KR20050090367A - Oxygen-containing organoaluminium complexes as cocatalysts - Google Patents

Abstract

The invention relates to novel oxygen- containing organoaluminum complexes of general formula (I) in which R 1 independently represents branched or unbranched C1-C 7 alkyl, C1-C7 cycloalkyl, C1-C7 alkenyl, C1-C7 cycloalkenyl, C1-C7 aryl, or C1-C7 alkinyl; R2 represents unsubstituted, monoalkylated or multialkylated, and/or monofluorinated or multifluorinated aromatic hydrocarbons from group; R3 and R4 independently represent CH2, CF2, or C(R1) 2; and m and n each independently represent 0, 1, 2. Said compounds can be used as cocatalysts in olefinic polymer reactions, particularly for producing novel Ziegler-Natta catalysts having improved properties, especially higher activities than conventional Ziegler-Natta catalysts using AIEt3, as a cocatalyst, or novel coordination catalyst systems which have higher activities than conventional Ziegler-Natta catalysts already at temperatures as low as 60 °C and at a pressure of 2 bar.

Description

Oxygen-containing aluminum complex as cocatalyst {OXYGEN-CONTAINING ORGANOALUMINIUM COMPLEXES AS COCATALYSTS}

The present invention relates to an organoaluminum complex containing oxygen of general formula (I).

[In the meal,

R ¹ independently of ^one another represents branched or unbranched C ₁ -C ₇ -alkyl, -cycloalkyl, -alkenyl, -cycloalkenyl, -aryl, -alkynyl;

R ² represents an unsubstituted mono- or polyalkylated and / or mono- or polyfluorinated aromatic hydrocarbon from the group:

;

R ³ , R ⁴ independently represent CH ₂ , CF ₂ or C (R ¹ ) ₂ ;

Independently of each other

m represents 0,1,2,

n represents 0,1,2].

The compounds can be used as cocatalysts in olefin polymerization reactions, which have improved properties compared to conventionally used compounds.

Conventional coordination catalyst systems are multipurpose catalysts used specifically for the chemical reaction of unsaturated olefin compounds. These are, in particular, processes for producing olefin polymers by coordination polymerization and processes for metathesis of alkenes or alkynes. The preparation of various polyethylenes for various applications, for example high density polyethylene (HDPE) or especially low density polyethylene (LLDPE), and polymers and copolymers of ethylene, propylene or other 1-alkenes and alkynes are of considerable industrial importance. Catalytic substitutions can be used for the preparation of higher unsaturated hydrocarbons from asymmetric alkenes or alkynes and for the particular production of long chain unsaturated hydrocarbons from unsaturated cyclic hydrocarbon compounds. Long chain unsaturated hydrocarbons are used, for example, in the preparation of elastomers. Moreover, coordination catalysts are used in further reactions, for example, hydrogenation of alkenes or organometallic synthesis.

Scientific knowledge for estimating the mechanism of coordination catalysts suggests that in each case the transition metal compound is the catalytic activity center, where the unsaturated olefin compound is coordinatively bound in the first step. Olefin polymerization occurs through coordination of the monomers to the transition metal-carbon or transition metal-hydrogen bonds and subsequent insertion reactions. The presence of organometallic compounds during the coordination catalyst system or catalysis is necessary to activate or maintain the catalyst by reduction and selective alkylation of the complex system (cation / anion). Thus the compound is also known as a promoter. Compounds containing catalytically active transition metal elements are known as primary or precatalysts.

Coordination polymerization using complex initiator systems has recently achieved considerable industrial importance, particularly for the polymerization of ethylene under low pressure. USA alone produced more than 8 10 ⁹ metric tons of PE in 1995 (SWBigger, Eur. Polym. J. Vol. 32, No. 4, pp. 487, 1996).

The most important catalysts in the industry in the art are the so-called Ziegler-Natta catalysts. This is the name given to a system consisting of a combination of elemental periodic table Group IV-VII metal compounds and, for example, alkyl or aryl compounds or hydrates of main Group I-III elements. Typical Ziegler catalysts include, for example, Et ₃ Al and TiCl ₄ ; It is formed in the reaction of AlEt ₂ Cl and TiCl ₃ . The system is heterogeneous catalysts; They are formed as fine suspensions in organic solvents (eg heptane).

Most important, preferably used alkylaluminum compounds are AlEt ₃ , Al-i-Bu ₃ , AlEt ₂ Cl, AlEtCl ₂ , AlEtCl ₂ and AlEt ₂ OR, all of which are very sensitive to atmospheric oxygen and moisture, are autoignitable and difficult to operate. Instead of titanium chloride, vanadium and chromium compounds, in certain applications also molybdenum, cobalt, rhodium, nickel are of particular interest. Instead of alkylaluminum compounds, many other organometallic compounds, in particular sodium, lithium and cadmium, have been described as effective for combination with titanium compounds (HJ Sinn et al., Polymerization und Insertionsaktivitat von Aluminumtrialkylen und Ziegler-Natta Katalysatoren [Polymerisation and Insertion Activity of Trialkylaluminum Compounds and Ziegler-Natta Catalysts], Angew. Chem. 72 (1960) 522).

An industrially important solution polymerization process for the production of HDPE is, for example, the Dow process.

In the above, a mixture of TiCl _x and AlR ₃ is made of hydrocarbon (C ₈ -C ₉ ) under a pressure of p> 10 bar and a reaction temperature of T> 180 ° C. In a continuous process (140 ° C., 30 bar; TiCl ₄ : AIR ₃ = 1: 5) the activity is 6.323 g of PE / h (Dow, US. 3491073, 1970).

In the Du Pont process, Ti / V halides are prepared with AlR _{3 in} cyclohexane under a pressure of 200 bar and a temperature of 180-270 ° C. Activity is 20-50 kg PE / g metal per hour; The molecular weight determined by the viscometer is M _η = 1.8 · 10 ⁵ g / mol (Du Pont, US 2862917, 1958; JP Forsman, Hydrocarbon Processing, 51 (11), 130 (1972).

An industrially important suspension polymerization process for HDPE production is, for example, the Mitsubishi process. In the above, HDPE is prepared in a stirred reactor using a titanium catalyst in n-hexane at 5-10 bar and 30-90 ° C. (A. Kageyama, Hydrocarbon Processing 51 (7), 115 (1972), or Montedison process). The Montedison process is carried out in a stirred reactor using titanium catalyst in benzine at 1-15 bar and 50-100 ° C. The activity is 200 kg of g of PE / Ti (A. Heath, Chemical Engineering ( Apr. 3) 66 (1972).

This heterogeneity, in particular, contributes to the catalytic activity ("catalyst surface portion") at an early stage, and subsequently soluble (homogeneous) systems with approximately the same activity are also subsequently found.

That is, for example, bis (cyclopentadienyl) titanium dichloride (Cp ₂ TiCl ₂ ) or vanadil chloride (VOCl ₃ ) and diethylaluminum chloride (Et ₂ AlCl) or alumoxane ([-OAl (CH ₃ The combination of _n ) provides a homogeneous Ziegler catalyst. There is a more important homogeneous catalyst system: Cp ₂ ZrMe ₂ / alumoxane (homogeneous).

The MgCl ₂ -bonded TiCl ₄ catalyst system was discovered in 1970 and is called a second regenerated catalyst system or “leave-in” catalyst. An example of such a heterogeneous system is: MgCl ₂ / ester / TiCl ₄ / AlR ₃ . The catalytic activity is 200 kg of PE / g of Ti per hour (ADJenkins, A. Ledwith; Reaktivity, Mechanism and Structure in Polymer Chemistry).

All of the above known catalyst systems bear the disadvantage that they can only be used at elevated temperatures and pressures above 10 bar, although satisfactory catalytic activity is not achieved in all cases.

In a wide variety of process variants developed, the practical use of the above catalysts and related types can in some cases provide products with very different properties. In the case of olefin polymers, there is a general importance known as the material, in which the usefulness and the scope of application are, first, due to their properties, the choice and proportion of the parent monomer type, or comonomer, and the typical physical parameters characterizing the polymer, For example, it depends on average molecular weight, degree of molecular weight dispersion, degree of branching, degree of crosslinking, crystallinity, density, presence of functional groups in the polymer, and secondly, properties caused by the process such as the content of low molecular weight impurities, catalyst It depends on the presence of residues and ultimately on cost.

In order to assess the performance of the coordination catalyst system, the desired product properties, e.g. the activity of the catalyst system, i.e. the amount of catalyst required for economic conversion of the predetermined amount of olefins, the product conversion and product yield per unit time, the loss of catalyst and the catalyst In addition to achieving the reuse rate, additional factors are important. There is therefore a need for a catalyst system with high specificity that favors the highest degree of production as well as the low degree of branching and high stereoregularity of the polymer.

However, problems of stability and operability of the catalyst or members thereof are also fundamental. Virtually all known coordination catalysts based on early transition metal compounds are extremely sensitive to air and moisture. Entry of (atmospheric) oxygen and / or moisture reduces activity or irreversibly destroys the coordination catalyst. Thus, the coordination catalyst must be strictly protected against the ingress of air and moisture during manufacture, storage, and use, which naturally makes operation more difficult and increases the complexity required.

Conventional catalyst systems are also sensitive to materials containing electron-rich atoms, ie, intramolecular oxygen or nitrogen. Compounds or polar monomers such as alcohols and amines of interest as additives for comonomers or polymers deactivate the catalyst.

Organometallic compounds used as active agents or cocatalysts, in particular alkylaluminum compounds mainly used for this purpose, are more sensitive in this respect and are therefore still more difficult to manipulate. The compounds present serious problems in practical situations depending on their extreme sensitivity and spontaneous flammability.

It is therefore an object of the present invention to find organoaluminum compounds which are suitable as activated members in the catalyst system and which show higher activity or productivity in the catalyst system as compared to the prior art. Moreover, the compounds have lower sensitivity, thereby facilitating easier manipulation.

This object is achieved by the novel compounds according to the general formula (I) of claim 1:

[Formula I]

[In the meal,

R ¹ independently of ^one another represents branched or unbranched C ₁ -C ₇ -alkyl, -cycloalkyl, -alkenyl, -cycloalkenyl, -aryl, -alkynyl;

R ² represents an unsubstituted mono- or polyalkylated and / or mono- or polyfluorinated aromatic hydrocarbon from the group:

;

R ³ , R ⁴ independently of one another represent CH ₂ , CF ₂ or C (R ¹ ) ₂ ;

Independently of each other

m represents 0,1,2,

n represents 0,1,2].

The compound may act as a promoter in the olefin polymerization reaction. In particular, the mixtures with improved properties are novel Ziegler-Natta catalysts with higher activity and productivity, or lower temperatures, such as 60, compared to the prior art using conventional Ziegler -Natta catalysts with AlEt ₃ as promoters. It can be used for the production of novel coordination catalyst systems with higher activity than conventional Ziegler-Natta catalysts at temperatures of 2 ° C. and 2 bar.

It has been found that organoaluminum compounds that are stable in the molecule of formula (I) are excellently suitable as members in the coordination catalyst system.

Accordingly, the present invention relates to the use of organoaluminum compounds which are stable in molecules of formula (I) as members in a coordination catalyst system and to coordination catalyst systems containing the compounds of formula (I).

The invention also relates, in particular, to the use of the compounds of formula (I) as members of the Ziegler-Natta catalyst.

Coordination catalyst systems containing a compound of general formula (I) according to the invention are present in the form of a combination between transition metal compounds of Groups IV to VIII of the Periodic Table of Elements.

The combination according to the invention of a coordination catalyst system containing a compound of the general formula (I) which is a transition metal compound is, in particular, a compound from the group of TiCl ₄ and VCL ₄ present.

The present invention also relates to a process for producing polymers by polymerization in which the above-mentioned coordination catalyst system is used. In particular, it is a process for the production of polyethylene and polypropylene, preferably for the preparation of high-molecular weight polyethylene and polypropylene.

The compounds of the general formula (I) according to the invention in each case have a cyclic structure in which the aluminum, which is a group IIIa element of the periodic table of the elements and oxygen, which is a group VIa element, represent members of the ring system. In the compounds of formula (I), in close proximity to the carbon atoms, covalently bonded atoms are present on the aluminum. Oxygen atoms are coordinated to aluminum and covalently bonded to two carbon atoms.

Alkyl substitution may in this case be straight or branched with 1-7 C atoms. They may also be part of a ring ring. They are preferably alkyl groups having 1-4 C atoms from the methyl, ethyl, n- and i-propyl, n-, i- and t-butyl groups. The corresponding alkyl group is represented by the symbol R ¹ in formula (I).

Suitable aryl substituents are phenyl as well as naphthyl. The aryl substituent is part of the ring ring. They may be bonded to the oxygen and / or aluminum elements directly or via an alkyl spacer having one or two carbon atoms. However, aryl substituents can be mono- or polyalkylated or -fluorinated hydrocarbons, in particular phenyl and naphthyl. Corresponding aryl groups are represented by the symbols R ² and R ¹ .

Suitable compounds of formula (I) have four substituents on the central aluminum atom, with the high probability that oxygen will have a coordinating bond and contribute to the stability of the compound. A more detailed description of the binding ratio is not possible.

The compounds according to the invention can be prepared by methods known to those skilled in the art for the preparation of organometallic compounds. The method for producing the compound is, for example, [G. Bahr, P. Burba, Methoden der organischen Chemie [Methods of Organic Chemistry], Vol. XIII / 4, Georg Thieme Verlag, Stuttgart (1970). In detail, the compounds may be prepared under suitable reaction conditions known for the reaction. However, it is possible here to use a variant known per se which is not described in more detail. Furthermore, a detailed description of the synthesis can be found in DE-A 38 17 090 A1 and DE-A 37 26 485 A1 or in Chem. Ber. 124 , 1113-1119, (1971). The technical teachings given in this article are part of the invention herein.

In particular, the compounds of general formula I according to the invention can be prepared by the reaction of alkoxyaryl metal compounds, for example alkoxyaryllithium or alkoxyaryl-grignard compounds, with dialkylaluminum chlorides, wherein the alkoxyaryl metals The molar ratio of compound to dialkylaluminum chloride is 1: 1.

The method is preferably carried out as follows:

a) an equimolar amount of dialkyl aluminum in which an alkoxyaryl metal compound, such as an alkoxyaryllithium or alkoxyaryl-grinyad compound, suspended in a hydrocarbon or diethyl ether is dissolved in a suitable hydrocarbon at a temperature of +20 to -78 ° C Mix with chloride,

b) stirring the mixture at a temperature of 20 to 80 ° C. for 2 to 60 hours, removing the solvent and separating the desired reaction product by distillation or crystallization.

Suitable solvents for carrying out the process can be hydrocarbon or aprotic polar solvents such as diethyl ether or tetrahydrofuran. Hydrocarbons can be aliphatic as well as aromatic hydrocarbons. Suitable hydrocarbons include, in particular, pentane, hexane, heptane, toluene. Additional suitable hydrocarbons are known to those skilled in the art and may be selected depending on the starting compound.

After the reaction, the produced product is worked up by methods known to those skilled in the art. After the solid formed is separated off, the workup is preferably carried out by distillation or crystallization.

Surprisingly it has recently been found that the compounds according to the invention are particularly suitable as members in coordination catalyst systems. Using the compounds according to the invention in a polymerization reaction using Group 4-8 transition metal compounds, in particular titanium compounds, in particular olefin polymerization, higher activity and productivity are obtained in comparison with the prior art. . On the one hand, in particular a catalyst system with high activity, stability and service life and on the other hand a polymerization product having a large molecular weight and at the same time a single structure are obtained.

The compounds according to the invention are quite stable also under the influence of oxygen, in particular atmospheric oxygen, and moisture. This also applies to coordination catalysts prepared with the aid of these compounds. Moreover, the corresponding coordination catalyst system has a particularly high stability under reaction conditions. They significantly lower the tendency to inactivate by compounds with free electron pairs, especially compounds containing hetero atoms such as sulfur, oxygen, nitrogen, or phosphorus. The catalyst system according to the invention has particularly advantageous properties in the polymerization reaction, in particular in the olefin polymerization reaction.

Very particularly good results are thus obtained using TiCl ₄ as a catalyst supported on MgCl ₂ and mixtures of the invention. Particularly good results are achieved by a system in which TiCl ₄ is activated by an organoaluminum compound which is stable to oxygen in which an aromatic ring is located in the vicinity of aluminum or an oxygen atom in the ring ring. MgCl ₂ / TiCl in the presence of _4, conventional Ziegler-Natta catalyst MgCl ₂ / TiCl ₄ and AlEt ₃ (4500 kg of _{PE / mol Ti * h * c} ethene) higher yields (of 6100 kg PE / mol _{Ti *} than h _* c _ethene ) activity with compounds (2-methoxy-benzyl) diisobutylaluminum and (8-ethoxynaphth-1-yl) diethyl-aluminum in Table 1 to give high molecular weight products The increase is excellent. Improved properties can similarly be achieved if compounds (2-methoxymethylphen-1-yl) diethylaluminum, (2-butoxy phen-1-yl) diisobutylaluminum are used.

      With the aid of all the catalyst systems tested according to the invention, very large molecular weight polyethylene and polypropylene are obtained in extremely high yields. This means that the reaction termination of the polymerization chain by the catalyst center is less during the polymerization reaction and the entire catalyst system is very stable to impurities and other external influences.

In total, the coordination catalyst system according to the invention has a high specificity, in particular in olefin polymerization reactions, and a product with a narrow molecular weight distribution of high molecular weight is obtained. Although this also depends on the reaction treatment and the reactants used, however, it belongs to the basic method to those skilled in the art and can optimize the reaction conditions if necessary.

The use according to the invention of the compounds of the formula (I) as activated members in coordination catalyst systems is similarly available in place of the conventional organometallic compounds thus far, and in particular in place of the less stable and dangerous alkylaluminum compounds.

Because of the high activity of the catalyst system, more products can be formed relative to the amount of catalyst or the amount of catalyst can be considerably reduced. The latter case results in little catalyst left in the product. In addition, the cost can be reduced by further lowering the catalyst consumption. Although the cost is affected by a series of additional factors such as the qualitative and quantitative composition of the catalyst system, the monomers used, the reaction conditions and the progression during the polymerization, however, the catalysts used are merely the amount of protective necessary to maintain activity Plays an important role. Due to the wide variety of oxygen stable organoaluminum compounds according to the invention, those skilled in the art can easily determine and optimize the most suitable catalyst system, usually for the purpose of assisting experiments.

As already mentioned above, the compounds of formula (I) according to the invention solve the problem considerably in their preparation, storage and use than in the case of previously known systems, and also assist in obtaining a very stable coordination catalyst system advantageously. Is a very stable compound. In particular, complexes in which the oxygen, the atmosphere and the moisture are completely excluded from the solvents, monomers and protective gases used in the polymerization reaction can be omitted.

Catalysts are prepared and used in a manner known per se, for conventional systems and for particular applications. In general, suspension processes are used in metathesis with olefin polymerization and heterogeneous catalysts. To this end, a support-bonded precatalyst is initially prepared from a catalytic transition metal compound and a finely divided support material, which is, if necessary, activated or preactivated in a conventional manner, and with solvents such as pentane, hexane Suspended in alkyl hydrocarbons such as heptane or octane. Cocatalysts are also added in other respects, usually just prior to the monomer reaction or at the current “in situ”. The reaction is controlled and the reaction product is also isolated and worked up by a totally similar method.

As already mentioned earlier, all process steps can be carried out under significantly easier and less stringent protective and stable quantities, due to the increased stability of the donor-stabilized organoaluminum compound and the significantly reduced sensitivity of the resulting catalyst compound. .

The present invention thus makes an accessible novel catalyst system having advantageous properties, for example higher activity and productivity compared to the prior art, in addition it can be tailored to the specific application needs.

The embodiments given below are intended to illustrate the subject matter of the present invention in more detail. However, this is not intended to limit the subject matter of the present invention to a given embodiment, but to inform those skilled in the art of the more general validity of the subject matter described in the present invention based on the information given.

Example

Oxygen Stabilized Organoaluminum Complex Synthesis

Example 1

2.5 ml (20 mmol) of Et ₂ AlCl were dissolved in 50 ml of diethyl ether, and 33 ml (56 mmol) of t-butyllithium (1.7 M solution in pentane) and 9.7 g (56 mmol) in 200 ml of hexane. To 3.5 g (20 mmol) of (1-ethoxynaphth-1-yl) lithium suspension prepared with 1-ethoxynaphthalene was added dropwise at -40 ° C. The mixture is slowly warmed to room temperature and stirred at room temperature for 24 hours. The mixture is then decanted from the solid to remove dissolution. The residue is taken up in 35 ml of toluene and filtered through D4 frit. After removal of toluene, fractional distillation affords (8-ethoxynaphth-1-yl) diethylaluminum as a light yellow liquid with a boiling point of 146 ° C. at 0.01 mbar.

Example 2

10.1 ml (50.2 mmol) of ⁱ Bu ₂ AlCl, 50.2 ml (50.2 mmol) of n-butyllithium (15% solution in hexane) and 10.1 g (50.2 mmol) in 100 ml of toluene, and 100 ml of heptane To a suspension of 6.43 g (50.2 mmol) of (1-methoxymethylphen-2-yl) -lithium prepared from 1-bromo-2-methoxymethylbenzene was added dropwise at -78 ° C. The mixture is slowly warmed to room temperature and stirred for 18 hours at room temperature. The mixture is then filtered through D4 frit. After removal of toluene, fractional distillation gives a viscous colorless (2-methoxymethylphen-1-yl) diisobutylaluminum having a boiling point of 120 ° C. at 0.8 mbar.

Example 3

150 ml (39 mmol) of (2-methoxybenzyl) magnesium chloride as a 0.26 mol solution is added dropwise to 6.83 g (38.7 mmol) of ⁱ Bu ₂ AlCl in 250 ml of tetrahydrofuran at 0 ° C. over 3 hours. . The mixture is slowly warmed to room temperature and stirred for 18 hours at room temperature. The solvent is removed under reduced pressure (0.05 mbar) and the residue is suspended in 125 ml of n-pentane. The mixture is then filtered through D4 frit. After removal of n-pentane, fractional distillation gives a viscous colorless (2-methoxybenzyl) diisobutylaluminum with a boiling point of 85 ° C. at 0.05 mbar.

Example 4

1 mol of n-hexane solution of diethylaluminum chloride (60.4 ml, 60.4 mmol) was added to a suspension of [2- (methoxymethyl) -phenyl] lithium (7.74 g, 60.4 mmol) in 120 ml of toluene at −50 ° C. Was added slowly. The mixture was warmed to room temperature and stirred for 2 days at 60 ° C. The solvent is removed under reduced pressure, and the residue is dissolved in 100 ml of toluene. The mixture is then filtered through D4 frit. After toluene removal, fractional distillation gives a viscous colorless (2-methoxy methylphen-1-yl) -diethylaluminum having a boiling point of 108 ° C. at 0.71 mbar.

Example 5

Diisobutylaluminum chloride (10.65 g, 60.3 mmol) is slowly added to a suspension of [2- (methoxy) phenyl] lithium (6.87 g, 60.3 mmol) in 120 µl of toluene at -60 ° C. The mixture is warmed to room temperature and stirred for 12 hours. The suspension is filtered through D4 frit. The solvent is removed and the residue is suspended in n-heptane. The suspension is passed through frit and the solid is washed twice with 20 μl of n-heptane. Recrystallization of the solid from toluene at 0 ° C. yields [2- (methoxy) -phen-1-yl] diisobutylaluminum having a melting point of 128 ° C. and colorless crystals.

Molecular weight determination of ice crystals in benzene: 376 g / mol.

Example 6

Diisobutylaluminum chloride (11.25 g, 63.7 mmol) was slowly added to a suspension of 0.41 mol of [2- (butoxy) phenyl] lithium (161 mL, 66.5 mmol) and n-heptane at -60 ° C. The mixture is warmed to room temperature and stirred for 12 hours. The solvent is removed and the residue is suspended in 100 ml of toluene. The suspension is passed through a D4 frit. After removal of toluene, fractional distillation yields a viscous colorless [2- (butoxy) phen-1-yl] diisobutylaluminum having a boiling point of 74 ° C. at 0.48 mbar.

Ethylene polymerization

All polymerizations were carried out under argon inert gas atmosphere using Schlenk technology. Solid catalyst and promoter members were weighed out in the Braun labmaster 130 Glovebox using an analytical balance. The catalyst used was TiCl ₄ supported with MgCl ₂ and was in the form of a 0.1 mol suspension. The cocatalyst was weighed in a 25 ml glass flask and used as the hexane solution for the polymerization.

The polymerization reaction was carried out in a Buchi 1 L glass autoclave. Prior to each experiment, the reactor was scrubbed with ethanol and toluene, hexane or heptane, emptied inside at 1O < 0 > C for 1 hour in an oil pump vacuum, and repeatedly flushed with argon in between. The autoclave was filled with 195 ml of hexane and catalyst suspension. The temperature was fixed at 60 ° C. The monomer was injected under a pressure of 2 bar. After saturating the suspension placed in the reactor with monomers, the polymerization was initiated by injection of the hexane solution of the promoter. The isostatic performance of the reaction was confirmed by the monomer feed of the reactor, which consisted of a Brooks PC8606 pressure regulator and a Brooks 5850TR mass flow regulator. Monomer consumption was measured using a Brooks Model 5876 controller and display unit and the personal computer was fitted with the assistance of an A / D exchange card and RTX View software connected to it.

The polymerization was terminated by injection of 5 ml of ethanol. Dilute hydrochloric acid was added to the polymerization suspension and stirred overnight. The organic phase was neutralized with saturated sodium bicarbonate solution and washed with water. The polymer was dried to constant weight in an oil pump vacuum.

Additional experimental results performed under the same or similar conditions are shown in Table 1. The table also includes experiments performed in the presence of an aluminum promoter and TiCl ₄ / MgCl ₂ as catalyst.

Ethylene pressure 2 bar Reaction temperature 60 ℃ Reaction time 60 mins Catalyst density TiCl ₄ : 5.3. 10 ^-4 mol / l Catalyst / Procatalyst Ratio 20 menstruum Hexane Solvent volume 200 ml

The results of the ethylene polymerization in the presence of the organoaluminum complexes prepared in Examples 1 to 6 as cocatalysts compared to Et ₃ Al are shown in FIG. 1.

Claims (14)

Compound of Formula I:  [Formula I] [In the meal, R ¹ independently of ^one another represents branched or unbranched C ₁ -C ₇ -alkyl, -cycloalkyl, -alkenyl, -cycloalkenyl, -aryl, -alkynyl; R ² represents an unsubstituted mono- or polyalkylated and / or mono- or polyfluorinated aromatic hydrocarbon from the group: ; R ³ , R ⁴ independently of one another represent CH ₂ , CF ₂ or C (R ¹ ) ₂ ; Independently of each other m represents 0,1,2, n represents 0,1,2].  The compound according to claim 1, wherein (8-ethoxynaphth-1-yl) diethylaluminum, (2-methoxymethyl) phen-1-yl) diethylaluminum, (2-methoxymethylphen-1-yl) diisobutylaluminum, (2-methoxybenzyl) diisobutylaluminum, [2- (methoxy) phen-1-yl] diisobutylaluminum, [2- (butoxy) phen-1-yl] diisobutylaluminum. Use of a compound of formula (I) as claimed in claim 1 as a member of a coordination catalyst system. Use of a compound of formula (I) as defined in claim 1 as a member of a Zieler-Natta catalyst. Coordination catalyst system containing a compound of formula (I) according to claim 1. A coordination catalyst system containing a compound of formula (I) according to claim 1 or 2 in which the Periodic Table IV-VIII transition metal compound of the periodic table is combined. A coordination catalyst system containing a compound of formula (I) according to claim 1 or 2 in which transition metal compounds from groups TiCl ₄ , VCl ₄ are combined. A coordination catalyst system containing the compound of formula (I) according to claim 1 or 2, wherein the coordination catalyst system is characterized by combining transition metal compounds from the groups TiCl ₄ and VCl ₄ supported on MgCl ₂ . A process for producing a polymer by polymerization, characterized in that the coordination catalyst system according to any one of claims 5 to 8 is used. A process for producing polyethylene, wherein the coordination catalyst system according to any one of claims 5 to 8 is used. The coordination catalyst system according to any one of claims 5 to 8 is used. A process for producing a compound of formula (I) according to claim 1 or 2, wherein the alkoxy aryl methane compound and the dialkyl aluminum chloride are reacted with a molar ratio of alkoxy aryl metal compound and dialkyl aluminum chloride as 1: 1. The method of claim 12, a) alkoxyarylmetal compounds suspended in hydrocarbons, diethyl ether or tetrahydrofuran are mixed with equimolar amounts of dialkylaluminum chloride dissolved in suitable hydrocarbons at temperatures from + 20 ° C. to −78 ° C. b) stirring the mixture at a temperature of 20 to 80 ° C. for 2 to 60 hours, removing the solvent and separating the desired reaction product by distillation or crystallization. The process according to claim 12 or 13, wherein the alkoxyarylmetal compound used is an alkoxyaryllithium or alkoxyaryl-grignard compound.