DE2441625A1 - PROCESS FOR LOW PRESSURE POLYMERIZATION OF ALPHA-OLEFINS - Google Patents

Description

Process for the low pressure polymerization of alpha-olefins

The invention "relates to an improved process for low pressure polymerization of olefins, the catalysts used for this purpose and a process for the preparation of these catalysts.

It is known that one can use catalytic systems for the low pressure polymerization of olefins, -which one Derivative of a transition metal and an organometallic compound.

From the applicant's British patent specification 1,140,649 it is known that as a derivative of the transition metal des Above-mentioned catalytic system can use a solid obtained by reacting a halogenated derivative of a Transition metal with an oxygen-containing compound of a divalent metal such as magnesium was obtained.

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The catalytic systems thus obtained are very active compared to those in which the halogenated derivative a transition metal is used as such.

In Belgian patent 791 676 by the applicant, catalytic systems are described which have one component own that by implementing:

(A) an oxygen-containing, organic compound of a Metal such as a magnesium alcoholate or phenate,

(b) an oxygen-containing, organic compound of a transition metal,

(c) an aluminum halide
was obtained with each other.

It is possible to use these catalytic systems to produce polyolefin, which has a high average molecular weight and have very good impact strength, can be used with high catalytic activities.

However, the production of the catalytic systems according to the Belgian patent 791 676 has some disadvantages, which result from the use of the oxygen-containing organic compounds (a), which are unstable and / or experience instant hydrolysis. These compounds are also extremely dangerous to handle. Therefore must they are stored and transported under inert conditions and handled with great care. They are also in Trade not available. In addition, the catalytic components prepared using them as a starting material often have poor flow properties (i.e. they may have too fine a grain size).

The object of the invention is to avoid these disadvantages.

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Surprisingly, it has now been found that catalytic Systems which have the same advantages as those mentioned above without using an organic, oxygen-containing one Compound (a) can be made from readily available products.

Further advantages of the invention emerge from the following Description.

The invention therefore relates to a process for the polymerization of α- olefins which is carried out in the presence of a catalytic system which contains an organometallic compound (component B.) of a metal from groups I to III of the periodic table and a solid, catalytic complex (component A) comprises, which is characterized in that component A by reaction of ■

(1) metallic magnesium

(2) a hydroxylated organic compound (which is in hereinafter referred to as "connection (2)"),

(j) an oxygen-containing organic compound of a Metal (Tr) of groups IVa, Va or VIa of the periodic table (hereinafter referred to as "compound (3)"),

(4) an aluminum halide (hereinafter referred to as "compound (4)"),

was obtained with each other.

Metallic magnesium (1), which is used to produce the catalytic Component A used can be in any physical form required for the chemical reaction is suitable e.g. B. in the form of powder, granules, shavings, tape or chips. Those used to carry out organic reactions Commonly used grades can be employed in practicing the invention.

In the description of the present invention, the term "hydroxylated organic compound" is intended to be used as it is for the compound (2) is used to denote organic compounds,

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which contain at least one hydroxyl group bonded to a carbon or silicon atom. the Compound (2) is preferably selected from compounds in which from 1 to 12 carbon atoms per hydroxyl group and more preferably from 1 to 6 carbon atoms per hydroxyl group contain. These compounds can be straight-chain or branched-chain, aliphatic compounds or alicyclic, be saturated or unsaturated compounds; aromatic and heterocyclic compounds and their substitution derivatives are also beneficial. In particular, they can belong to the following groups: alkyl, cycloalkyl, alkenyl, Cycloalkenyl, aryl, alkylaryl and arylalkyl compounds.

Particularly advantageous compounds (2) are the monohydric and polyhydric alcohols, which are 1 to 12 and are particularly preferred Have 1 to 6 carbon atoms in their molecule * Es can be saturated or unsaturated, straight-chain or branched-chain, aliphatic or alicyclic alcohols; Likewise it can be aromatic and heterocyclic alcohols. Other suitable compounds are hydrocarbylsilanols, the Hydrocarbyl or hydrocarbon radicals have a number of carbon atoms which corresponds to the values given above.

Among the compounds (2) which can be used according to the invention, there may be mentioned:

- saturated or unsaturated, straight-chain or branched-chain, monohydric and polyhydric, aliphatic alcohols: z. B. methanol, ethanol, butanol, isobutanol, isopentanol, Octanol and the like; Allyl alcohol; Ethylene glycol;

- Substituted or unsubstituted, saturated or unsaturated, monohydric, alicyclic alcohols: z. B. Cyclopentanol, Cyclohexanol and the like; 2-cyclopenten-1-ol;

- substituted or unsubstituted, monovalent and polyvalent, aromatic alcohols: e.g. B. phenol, benzyl alcohol, o-, m- and p-cresols, xylenols, resorcinol, hydroquinone and the like; alpha- and beta-naphthols and the like;

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- heterocyclic alcohols: ζ. B. 3-hydroxypiperidine;

- Alkyl and aryl silanols: e.g. B. trimethylsilanol, triphenylsilanol.

Among oxygen-containing, organic compound (3) one Metal (Tr) of groups IVa, Va or VIa of the Periodic Table is to be understood as any compound in which a organic residue bound to the metal (Tr) via oxygen is; Compounds which have metal-halogen bonds do not belong to the scope of the invention. However, connections, which metal-oxygen bonds contain and condensed compounds, which consequences of metal-oxygen-metal bonds have, also. used, provided that they have at least a sequence of metal-oxygen organic Have residual bonds per molecule.

Among the metals (Tr) are titanium, zirconium, and vanadium Chromium preferred. The best results are obtained with titanium. The organic ones bound to the metal (Tr) via oxygen Leftovers can be of any type. Generally they contain from 1 to 18 carbon atoms and preferably they have 1 to 10 carbon atoms. The best results are obtained when they have 1 to 6 carbon atoms. The organic radicals are preferably hydrocarbon radicals and alkyl radicals (branched or not branched), cycloalkyl, arylalkyl, aryl or alkylaryl radicals.

The compounds (3) can be represented by the following general formula:

[TrO _x , (OR ') _y ] _m

in which Tr is a metal from group IVa, Va or Via of the periodic table, R ^{1 is} an organic radical as previously defined,

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χ ¹ and y are numbers such that x ¹ > _ 0 and y> 0, where they match the valence of the metal Tr, and where m is an integer. Preferably, compounds (3) are used in which x ^{1 has} a value that 0 <_ x ¹ <. and m has a value that 1 <m <6.

Among the compounds (3) which can be used in the context of the invention, there may be mentioned:

- alkoxides, e.g. B. Ti (OC ₂ H ₅ ) ₄ , Ti (OnC, H ₇ ) ₄ , Ti (OnC ₄ Ha) ₄ , Ti (OiC ₃ Iy ₄ , TiC0-tert-C ₄ H ₉ ) ₄ , Ti (OiC ₄ H ₉ ) ^, V (OiC ₃ H ₇ J ₄ and Zr (OiC ₅ H ₇ ) ^ j

- phenates, e.g. B. Ti (OC ₆ Hc) ₄ ;

- oxyalkoxides, e.g. B. VO (OiC ₅ H ₇ );

- condensed alkoxides, e.g. B. Ti ₂ O (OiC-, H ₇ ) ₆ ; and

- enolates, e.g. B. titanium acetylacetonate.

The use of compounds (3) which contain several different organic radicals is also within the scope of the invention as well as the use of several different oxygen-containing organic compounds and the same metal and the use of a number of oxygen-containing organic compounds of different types Metals.

The compound (4-) which is used for the preparation of the catalytic component A is an aluminum halide. The aluminum halide generally used as the compound (4) can be represented by the formula AIR X ₇ . wherein: R is a hydrocarbon radical having 1 to 20 carbon atoms and preferably 1 to 6 carbon atoms, X is halogen, and χ is a number such that 0 <χ Ό.

R is preferably a saturated, aliphatic radical, a saturated, alicyclic radical or an aromatic radical.

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The best results are obtained when R is an alkyl group, X is chlorine and 0 < χ £ 2. As examples of aluminum halides which can be used according to the invention, there may be mentioned: AlCl ,, Αχ ν OH- *) s * Xt 1.. Αχ IO ₀ XIr- / ^ sOX, AXl O ^ vIIr-J ν / X λ, AXl \ y - ^ lif-jj ^ J? »AXl XO-jXlr-j ^ ₀ 0 X,

^ pH ₁ -; , οι ,.

₉ ,; "Cl, Al (C ₉ H ^) CIp, Al (C ^ H _9. ) _P

C-JC. C. J C- J (C.

According to one embodiment of the invention, it is not necessary that the connection (4) is a single connection. In particular, a compound of the formula AlX, and a compound of the formula AlR in combination or in succession be used.

The solid complex forming the catalytic component A can be prepared by various methods. Every Compound (2), (3) and (4) can, if the working conditions are suitable, in solid state, in liquid state, in Can be used in the form of a solution or in the form of a vapor or gas.

The catalytic component A is preferred in a liquid medium, optionally in the presence of an inert one Diluent, which is preferably a diluent in which at least one of the reactants is soluble, produced. In fact, all solvents used in preparative organic chemistry commonly used. However, the use of alkanes and cycloalkanes, their molecules Contain 4 to 20 carbon atoms, preferably, e.g. B. from Isobutane, n-pentane, η-hexane, cyclohexane, methylcyclohexane or the dodecanes. If a diluent is used, the total concentration of the dissolved reactant (s) is preferably greater than 5% by weight and especially preferably greater than 20% by weight, based on the diluent.

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As for the order of addition of the reactants ", so they are preferably added to the magnesium in the following order: first the compound (2), then the compound (3) and finally the compound (4) or the compound (2) and (3) together and then the compound (4) or the Compound (2) and then compounds (3) and (4) together.

According to a preferred method, magnesium is mixed with the compounds (2) and (3J and the mixture is heated and allowed to age. The heating and aging are preferably carried out under reflux and / or at elevated pressure, the reaction medium being liquid the reactants are solid, they are preferably suspended or dissolved in one of the aforementioned diluents, or they are melted if this does not cause their decomposition. If one of the reactants is liquid at the heating temperature, it can be used as the reaction medium. In any case the mixing of a liquid diluent can be carried out in the presence. the heating temperature depends on the type of reducing {2) and (3) from, and is preferably selected between 30 C and 150 ⁰ C. The duration of the heating and aging is not critical and is generally between 30 minutes and 15 hours, preferably between 1 and 6 hours.

When performing the method described above, the heating and aging reaction can be accelerated by one or more of the substances known per se in the art is added which react with metallic Magnesium or are able to form an adduct herewith, e.g. B. iodine, mercury (II) chloride, xylene and alkyl halides, polar substances such as organic acid esters and organic acids.

After the completion of the heating and aging reaction, it is preferable to use low boiling point substances, if any

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still present, removed by distillation. In general, the aged composition thus obtained is a homogeneous liquid substance. The aged composition thus obtained is then brought into contact with the compound (4), preferably in the presence of an inert diluent of the type mentioned above. The duration and temperature of this reaction are not critical; the temperature is generally lower than 200 ° C., preferably in the range from 0 to 60 ^° C. The duration is generally between Λ and 8 hours, preferably between 2 and 4 hours. If a compound of the formula AlX, (compound 4a) and a compound of the formula AlEU (compound 4b) are successively used for this reaction as described above, the reaction conditions are similar to those in which a single compound (4) is used . However, the first reaction with the compound (4a) is then generally carried out under reflux for 30 minutes to 5 hours, preferably for Λ to 3 hours / s.

However, it is recommended that the presence of oxygen and water be carefully checked during the preparation of component (A) is avoided.

The rate of addition of the reactants is also not critical. However, it is advisable that they not is so great that an abrupt heating of the reaction medium is brought about as a result of an excessively rapid reaction will. The reaction can be carried out continuously or discontinuously.

Furthermore, it often happens in practice that the connection (3)> if kept in the "liquid" state, the product is able to dissolve by reaction of magnesium with the compound (2). the

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Use of an inert diluent can then be avoided will. However, if this is not the case, and since it is preferred that the aged composition contain the compound (4 ·) is brought into contact in the liquid state, it is also possible to use a second, oxygen-containing, organic To use a compound of a metal from groups IHb or IVb (preferably silicon and particularly preferably aluminum), which is liquid and to dissolve the first, d. H. the oxygen-containing, organic compound of a metal (Tr) «connection (3) in. Is able. As far as the structure of the second, oxygen-containing, organic compound is concerned is, it can be defined in the same way as the compound (3), and in the following description it is referred to as the compound (5). Specific examples of oxygen-containing organic compounds used as the compound (5) are Al (OC ^ Hn), and)

The preferred amounts of compounds (2), (3) and (4) used are shown below.

The total amounts of metallic magnesium (1) and compound (2) are generally such that the ratio Mg / compound (2) is less than 1 g-at (gram-atom) per mole, and preferably less than 0.5 g-at / mole. The best results will be obtained when this ratio is close to 0.3 g-at / mole lies.

The total amount of compound (3) is such that the atomic ratio Mg / metal (Tr) is between 20 and 0.05 g-at / g-at, and preferably between 5 and 0.2 g-at / g-at. The best
Results are obtained when this atomic ratio is in
is close to 0.5.

The compound (4-) is generally used in such an amount that the atomic ratio of magnesium to aluminum

of compound (4) between 10 to 0.01 g-at / g-at and preferably

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is between 1 and 0.05 g-at / g-at. The "best results are obtained when this atomic ratio is close to." 0.2 lies. However, if the production · the catalytic Component (A) using one compound in sequence (4a) and a compound (4b), the atomic ratio of magnesium to aluminum of the compound is (4a) preferably between 4 and 0.02 g-at / g-at, and the compound (4b) is then used so that the atomic ratio from aluminum of connection (4b) to metal (Tr) of connection (3) is preferably higher than 0.50 g-at / g-at.

Finally, if a compound (5) is used as previously defined, the amounts of magnesium and that of the using compound (5) preferably such that the Ratio between the amount of magnesium and that of the compound (5) between 0.01 and 100 gram atom per mole lies. Preferably this ratio is between 0.1 and 10 gram atoms per mole. The best results have been achieved when it is between 0.5 and 1.5 gram atom per mole.

The catalytic components A prepared according to the invention are pesticides. You in alkanes and cycloalkanes, which can be used as a diluent, insoluble. They can be polymerized in the form in which they are were obtained, can be used without separation from the reaction medium. If the reaction medium is liquid, it may be possible to separate them off, e.g. B. by Filtration, decanting or centrifugation.

After the separation, the catalytic components A can be used to remove excess reactants, which are still can adhere to them, can be washed. Any inert diluent can be used for this washing process, z. B. any of the diluents which can be used as constituents of the reaction medium, e.g. B, alkanes

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and ^N cycloalkanes. After washing, the catalytic complexes can also be dried, e.g. B. by passing a flow of dry nitrogen or in a vacuum.

The mechanism of formation of the manufactured according to the invention th, catalytic component A has not yet been fully elucidated. The elemental analysis of the catalytic complexes according to the separation and washing shows that they are chemically bound complexes, d. H. Products of chemical reactions, and that it is not the result of mere mixing or adsorption.

After being washed, the catalytic component A can be stored in powder form. Two important advantages of these catalytic components are their very good storage stability and the limited loss of metal (Tr) during the possible washing stage: If the metal (Tr.) Is titanium, t / mA ^ - & 80% by weight remains in the catalytic Component A bound back; therefore, the cleaning treatment of the washing liquids is greatly reduced.

The catalytic components A of the invention, the exact structure of which has not been fully elucidated, contain magnesium, Metal (Tr), aluminum and halogen in different amounts. Most of them contain between 10 and 150 g per kg Magnesium, between 20 and 250 g of metal (Tr), more than 10 g of aluminum and between 200 and 700 g of halogen. they draw are characterized by a high specific surface area, which is predominantly greater than 50 m / g, and which have values as high as Can have 300 to 400 m / g.

The catalytic systems according to the invention further comprise an organometallic compound (component B) which serves as an activator, namely an organic compound of a Metal of groups I to III of the periodic table, e.g. Legs

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organometallic compound of lithium, magnesium, zinc or aluminum. The best results were obtained with organometallic compounds of aluminum.

It is possible to use fully alkylated compounds whose alkyl chain contains 1 to 20 carbon atoms and branched or not branched e.g. B. n-butyllithium, Diethyl magnesium, diethyl zinc, trimethyl aluminum, triethyl aluminum, Triisobutyl aluminum, tri-n-butyl aluminum, Tri-n-decyl aluminum, tetraethyl tin or tetrabutyl tin. However, the use of trialkylaluminum is preferred, the alkyl chain of which contains 1 to 10 carbon atoms and is either not branched or branched.

It is also possible to use alkyl metal hydrides, in which the alkyl radicals also contain 1 to 20 carbon atoms, e.g. B. diisobutylaluminum hydride or trimethyltin hydride; as well as alkyl metal halides in which the alkyl radicals in turn have 1 to 20 carbon atoms, e.g. B. ethyl aluminum sesquichloride, Diethyl aluminum chloride. or diisobutyl aluminum chloride.

Finally, it is also possible to use organo-aluminum compounds to use which by converting trialkylaluminum or dialkylaluminum hydrides whose radicals contain 1 to 20 carbon atoms, with diolefins which contain 4 to Containing 20 carbon atoms, these compounds also known as isoprenylaluminum compounds are.

The process of the invention can be applied to the polymerization of olefins having terminal unsaturation whose molecule contains 2 to 20 and preferably 2 to 8 carbon atoms, e.g. B. ethylene, propylene, butene- (1),

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4-methylpentene (i), hexene (1) or octene (1). Is also it affects the copolymerization of these olefins with one another as well as with diolefins, which preferably have 4 to 20 carbon atoms have applicable. These diolefins can be non-conjugated, aliphatic diolefins, e.g. B. hexadiene- (1.40; monocyclic diolefins, e.g. B. 4-vinylcyclohexene, 1,3-divinylcyclohexane, Cyclopentadiene or cyclooctadiene (1,5J; alicyclic Diolefins with an endocyclic bridge, e.g. B. dicyclopentadiene or norbornadiene; or conjugated, aliphatic diolefins, z. B. butadiene or isoprene.

The process according to the invention can be used particularly well for the production of homopolymers of ethylene and of copolymers, which is at least 90 mol% and preferably 95 mol% Containing ethylene, can be applied.

The polymerization can be carried out by any suitable process; in particular, it can be in solution or in suspension in a solvent or hydrocarbon diluent or in the gaseous phase be performed. For processes carried out in solution or suspension, solvents or diluents can be used used in the manufacture of the catalytic Component Ä used are similar; these are preferably alkanes or cycloalkanes, e.g. B. butane, pentane, hexane, heptane, Cyclohexane, methylcyclohexane, or mixtures thereof. It is also possible to carry out the polymerization in the monomer or one of the monomers, if this is kept in the liquid state.

The polymerization pressure can generally be between atmospheric pressure and 100 kg / cm, preferably it is 1.5 to 50 kg / cm. The temperature can generally be between 20 ^° C. and 200 ^° C .; in particular, if an olefin with terminal unsaturation (as previously defined) is to be polymerized, the temperature is

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between ί? 0 ° C and 120 ⁰ C, if the polymerization is carried out in suspension, and at 120 ⁰ C to 150 C, when the polymerization is carried out in solution. The polymerization can be carried out batchwise or continuously.

The catalytic components A and B can be added separately to the polymerization medium. You can, however, also optionally brought at a temperature between -40 ⁰ C and 80 ⁰ C for a period up to 2 hours before iiirer introduction into the polymerization reactor in contact. Furthermore, it is possible to bring them into contact with one another in a number of stages, or some of the organometallic compound (component B) can also be added before introduction into the reaction vessel, or a number of different components B can also be used will.

The total amount of component B used is not critical; in general it can be between 0.02 and 50 mmoles per dnr Solvent, diluent or reaction vessel volume, it is preferably between 0.5 and 5 mmol per dm *.

The amount of the catalytic component A used may suitably according to the transition metal (Tr) content thereof be determined. In general, it can be so great that the concentration is between 0.001 and 2.5 and preferably between 0.005 and 1.5 milligram atom of metal per dm ^ of the solvent, diluent or reaction vessel volume amounts to.

The ratio of the amounts of components A and B is also not critical. In general it can be such that the ratio of organometallic compound to transition metal, expressed in mol / gram atom, is greater than Λ and preferably greater than 10.

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The average molecular weight, as indicated by the melt index of the polymers produced by the process according to the invention is expressed, by adding one or more molecular weight regulators such as. B. hydrogen, diethyl zinc or diethyl cadmium, an alcohol or carbon dioxide, can be set.

The specific gravity of the method according to the invention Homopolymers produced can also by adding an alkoxide of a metal of groups IVa or Va des Periodic table to be regulated to the polymerization medium. In this way it is possible to use polyethylene with an in the middle lying specific gravity between that of polyethylenes produced by the high pressure process and that of the classic high-density polyethylene.

Among the alkoxides that are suitable for controlling the specific gravity are those of titanium and vanadium, whose alkoxy radicals each contain 1 to 20 carbon atoms, to be mentioned as particularly effective. These alkoxides include

, Ti £ 0CH ₂ CHCCH ₃ ) 2] ₄ , TKOCgH ^) ^ and

The process of the invention makes the production of polyolefins possible with productivities as high as those described in Belgian patent 791 676, catalytic systems. Thus, the productivity, expressed in grams of polyethylene per gram of catalytic complex, exceeds Homopolynerization of ethylene usually 10,000 and in numerous cases 20,000. The activity based on the Amount of transition metal present in catalytic component A, is also high. In the homopolymerization of ethylene, the activity, expressed in grams, exceeds polyethylene per g of transition metal used, usually 50,000 and in numerous cases 100,000. The cheapest

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Cases it is greater than 1 million.

For this reason, the content of catalytic residues in polymers produced by the process according to the invention be extremely low. In particular, the residue content of transition metal can be extremely low. It however, the derivatives of transition metals, which are in the catalytic residues due to certain colored complexes, which they use phenolic antioxidants, which are commonly are entered into the polyolefin compositions, are particularly harmful. For this reason, the polymers must be used in the known processes for the polymerization of olefins by means of catalysts containing transition metal compounds cleaned of the catalytic residues they contain, e.g. B. by alcohol treatment. In the inventive Process, the content of harmful residues is so low that the cleaning treatment is omitted can be a costly operation in terms of raw materials and the energy they consume as well as, on the sizeable capital investments they are having bring yourself is.

Like the polyolefins produced by the process of Belgian patent 791 676, the Polyolefins produced by the process according to the invention have a remarkably high impact strength. So own Homopolymers produced by the process according to the invention with a melt index of about 5 an impact strength, measured according to the Izod test, from approximately 10kg.cm/cm notch. The polyethylenes with the same melt index, which are produced using known, highly active, catalytic systems do not have an impact strength of more than about 6 kg, measured by the same test method. cm / cm Score.

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The polyolefins produced by the process according to the invention can generally be used in any deformation technique; so they can be used in extrusion, Injection molding, blow molding and calendering processing. They can advantageously be used in applications where good impact strength is required, especially for the production of containers, tubs, pallets and bottles.

Finally, the catalytic systems are according to the invention excellent catalysts for the production of polymers which are suitable for blow molding. In general It is necessary in the case of polymers for blow molding that they have a wide range of molecular weight distribution own. The range of the molecular weight distribution is approximated by the ratio of the melt index at high Load (HLMI, determined under the condition E according to ASTM D-1238) to the melt index (MI, determined under the Condition F according to the form ASTM D-1238), i.e. H. the HLMI / MI value, reproduced. If the catalysts according to the invention are used, a polymer can be produced which has this HLMI / MI value over 70, this being the Blow molding is advantageous. It was found that the catalyst according to the invention is not only suitable for the production of Polymers for injection molding but also for polymers for blow molding is suitable.

In summary, this means that the method according to the invention leads on the same economic route to polymers which have the same basic advantages as the polymers prepared in accordance with Belgian patent 791 676; the outstanding technical progress the invention lies in the fact that the catalytic systems according to the invention are produced in a simpler way, and that no complicated magnesium compound is used,

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which require strict control or difficult conditions to be met in manufacture, handling and in terms of the quality standards required. In addition, the response is of magnesium with the compounds (2) and (3) often exothermic; the heat of reaction can therefore be recovered, by part of the energy costs at other stages of manufacture of component A to save. In contrast, the mixture of the magnesium compound and the transition- metal compound in the process of Belgian patent 791 676 are generally heated to high temperatures.

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

Examples 1 to 3

In the following examples 1a to 3a, the production the solid, catalytic complexes (components A) explained.

Beisj) iel_1a

Into a 1-1 flask equipped with a stirrer was placed 21 g (0.45 mol) of dehydrated ethanol; 3.7 6 (0.15 mol) of metal magnesium in powder form and 102 g (0.3 Hol) of titanium tetrabutylate, Τΐ (0-η-0 ^ Η, Ο ^ were added. The mixture was heated under reflux to I30 C ⁰ kept moving for 2 hours in the absence of water or steam, removing the hydrogen formed in the reaction, the low boiling point substances being distilled at 90 ° C. and removed from the reaction mixture, the remaining mixture (1) being cooled to 60 ° C. Then 200 ml of η-hexane was added to the mixture and 95 6 (0.75 mol) of ethylaluminum dichloride, Al (C ₂ H ₅ ) Gl ₂ , was added dropwise to the mixture over a period of 4 hours at 45 ° C , then the reaction mixture was ^{stirred for 1 hour at 60 °} C. Then η-hexane was added to the reaction product, and it was decanted

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washed, d. H. washing was carried out by repeating the steps of stirring the mixture, allowing it to rest, the Removal of the supernatant liquid and the addition of fresh η-hexane to the residue repeatedly until no more chlorine ions are detected in the supernatant liquid could become. The volume of the suspension obtained was adjusted to 500 ml by adding η-hexane.

When determining the titanium content of the suspension formed in this way with hydrogen by means of a colorimeter according to the method described by G .. 0. Muller, Praktikum der Quantitativen Chemischen Analyze (1957) _? P. 243 »described method, it was found that 10 ml of the suspension contained 5» 0 mmol of titanium compound. The supernatant liquid of this suspension was then removed and the η-hexane was removed by drying the residue in the presence of nitrogen, 72 g of a reddish-brown powder in which the titanium content was determined to be about 15 * 9% by weight became.

The procedure was the same as in Example 1a with the following exceptions:

The remaining mixture (U, cooled to 60 ^° C., was diluted with 400 ml of η-hexane. Then 100 g (0.75 mol) of aluminum chloride, AlCl ,, were gradually added to the contents in the flask so that the temperature fell below 50 ⁰ C remained. Thereafter, the temperature was raised, and the reaction mixture (2) was stirred under reflux for 2 hours at 72 ° C. the product was then washed as in example 1 and dried. 20 g of a white powder was obtained, whose Titanium content was 4.30 wt%.

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Example 3§

The procedure of Example 2 a * was repeated, and after the reaction mixture) was stirred under reflux for 2 hours at 72 ⁰ C, it was cooled "and there were 44 g (0.385 mol) of triethyl aluminum, Al (CpH, -) ,, dropwise added at 45 ° C for 4 hours. After stirring the mixture for 1 hour at 60 ⁰ C, the product was washed as in example 1 and dried. There were 77 6 receive a light brown powder, the titanium content of 18.6 wt .-% fraud.

In the following examples 1b to 3 *> describes the polymerization of ethylene.

Example_1b

The internal atmosphere of a stainless steel autoclave with a capacity of 1600 ecm, the one with an electromagnetic The stirrer was completely replaced by nitrogen, and 1 liter of η-hexane was added to the autoclave filled in and the internal temperature set to 90 ° C.

Then 0.98 g (5 mmol) of triisobutylaluminum,

and 20 mg of the dry, powdery catalyst obtained in Example 1a above are introduced into the autoclave.

The internal pressure of the autoclave was adjusted to one atmosphere and hydrogen under a partial pressure of 7 atmospheres and ethylene under a partial pressure of 12 atmospheres were introduced into the autoclave. In this way the polymerization was carried out using ethylene was replenished so that the total pressure in the autoclave was kept at 20 atmospheres. After two hours it was the ethylene supply shut off and the unreacted gas was removed from the autoclave. The obtained polyethylene was taken out of the autoclave from the solvent separated by filtration and dried. 330 g of a polyethylene (PÄ) with a melt index (KI) of

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5.8 g / 10 min, a bulk density (AD) of 0.39 g / cm ^, a density (D) of 0.965 g / cm * and an Izod impact strength (IZ) of 13 kg.cm/cm received.

Example 2b

The procedure of Example 1b was repeated with the exception

that: · ·

- an autoclave with an internal capacity of 2.2 l was used;

- 0.91 6 (^ i6 mmol) Al (iC.HL) _ and 6.9 mg dry, powdery, catalytic ^ component A, prepared according to Example 2a »were added;

the partial pressure of hydrogen was 6.7 atmospheres and a total pressure of 20 atmospheres was maintained for 2 hours became.

161 g PA were obtained, which had an Mi value of 2.5 g / 10 min

and had an IZ value of 25.2 kg.cm/cm. Yield of PA / mg Ti «5 ^ 0 g
HLMI / M ratio of the PA - 28.

The procedure of Example 2b was repeated with 0.90 S (^, 5 mmol) Al (iBu), ^s and 24.9 mg of the dry, powdery catalytic component A, as it had been obtained in Example 3a. The results were as follows: 258 g PÄ with a Mi value of 8.3 g / 10 min, an AD value of 0.35 g / cm- ⁵ , a D value of 0.964 g / cnr and an IZ- Value of 5.9 kg.cm/cm. Yield of PA / mg Ti. 56 g
HLMI / MI ratio of the PA - 29.

Example 4

Production of the catalytic component A (example 4a) The procedure of Example 1a was repeated with:

8.6 g (0.27 mol) of methanol;

1.95 g (0.08 mole) powdered magnesium;

509812/0996

109 g (0.32 mole) Ti (0-nC ₄ H ₉ ) ₄ j

0.21 g of iodine. ·

The mixture was stirred under reflux for 3 hours at 120 ⁰ C, as in Example 1a (with the exception that 220 ml of η-hexane and 51 g (0.40 mol) of Al (CpHc) CIp were used), washed and dried. 71 g of a yellow-brown powder were obtained, the titanium content of which was 16.7% by weight.

(Example 4b)

Following the procedure of Example 1b "was ethylene at 22 mg polymerized the dry, powdery, catalytic component of Example 4a. 350 g of PA were obtained with a Mi value of 1.5 g / 10 min, an AD value of 0.40 g / cm ^, a D value of 0.964 g / cnr and an IZ value of 48 kg.cm/cm.

Example 5

The solid catalytic component A was prepared in the same manner as in Example 1a with the following exceptions: n-butanol was used in place of ethanol (0.45 mol), and 0.4 g of iodine was added to the mixture which was refluxed during Was stirred at 120 ⁰ C for 3 hours, added; The distillation was carried out at 140 ⁰ C.

The brown powder finally obtained in an amount of 81 g had a titanium content of 15-5% by weight.

The polymerization conditions were the same as in Example 1b, 310 g PA were obtained with an Mi value of 6 g / 10 min, an AD value of 0.39 g / cm *, a D value of 0.965 g / cm and an IZ value of 10 kg.cm/cm.

Example 6

The changes in activity after different periods of time were on the catalytic components A, which in

50981 2/0996

2U1625

Examples 1a and 5 had been prepared, examined .

The catalytic components A were prescribed under the conditions shown in Table I below for a Period of time, and using the stored catalyst, homopolymerization was carried out of ethylene under the same conditions as in Example 1b described, carried out.

The results are shown in Table I.

509812/0996

Table I.

Catalytic component, produced according to the example

Storage method of the catalytic component (under dry nitrogen) Change in activity over time Cg PÄ formed / g catalytic component: hours of reaction)

O CD CO

O CD CO

1a

1a

1a

immediately after manufacture

1 month
after
herstel development

2 months
after
herstel development

dried and in powder form kept 16

stored in a state suspended in n-hexane (concentration of slurry β 9 ^υ / ο) 17

the catalyst was suspended in η-hexane and it became triisobutylaluminum in an amount of 50 ppm, calculated as aluminum, added 16

dried and in powder form kept 15

*) eight months after production 16,000

16 500

18,000

16,000

17 ooo

16 800

17 500

15 500

6 months after manufacture

16,000

17,000

17 500

15 500 *)

CD ISJ

The values given in Table 1 show that the catalytic systems of the invention have very good activity which does not sink during storage.

Examples 7-11

Ethylene was 2 hours at 80 ⁰ C with propylene or butene (1) were fed in amounts shown in Table II values using the Examples 1a obtained according to 5a and 5, catalytic components, among those in the Example 1b copolymerized indicated polymerization conditions, the values given in the following Table II were obtained.

Examples 12 to 29 ■ '

Catalytic components A were prepared as in Examples 2a and 3a using compounds {2) other than ethanol. The specific conditions of manufacture are summarized in Table III below.

In the same way as described in Example 2b, was Ethylene for 2 hours with triethylaluminum and the dry obtained in Examples 12a to 29a, powdery, catalytic components A polymerized. The polymerization conditions and results are shown in Table IV below.

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Table II

At- cataly- general water- amount type of acti- MI AD D IZ

Playful polymeric comonovity

Composition partial comomers (2) (g / iOminHg / cm ^ Kg / cmr.) (Kg.cm/cm,)

element A, conditional pressure ρ nome-

against (kg / cm) ren

represents example (gXi)

according to

example

5098 ' 7th 1a 1b 4.7 34 ButeneC1) 20800 3.9 0 , 40 0.944 13th - ro
-ο ro 8th 1a 1b 6.3 17th Butene (1> 16800 2.8 0 , 39 0.946 18th mm I. ο
co 9 1a 1b 5.7 12th Butene (1) 18800 6.3 0 , 40 0.947 7.8 co
CD 10 1a 1b 4.8 11.3 Propene 17000 3.1 - 0.938. 11 1a 1b '2/4 "57 Propene 18300 8.5 _ 0.914

Amount of comonomer introduced into the autoclave before the polymerization

(2) g of copolymer formed after 2 hours of reaction per g of the catalytic component A

cn K) cn

Table III

When- type of used used kata- amounts of other, used amount of titanium

game connection (2)

dete
lot

lytisehe

G
Connections (g)

to Genalt

won- (weight- )

on Compo- Mg Ti (OnBu) ₄ Iodine AlCl Al (CH ₁ -) ,. nener #)

bond nente ^ ^ PP kata-

(2) (g) A, her-

put shear

according to compo-

Example nente

A (κ)

cn 12a
13a n-propanol
11-CH ₇ OH 26.6 2a
3a 3.7
3.7 101
101 0.4
0.4 67.0
67.0 28.5 23.7
73 3.85
15.5 ro
03
I. σ
co
00 14a
15a
16a
17a n-butanol
nC ₄ H ₉ OH
n-octanol 33.6
105 cd cd cd cd
CM KN CMKN 3.7
3.7
3.7
3.7 102
102
104
104 0.4
0.4
0.4
0.4 68.2
68.2
67.4
67.4 29.2
28.3 25.1
77.2
2 B 4.38
15.5
4.30
16 12/0996 18a
19a n-decanol 53 2a
3a 7.3
7.3 206
206 0.8
0.8 135
135 57.8 46.2
144 4.21
16.5 ro 20a
21a Stearyl alcohol
ⁿ ~ ^C 18 ^H 37 ^OH 122 2a
3a 3.7
3.7 101
101 0.4
0.4 67.2.
67.2 28.5 21.8
73.1 5.68
15.3 CD 22a
23a Isooctanol
iC ₈ H OH 57.6 2a
3a 3.7
3.7 101
101 0.4
0.4 68.5
68.5 29.4 25.2
74.5 5.30
17.5

Table III (continued)

When- type of used- used- kata- amounts of other, used played th compound (2) dete lyti- compounds ()

Crowd see

cn
CD
CO 25a Cyclopentanol co K) 26a
27a ^ -0H CD
CO ■ 28a
29a phenol CO
CD Ethylene glycol
HIGH ₂ CH ₂ OH

Amount of Ti in content gained (wt.

on Compo- Mg Ti (OnBu), Iodine AlCl _x Al (CJH ₁ J * nener %)

bond nente UXg) A, established according to example

79

36.2

2a 7.3 205 0.8 134

3a 7.3 205 0.8 134 57.9

2a 4.4 152 "0.6 101

3a 4.4 152 0.6 101 43.3

2a 3.7 103 0.4 66.2

3a 3.7 103 0.4 66.2 28.3

catalyti shear component A (g)

48.9 4.91 139 '16, 2

33
129

130
105

4.40 13.7

6.57 12.5

Table IV

Polymerization

(Examples 12b to 29b were each with the catalytic components, which were produced in Examples 12a to 29a)

at Al (CpH ₁ -), . used amount of game ( ₆ r ⁵ ' powdery, drier, kataly table component A CmK) 12b 0.94 10 13b 0.96 16.8 14b 0.96 9.5 15b 0.96 17.1 16b 0.96 8.3 17b 0.95 20.1 18b 0.95 11.0 19b 0.94 12.5 20b 0.96 8.6 21b 0.96 18.2 22b 0.96 9.2 23b 0.95 21.3 24b 0.96 8.8 25b 0.95 16.9 26b 0.96 10.5 27b 0.96 17.1 28b 0.96 34 29b 0.96 30.0 *) ■ Yield (g) of polymer

activity MI AD, C) (g / 10min) (g / cnrj 280 0.38 65 5.0 0.39 260 0.39 71 4.2 0.40 240 5.9 0.39 81 4.8 0.41 270 4.2 0.39 49 6.1 0.39 250 6.0 0.38 63 2.9 0.40 240 2, β 0.39 51 5.8 0.40 210 3, S> 0.38 74 4.1 0.39 230 4.6 0.39 62 4.1 0.40 87 5.8 0.33 45 5.2 0.37

Examples 30 "to 52

The preparation of each of the catalytic components of Examples 1a to 3 & was repeated, except that titanium isobutoxide was used was used in place of titanium n-butoxide. The following were obtained in each case:

? üi§Ei2-L_3Oa ^ 63 g of a reddish-brown powder, whose Titanium content was 16.3% by weight (preparation according to Example 1a);

Beisp_iel_31a: 21 g of catalytic complex, its titanium content 4.0% by weight (preparation according to Example 2a, with the exception that 66 g (0.4-9 mol) AlCl, were added);

2®i ^ Ei £ i_52aj_ 72 g of catalytic complex, the titanium content of which was 17.9% by weight (preparation according to Example 3a, with the exception that 66 g (0.4-9 mol) of AlCl and 29 g of Al (C ₂ Hc)).

The investigation of the polymerization of ethylene, which under * the general conditions given in Example 1b with These catalytic complexes were carried out, gave the results summarized in Table V under the specific, listed conditions:

509812/0996

Table V

When the amount of AlCiBu used catalytically, yield MI AD, D, IZ

play complex, to catalytic Cg) to PA / mg Cg / 10min) Cg / cm ^:? ) Cg / cm ^) Ckg.cm/cm)

set according to complex C mg) Ti Cg)

example

30b 30a 19th , 5 0 , 57 C2) 300 C3) LfX , 2 0 , 40 0 , 965 13th 31bCi) 31a 11 , 5 0 , 92 260 5 , 3 0 , 37 - - 32b 32a 18th 0 , 94- 57 4th , 3 0 , 39 _

cn

cd CO autoclave with an internal capacity of 2.2 l

_ »C2) AlCCgHc) - instead of triisobutylaluminum

C3) 6 PAY 19 6 used, catalytic complex

VM ΓΟ

co

CO I

Table VI

When using the catalytic amount of AlCiBu), gain- MI AD, D, IZ

game complex, towards catalytic Cg) nes PÄ Cg / 10min) (g / cm ^:? ) Cg / cm ^p ) Ckg.cm/cm)

provided according to complex Cmg) Cg)
Example ___ _

33b 33a 17 0.98 320 2.8 0.44 0.964 25

34b 34a 20 0.95 320 7.9 0.38 0.967 7.5 ¹ ^

-P-

<75 Ki (JI

Examples 33 and 54-

The procedure of Example 1a was .with the exception repeats that:

- 0.37 g of iodine dissolved in 2 ml of ethanol added to the reactants became. The brown catalytic complex obtained (80 g) contained 15.1% by weight of titanium (Example 33a);

The remaining mixture (1) of Example 1a was ^{cooled to 45 °} C., and 181 g (1.5 mol) of Al (C ₂ H ₅ ^ Cl were added. The black-brown catalytic complex obtained (76 g) contained 18.2% by weight of titanium (Example 34a)

Studies of the polymerization of ethylene under the conditions of Example 1b with this catalytic Complexes were carried out, gave the results compiled in Table VI under the specific ones given Conditions.

Examples 35 to 40

The procedure of Example 4-a was followed with other compounds (2) as methanol and under the specific conditions set out in Table VII below along with the Titanium content and the amount of recovered, catalytic complexes are given.

In the same manner as described in Example 1, ethylene was made for 2 hours with triisobutylaluminum, AlOiC ^ Hg) ,, as Component B and the dry, powdery, catalytic component A, which were obtained in Examples 35a to 40a, polymerized. The specific polymerization conditions and results are summarized in Table VIII below.

5098 12/099 6

Table VII

cn o co

O CO CO CD

Be kind to playful

link

(2)

35a 36a 3'7a

38a

39a 40a

HOGH ₂ -CH ₂ OH

amount of compound used (2)

Cs;

40

125

88

48

42.2 18

quantities used
on other connections

Mg

0.79 0.326

0.56

0.45 0.29

2.51 3.65 2.62

4.45

3.65 1.82

0.103

0.15 0.108

0.183

0.15 0.075

iodine

0.206

0.30

0.216

0.367

0.30
0.15

Distillation of

low boil the
Substanceaa at (° C;

0.22

1.2

0.2 pounds

0.4

0.2

sound like that
Gemisdi added tem
n-hexane

600 400 400

25O

200 200

added CMoI) "Narrow Too much at link won (4) CAthyl 0.52 nener aluminum- 0.75 cata- dichloride) 0.54 Lyti- Cs) 0.915 3cher 0.75 iompo- 0.375 ienteA 66 78 95 108 69 64 116 106 95 91 47 . 77

Ti content of the grain component A (% by weight)

10.5 11.6

11.3 14.9

9.3 10.1

ΓΟ

CT)

ro cn

Table VIII

Polymerization

(Examples 35 "b to 40b were each with the catalytic complexes, which were produced in Examples 35a to 40a)

When amount of AlCiC ^ HgK amount of amount of MI AD D IZ ^game C ₆ ; CmMoI)

35b 1.02 36b 0.98 37b 0.95 38b 1.01 39b 0.98 40b 0.96

_σ drier

to catalytic

oo shear

Component

¹⁰ . te A (mg) ^ ₁

% 35b 1.02 5.1 25 255 2.3 0.37 0.965 24

cn IC ^ π a « _4> 95 28 '315 8.4 0.38 0.964 5.8

4.8 18 260 3.0 0.37 0.965 24

5.1 28 420 9.8 0.40 0.966 6 '

4.95 24 350 6 0.45 0.965 12

4.85 25 160 3.3 0.37 0.965 20

CD CTJ

2A41625

Example 41 Comparative example

The procedure of Example 34a was repeated with the exception that the remaining mixture (1) was ^{cooled to 60 °} C. and diluted with 200 ml of η-hexane. 85.5 g (0.75 mol) of Al (C ₂ H) were added dropwise over 4 hours at 45 ° C. A homogeneous liquid of black-brown color was obtained, which was used in a polymerization experiment as described in Example 1b.

When Al (CpH, -) was used as component B, formed there is no polymer, and if Αΐ (0ρΗ £ -) 01ρ as component B was used, the polymerization could proceed, but the yield was only 3,700 parts by weight of polymer per Part by weight of the titanium atom of the mixed catalytic composition. This shows that the catalytic activity is practically negligible is when reactants (4) and component B are used free of chlorine.

Example 42

About 1 g of pure magnesium in the form of chips was heated together with 30 g of titanium tetrabutylate (product of Dynamit Nobel), 24.3 g of triphenylsilanol (product of Aldrich, No. 14372-3) and 4.5 g of butyl chloride (product of Merck) . A few crystals of iodine were added and the mixture was held at a temperature of about 150 ° ^C. for a period of 270 minutes. The Mg / Ti atomic ratio of the mixture was about

70 ml of a 50% strength by weight were added to the cooled mixture A solution of ethylaluminum dichloride (product of Schering) in hexane was added, the Mg / Al atomic ratio being about 0.2. An exothermic reaction occurred and the mixture was held at ambient temperature for 0.5 hour. The received, catalytic solid component was separated, with

509812/0996

1625

1.5 1 0.5 1 6th mg 200 mg 85 ⁰ C 1 hour 10 ρ
kg / cm 4th kg / cm.

Washed hexane and dried. Elemental analysis showed that it contained: 166 g / kg titanium, 343 g / kg chlorine, 47 g / kg Magnesium, 32 g / kg aluminum and 37 g / kg silicon.

A polymerization test was carried out with this component under the following conditions:

- autoclave

- hexane

- amount of catalytic solid

- Type and amount of component B: triisobutyl

aluminum

- temperature

- Duration

- ethylene partial pressure

- partial pressure of hydrogen

Approximately 108 g PA was recovered, the MI value of which was 0.38. This represents a catalytic productivity of 1,800 g PA / g catalyst χ hour χ atm. Cp ^H 4 and a specific activity of 10 800 g PA / g Ti χ hour χ atm. Represents C ₃ H _4. The HLMI was 9.85 and the HLMI / MI ratio was 26; the AD and D values were 0.30 and 0.960 g / cnr, respectively.

Example 43

About 4.86 g of pure magnesium in powder form were heated together with 47 ml of dehydrated ethanol and 152 g of zirconium n-butoxide (product of Dynamit Nobel). This mixture was ^{kept at about 90 °} C. for ^{2 hours, then heated to 150 °} C. until all of the excess alcohol had been removed. The mixture was then diluted with 250 ml of η-hexane. The Mg / Zr atomic ratio in the mixture was about 0.5

300 ml of a 50% strength by weight solution of Al (C ₂ H ₅ ) Cl ₂ (product of Schering) in hexane were added to the cooled mixture. The Mg / Al atomic ratio was therefore about 0.2.

509812/0996

An exothermic reaction occurred and the mixture was ^{kept at 50 °} C. for 1 hour. The solid, catalytic component that was recovered was separated, washed with hexane and dried. Elemental analysis showed that it contained: 125% zirconium, 387 g chlorine, 91 g magnesium and 48 g aluminum per kg.

A polymerization test was carried out on this component under the same conditions as in Example 42 with the exception carried out that 33 mg of catalytic solid along with 100 mg of triethylaluminum were used.

About 75 g PA ″ were obtained, the Mi value of which was about 1.53. This corresponds to a catalytic productivity of 230 g PA / g catalyst χ hour χ atm. CH. And a specific activity of 1840 g PA / g Zr χ hour χ atm. C ₀ H .. The AD value of the polymer was 0.17 g / cm and the HLMI value could not be measured. The D-Vert of the polymer was 0.962 g / cm

Example 44

9 »7 6 powdered magnesium, 94 ml dehydrated ethanol

and 58 S vanadyl n-butoxide, VO (OnC.H ₁ O- ,, were mixed and heated in the same manner as in Example 43 (Mg / V atomic ratio

■ about 2). 75 S of ^the by crushing the cooled, solid

Product obtained powder were with 600 ml of a 25 wt .-% Solution of Al (CpHc) CIp diluted (Mg / Al atomic ratio - approx

0.4). Elemental analysis of the solid obtained in the same manner as in Example 43 showed that it was 104 g

Vanadium, 113 g magnesium and 66 g aluminum per kg.

One with 16 mg of this solid among those given in Example 42 The polymerization test carried out under conditions gave 10 g of solid PA, the melt index of which was about 40. Accordingly the hourly productivity and the specific activity are 600 g FÄ / g catalyst χ hour and 6000 g PÄ / g V χ hour.

50981 2/0996

Example 45

The solid catalytic complex was made according to the procedure of Example 1a with the exception that Al (O-ISoC-JE, -,) -, as compound (5) together with Mg, Ti (OCJ3qK, n-C ^ HqOH and Iodine was implemented. For this purpose, a mixture of;

45.4 g nC ₄ H ₉ 0H 2.43 g powdered magnesium 9.57 S Ti (0-nC ₄ H ₉ ) ₄ 24.0 g Al (0-isoC H) and 0.5 g iodine

stirred under reflux for .2 hours at 100 ⁰ C.

Substances with low boiling points were distilled off from the reaction mixture. Then after cooling to 60 ⁰ C

300 ml of η-hexane added and were g pp added 76.2 over a period of 2 hours at 45 ⁰ C.

23, 7 g of red-brown, powdery catalytic complex obtained after washing and drying. The titanium content was 5.1% by weight.

A polymerization experiment was carried out under the following conditions carried out:

- autoclave

- hexane

- amount of catalytic solid

- Type and amount of component B: triisobutylaluminum

- Duration

- ethylene partial pressure

- Hydrogen partial pressure

- temperature

1 , 6 1 1 1 36 mg 200 mg 2 hours 11 ρ
, 4 kg / cm 7th , 6 kg / cm 60 ⁰ C

509812/0996

24A1625

Approximately 382 g of PA were recovered. The AD », MI and HLIil / HI values were 0.30 g / cm ^, 170 and 56.2, respectively.

Example 46

The procedure for preparing the catalytic complex of Example 45 was repeated except that Si (OC ₂ H ₅ ) _{4 was used} as compound (5) and C ₂ H ₅ OH was used in place of ^ C ₄ H ₉ . Accordingly, a mixture of:

13.7 6

2.43 g powdered magnesium 10.2 g TiC0-nC ₄ H ₉ ) ₄ 24.2 g Si (OC ₂ H ₅ J ₄ and

0.25 g of iodine

with each other in almost the same procedure as in Example 45 (except that 76.2 g of AICpHc-Cl _{2 was} used). 24.2 g of a red-brown, powdery, catalytic complex were obtained, the titanium content of which was 4.9% by weight.

The polymerization test was carried out under the same conditions as in Example 45 except that 100 mg of the catalytic complex was used. About 216 g of PA were recovered. The AD, MI and HLMI / MI values were: 0.40 g / cm ⁵ , 015 and 51.9, respectively.

Examples 47 to 49

Catalysts were prepared in the same manner as in Example 42 with the exception that (CH 1), SiOH, (C ₂ H ₅ ) ^ SiOH and (tert-C ₄ Hg) (CH ^) ₂ SiOH, respectively, in the examples 47, 48 and 49 were used instead of (CJEI ₁ -), SiOH.

509812/0996

2 ^ 1625

The polymerization was carried out under the same conditions as in Example 42 performed. The details of manufacture the catalytic component A and the polymerization results are summarized in the following Table IX:

Table IX example

47 48

Amount of Mg (g) 0.97 0.98 0.97

Type of compound (2) (CH; SiOH (C ₀ H ₅ ) ^ SiOH (^ C ₄ H ₉ ) (CH) ₀ SiOH

Amount of connection

(2; Q ₅ ; 10.8 11 ·, 4 11.5 Amount of Ti (On-Bu) ^
(G) 27.2 27.5 27.0 Amount of Al (C ₀ H ^) Cl ₀
(g) ^d ^ ^d 29.5 31.0 30.4 Ti content of the catalyst
sators (%) 17.1 15.1 14.0 Activity of the Kataly
sators (g PÄ / g Ti) 128,000 152,000 112000 Melt index of the poly
ethylene 1.5 2.1 0.9

Examples 50 and 51

Catalysts were prepared in the same manner as in Example 43 with the exception that the Zr (0-nC ₄ H ₉ ) _{4 was} replaced by VO (OCgH. ") In Example 50 and by condensed titanium butylate of the following average structural formula in Example 51:

? 4 ^H 9 ^C 4 ^H 9 C.
I. 4 ^H 9 0 Ό 0 I. I. I. C ₄ H ₉ O-Ti 0- I. T
• i OC ₄ H ό 0 0 I. I. I. ^C 4 ^H 9 ^C 4 ^H 9 C. 4 ^H 9

509812/0996

INSPECTED

The polymerization was carried out under the same conditions as
carried out in Example 43. The particulars of the preparation of the catalytic component A and the polymerization results are summarized in Table X below.

Table X example

50 51

Amount of Mg (g) 4.86 4.86

Connection (3)

Amount of compound (3) (g) amount of Al (C ₂ H ₅ ) Cl ₂ (g)

Atomic ratio: transition metal (Tr) AIg

Al / Mg atomic ratio Transition metal content of the catalyst (%)

Activity of the catalyst (g PA / g Tr)

Melt index of polyethylene

91 51 127 127 1 1 5 5 • 9.2 12.8 33,000 203,000 0.05 0.70

509812/0996

Claims (21)

Claims 1. Process for the low pressure polymerization of alpha-olefins in the presence of a catalytic system which is an organometallic compound (component B) of a metal of groups I to III of the periodic table and contains a solid, catalytic complex (component A), thereby, characterized in that component A is obtained by reacting: (1) metallic magnesium; (2) a hydroxylated organic compound; (3) an oxygen-containing organic compound of a metal (Tr) of groups IVa, Va or Vlades Periodic table; (4) an aluminum halide \ has been obtained with each other. 2. The method according to claim 1, characterized in that the compound (2) is selected from the organic compounds which contains at least one hydroxyl group bonded to a carbon or silicon atom. 3 · The method according to claim 2, characterized in that the compound (2) among monohydric and polyhydric organic alcohols containing 1 to 12 carbon atoms contained per hydroxyl group is selected. 4. The method according to claim 2, characterized in that the compound (2) is selected from hydrocarbylsilanols has been. 5. The method according to claim 3 »characterized in that the compound (2) is a saturated, monohydric, aliphatic alcohol having 1 to 6 carbon atoms. 509812/0996 6. The method according to claim 3, characterized in that the compound (2) is an unsubstituted, monohydric aromatic alcohol having 1 to 6 carbon atoms. 7. The method according to claim 1, characterized in that the compound (3) ^{corresponds to the general formula [TrO, (OR 1} ) J, in which: - Tr is a metal of groups IVa, Va or VIa of the periodic table; - R ^{1 is} an organic radical containing 1 to 18 carbon atoms; - y> 0; - x ¹ and y are numbers compatible with the valence of the metal Tr, and - m is an integer. 8. The method according to claim 7 -> characterized in that .. Tr is titanium, zirconium, vanadium or chromium. 9- The method according to claim 1, characterized in that the compound (4) corresponds to the formula AIR X, _ in which: - R is a hydrocarbon containing 1 to 20 carbon atoms rest is; - X is a halogen; - 0 <χ <3. 10. The method according to claim 9, characterized in that - R is a saturated, aliphatic radical with 1 to 6 carbon atoms is; - X is chlorine; - 0 < χ <2. 509812/0996 11. The method according to claim 1, characterized in that the connection (4) consists of: - A compound of the formula AlX, and - a connection of the formal AlR-, wherein E is a hydrocarbon radical containing 1 to 20 carbon atoms and X are halogen. 12. The method according to claim 1, characterized in that component A was obtained by adding the compound (2), the compound (3) and the compound (4) are added to the metallic magnesium in the order given have been. 13 »The method according to claim 12, characterized in that component A has been obtained by adding the compound (2) and the compound (3) were added to the metallic magnesium and adding the compound (4) to the reaction product obtained was added. 14. The method according to claim 12, characterized in that the component A has been obtained by ^ adding the compound (2) was added to the metallic magnesium, and adding the compound (3) and the compound (4) to it were added to the obtained reaction product. 15 · The method according to claim 1, characterized in that metallic magnesium and the connection (2) with each other were brought into contact that the molar ratio of magnesium to compound (2) is less than 1 g-at / mol is. 16. The method according to claim 1 ,. characterized in that metallic magnesium and the connection (3) so in contact: be brought that the atomic ratio of magnesium to metal (Tr; between 20 and 0.0β g-at / g-at is. 50981 2/0996 17 «Method according to claim 1, characterized in that metallic magnesium and the compound (4) are brought into contact with each other so that the atomic ratio from magnesium to aluminum is between 10 and 0.01 g-at / g-at. 18. The method according to claim 1, characterized in that component A was obtained by starting from a further compound (5), which is derived from the oxygen-containing, organic compounds of a metal of groups IHb or IVb of the periodic table. 19 «Solid, catalytic complexes, characterized in that they are produced by the reaction of: (1) metallic magnesium; (2) a hydroxylated organic compound; (3) an oxygen-containing organic compound a metal (Tr) of groups IVa, Va or VIa of the periodic table; (4) an aluminum halide have been prepared with each other. 20. Process for the preparation of a solid, catalytic complex (component A), which together with a organometallic compound (component B) of a metal from groups I to III of the periodic table for polymerization of olefins, characterized in that these components A are prepared by: (1) metallic magnesium; (2) a hydroxylated organic compound; (3) an oxygen-containing organic compound of a Metal (Tr) of groups IVa, Va or VIa of the periodic table; (4) an aluminum halide can be reacted with one another. 5098 12/0996 21. Application of the method according to claim 1 for the polymerization of alpha-olefins, the molecule of which is 2 to 8 coals substance contains atoms. 50981 2/0996