CS226435B2

CS226435B2 - Method of preparing catalysts of stereoregular alpha-olefin polymerization

Info

Publication number: CS226435B2
Application number: CS816044A
Authority: CS
Inventors: Sandro Parodi; Roberto Nocci; Umberto Giannini; Pier C Barbe; Umberto Scata
Original assignee: Sandro Parodi; Roberto Nocci; Umberto Giannini; Pier C Barbe; Umberto Scata
Priority date: 1981-08-12
Filing date: 1981-08-12
Publication date: 1984-03-19

Description

The invention relates to a process for the preparation of stereoregular polymerization α-olefins of the formula ch ₂ = chr where

R is C 1 -C 4 alkyl or aryl, and a mixture of these olefins with ethylene.

The hitherto known highly potent and highly stereospecific supported catalysts for the polymorphization of propylene and higher olefins, which are supported, are obtained by reacting an alkyl-aluminum compound, partly in the form of a complex with an electron donor compound, a solid component containing titanium compound and electron donor compound ( internal donor), which are deposited on the magnesium halide in an effective form.

Examples of such catalysts have been disclosed in British Patent No. 1,559,194, and in Belgian Patent No. 868,682.

External donors containing silicon compounds having Si-O-Si linkages have also been described (Japanese Patent Applications Sho 79/94 590 and Sho 80/363203). Among the various numerous internal donors, compounds such as methyl methacrylate and ethyl pivalate have already been cited.

However, in all known catalysts in which Si-O-Si bonds are used as the external donor, benzoic esters and derivatives thereof are used as the internal donor.

The activity of these catalysts, expressed as activity and stereospecificity, does not differ from that of catalysts which contain ethyl benzoate and similar benzoic esters as external donor.

It has now unexpectedly been found that the activity and stereospecificity of known supported catalysts containing an Si-O-Si silicon compound as external donor can be increased by using an ester having a particular structure as the internal donor.

The present invention provides a process for preparing stereoregular polymerization of α-olefins of the general formula

CH ₂ = CHR where

R represents an alkyl radical containing up to 4 carbon atoms or an aryl radical and a mixture of these olefins with ethylene, in a palladium phase, optionally in the presence of an inert hydrocarbon solvent, or in a gas phase, characterized in that they interact

(a) a trialkylaluminum compound or an alkyl aluminum compound containing at least 2 aluminum atoms bound to each other via oxygen or nitrogen atoms or SO ₄ or SO ₃ groups;

(b) a silicon compound containing at least one bond of the formula Si-OR, Si-OCOR or Si-NR ₂ , wherein R is a hydrocarbon radical; and

(c) a solid component containing anhydrous magnesium halide in active form as the carrier base, on which the titanium halide or titanium haloalkoxide and an ester selected from the following classes of compounds are deposited:

1] mono- and polyesters of saturated polycarboxylic acids in which at least one ester carbonyl group is bonded to a tertiary or quaternary carbon atom or to a linear or branched chain containing at least 4 carbon atoms,

2] mono- and polyesters of unsaturated polycarboxylic acids in which at least two carboxy groups are bonded to vicinal carbon atoms between which there is a double bond and in which at least one of the hydrocarbon groups R which is part of the COOR groups is a branched saturated or unsaturated group (C 3 -C 20) or (C 6 -C 20) aryl or arylalkyl group,

3] mono and diesters of aromatic dicarboxylic acids containing COOH groups in the ortho position, wherein at least one of the hydrocarbon radicals R which is part of the COOR groups contains 3 to 20 carbon atoms,

4j mono- and polyesters of aromatic hydroxy acids containing at least 2 hydroxy groups in the ortho position,

5) esters of aromatic hydroxy acids in which at least the hydroxy group is ortho to the carboxy group;

6) esters of saturated or unsaturated carboxylic acids in which at least one of the hydrocarbon radicals R and R 'which are part of the RCOOR' groups is a saturated or unsaturated branched radical having 3 to 20 carbon atoms, or an arylalkyl radical having 7 to 20 carbon atoms or R is a C 3 -C 20 aryl group bonded to the ester carbonyl group directly or through a methylene group, and wherein the radical of formula R 'when it is a linear hydrocarbon group contains 3 to 20 carbon atoms,

7) esters of carbonic acid of general formula

OR /

CO \

OR wherein at least one of R, which may be the same or different, represents a hydrocarbon group having from 3 to 20 carbon atoms.

Representative esters suitable for the preparation of component cj are:

Class 1.

diethyldiisobutylmalonate, diethyl-n-butylmalonate, diethylphenylmulonate, diethyl-1,2-cyclohexanedicarboxylate, dioctyl sebacate, dlisobutyl adipate.

Class 2.

di-2-ethylhexyl maleate, diisobutyl maleate, diisobufyl-3,4-furanedicarboxylate, di-2-ethylhexyl fumarate, 2-ethylhexyl malonate.

Class 3.

Diisobutyl 2,3-naphthalenedicarboxylate, di-n-propyl, di-n-butyl, diisobutyl, di-n-heptyl, di-2-ethylhexyl, di-n-octyl and dineopentyl phthalate, monobutyl and monoisobutyl phthalic acid esters, ethyl isobutyl phthalate, ethyl n-butyl phthalate.

Class 4.

2,3-diacetoxynaphthalene, 1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene.

Class 5.

Benzoylethyl salicylate, acetyl methyl salicylate. Class 6.

Ethylene glycol pivalate, 1,4-butanediol pivalate, benzyl and iisubutyl pivalate, propyl pivalate, ethyl diphenylacetate, isobutyl methacrylate, isobutyl acrylate, ethylbentoylacetate, isobutylpyruvate, isobutyl trains-3-methoxy-2-butenoate.

Class 7.

phenylethyl carbonate, diphenyl carbonate.

Preferred compounds are maleic, pivalic, methacrylic, carbonic and phthalic acid esters.

As already mentioned, polycarboxylic acid esters may contain, in addition to ester groups, also non-esterified carboxy groups.

In preparing component (c), the esters are contacted with the active magnesium halides or precursors thereof. Preformed compounds may be used for the reaction, or the esters may be prepared in situ by known reactions, such as by esterification of an alcohol or an alkoxide with an aryl halide, or by reaction of a polycarboxylic acid anhydride or semi-ester with an alcohol or transesterification. The esters may also be used in admixture with other known internal donors.

The active magnesium halides which form the carrier of component cj are magnesium halides which, in the X-ray spectrum of component cj, exhibit at least a 30% extension of the most intense diffraction line contained in the powder spectrum corresponding to magnesium halide having a specific surface area of 1 m ² they are magnesium halides, in which the most intense line in the diffraction spectrum is replaced by a ring with a maximum intensity shifted relative to the interplanar distance of the most intensively line, or are magnesium halides having a specific surface area of more than 3 m ² / g.

Measurement of the specific surface area of the iodide halides is carried out on component c) after treatment with titanium tetrachloride for 2 hours. The value found is considered to be the specific surface area of the magnesium halides.

Highly effective forms of magnesium halides are those which exhibit, in the X-ray powder spectrum, a reduction in the relative intensity of the most intense diffraction lines contained in the spectrum of the corresponding magnesium halide with specific surface area of 1 m ² / g. replaced by a ring whose maximum intensity is shifted relative to the interplanar distance of the most intense line. The specific surface area of the aforementioned forms is usually higher than 30 to 40 m ² / g and in particular ranges from 100 to 300 m ² / g.

The active forms are also those obtained from the above-mentioned forms by heat treatment of component cj in internal hydrocarbon solvents. These forms exhibit sharp diffraction lines in the X-ray spectra in place of the rings.

However, the sharp most intense lines of these forms show at least 30% extension with respect to the corresponding magnesium halide line with a specific surface area of 1 m ² / g. Preferred magnesium halides are magnesium chloride and magnesium bromide. The water content of the magnesium halides is usually less than 1% by weight.

Titanium halides or titanium haloalcoholates and esters deposited on active magnesium halides are systems in which the above compounds are chemically or physically bound to a support such that they are not removable from component cj by extraction with boiling 1,2-dichloroethane for 2 hours.

The components a), bj and c) are allowed to react with each other in any order. Preferably, however, components a and b) are mixed together prior to contacting the component

C).

Component cj may be premixed with any of components a and b). The premixing of the components aj and bj is usually carried out at a temperature from room temperature to the temperature used for the polymerization.

The preliminary reaction of components c) and b) can also be carried out at higher temperatures. Compound bj can also be introduced into component c) and reacted directly with it. The molar ratio of component b) to the halogenated titanium compound deposited on component cj is at least 1 and to the alkyl aluminum compound (component a) is less than 20. Preferably, the molar ratio of component b) to component

(a) in the range of 0.05 to 0.3.

In component (c), the molar ratio between the magnesium halide and the halogenated titanium compound deposited thereon is between 1 and 500 and the molar ratio between the halogenated titanium compound and the electron donor compound deposited on the magnesium halide is between 0.1 and 50.

The silicon compounds that form component bj include compounds of the general formula

R _m SiY _n Xp where

R is alkyl, alkenyl, aryl, arylalkyl, or cycloalkyl of 1 to 20 carbon atoms,

Y is --OR ', - OCOR', - NR * 2, where R 'has the same meaning as R and R and R' are the same or different,

X is halogen, a hydrogen atom, or a group of formula —OCOR “, or —NRa“, wherein R “has the same meaning as R ', wherein R' and R 'are the same or different, m is from 0 to 3, n is from 1 to 4, ρ is 0 or 1, and the sum of m + n + ρ is 4.

Other silicon compounds that can be used are those in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms.

Examples of such compounds include hexaethoxydisiloxane and symmetrical diphenyltetraethoxydisiloxane of formula (C 2 H 5 O 2 -Si-O-CH 2 -CH 2 -O-).

Ú6H5

-Si - (OC 1 H 5) 2

C6H5

2 ti 4 3 5

Preferred silicon compounds are phenylialkoxysilanes, such as phenyltrietihoxysilain or femyithimethoxysilane, diphenyldimethoxysilane and -diethoxysilane and monochlorophenyldiethoxysilane, allalkoxysilanes, such as ethyltrlethoxysilam and ethyltriisoprop.

Examples of other suitable compounds include brothortriethoxysilane, lacetoxytrietihoxyisilane, vinyltriethoxysilane, trifemylmonoethoxysilane, phenyltricycloethoxysilane, phenyldiethoxydiethyl amimosllan, tetrafenoxysllan and tetraaTkoxysilanes such as tetrametho. The silicon compound can also be prepared "in situ", for example by reacting a halogenated silicon compound, such as silicon tetrachloride, with an alcohol or a magnesium or aluminum alkoxide.

In the catalysts of the invention, the silicon compound is present in bound form in the solid reaction products of the various catalyst-forming components. The molar ratio between the silicon compound and the halogenated titanium compound in the catalyst is greater than 0.05, and is usually in the range of 0.1 to 5.

Alkylaluminum compounds that form component aj include trlalkylcarbons such as triethyl, triisobutyl, and triisopropyl aluminum and compounds containing two or more aluminum atoms bonded together through heteroatoms, such as compounds of the following formulas:

(C2H5) 2A1 — O — AljCaHsja, (C2H5) 2A1 — N — A1 (C2H5) 2,

CeHs a

O (CaH 5) 2 Al — O — S — O — A1 (C2 H5) 2.

O

As already mentioned, it is also possible to use alkyl aluminum compounds in which the aluminum atoms are linked by groups such as SO4 or SO3.

The alkyl aluminum compounds can be used in admixture with alkyl aluminum halides, such as diethyl aluminum ammonium chloride.

Component cj is prepared by known methods. One of these methods consists in co-grinding the magnesium halide and the electron donor compound according to the invention until the X-ray diffraction spectrum of the milled product shows the above-mentioned deviations from the magnesium halide spectrum and then the milled product is reacted with the titanium compound. Preparation of this type is described in British Patent No. 1,559,194.

Similar methods of preparation are described in U.S. Patent Nos. 4107,413, 4,107,414 and 4,107,415.

Another method consists in reacting a magnesium halide adduct with an alcohol compound with a titanium compound in the presence of electron donations of a compound which does not contain reactive hydrogen atoms. This method is described in Belgian Patent No. 868,682.

According to another method as described in the published patent application USSR 3,022,738, a magnesium halide adduct with an alcohol is reacted in liquid form with a halogenated titanium compound and an electron-divalent compound.

Other methods are described in published German Patent Application No. 2,924,029, US Patent No. 4,220,554, and Italian Patent Application No. 27,261/79.

Another method consists in co-grinding the magnesium halide with the halogenated titanium compound and the electroidonor compound until the magnesium halide is activated, after which the milled product is treated with a halogenated hydrocarbon slurry such as 1,2-dichloroethane, chlorobenzene, methylene chloride and hexachloroethyl chloride. .

This treatment is carried out at a temperature of from 40 ° C to the boiling point of the halogenated hydrocarbon, usually for 1 to 4 hours.

According to another method, a porous carrier such as silica or alumina having a low hydroxy group content (preferably less than 1% by weight) is impregnated with a liquid magnesium halide adduct with alcohol and then treated with an excess of titanium tetrachloride chloride containing dissolved. This process is described, for example, in German Patent Application No. 3,022,728 and in Belgian Patent No. 868,682.

In all the above cases, the final product contains magnesium halide in the active form as defined above.

Others Known methods which lead to the formation of magnesium halide in active form or to titanium-containing magnesium halide carrier components in which magnesium halideirtide is contained in the active form are based on the following reactions:

reacting a Grignard reagent or a compound of formula MgR 2, wherein R is a hydrocarbon residue, or a coplex of these compounds of formula MgR? and trialkylaluminium compounds with halogenating agents such as compounds of formula AIX3 or AlR _m X _n , wherein X is halogen, R is a hydrocarbon residue and the sum of m + n is equal to 3, silicon tetrachloride and the compound of formula HSiCb;

reacting the Grignard reagent with silanol or polysiloxane, water or alcohol and further reacting with the halogenating agent or titanium tetrachloride;

reacting magnesium with an alcohol and a hydrohalic acid, or reacting magnesium with a hydrocarbyl halide and an alcohol;

reacting magnesium oxide with chlorine or aluminum chloride;

reacting the hydrated magnesium halide of the formula MgX2.nH2O (X = halogen) with a halogenated reagent or titanium tetrachloride;

reacting magnesium mono or dialkoxides or magnesium carboxylates with a halogenating agent.

Titanium halides with titanium haloalkoxides include, in particular, titanium tetrahalides, titanium trihalides and titanium trihalogen alkoxides.

Preferred compounds are titanium tetrachloride, titanium bromide and 2,6-dimethylphenoxytrichlorotitanium.

Titanium trihalides are obtained by known methods, for example by reduction of titanium tetrachloride with aluminum or an organoaluminum compound or hydrogen.

In the case of titanium trihalides, it may be desirable to perform titanium oxidation, optionally only partially, either during or after the preparation of component (c) in order to achieve improved catalyst efficiency.

Halogens or iodhalogens can be used for this purpose.

Preference is given to catalysts in which component (c) is obtained from magnesium chloride, titanium tetrachloride and maleic, pivalic or phthalic acid esters and wherein component (b) is phenyl- or ethyltriethoxysilane or diphenyldimethoxy or diphenyldiethoxysilane.

Preference is given to using a trialkyl aluminum, such as titanium aluminum or triisobutyl aluminum, as bed (a).

Component c) is prepared according to the methods described in British Patent No. 1,559,194, Belgian Patent No. 868,682, published German Patent Application No. 2,924,029, U.S. Patent 4,220,554, Italian Patent Application 27,261/79, or published German Patent Application DOS No. 3,022,738.

A preferred process for preparing component cj is also a process that involves co-grinding magnesium chloride, titanium tetrachloride and an ester, after which the milled product is treated with a halogenated hydrocarbon such as 1,2-dichloroethane.

The polymerization of α-olefins using the catalysts according to the invention is carried out according to known methods, i.e. the polymerization is carried out in the liquid phase either in the presence or absence of an inert hydrocarbon solvent or in the gas phase or also by a combined process comprising a liquid phase in the gas phase.

The polymerization temperature is usually from 40 to 160 ° C, but is preferably operated at a temperature of from 60 to 90 ° C at either atmospheric pressure or above atmospheric pressure.

Hydrogen or other regulators of known type may be used as the molecular weight regulator.

The catalysts according to the invention are particularly advantageously used for the polymerization of propylene

-buton, styrene, and 4-methylpentene. The catalysts can also be used in a known manner to polymerize mixtures of propylene and ethylene to visualize modified polypropylenes having better low temperature impact toughness (so-called propylene-ethylene block copolymers) or to obtain irregular crystalline propylene copolymers with minor amounts of ethylene.

The invention is illustrated by the following examples. The examples are illustrative only and do not limit the scope of the invention in any way.

Examples 1 to 10

A 3 L stainless steel autoclave equipped with a magnetic stirrer and thermocouple, thermostatized to 60 ° C and pressurized under a nitrogen atmosphere, was charged with a 1000 mL suspension of 5 mmol of triethyl aluminum, phenyltriethoxysilam (PES) and solid catalyst components. prepared as described in Example 1 of Italian Patent Application Ser. 27 261/79, except that the esters listed in Table I are used instead of ethyl benzoate. Degased and anhydrous n-heptane is used as the solvent for the suspension. Propylene is also introduced into the autoclave. The catalyst components thus prepared exhibit powder X-ray spectra in which the most intense diffraction line appearing in the magnesium chloride spectrum with a specific surface area of 1 m ² / g is attenuated in intensity and replaced by an expanded ring.

The autoclave is sealed, 0.02 MPa of hydrogen are introduced, the temperature is raised to 70 ° C and propylene is brought to a total pressure of 0.7 MPa.

During polymerization, the pressure is kept constant by continuously feeding the monomer. After 4 hours, the polymerization was terminated by rapid cooling and degassing of the reaction mixture. The polymer was separated from the solvent by filtration and then dried with a stream of hot nitrogen (70 ° C). The solvent soluble polymer fraction is isolated from the filtrate and added to the boiling n-heptane soluble polymer to calculate the isotactic index (IIj).

Table I gives the following: amount of catalyst component used titanium content of this component, molar ratio of phenyltriethoxysilane to triethylaluminum, polymer yield with respect to introduced catalyst component, isotacticity index (IIj, surface area, solid catalyst components and viscosity limit value (η) ), determined in tetrahydrofuran at 135 ° C.

Example 11

The procedure of Example 8 is repeated under the same polymerization conditions as those used in Examples 1 to 10, except that the solid catalyst components prepared according to Example 7 of German Patent Application No. 2,643,143 are used.

The catalyst component shows a powder spectrum in which the most intense diffraction line appearing in the spectrum of magnesium chloride with a specific surface area of 1 m ² / g is reduced in relative intensity and replaced by an expanded ring.

Table I gives the following data: titanium dioxide in the solid catalyst component, the amount of said component, the molar ratio between triethyl aluminum and PES, and the polymerization results.

Example 12

The solid catalyst component prepared as described in Example 11 is suspended in an inert hydrocarbon solvent Isopar G (a mixture of isoparaffinic hydrocarbons having a boiling point in the range from 158 to 172 ° C) and the suspension was heated for 24 hours at 120 C. The catalyst component ^Q which is thus however, the peak width at half of its height is 30% greater than the corresponding peak width in the 1 m ² / g surface area of the magnesium chloride x-ray powder spectrum.

The catalyst components thus prepared were used under the same polymerization conditions as described in Example 11.

The characteristics of the solid catalyst component and the polymerization results are shown in Table I.

Comparative Examples 1 and 2

The procedure described in Example 1 is repeated except that the solid catalyst component used is that prepared according to Example 1 of Italian Patent Application No. 27 261/79. The X-ray powder spectrum of this component is similar to that of Example 1. The results of the polymerization tests are shown in Table I.

Comparative example

The procedure described in Example 11 was repeated except that the catalyst component prepared according to Example 7 of German Patent Application No. 2,643,143 was used. The X-ray powder spectrum of this component was similar to that of the catalyst component of Example 11. Table I.

Examples 13 to 18

The procedure described in Example 1 was repeated using a solid catalyst component prepared as follows:

The anhydrous magnesium chloride, the ester listed in Table II and the titanium tetrachloride in a 1: 1 molar ratio relative to the ester are milled together in a 1 liter vibratory mill containing 3 kg of 16 mm diameter stainless steel balls.

The grinding is carried out for 72 hours and using a loading coefficient equal to 100 g / l of the total volume (under vacuum) at an internal mill temperature of 25 ° C. The filling of the mill, grinding and emptying of the mill is carried out under a nitrogen atmosphere.

g of the co-milled product was contacted with 1,2-dichloroethane at 80 ° C for 2 hours. After this time, the 1,2-dichloroethane is filtered off at 80 ° C and the remaining solid product is washed several times with n-heptane at room temperature until the chlorine ions in the filtrate have disappeared and then kept in the heptane suspension.

The catalyst components prepared in this manner showed an X-ray powder spectrum in which the most intense diffraction line appearing in the magnesium chloride spectrum of 1 m ² / g specific surface area is attenuated in relative intensity and replaced by an expanded ring.

The ester type, the solid catalyst component characteristics, and the polymerization test results are shown in Table II.

Examples 19 to 26

The procedure described in Example 1 was repeated except that the solid catalyst component prepared according to Example 3 of Italian Patent Application No. 26,908 A / 78 was used.

To the suspension of titanium tetrachloride adduct and ester is added slowly a solid adduct of MgCl2.5 C2H5OH in the form of spherical particles. The molar ratio of titanium tetrachloride to ethanol is 10 and the molar ratio of magnesium to ester is also 10.

The resulting mixture was heated to 100 ° C and maintained at this temperature for 2 hours. The solid product is then filtered off at 100 DEG C. and treated with 110 ml of titanium tetrachloride at 120 DEG C. for two hours. After this treatment, the titanium tetrachloride was removed by filtration and the solid product was washed with n-heptane at a temperature gradually decreasing from 90 ° C to room temperature until the chlorine ions in the filtrate had disappeared. The resulting product is maintained in a heptane suspension.

The catalyst components prepared as described above show similar X-ray spectra to those of the catalyst components of Examples 1 to 10.

The esters, the characteristics of the solid catalyst components and the results of the polymerization tests are shown in Table III.

Comparative Example 4

Example 19 was repeated except that the solid catalyst component used was that prepared according to Example 3 of Italian Patent Application No. 26908 A / 78. The X-ray spectrum of this catalyst component is similar to that of the catalyst components prepared according to Examples 1 to 10. The characteristics of the solid product and the results of the polymerization test are shown in Table III. Examples 27 to 29

The procedure described in Example 1 is repeated except that the solid catalyst component used is that prepared according to Example 1 of German Patent Application No. 3,022,738, using instead of ethylbenzoate the phthalic esters listed in Table IV and chloride treatment. titanium dioxide is carried out at 120 ° C.

The X-ray spectrum of the catalyst component thus obtained is similar to that of the components prepared in Examples 1 to 10.

The ester type and ratios are shown in Table IV.

Polymerization conditions and polymerization test results are also shown in Table IV.

Comparative Example 5

Example 27 is repeated except that the solid catalyst component used is that prepared according to Example 1 of German Patent Application No. 3,022,738.

The operating conditions and the results of the polymerization test are shown in Table III. Examples 30 to 34

The procedure described in Example 8 was repeated except that an equimolar amount of the alkoxysilanes listed in Table V was used instead of phenyltriethoxysilane.

The characteristics of the catalyst components used and the results of the polymerization tests are shown in Table V.

Example Solid catalyst component Polymerization No. Ester MgCl2 Content Ti Specific Al (C2H5) 5 Catalyst Yield II η ester in solid PES surface [mg] g pol- [%] [dl / g] grinding component [m ² / g] [mol / mol] g cat.

[mol / mol] [% by weight] of the component

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Table III

Example Solid catalyst component Polymerization number Ester Content Tl A1 (C ₂ H ₅ ) 3 Yield g II in solid PES ί ^Γ mg polymer folder mol / mol g kataly- % wt. tic. folders 1 2 3 4 5 6 7

19 dioctylphthalate 2.7 20 May 19 Dec 12 100 92.2 1,8 20 diisobutylfíaláit 2.4 20 May 22nd 13 900 96.9 1,2 21 dineopentyl phthalate 3.5 20 May 15 Dec 18 500 97 1,2 22 dilphenylphthalate 2.6 10 25 11000 94.5 1,8 23 diethylbutyl malonate 3.9 10 29 12 800 93.3 1.7 24 benzylbutyl phthalate 3.1 20 May 24 14 000 96.1 1.4 25 mono-2-ethylhexyl- 2.8 10 50 8 000 92.5 1.3 maleate 26 monoisobutyl phthalate 3.1 10 24 10 000 94.3 1.6 compares- incoming feed example 4 ethylbenzoate 3.8 5 38 6 850 91.5 1.5

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Table IN Example Polymerization number Alkoxysilane Catalyst mg Yield g

Claims

A process for preparing stereoregular polymerization of α-olefins of the general formula

CH ₂ = CHR where

R is an alkyl radical containing

1-4 carbon atoms or an aryl radical, and mixtures of these olefins with ethylene, in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase, characterized in that they are also interacted with a trialkyl aluminum compound or an alkyl aluminum compound containing at least

2 aluminum atoms bonded together through oxygen or nitrogen atoms or SO ₄ or SO ₃ groups,

Mono- and polyesters of saturated polycarboxylic acids in which at least one ester carboxyl group is bonded to a tertiary or quaternary carbon atom or to a linear or branched chain containing at least 4 carbon atoms,

2] mono- and polyesters of unsaturated polycarboxylic acids in which at least two carboxy groups are bonded to vicinal carbon atoms with a double bond between them and in which at least one of the hydrocarbon groups R, which are invented as part of the COOR groups, is branched unsaturated or saturated (C 3 -C 20) or (C 6 -C 20) aryl or arylalkyl group;

3) mono- and diesters of aromatic dicarboxylic acids containing COOH groups in the ortho position, wherein at least one of the hydrocarbon radicals R which is part of the COOR groups contains 3 to 20 carbon atoms,

(4) mono- and polyesters of aromatic hydroxy acids containing at least two ortho-hydroxy groups;

5) esters of aromatic dyroxy acids in which at least the hydroxy group is ortho to the carboxy group;

6) esters of saturated or unsaturated carboxylic acids in which at least one of the hydrocarbon radicals R and R 'which are part of the RCOOR ¹ groups is a saturated or unsaturated branched radical having 3 to 20 carbon atoms or an arylalkyl radical having 7 to 20 carbon atoms or R is (C až-Cry a) aryl and in which the radical of formula R 'when it is a linear hydrocarbon group contains from 3 to 20 carbon atoms; and

(7) carbonic acid esters of the formula CO (OR) 2, wherein at least one of the synbols R, which may be the same or different, represents a hydrocarbon group having from 3 to 20 carbon atoms.

2. The process of claim 1, wherein the magnesium halide in component c) is magnesium chloride or magnesium bromide, the titanium halide is titanium halide, and the ester is selected from class 2, 3, 6, or 7 referred to in point 1.

3. The process according to claim 1, wherein the silicon compound in component b) is phenyldi- or -trialkoxysilane or alkyldi- or -trialkoxysilane.