DE2455415A1 - METHOD OF POLYMERIZATION OF OLEFINS - Google Patents

Description

PATENT LAWYERS

DR. ING. A. VAN DERWERTH DR. FRAN Z LE DE RE R

21 HAMBURG 90 8 MUNICH 8O

WILSTORFER STR 32 TEL. IO «0> 77O8 6I LUCl LE-C RAHN-STR. 22 TEL. (089) 47 29 * 7

Munich, Oct. 25, 1974 pp. 73/57

SOLVAY & CIE.

33 * Rue du Prince Albert, Brussels, Belgium

Process for the polymerization of olefins

The invention relates to an improved process for low pressure polymerization of olefins and solid, catalytic ^ complexes that can be used for the polymerization of olefins, a process for the preparation of these complexes as well as those with Polymers produced by the process according to the invention.

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

Furthermore, it is from the Belgian patent specification 705 220 of Applicant known to use a solid as the transition metal compound of the above-mentioned catalytic systems,

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GERMAN BAKK AC. HARiUBC 99 / SOBIS POSTSCHECK HAMBURO 1173 20-206

TELEGRAMS: LEATHER PATENT MÖNCHEN

obtained by combining a halogen compound of a transition metal with an oxygen-containing compound of a divalent metal such as magnesium. The catalytic systems obtained in this way are very active when compared with those in which the halogen compound of the transition metal is used as such will.

In Belgian patent 730 068 of the applicant are catalytic ^ systems described in which one of the constituents is also the product of the reaction between a transition metal compound and a solid support that passes through a hydroxylated and / or hydrated halide of a divalent metal is formed.

In Belgian patent specification 767 586 of the applicant are catalytic systems described, one component of which was produced by the fact that an oxygen-containing organic Compound of a divalent metal with an alkyl aluminum halide has been reacted, the product of this reaction separated and then allowed to react with a halogen compound of the transition metal.

In Belgian patent 791 676 of the applicant are catalytic systems described in which one of the constituents was produced by the fact that an oxygen-containing organic compound of a metal such as magnesium, an oxygen-containing, organic compound of a transition metal and an aluminum halide have been reacted with one another.

Although the activity of the previously described in these publications, catalytic systems is much better than that of catalytic systems in which the transition metal compound was used as such, it has nevertheless been found that they do not work satisfactorily since the with the help

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such systems obtained polyolefins for "certain applications have too high concentrations of catalytic residues.

The object of the invention is to create an improved method and catalytic systems for implementation this method, whereby the disadvantages indicated above are not given.

It has now been found that the use of a new type of catalytic complexes based on organometallic Compounds of transition metals have been made, the production of polyolefins having a higher activity than that of the constituents of the prior art belonging catalysts allows, the polyolefins at the same time a higher, average molecular weight and a have broader molecular weight distribution.

The invention therefore relates to a process for low-pressure polymerization of alpha-olefins, which is characterized by that one works in the presence of a catalytic system which is an organometallic compound of a metal of groups Ia, Ha, Hb, IHb and IVb of the periodic table and a solid catalytic complex made by reacting with one another

1) a compound (M) of magnesium,

2) an organometallic compound (T) of a metal (Tr) of groups IVa, Va and VIa of the periodic table and

3) an aluminum halide (A)
lets react.

The reactant (1) used to prepare the catalytic complexes according to the invention, namely the Compound (M) of magnesium, is a compound that is made up of

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is selected from the oxygen-containing compounds and the halogen compounds of magnesium, d. H. among all Compounds of this metal which have at least one magnesium - oxygen bond or at least one magnesium bond Have halogen in their molecule.

A first class of compounds (M) of magnesium, which are suitable for carrying out the invention, is formed by the magnesium compounds, the at least one bond Have magnesium-oxygen.

It can be oxygen-containing, inorganic compounds of magnesium act, in the molecule of which the magnesium is only an. Oxygen is bound. Among these connections are to call:

- the hydroxide, Mg (OH) ₂

- the salts of inorganic oxy acids, e.g. B. MgCO ₃ , MgSO ₄ , Mg (N0 ₃ ) ₂ , Mg ₃ (P0 ₄ ) ₂ , Mg ₃ (BO ₃ ) ₂ and Mg (C1O ₄ ) ₂

the basic, optionally hydrated, salts of magnesium, e.g. B. 4 MgCO ₃ JSg (OH) ₂ .5H ₃ O and 3 MgCO ₃ ^ Mg (OH) ₂ .

- the basic, optionally hydrated, salts of Magnesium and another metal, e.g. B.

Furthermore, it can be oxygen-containing, organic Act magnesium compounds, d. H. to compounds which any organic to magnesium with the interposition of have oxygen-bound residues.

The organic residues bound to magnesium via oxygen can be any.

They are preferably chosen from among the radicals up to 20 carbon atoms and especially 1 to 6 carbon atoms contain. Such residues can be saturated or unsaturated,

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be branched, straight, or cyclic; they can also be substituted and / or heteroatoms such as 0, S, Have N, P, etc. in their chain. Preferably they will selected from the hydrocarbon radicals and particularly preferably from the alkyl, alkenyl, aryl, cycloalkyl, Arylalkyl, alkylaryl, acyl radicals and their substituted Derivatives.

Such compounds can be named:

- the alkoxides of magnesium such as methylate, ethylate, isopropylate, Decanolate, cyclohexanolate and benzylate;

- the phenoxides of magnesium such as phenate, naphthenate, Anthracenate, phenantrenet and cresolate;

the carboxylates of magnesium, if necessary hydrated like the acetate, stearate, benzoate, phenyl acetate, adipate, Sebacate, phthalates, acrylate and oleate;

- the oxygen and nitrogen containing organic compounds of magnesium, d. H. Compounds which bond sequences magnesium-oxygen-nitrogen-organic residue contain like, the Oximate, especially the Butyloximate, the dimethylglyoximate and the cyclohexyloximate, the hydroxamic acid salts and the hydroxylamine salts, especially the derivative of N-nitroso-N-pheny-hydroxylamine;

- the chelates of magnesium, d. H. oxygenated, organic Compounds in which the magnesium has at least one sequence of normal bonds of the magnesium-oxygen-organic type Rest and at least one coordination bond with the formation of a Heteroeyclus in which the magnesium is included is, possesses, e.g. B. the enolates and especially the acetylacetonate, as well as the complexes, which from phenolic derivatives containing an electron donor group in the ortho position, based on the hydroxyl radical, and in particular the 8- * hydroxyquinolinate.

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

- the compounds, which contain several, different, organic bests such. B. the magnesium methoxyethylate,

- the complex alkoxides and phenoxides of magnesium and

a metal other such. B. Mg (Al (OR) ^ ₂ and Mg ^ [Al (OR) ₆ "] ₂ ;

- the mixtures of two or more oxygen-containing, organic compounds of magnesium of the type mentioned above .

The oxygen-containing magnesium Verbindungen.des eventually also include complex compounds which comprise a plurality of types of magnesium bonded to the interposition of oxygen radicals.

For example, the oxygen-containing compounds of magnesium can simultaneously be oxygen-containing, organic and have inorganic radicals or residues.

They can also have organic residues which are bound directly to magnesium via the carbon. Among such compounds are e.g. B. to be mentioned: Magnesium hydroxymethylate and magnesium ethyl ethylate.

Among all the above-mentioned oxygen-containing compounds are preferably magnesium de8 the organic oxygen-containing compounds of this metal used, and in particular those which have only binding sequences magnesium-oxygen organic radical. Among the latter, the best results are obtained with the alkoxides and phenoxides of this metal .

A second class of compounds (M) of magnesium which is suitable for carrying out the invention is represented by the magnesium compounds, which are at least one

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Magnesium-halogen bond included. The one bound to magnesium Halogen can be fluorine, chlorine, bromine or iodine. Preferably this halogen is chlorine. Under such connections are to be mentioned:

..- the commercially available dihalides of magnesium, which commonly referred to as "anhydrous" and which are actually hydrated dihalides that are one mole and have less water per mole of dihalide; the "anhydrous" dihalides of magnesium on the market are a typical example of such compounds;

- The complexed with various electron donors magnesium dihalides such. B. the complexes with ammonia such as MgClp.6KH ^, MgCl ₂ .2HH, and the complexes with alcohols such as MgCl ₂ .6CH ₅ OH, MgCl ₂ .6C ₂ H ₅ OH and MgClg.6C ₃ H ₇ OH;

the hydrated magnesium dihalides which contain more than one mole of water per mole of dihalide, such as MgCl ₂ .6H ₂ MgCl ₂ .4H ₂ O and MgCl ₂ .2H ₂ O;

- the halogenated compounds of magnesium, in which the metal ah a "halogen and a hydrocarbon residue, as previously defined, is bound, e.g. B.

and Mg (C ₆ H ₅ ) Cl.

Among the magnesium compounds belonging to this second class the dihalides are preferred for practicing the invention, with best results with the hydrated. Magnesium dichlorides can be achieved. The use of two or several different compounds from the compounds defined above is also within the scope of the invention.

A third and final class of compounds (M) of magnesium, which are suitable for carrying out the invention is formed by the compounds of this metal, which simultaneously Magnesium-halogen bonds and magnesium-oxygen

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Have bonds in their molecule. Examples of such compounds include:

- the compounds which, in addition to the magnesium-halogen bond (preferably the magnesium-chlorine bond) an inorganic residue bound to the magnesium via oxygen,

z. B. have a hydroxyl radical such. B. in Mg (OH) Cl and Mg (OH) Br;

the compounds which, in addition to the magnesium-halogen bond (preferably the magnesium-chlorine bond), contain any organic radical bonded to the magnesium via oxygen. This organic radical is preferably selected from the radicals defined above, the best results being obtained with the chloroalkoxides and the chlorophenoxides of magnesium, e.g. B. Mg (OCH ₅ ) Cl, Mg (OC ₂ H ₅ ) Cl

and Mg (OC ₆ H ₅ ) Cl;

- the hydrolysis products of the hydrated magnesium halides (preferably the chlorides), provided these products still contain magnesium-halogen bonds exhibit;

the mixed compositions containing halogenated magnesium compounds and oxygenated compounds. Typical examples of such compositions are the basic magnesium halides (preferably the chlorides), e.g. B. MgCl ₂ -MgO.H ₂ O, MgCl ₂ .3MgO.7H ₂ O and MgBr ₂ .3MgO.6H ₂ O.

Finally, it should be noted that the use of two or more, to one of the three previously defined Compounds belonging to classes are of course within the scope of the invention.

Among all the compounds (M) of magnesium listed above, the most important compounds are the alkoxides, as they allow the preparation of catalytic complexes that have the highest catalytic activity.

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The reactant (2) used to prepare the catalytic complexes according to the invention is an organometallic Compound (T) of a metal (Tr) of groups IVa to VIa of the periodic table.

All organometallic compounds of these metals are suitable for carrying out the invention. Organometallic compounds are to be understood as meaning those compounds (T) in which one or more organic ligand (s) (as will be defined below) to the metal (Tr) via a bond (metal Tr-carbon) from the C- or IT type are bound. Such compounds can be represented by the general formula R TrX (I), where:

- R one or more, identical or different, organic

Ligands which are bonded to the metal (Tr) via a metal-carbon bond of the <y or Tf type; Such organic ligands R are preferably free of oxygen;

- X one or more anionic, monovalent, identical or

different ligands attached to the metal (Tr) via a. atoms other than carbon are bonded;

- m an integer number indicating the number of parts attached to the metal (Tr)

represents bound ligand R and which can vary from 1 to the maximum valence of the metal (Tr);

- n. an integer from 0 <η ^ m; organic compounds,

however, which contain no ligand X are preferred. Such compounds therefore correspond to the general formula R _m Tr (II), in which R, Tr and m 'have the meanings given above.

The metal (Tr) is selected from the transition metals belonging to one of the groups IVa, Va or VIa of the periodic table include, and preferably made of titanium, vanadium, zirconium and chromium. The best results are obtained when (Tr) titanium is. -

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The organic ligands E are selected from:

(a) the organic radicals which contain 1 to 20 carbon atoms and in particular 1 to 10 carbon atoms, preferably from aliphatic and alicyclic, saturated and unsaturated hydrocarbon radicals, aromatic Hydrocarbon radicals and their substituted derivatives;

(b) the aliphatic and alicyclic, unsaturated hydrocarbons, the aromatic hydrocarbons and their substituted derivatives, hydrocarbons, their Molecule has 1 to 20 and preferably 1 to 10 carbon atoms.

Examples of organic radicals (a) which can be used as ligands R include:

- optionally substituted alkyl and cycloalkyl radicals,

z. B. methyl, ethyl, butyl, 2,2-dimethylpropyl and 1-bicycloheptyl; ■

- Optionally substituted alkenyl and cycloalkenyl radicals, e.g. B. vinyl, allyl, methylallyl and cyclooctenyl,

The above-mentioned radicals can also carry inorganic substituents and, in particular, halogen atoms, examples are: tetrachlorocyclopentyl and dichlorocyclopentyl, or even have substituted, inorganic radicals themselves, ζ. B. trimethylsilylmethylene;

- The cycloalkadienyl, cycloalkatrienyl, cycloalkadienylene radicals and their substituted derivatives, eg. B. Cyclopenta-

. dienyl, methyl, acetyl, phenyl and benzylcyclopentadienyl, cycloheptatrienyl and cyclopentadienylene;

- aryl, alkylaryl and arylalkyl radicals, e.g. B. Phenyl, Tolyl, Naphthyl, benzyl, p-methylbenzyl, 1-methylene-1-naphthyl.

The abovementioned radicals can also carry substituents which carry groups free of carbon and oxygen

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such as azo and amino groups, ζ. B. the radicals phenylazocyclopentadienyl and dimethylaminophenyl.

Examples of hydrocarbons which can be used as ligands R. (b) can be named:

- linear alpha-olefins such as heptene and decene;

- cyclic olefins, e.g. B. Cycloheptatriene;

- Mono- and polyaromatic compounds and their substituted ones Derivatives, e.g. B. benzene, toluene, ethylbenzene, cumene, Naphthalene, anthracene, phenanthrene, mesitylene.

Good results are obtained if the ligands R defined above from alkenyl, cycloalkadienyl, aryl, alkylaryl and arylalkyl radicals are selected. The best results are obtained when the organometallic compounds (T) of transition metals (Tr) only use arylalkyl radicals as ligands R and do not include a X ligand.

However, if the organometallic compound free of oxygen of the transition metal also has one or more ligands X, these ligands are selected from monovalent, anionic ligands, and preferably from:

- halogen residues, d. H. Fluorine, chlorine, bromine and iodine residues, the chlorine residue is used in particular. . "■.

Among the compounds of the general formula R _m _ _n i which lead to advantageous results, the following can be mentioned:

- methyl titanium trichloride, diethyl zirconium dichloride, tetrakis (2,2-dimethylpropyl) titanium, Tetrakis-Ci-bicycloheptyl) vanadium, Tetrakis-d-bicycloheptyl) titanium;

-Tris-Cif-allyl) -zirconium chloride, Tris- (T-methylallyl) -chrom, and tetrakis (Tr-allyl) zirconium;

- Tetrakis-CtrimethylsilylmethyleneO-zirconium;

- bis (cyclopentadienyl) titanium dichloride, cyclopentadienyl zirconium trichloride, Cyclopentadienyl chromium dichloride,

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Benzylcyclopentadienyltitanium tribromide, dimethyl bis (methylcyclopentadieny1) titanium, Cyclopentadienylene zirconium dichloride, Bis (phenyl-azocyclopentadienyl) -titanium dicliloride;

- tetraphenyltitanium, phenylzirconium trichloride, tetrabenzyltitanium, Tris (benzyl) zirconium chloride, tetrakis (p-methylbenzyl) zirconium, Tetrakis (1-methylene-1-naphthyl) titanium, Bis (dimethylaminophenyl) bis (cyclopentadienyl) titanium;

Bis (phenyl) bis (cyclopentadienyl) titanium, (cyclopentadienyl) (methylcyclopentadienyl) titanium dichloride;

- bis (benzene) zirconia, bis (benzene) chromium, bis (benzene) vanadium, Cycloheptatriene cyclopentadienyl chromium, benzene cyclopentadienyl chromium.

It goes without saying that the use of two or more organic compounds (T) that are free of oxygen are, and correspond to the general formula (I) or (II), is also within the scope of the invention.

The preparation of compounds of general formula (I) is known per se in the art. The manufacturing methods Such compounds are described in: M. Dub., Organometallic Compounds, Vol. I, Compounds of Transition Metals, Springer-Verlag 1966.

The preparation of compounds of the general formula (I) in which (Tr) denotes titanium is described in detail by Feld and Cowe. The Organic Chemistry of Titanium, Butterworths 1965, Chapter 1 specified.

The reactant (3) used to prepare the catalytic complexes according to the invention is an aluminum halide (A). It is preferably selected from the aluminum halides of the general formula AlR ¹ , Z_, (III), in which R ^{1 has} 1 to 20 carbon atoms and preferably 1 to

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Hydrocarbon radical containing carbon atoms, Z is a halogen (fluorine, chlorine, bromine or iodine) and n ^{1 is} a number from 0 < n '<3. Preferably, R 'is selected from alkyl radicals (linear or branched), cycloalkyl radicals, arylalkyl radicals, aryl radicals and alkylaryl radicals. The best results are obtained when Z represents chlorine and n ¹ = 0 £ n ¹ £ and preferably = 1 £ n ¹ £ 2.

As examples of aluminum halides usable in the invention can be named: AlCl "(() and ()

Several different aluminum halides can also be used.

To carry out the reaction to form the catalytic Complex can use the compound (M) of magnesium, the organometallic compound (T) and the aluminum shark ο genid (A) will:

-in solid form, e.g. B. in suspension in an inert diluent or in the form of dry particles;

- in liquid form, if the operating conditions permit;

- in the form of a solution; "" *

- in the form of steam or gas.

The reaction to form the solid complex becomes preferable carried out in liquid medium. To do this, one can work in the presence of a diluent, this being a represents preferred embodiment of the invention, wherein. the temperature and pressure conditions are chosen so that at least one of the reactants is soluble in the diluent. All common in organic chemistry used diluents can be used. the

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Organometallic compounds (T) of the general formula (I) or (II) are often soluble in such diluents. ■ Preference is given to using the alkanes, cycloalkanes and aromatic hydrocarbons, the molecule of which is 4 to. 20 carbon atoms contains, e.g. B. isobutane, n-pentane, η-hexane, n-heptane, cyclohexane, Methylcyclohexane, the dodecanes, benzene and toluene. The polar solvents generally used in the preparation of organometallic compound (T) can also be used use, such as B. the ether, the molecule contains 1 to 12 carbon atoms (e.g. diethyl ether), tetrahydrofuran, Pyridine, methylene chloride, etc. If a diluent is used, the total concentration of the or the dissolved reactants preferably above 5% by weight and particularly preferably above 20% by weight, based on the diluent.

The reaction to form the complex can also be carried out in a liquid medium in the absence of a diluent. However, the organometallic compound (T) is often "in the solid state under the usual temperature and pressure conditions before; in such a case it is still possible to avoid the diluent by using a reactant (4) which is liquid. The respondent (4) used for this embodiment of the invention is made by an oxygen-containing organic compound of a metal (Me) of groups IHb and IVb of the periodic table, preferably by an organic oxygen containing compound of aluminum or silicon, with the best results with organic, oxygen-containing Compounds of aluminum are obtained. With regard to the respondent (4) it should be noted that the Definition of "organic, oxygen-containing compound" all Designates compounds in which there is an organic residue

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is bonded to the metal (Me) with the interposition of oxygen, the organic radical being selected from the radicals which correspond to the definitions and restrictions given above with regard to the organic, oxygen-containing compounds (M) of magnesium. The alkoxides of aluminum and silicon are preferably used, examples of such compounds being Al (OCJi ₇ ) * and Si (OCZiHq) ^.

The temperature at which the reaction to form the catalytic complex is carried out is not critical. In general, they are chosen so that one of the reactants is liquid or dissolved in the diluent and so that any decomposition of the organometallic compound (T) is avoided; in general, the temperature is between -50 and 200 ^° C .; in most cases where the organometallic compound (T) is used in the dissolved state -. ambient temperature (25 ⁰ C) is suitable.

The pressure is also not critical; generally works one under atmospheric pressure. In order to homogenize the To favor the reaction medium, this is generally stirred or kept in motion for the duration of the reaction. The reaction can be carried out continuously or batchwise. Finally, it is also important to that the reaction medium remains free of water and oxygen as far as possible, with which the organometallic compounds (T) and the aluminum halides (A) could react.

The order in which the reactants are added is arbitrary. However, one of the following methods is preferred:
1) You give the reactant (1) ^ compound (M) of magnesium3 and the reactant (2) ^ organometallic ^

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Compound (T) J together by gradually moving them together mixed or added one to the other; if necessary, the reaction participants are added in the same way (4-) ([Organic, oxygen-containing compound of the metal (Ke) J is added; then the Reactant (3) Add aluminum halide (A) J;

2) the reactant is mixed, preferably very rapidly (2) and the reactant (3) »then one gives adding the reactant (1);

3) mix all of the reactants at the same time and gradually. . .

The rate of addition of the reactants is also not critical. It is generally chosen in such a way that that no excessive heating or heating of the reaction medium as a result of a possible runaway of the Reaction is evoked.

The preferred amounts of reactants to be used are explained in more detail below:

The amount of reaction participant (2) is defined based on the amount of compound (M) of magnesium used. It can vary to a great extent. In general, it is between 0.01 and -100 at.-g (atomic gram) of metal (Tr) present in the organometallic compound (T) per at.-g of magnesium present in the compound (M). It has been found that the efficiency of the catalytic complexes (productivity and specific activity) is highest when the atomic ratio is Tr / Mg between 0.025 and 5 at.-g / at.-g. The best results are obtained when this ratio varies between 0.05 and 2.5 at-g / at-g.

If the variant of the process according to the invention is used in which one uses a reactant (4),

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are the amounts of this reactant to be used such that the ratio between the amount of metal (Me) and the amount of metal Tr that is in the reactant (2) is present, between 0.01 and 100 at.-g / at.-g. The atomic ratio s Me / Tr is preferably between 0.1 and 50 at.-g / at.-g. The best results are obtained when it varies between 1 and 20 at-g / at-g.

The amount of reactant (3) is calculated based on the amount _v of the amount of reactant (2) and of the optionally used reactant (4). It can also vary widely. In general, it is between 0.1 and 10 mol of aluminum halide per eq.-g (equivalent gram) of metal (Tr) which is present in the organometallic compound (T) and of the metal (Me) which is present in the organic, oxygen-containing compound of a metal of groups IHb and IVb is present. The equivalent gram is the weight of these metals in grams, which one atom gram of hydrogen can replace or react with. Preferably this amount is between 0.25 "and 2.5 MpI per eq.-g. The best results are obtained when it is between 0.5 and 1.5 mol per eq.-g.

The catalytic complexes prepared according to the invention are firm. They are in alkanes and cycloalkanes, which as Diluents can be used, insoluble. They can be polymerized in the form in which they are received were used without being separated from the reaction medium. However, separation is preferred from this reaction medium, the separation process having no effect. If the reaction medium is liquid, you can z. B. Use filtration, decantation or centrifugation.

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After the separation, the catalytic complexes can be washed in order to remove the excess reactants with which they could still be impregnated. Any inert diluent can be used for this washing process, e.g. B. those that are applicable as constituents of the reaction medium, e.g. B. alkanes and cycloalkanes. ^: After washing, the catalytic complexes can be dried, for example by purging with a flow of dry nitrogen or under vacuum.

The mechanism of the reaction to form the catalytic complexes of the invention is not known. The elemental analysis However, these complexes after separation and washing show that they are more complex, chemically bound Products of chemical reactions, and not the result of mixtures or adsorption phenomena. Indeed, it is impossible to include one or the other of the reactants. Or constituents of these complexes Use of only physical separation methods to split off.

The inventive, catalytic complexes, their exact Nature also not well known, contain magnesium, metal of groups IVa, Va and VIa, optionally metal of groups IXIb and IVb, aluminum and halogen in variable amounts. - ■

The catalytic systems according to the invention also contain an organometallic compound that acts as an activator serves. Organometallic derivatives of metals from groups Ia, Ha, Hb, IHb and IVb of the periodic table are used, z. B. the organometallic compounds of lithium, magnesium, zinc, aluminum or tin. The best results are obtained with organometallic compounds of aluminum.

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Completely alkylated compounds can be used, the alkyl chains of which contain 1 to 20 carbon atoms and are straight-chain or are 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 and tetrabutyl tin. However, it is preferred to use Trialky aluminum compounds whose alkyl chains are 1 to Contains 10 carbon atoms and is straight or branched are.

Alky! Metal hydrides can also be used in which the Alkyl radicals also contain 1 to 20 carbon atoms, e.g. B. Diisobutyl aluminum hydride and trimethyl tin hydride. Likewise alkyl halides of metals in which the alkyl radicals also contain 1 to 20 carbon atoms are suitable, e.g. B. Ethyl aluminum sesquichloride, diethyl aluminum chloride and Diisobutyl aluminum chloride.

Finally, you can also use organoaluminum compounds use which have been obtained by trialkylaluminum compounds or dialkyl aluminum hydrides, the groups of which contain 1 to 20 carbon atoms, with 4 to 20 carbon atoms containing diolefins were reacted, in particular the substances referred to as isoprenylaluminum compounds.

The inventive method -is for the polymerization of Olefins with terminal unsaturation are suitable, their molecule Contains 2 to 20 and preferably 2 to 6 carbon atoms, z. B. ethylene, propylene, butene- (1), 4-methylpentene- (i) and Witch- (T). It is also used for the copolymerization of such olefins with one another as well as with diolefins, which preferably contain 4 to 20 carbon atoms, can be used. Such diolefins aliphatic, non-conjugated diolefins such as hexadiene (1,

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be, monocyclic diolefins such as 4-vinyl yelohexene, 1,3-divinylcyclohexane, Cyclopentadiene- (1,3) or cyclooctadiene-d, 5), alicyclic, diolefins with an endocyclic bridge, e.g. Dicyclopentadiene or norbornadiene, as well as aliphatic conjugated Diolefins such as butadiene and isoprene.

The inventive method is particularly good for the production of homopolymers of ethylene and of copolymers, which contain at least 90 mol% and preferably 95 mol% ethylene are suitable.

The polymerization can be carried out by any of the known methods: in solution or in suspension in one. Hydrocarbon solvents or diluents, or in the gas phase. I for the procedures in In solution or in suspension, solvents or diluents that are used for washing the catalytic complex are used used are analog; these are preferably the alkanes or the cycloalkanes such as butane, pentane, hexane, heptane, Cyclohexane, methylcyclohexane or mixtures thereof. Likewise the polymerization can be carried out in the monomer or one of the monomers which is kept in the liquid state.

The polymerization pressure is generally between atmospheric 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 organometallic compound and the catalytic complex can be added separately to the polymerization medium. You can also bring them at a temperature between -40 and 80 ⁰ C for a period of up to two hours in contact before they are in the reaction vessel for the

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Polymerization are introduced. You can also use them in
bring several stages into contact with one another, or else
part of the organometallic compound previously in the
Enter reaction vessel or several, different ones
add organometallic compounds.

The total amount of the organometallic compound used is not critical; in general it is between 0.02 and 50 mmol per dm ^ solvent, diluent or volume of the reaction vessel, and preferably between 0.2 and 5 mmol / dnr.

The amount of catalytic complex used is determined as a function of the metal (Tr) content of the complex. It is generally selected so that the concentration
between 0.001 and 2.5 and preferably between 0.01 and 0.25 mat.-g metal per dm ^ solvent, diluent or
Volume of the reaction vessel is.

The ratio of the amounts of organometallic compound and catalytic complex is also not critical. In general, it is chosen so that the ratio of organic compound / metal (Tr), expressed in mol / at.-g, is above
of 1 and preferably above 10.

The average molecular weight and therefore the melt index of the polymers produced by the process according to the invention can be adjusted by adding one or more molecular weight regulators such as hydrogen, zinc or cadmium diethyl alcohols
or carbon dioxide can be controlled to the polymerization medium.

The specific gravity of the homopolymers produced by the process according to the invention can also be determined by adding an alkoxide of a metal from groups IVa and Va des
Periodic table to the polymerization medium are regulated. on

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In this way one can obtain polyethylene with specific weights between those produced by a high pressure process "Manufacture polyethylenes and the classic high-density polyethylenes. ■

Among the alkoxides suitable for this scheme are those of titanium and vanadium, the remains of which are 1 contain up to 20 carbon atoms, particularly effective. Examples are: Ti (OCEU) ^,

H ₁₇ ) ₄ and

The process according to the invention enables the production of polyolefins with remarkably high productivities. So exceeds productivity in the homopolymerization of ethylene, if the catalytic complex of magnesium alkoxides used and organometallic compounds (T) of the formula (II) in which R is an aralkyl radical, was prepared, regularly 3000 and in certain cases 10,000. Which depends on the amount of transition metal (Tr) present in the catalytic complex related activity is also very high. In the homopolymerization of ethylene, again expressed in grams of polyethylene per g metal (Tr) used, it regularly exceeds 10,000 and in certain cases 100,000.

The catalytic residue content is due to this extremely low in the polymers produced by the process according to the invention. In particular, the content of remaining transition metal (Tr) extremely low. However, it is these derivatives of transition metals that are found in the catalytic Residues as a result of the colored complexes interfere with those commonly used in polyolefins, phenolic antioxidants. Therefore, the polymers in the classical procedures for the polymerization of olefins with the aid of derivatives of transition metals

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of the catalytic kickstands they contain be cleaned, e.g. B. by alcohol treatment. In the process according to the invention, the content of interfering Residues are so small that the inclination treatment is skipped which is an expensive operation in terms of raw materials and energy, requires considerable facilities requires.

The polyolefins produced by the process according to the invention can be converted into end products by all known procedures, e.g. B. by extrusion, blow molding ,. Injection molding, etc. You can e.g. B. for the production of objects for handling (bags, bottle containers), for receptacles (Bottles) are used for foils and for adhesive strips.

In addition, the molecular weight distribution of the polyolefins obtained, if the catalytic complex used from alkoxides or chlorides of magnesium and organometallic Compounds (T) of the formula (II) in which E is an arylalkyl radical represents, was made, 'broader than the molecular weight Distribution of polyolefins with catalytic complexes with a ratio of Tr / Mg and Al / Tr, which those in the aforementioned Belgian patent 791 are obtained. This wider distribution, combined with a higher, average molecular weight and obtained with lower hydrogen concentrations of the polymerization medium than in the previously known mode of operation, in particular in procedures for further processing, through Extrusion (extrusion) and blow molding advantageous.

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

example 1

a) _Herstellung_des_katal2tischen complex 11.4 g magnesium ethylate, Mg (OC ₂ Hc) ₂ , (commercial product of

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Dynamit Nobel) are transferred to 50 ml of petroleum ether (fraction with a boiling range between 60 and 80 ⁰ C) in suspension. 75 ml of a 40 is added to this suspension

% By weight solution of tetrabenzyltitanium. Ti (CVHc-CH ₅ )., In ASieaeDereich BD to IDO ¹³ Uy ο ρ 2 4 ^Τ

Petroleum ether / to. The tetrabenzyltitanium was previously by action from TiCl ^, to Benzy! magnesium chloride, C JIt-MgCl, in Diethyl ether with the addition of pyridine according to that described in Helvetica Chimica Acta, Vol. 50 (1967), pp. 1305-1 * 313 Working method established. The mixture obtained in this way is for 3 hours at ambient temperature in Movement kept. The atomic ratio Ti / Mg is approximately equal to 0.5 at.-g / at.-g.

80 ml of a solution with 400 g of ethylaluminum chloride, Al (CJa ₁ OCl ₂ (product of Schering), in 1 liter of hexane are then added to the mixture. The Al / Ti ratio is therefore approximately equal to 1.25 mol Al (C ₂ H ₅ ) Cl ₂ per eq.-g Ti. After the

₂₅₂

Allowing to boil for one hour at approximately 79 ° ^C. , the black precipitate obtained is separated off. This precipitate is washed with hexane and dried under vacuum for one hour. The elemental analysis of the catalytic complex thus obtained showed the following contents per g:

675 mg Cl

42 mg Ti
182 mg Hg

29 mg Al.

With the above, catalytic complex was among the following Conditions of a polymerization test carried out: 12 mg of the catalytic complex were in 500 ml of hexane in a stainless steel autoclave of 15ΟΟ ml, which was equipped with a paddle stirrer, transferred into suspension. 200 mg of triisobutyl aluminum were added. the

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Temperature was brought to 85 ⁰ C, and it was ethylene and '

Hydrogen under respective partial pressures of 5 kg / cm and 2 kg / cm introduced. The polymerization was carried out for one hour, the ethylene pressure by continuous Supply of ethylene was kept constant. After blowing off the autoclave, 95 g of polyethylene with a melt index MI, measured under normal load (2.16 kg) according to the ASTM 1238-57 T standard, of 0.51 g / 10 min (2) and a melt index at high load, HLMI, measured under heavy load (21.6 kg) according to the ASTM 1238-57 T standard, of 18.7 g / 10min (1) won. The ratio (i) / (2), which is typical for the expansion of the molecular weight distribution, was therefore to 37 · The catalytic productivity was about 8000 g PÄ (PÄ * = polyethylene) per g of catalytic complex, and the specific activity was 38,000 g PA / h g Ti χ kg / cm

For comparison, one of ethylene in the presence of one of magnesium ethylate, titanium tetrabutylate and ethylaluminum dichloride (atomic ratio Ti / Mg 0.5 at.-g / at.-g; ratio Al / Ti * 1 mol / eq.-g) the Belgian patent 791 676 carried out polymerization experiment under respective

'· 2

Partial pressures of ethylene and hydrogen of 10 and 4 kg / cm only a yield of 42 g of polyethylene for 10 mg of the catalytic complex used (Ti content = 70 mg / g) can be obtained. This polyethylene had a melt index (MI) of 0.75 g / 10 min and a high load melt index (HLMI) of 17 * 8 g / 10 min, so that this is only a ratio HLMI / MI of 23.8 gives.

Example 2

a) _Manufacture_of_catalytic_com £ lexes

Magnesiumchloridtetrahydrat, MgCl ₂ .4HpO '(commercial product of Rhßne-Poulenc) was heated to 185 ⁰ C, until the monohydrate obtained. 27 g of thus obtained Magnesiumchloridmonohydrat were dissolved in 40 ml of a solution containing 40 wt -.% Ti (C ₆ H _j-CH2) ^. in

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Petroleum ether, which has been prepared according to Example 1 a) was transferred into suspension. The mixture thus obtained, the atomic ratio of which Ti / Mg was approximately equal to 1.25 at.-g / at.-g, " was kept in motion for two hours at ambient temperature and refluxed for one hour. Afterward 40 ml of a 50% strength by weight solution of Al (CpH, -) Clp added in hexane. The ratio Al / Ti, expressed in moles of AlCCpHcOCl per eq.-g of Ti, was therefore approximately equal to 1. After After refluxing the suspension for one hour, the resulting precipitate was separated off and washed and dried as described in Example 1 a). The catalytic complex produced in this way contained per g:

504 mg Cl 121 mg Ti
39 mg mg
140 mg Al.

b) Polymerization attempt

In a polymerization test carried out under identical conditions as in Example 1 b) but with 20 mg of the catalytic complex, 24 g of polyethylene with a melt index under normal load (MI) which was not measurable and a melt index under heavy load (HLMI) of 1.05 The catalytic productivity was 1200 g PI / g catalytic complex and the specific activity was 2000 g PA / h g Ti kg / cm ² C ₂ H ₄ .

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Claims (1)

Claims Λ. " Process for the low-pressure polymerization of alpha-olefins, characterized in that one works in the presence of a catalytic system which contains an organometallic compound of a metal from groups Ia, Ha, Hb, IHb and IVb of the periodic table and a solid, catalytic complex which was produced by: (1) a compound (M) of magnesium, ^ (2) an organometallic compound (T) of a metal (Tr) belonging to groups IVa, Va and VIa of the periodic table, and (3) an aluminum halide (A)
implemented. - 2. The method according to claim 1, characterized in that a connection is used as the connection (M), which at least has a magnesium-oxygen bond in its molecule. ".-." 3. The method according to claim 2, characterized. That as Compound (M) an organic, oxygen-containing compound is used, which organic, to the magnesium has residues bound via oxygen. · 4. The method according to claim 3? characterized in that as Compound (M) is an alkoxide or phenoxide of magnesium is used whose organic radical contains 1 to 6 carbon atoms. . - 5. The method according to claim i, characterized in that as Compound (M) a compound is used which at least has a magnesium-halogen bond in its molecule. 50 9822/0910 6. Procedure according to. Claim 5 »characterized in that as Compound (H) a hydrated magnesium chloride is used. 7. The method according to claim 1, characterized in that a connection is used as connection (M) which simultaneously Has magnesium-oxygen bonds and magnesium-halogen bonds in its molecule. 8. The method according to claim 1, characterized in that an organometallic compound (T) is used which _{corresponds to the general formula ^ m} _ _n ^ ^r ^ _n , 'in which: - R an organic, attached to the metal (Tr) via a bond Metal-carbon bonded ligand, - X is a monovalent, anionic ligand bound to the metal (Tr) via an atom other than carbon, - m is an integer which represents the ligands E bound to the metal (Tr), and ■. - η a whole count of 0 ^ η 9 · The method according to claim 8, characterized in that an organic compound (T) is used, which of the general Formula E corresponds to Tr. 10.Verfahren according to claim 8, characterized in that the Metal (Tr) is titanium, zirconium, vanadium or chromium. 11. The method according to claim'10, characterized in that the metal (Tr) is titanium. 12. The method according to claim 8, characterized in that the Ligand E is an aliphatic or alicyclic hydrocarbon radical, an aromatic hydrocarbon radical or a substituted derivative thereof which has 1 to 20 carbon atoms. 509822/0910 13 · Method according to claim 8, characterized in that the ligand B is an unsaturated, aliphatic or alicyclic one Is a hydrocarbon, an aromatic hydrocarbon or a substituted derivative thereof, of which Molecule contains 1 to 20 carbon atoms. Process according to Claim 12, characterized in that the ligand E is an arylalkyl radical. Process according to Claim 1, characterized in that the aluminum halide ^{corresponds to the general formula AlE 1} .Z,, in which E ^{1 is} a hydrocarbon radical containing 1 "to 20 carbon atoms, Z is a halogen and n ^{1 is} any number from 0 <: n ¹ c 3 are. 16. The method according to claim 15, characterized in that E ^{1 is} a hydrocarbon radical containing 1 to 6 carbon atoms, Z is chlorine and n ^{1 is} any number from 1 <. n ¹ <. 17. The method according to claim 1, characterized in that the solid, catalytic ^ complex was prepared by except the compound (M) of magnesium, the organometallic compound (T) and the aluminum halide (A) an organic, oxygen-containing compound of a metal (Me) of groups IHb and IVb of the periodic table with one another implemented. 18. The method according to claim 17, characterized in that the metal of groups IHb and IVb of the periodic table Is aluminum or silicon. 509822/0910 19. The method according to claim 1, characterized in that the amount of organometallic compound (T) to be used is selected such that the atomic ratio between the total amount of metal (Tr) and the total amount of magnesium is between 0.01 and 100 at.-g /at.-g lies. 20. The method according to claim 19, characterized in that the atomic ratio is between 0.025 and 5 at.-g / at.-g. 21. The method according to claim 1, characterized in that the amount of aluminum halide (A) to be used is selected such that the ratio between the total amount of the aluminum halides and the total amount of the metal (Tr) and optionally the metal (Me) of Groups IHb and IVb of the periodic table is between 0.1 and 10 mol / eq.-g. 22. The method according to claim 21, characterized in that the ratio is between 0.25 and 2.5 mol / eq.-g. 23- Process for the preparation of solid, catalytic complexes, characterized by reacting with one another: (1) a compound (M) of magnesium, (2) an organometallic compound (T) of a metal (Tr) belonging to groups IVa, Va and VIa of the periodic table and (3) an aluminum halide (A). 24. Solid, catalytic complexes for the low-pressure polymerization of alpha-olefins, characterized in that they have been prepared by reacting with one another: (1) a compound (M) of magnesium, (2) an organometallic compound (T) of a metal (Tr) belonging to groups IVa, Va and VIa of the periodic table, and (3) an aluminum halide (A). 509822/0910 25 · Application of the process according to claim Λ for the polymerization of olefins with terminal unsaturation, the molecule of which contains 2 Ms 6 carbon atoms. 26. Polyolefins produced by the process of claim 1. 509822/0910