 g Pl / h χ g Ti χ kg / cm

If one compares the results of this experiment with those of the Comparing comparative experiment R21, it is found again that it is in the presence of the catalytic complexes according to the invention it is possible to use a polyethylene with a comparable melt index and a higher factor TJ at a much lower one To obtain ratio of the partial pressures of hydrogen and ethylene.

Example 24-

To prepare the catalytic complex used in this experiment, the method used in Examples 1 to δ was first used, hydrated magnesium chloride to 185 ° C until recovery

409824/0959

ORlGlHAL INSPECTED

. 235 "154

de "s monohydrate heated. 15" 5 6 ^avi f obtained in this way Magnesiumchloridmonohydrat were added to 85 g of titanium tetrabutoxide, and the mixture was' heated for 6 hours with stirring at 130 ⁰ C it was observed almost complete dissolution of the magnesium chloride. was in the mixture the atomic ratio Ti / Mg 2 at-g / at-g with - 10 % error as a result of impurities in the compounds used

■ z contained. To the cooled mixture 3QO cm ^ hexane were added, and the whole was heated under Eühren at 90 ⁰ C for 1 hour. The soluble fraction of the cooled mixture was recovered; analysis showed that it contained 6.5 g Mg / l.

20 g of an according to paragraph A of Examples 19 and 20

■ 7. Provided, fluorinated aluminum oxoides were suspended in 100 cnr hexane and then treated with 56 cnr of the soluble fraction of the mixture described above. The production sequence of the catalytic complex is the same as that described in Example 23. The solid obtained contained 2.5-10 mat-g Mg / m 2 on a specific surface. The catalytic complex contained 24 g titanium, 23 g fluorine and 73 g chlorine as well as 11 g magnesium per kg. A polymerization test carried out under the same conditions as in Example 23 with 52 mg of the catalytic complex made it possible to produce 69 g of polyethylene with a melt index (1) of 0.18 g / 10 min and a melt index under heavy load (2) of 10.67 g / 10 min and a factor U of 19- The ratio

(2) / (i) is therefore approximately equal to 59 · The catalytic productivity is 1350 g PÄVg catalytic complex, and the specific activity is 5600 g Pl / h χ g Ti χ kg / cm ²

Example 25

12 g of one prepared as in paragraph A of Examples 1 to 8,

■ z

activated aluminum oxide was treated with 24 cnr of a solution containing 18 g / l magnesium methylate, MgXOCHO ₂ , (commercial product

40-9824 / 0 95 9

ORIGINAL iUSPECTED

235 "> Ϊ54

von Dynamit Nobel) in methanol. The treatment was carried out in such a way that the reaction mixture retained its powdery character. The solid obtained was ^{dried in vacuo at 50 °} C. for 1 hour. Its magnesium

-3 / 2
content was 1.1.10 ^y mat-g / m on specific surface. .

This solid was then treated with TiCl ^, as described in paragraph A of Examples 1 to 8. The obtained catalytic complex containing 20 g of titanium, 90 g of chlorine and S 7 9 ₅ mg per kg according to the analysis.

One under the general conditions mentioned in paragraph B of Examples 1 to 8, however, with 102 mg of the catalytic Complex and under partial pressures of ethylene or water

2 2

fabric of 10 kg / cm or. A polymerization test carried out at 6 kg / cm made it possible to obtain 71 S polyethylene with a melt index (1) of 0.19 g / 10 min, a melt index under heavy load (2) of 12.65 g / 10 min and a U factor of 16 The ratio (2) / (i) is therefore about 67. The catalytic productivity is 700 g PA / g catalytic complex and the specific activity amounts to 3500 g PA / h g Ti χ kg / cm ²

409824/0959

OBSGIMAL INSPECTED

Claims (1)

Claims 1. Process for the low-pressure polymerization of alpha-olef Lrieri, carried out in the presence of a catalytic system, which is an organometallic compound of a metal of groups Ia, Ha, lib, HIb and IVb of the periodic table and contains a solid, kafcalytisehen complex, thereby marked that the solid, catalytic complex was produced by adding a compound of a Meta L les of groups IVa, Va and VIa of the periodic table with a porous aluminum oxide, on which as a magnesium compound an oxygen-containing or halogenated compound is deposited, has been allowed to react. 2. The method according to claim. 1, characterized, that the amount of deposited on the porous oxide —4 —Ί a Mayies connection between 1.10 and 1.10 milliatom- grams of magnesium per m of specific surface area of the porous oxide. 3. The method according to claim 2, characterized in that the amount of deposited on the porous oxide magnesium ^{compound between 1.10 'and 5-10 J} Hilliatomgramm Magnes
Oxide lies. grams of magnesium per m of specific surface area of the porous 4. The method according to claim 1, characterized in that a compound is used as the magnesium compound used, which at least one bond magnesium-oxygen in their KoleKül. 5- The method according to claim 4, characterized in that that the magnesium compound is an oxygen-containing, Organic compound used, many organic residues bound to the magnesium via oxygen. 409824/0959 ORIGINAL INSPECTED 235? I $ 4 6. The method according to claim 5 »characterized marked eichn e t _% that a magnesium alkoxide or phenoxide is used as the magnesium compound _y whose organic best has 1 to 6 carbon atoms« 7 «, procedure according to. Claim i, characterized t ^ that a magnesium compound is a connection used, which © at least one bond magnesium-halogen has in its molecule, 8. The method according to claim 7 * characterized in that the magnesium compound used is ^e i ^{n hydrated magnesium chloride.} 9. The method according to claim 1, characterized e t that one is a compound as a magnesium compound uses, which at the same time bonds magnesium-oxygen and has magnesium halide bonds in its molecule. 10. The method according to claim i _t, characterized in that the magnesium compound has been deposited on the porous aluminum oxide in the form of a solution in water or in an organic diluent. 11. The method of claim 1:,. characterized in that the Hagnesiuciverbindung Cass on the porous aluminum oxide in a mixture with a Forpi sauerstoffheltigen organic compound (M) of a metal of Groups Ia, Hb, IIIb, IVa IVb _5; Va »Via * VIIa nrA VIII of the periodic table has been peeled off. i2> Method according to claim IT, characterized thereby eichn e t that as oxygen-containing ^, organic compound (M) -ein Connection of the general lormel FMeO (OR) 1 is used 4: 0.a δ 2 4/0 ft 5 3 ORIGINAL SNSPECTED is, wherein the metal (Me) of lithium, sodium, potassium, zinc, boron, aluminum, silicon, tin, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt or nickel, E is an organic Eest having 1 to 2.0 carbon atoms is, χ and y are any numbers from χ > _ 0 and y> O, which are compatible with the valence of the metal (Me), and m is an integer. Process according to claim 12, characterized in that (Me) is aluminum, silicon, titanium, zirconium, vanadium or chromium, E is a hydrocarbon radical containing 1 to 6 carbon atoms, χ 0 <^ χ £ 1 and ^m Ί H ^m S 6 are. Method according to Claim 11, characterized in that it is marked t that the magnesium compound on the porous alumina in the form of a solution in an organic diluent of the mixture of the magnesium compound with the oxygen-containing organic compound (M) has been deposited is. Method according to claim 11, characterized in that that the magnesium compound "and the oxygen-containing, organic compound (M) are mixed in such amounts that the atomic ratio between the metal (Me) of the oxygen-containing, organic compound and the magnesium is between 0.5 and 100 at-g / at-g. 16. The method according to claim 1, characterized in that the porous aluminum oxide has an internal porosity above 0.3 cnr / g. 17- The method according to claim 1, characterized in that the ρ rose aluminum oxide has a specific surface area between * ^: 'JÖ and 400 m / g. 409824 / Q959 itf * «- INSPECTED 235 "M 54 18. The method according to claim 1, characterized in that that the porous alumina is an alumina or a complex oxide of aluminum and at least one other metal is. 19. The method according to claim 18, characterized in that the complex oxide of aluminum and at least one other metal is a complex oxide of the formula MgO. Al ₂ O ₅ , SiO ₂ .Al ₂ O ₅ or Mg0.Si0 ₂ .Al ₂ 0 is. 20. The method according to claim 1, characterized in that it is marked e t that the porous oxide undergoes a halogenation treatment before it is brought into contact with the magnesium compound. 21. The method according to claim 20, characterized in that that the porous aluminum oxide is a fluorinated aluminum oxide, in which the atomic ratio fluorine / Aluminum is between 0.01 and 1. 22. The method according to claim 10, characterized in that the porous aluminum oxide on which a Magnesium compound is deposited, is subjected to an activation treatment which is carried out at a temperature is carried out below the decomposition temperature of the magnesium compound. 23. The method according to claim 1, characterized in that the compound of a metal from groups IVa, ■ Va and VIa of the periodic table is a titanium compound. 24-. Solid, catalytic complexes for low-pressure polymerization of alpha-olefins, characterized by this, that they are made by reacting a compound of a metal 409824/0959 "' ORIGINAL INSPECTED 235? -Ι /, Groups IVa, Va and Via of the periodic table with a porous alumina on which a magnesium compound deposited. 25. Use of the method according to claim 1 for polymerization of alpha-olefins, whose molecule has two to six carbon atoms owns. 26. Polyolefins, produced by the process according to. claim 409824 / 0S59 ORIGINAL INSPECTED Blank page