CA1185960A

CA1185960A - Components and catalysts for the polymerization of olefines

Info

Publication number: CA1185960A
Application number: CA000383747A
Authority: CA
Inventors: Umberto Scata; Sandro Parodi; Roberto Nocci; Pier C. Barbe; Umberto Giannini
Original assignee: Montedison SpA
Current assignee: Montedison SpA
Priority date: 1980-08-13
Filing date: 1981-08-12
Publication date: 1985-04-23
Also published as: EP0223010A1; EP0045977B1; ZA815487B; JPH09202808A; JPS5763312A; NO159283C; PH17763A; US6194342B1; EP0045976B2; EP0045977B2; AU559388B2; DK349781A; IN154219B; DK163248C; ATE68794T1; PL140238B1; JPH072921A; ZA815496B; EP0045975B1; EP0045976B1

Abstract

ABSTRACT OF DISCLOSURE

Disclosed are catalysts for the polymerization of alpha-olefins which comprise the reaction product of:
(a) an Al-alkyl compound;
(b) a silicon compound containing at least one Si-OR
or Si-OCOR or Si-NR2 bond, R being a hydrocarbyl radical;
(c) a solid comprising, as essential support, a Mg dihalide in active form and, supported thereon, a Ti halide or a halo-Ti-alcoholate and a particular type of electron donor compound.
The present invention refers to new supported com-ponents of catalysts for the polymerization of CH2=CHR
olefins wherein R is an alkyl radical with 1 to 4 carbon atoms, or an aryl radical, and mixtures of said olefins with ethylene and the catalysts obtained from said components.

Description

BACXGROUND OF THE INVENTION

The supported highly ac-tive and highly stereospecific catalyc.ts for the polymerization of propylene and higher olefins, known up to now are obtained by the reaction of an Al alkyl compound partially complexed with an electron donor compound (outside donor) ~ith a solid component comprising a .

Ti compound and an electron-donor compound (inside donor) supported on a Mg halide in active form.
Examples of such catalysts have been described in British Patent No. 1,55~,194 and Belgian Patent No. 868,682.
Outside donors consisting of silicon compounds con-taining Si-O-C bonds also have been described (published Japanese patent applications Sho 79/94590 and Sho 80/36203).
Among the various and numerous inside donors such compounds as methyl methacryla-te and ethyl pivalate also have been cited.
However, in all the prior art cataiysts in which a silicon compound containing Si-O-C bonds is used as outside donor, esters of benzoic acid and derivatives thereof are used as inside donor.
The performance of the above ca-talysts, expressed in terms of aetivity and stereospecificity, is not different from the performance of the catalysts in which ethyl benæoate and similar csters oE benzoic acid are used as outside donor.

THE PRESENT INVENTION

One object of this invention is to provide new cataly~t-Eorm.ing components comprising, as outside donor, a siLlcon eompound containing Si-O-C bonds and an inside ester di~Eerant Erom the esters of benzoic acid and derivatives, and whieh result in EinaI c~talysts of increased activity and stereospeciEicity as compared to the components heretofore known compris.ing, as inside donor, an ester of benzoic acid or derivative thereof; and the catalysts based on such components .
This and other objects are achieved by this invention in accordance with which, and unexpectedly, it has been found . -2-.

that it is possible to increase the activity and stereo-specificity of the prior art supported catalysts comprising, as outside donor, a silicon compound containing Si-O-C bonds, by using as inside donor an ester having a particular structure as described hereinafter.
The catalysts of this invention comprise the product of reaction between the following components:
(a) an Al trialkyl or an Al-alkyl compound containing

2 or more aluminum atoms linked to each other through oxygen or nitrogen atoms or through SO4 or SO3 groups;
(b) a silicon compound containing one or more SI OR, 5i-OCOR or Si-NR2 bonds (R being a hydrocarbyl radical~;
].S (c) a solid comprising, as essential support, an anhydrous Mg dihalide present in active form and, supported on said dihalide,a Ti halide or a Ti haloalcoholate and an electron-donor compound selected from the following groups of compounds:
mono- and polyes-ters of sa-tura-ted polycar-boxylic acids wherein at least one of the esteric carbonyl groups is linked to a ter-tiary or quaternary carbon atom or to a linear or branched chain of at least ~ car-2~ bon atoms;
(2) mono- and polyesters of unsaturated polycar-boxylic acids wherein two carboxy groups are linked to vicinal double bond-forming carbon atoms and in which at least one of the R

3~ hydrocarbyl radicals of the COOR groups is a branched saturated or unsaturated radical with 3 to 20 C atoms or is an aryl or aryl- ~
alkyl radical with 6 to 20 C atoms;
(3) mono- and diesters of aromatic dicarboxylie acids having the COOH groups in ortho position wherein at least one of the R hydro-carbyl radicals of the COOR groups contains from 3 to 20 carbon atoms;

(4) mono- and polyesters of aromatic hydroxy compounds containing at least 2 hydroxyl groups in ortho position;

(5) esters of aromatic hydroxy acids wherein at - least a hydroxyl group is in ortho position to the carboxy group;

(6) esters of saturated or unsaturated carboxylic acids wherein at least one of the hydxocarbyl R and R' radicals of the R COOR' group is a saturated or unsaturated branched radical con-taining from 3 to 20 C atoms, or is an aryl-. alkyl radical with 7 to 20 C atoms or R is an '~0 aryl radical with 3 to 20 carbon atoms linked to the esteric carbonyl group directly or through a methylene group, and in which the R' radical contains from 3 to 20 C when it is a linear hydrocarbyl radical; and OR

(7) esters oE carbonic acid of formula CO ~ in OR
which at least one of the R radicals which can be the same or different is a hydrocarbyl radical with 3 to 20 carbon atoms.

Representative esters which are suitable in preparing eomponent tc) are the following: -~ .
.~:

~8~ g~

Class 1 diethyl diisobutylmalonate, diethyl n-butylmalonate, diethyl-n-dibutylmalonate, diethylphenyl~alonate, diethyl-1,2-cyclohexane-dicarboxylate, dioctylsebacate,diisobutyl adipate.
Class 2 di-2-ethyl~hexyl-maleate, diisobutylmaleate, diisobutyl-3,4-furan-dicarboxylate, di-2-ethylhexylfumarate~ 2-ethylhexyl-monomaleate.
Class 3 diisobutyl-2,3-naphthalen-dicarboxylate, di-n-propyl, di-n-butyl, diisobutyl, di-n-heptyl, di-2-ethyl-hexyl, di-noctyl, di-neopentil phthalates, monobutyl and monoisobutyl esters of phthalic acid, ethyl-isobutyl-phthalate, ethy;L-n-butyl-phthalate.
1.5 Class 4 2,3-diacetoxynaphthalene, 1,2-diacetoxybenzene, l-methyl-2,3-di.acetoxybenzene.
be~ .oyl-ethylsa:Licylate, acetyl-methylsalicylate.
~'Las 6 ~thyl~ne-~lyco].-pivalate, 1,4-butanediol-pivalate , benzyl and i.sobutyLpi.val.ate, n-propylpivalate, ethyl diphenylacetate, I.sob-ltylmethacrylate, isobutylacrylate, ethyl-benzoylacetate, iso~utylpyruvate, isobutyl-trans-3-methoxy-2-butenoate.
Clc~ss 7 phenyl-ethylcarbonate, diphenyl carbonate.
Preferred compounds are the esters of maleic, pivalic, methacrylic, carbonic and phthalic acids.
As indicated, the esters of the polycarboxylic acids can contain, besides the ester groups, also unesterified COOH , .
~roups.

~ ~ ~r~ ~ ~

In preparing component (c) the esters are contacted - with the active Mg dihalide or the precursors of said dihalides as preformed compounds or the esters can be formed in situ by means of known reactions as, for instance, by esterification between an alcohol or an alcoholate and an aryl halide or between an anhydride or a hemiester of a polycarboxylic acid with an alcohol or by transesterification. The esters can be used, also, in mixture with other known inside donors.
The active anhydrous Mg dihalides forming the essential support of component (c) are the Mg dihalides showing in the X-rays powder spectrum of component (c) a broadening of at least 30% of the most intense diffraction line which appears in the powder spectrum of the corresponding dihalide having 1 m2/g of surface area or are the Mg dihalides showing an lS X-rays powder spectrum in which said most intense diffraction line is replaced by a halo with the intensity peak shifted with respect to the interplanar distance of the most intense line and/or are the Mg dihalides having a surface area greater than 3 rn /g.
I'he measurement of the surface area of the Mg dihalides is made on component (c) after treatment with boiling '~iC14 for 2 hours. The found value is considered as surface area of the Mg dihalide.
Very active forms of Mg dihalides are those showing 2ti an X-rays powder spectrum in which the most intense diffraction line appearing in the spectrum of the corresponding hallde having 1 m /g of surface area is decreased in relative intensity and broadened to form a halo or are those in which said most intense line is replaced by a halo having its intensity peak shifted with respect to the interplanar dis-tance of the most intense line. Generally, the surface area ~s~

of the above forms is higher than 30-40 m2/g and is comprised in particular between 100-300 m2/g.
Active forms are also those deriving from the above forms by heat-treatment of component (c) in inert hydrocarbon solvents and showing in the X-rays spectrum sharp diffraction lines in place of the halos.
The sharp, most intense line of these forms shows, in any case, a broadening of at least 30% with respect to the corresponding line of the Mg dihalide having 1 m2/g of surface area. Preferred Mg dihalides are Mg dichloride and Mg dibromide. The content in water of the dihalides is generally less than 1% by weight.
By Ti halides or Ti haloalcoholates and esters supported on active Mg dihalide is meant the above compounds which may be chemically or physically fixed on the support, and not extractable from component (c) by treatment of the same wlth boiling 1,2-dichloroethane for 2 hours.
Components (a), (b) and (c) are made to react with each other in any order; preferably, however, components (a) and ~b) are premixed beEore being contacted with component (c).
Component (c) may be premixed with either component ~a) and/or (b). The pre-mixing of (a) and (b) is conducted at ~mpfJratures comprised, usually, between room temperature and ~he ~emperature used in the polymeri~ation process.
~5 The pre-reaction of (c) and (b) may be carried out also at higher temperatures. Compound (b) may be also incor-porated and made to react with component (c) itself.
Component (b) is made to react in a molar ratio with respect to the halogenated Ti compound supported on component (c) of at least 1 and in a molar ratio with respect to the Al-alkyl , compound used as component (a) of less than 20 and preferably comprised between 0.05 to 0.3.
In component (c), the molar ratio between the Mg dihalide and the halogenated Ti compound supported therein is comprised between 1 and 500 and the molar ratio between said halogenated Ti compound and the electron-donor supported on the Mg dihalide is comprised between 0.1 and 50.
The silicon compounds set forth in (b) include compounds of general formula:
RmSiYnXp wherein:
R is an alky, alkenyl, aryl, arylalkyl, cycloalkyl radical with from 1 to 20 carbon atoms;
Y is -OR', -OCOR', -NR2' wherein R', either equal to 1~ or different from R, has the same meaning as R;
X is either a halogen or hydrogen atom or an -OCOR"
or -NR2" group wherein R", either equal to or di.eEerent Erom R', has the same meaning as R';
m, n ancl p are numbers comprised respectively between:
r2~ m between 0 and 3, n between 1 and 4 and p between O and l; and m ~ n ~ p is equal to 4.

Other silicon compounds -that may be used are com-pouncls ln which two or more silicon atoms are bound to each other through oxygen or nitrogen atoms.
~5 Examples of these compounds are hexaethoxydisiloxane, and symmetrical diphenyltetraethoxydisiloxane ( 2H5)2 7i O-cH2-cH2-o-si-(oc2H5)2.

Preferred silicon compounds are: phenylalkoxysilanes such as phenyl-triethoxy or trimethoxysilane, diphenyldimethoxy .
- -a-and diethoxysilane, monochlorophenyldiethoxysilane, alkyl-alkoxysilanes such as ethyltriethoxysilane, ethyltriisopro-poxysilane.
Examples of other suitable compounds are: chloro-triethoxysilane, acetoxytriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, triphenylmonoethoxysilane, phenyltriey-cloethoxysilane, phenyldiethox'ydiethylaminosilane, tetra-phenoxysilane or tetralkoxysilanes as tetramethoxysilane.
The silicon compound can be also formed in situ by reaction of, for instance, a halogena-ted silicon compound sueh as SiCl4 with an aleohol or an aleoholate of Mg or Al.
In the catalsyts of the invention, the silicon com-pound is present, in a combined form in the solid produet of the reaction between the various catalyst-forming components in a molar ratio between the silicon compound and the halo-cJenated Ti compound greater than 0.05 and generally comprised between 0.1 and 5.
The Al-alkyl eompounds forminy component (a) include ~L-trialkyls as, for ins-tance, Al triethyl, Al triisobutyl, ~0 Al triisopropyl and cornpounds containing two or more Al atoms linked to eaeh other through hetero-atoms, such as:
(~2lt5)2Al-O-~l(C2~15)2; (C2H5)2Al I Al(C2H5)2;

(C2~l5)2~l-O-~-o-Al(c2H5)2 O
As indicated, Al alkyl eompounds in which Al a-toms are linked through groups sueh as SO4 or SO3 are also suitable.
The Al alkyl eompounds may be used in mixture wi-th Al-alkyl halides such as, for example, AlEt2Cl.
Component (c) is prepared aceording to known methods. ~ -One of these methods Collsi.sts in co-milling the Mg dihalide and _9_ the electroil-donor compound of this invention until the appeal^ance in the X-ray spectrum of the milled product of the modifications above set Eorth for the spectrum of the Mg dihalide, and thereafter reacting the milled product with the Ti-compound.
Preparations of this type are described in British Patent No. 1,559,194.
Another method consists in reacting the adduct of a Mg halide with an alcohol, with a Ti compound in the presence of an electron-donor compound not containing active hydrogen atoms. This method is described in Belgian Patent No. 868,682.
According to another method, which is described in published German patent application No. 3,022,738, the adduct between the Mg dihalide and the alcohol is reacted in liquid form with the halogenated Ti compound and the electron-donor compound.
Further methods are described in published German application 2,924,029 and U.S. Patent 4,220,554 as well as l.n publlshed European patent 29,232 of ~ntonio Monte 2~ et al.
Another method consists in co-milling the Mg dihalide, the halogenated Ti compound and the electron-donor compound until the Mg dihalide is a~tivated and in treating s suspension of the milled product in a halogenated hydrocarbon~ for instance 2~ 1,2-dichloroethane, chlorobenzene, methylene chloride or heYachloroethane.
The treatment is carried out at temperatures comprised between 40C and the boiling point of the halogenated hydro-carbon for a time ranging in general from 1 to 4 hours.
According to another method, a porous support like SiO2 or A12O3, having a low content of OH groups (preferably less than 1% by weight) is impregnated with a liquid adduct between the Mg dihalide and an alcohol; the support is then treated with an exeess of TiC14 containing, dissolved therein, the electron-donor compound, the procedure being as described, for instance, in published German patent application No.
3,022,738 or Belgian patent 868,682.
In all the above methods, the final produc-t eontains a Mg dihalide present in the active form as set forth herein-above.
Other known methods which lead to the formation of Mg dihalide in active form or to Ti containing Mg dihalide supported components, in which the dihalide is present in active form, are based on the following reactions:
reaction of a Grignard reagent or a MgR2 compound (R
beirlg a hydrocarbyl radical) or complexes of said MgR2 com-pounds with Al trialkyls, with halogenating agènts as AlX3 or ~lRmXn eompounds (X is halogen, ~ is a hydrocarbyl, m + n = 3), SiCl~ or HSiC13;
reaction of a Grignard reagent with a silanol or ~r) t~o:Lys.iloxalle, IS2O or w;.th an alcohol and fur-ther reaetion with a halocJenating acJent or with TiCl~:
reaetlon of Mg with an alcohol and a halogenhydric ae.id or o.f Mg with a hydrocarbyl halide and an alcohol;
reaction oE MgO with C12 or AlC13;
2~ reaction of MgX2.nH2O (X = halogen) with halogenating agent or TiC14;
reaction of Mg mono- or dialcoholates or Mg carboxy-lates with a halogenating agent.
The Ti-halides or Ti halogenalcoholates include, in particular,the Ti tetrahalides, Ti trihalides and Ti trihalogen-3~

alcoholates. Preferred compounds are: TiCl~, TiBr4, 2,6-dimethylphenoxytrichlorotitanium.
The Ti trihalides are obtained according to known methods, for instance by reduction of TiClg with Al, an organometallic Al compound or hydrogen.
In the case of the Ti trihalides, it may be con-venient, for the purpose of improving the performance of the catalysts, to carry out an oxidization, even if partial, o~
the titanium, either during or after the preparation of component (c). For this purpose there may be used halogens, iodine halides.
Preferred catalysts are those in which component (c) is obtained from MgC12, TiCl~ and esters of maleic, pivalic and phthalic acids and in wh:ich component (b) is phenyl or ethyl-triethoxysilane or diphenyldimetho~y or diethoxysilane.
Component (a) is an Al trialkyl as Al triethyl or A1 triisobutyl.
Component (c) is prepared according to the methods described in British Patent No. 1,559,194, Belgian Patent No.
368,682, published German application No. 2,924,029, U.S.P.
~,220,55~, published German application No. 3,022,738 or in the Mon-te et al published European patent referred to supra.
The preferred method of preparing component (c) incl.udes also the co-milling of MgC12, TiCl~ and the ester and in treatiny the milled product with a halogenated hydrocarbon, such as 1,2-dichloroethane.
The catalysts according to the invention are used to polymerize the alpha-ole:Eins according to known methods that is, by carrying out the polymerization in a li.quid phase, either in the presence or absence of an inert hydrocarbon solvent, or in gas phase or also by combining, for instance, a liquid phase polymerization step with a step in gas phase.

-]2-~s~

In general, the polymerization temperature is com-prised between 40 and 160C, but prePerably between 60 and 90C, opera-ting either at atmospheric or at greater than atmospheric pressure.
~s a molecular weight regulator hydrogen or other regulators of a known type are used.
The catalysts are particularly suitable-for polymer-izing propylene, butene-l, styrene and 4-methylpentene. The catalysts may also be used according to known methods to polymerize mixtures of propylene and ethylene to form modiEied polypropylenes having better shock-resistance at low tempera-tures (the so called block copolymers of propylene and ethylene) or to obtain random crystalline copolymers of propy-lene with minor proportions of ethylene.
The following examples are given for merely illustra-tive purpose and are not intended to be in any way limiting with respect to the scope of the invention.

EXAMPLES 1-lO

Into a stainless steel autoclave having a total 2~ vo.lume oE 3 1, equipped with a magnetized stirrer and a thermo-couple heat-sta~ilized at 60C and kept under pressure by a nitrogen atmosphere, there were introduced 1,000 ml of a suspension in degassed and anhydrous n-heptane containing 5 m mols of triethylaluminum, the phenyltriethoxysilane (PES~ and a solid catalytic component prepared according to Example 1 of the aforementioned Monte et al published h~ropean patent, but using instead of ethylbenzoate, the esters listed in Table I, while propylene was also fed in~ The catalytic components thus prepared showed X-rays powder spectra in which the most intense 35~D~

diffraction line appearing in the spectrum of MgC12 having 1 m2/g of surface area is decreased in relative intensity and broadened to form a halo.
The autoclave was closed and thereafter hydrogen was introduced up to a pressure of 0.2 atmospheres, the temperature was brought to 70C and slmultaneously, propylene was intro-duced up to a total pressure of 7 atmospheres.
Durin~ the polymerization, the pressure was kept constant by continuous feeding of the monomer. After 4 hours, the polymerization was stopped by quick cooling and degassing of the polymeric slurry. The polymer was separated from the solvent by filtering and was dried in a hot nitrogen flow at 70C. The quantity of polymer dissolved in the filtrate was thereupon isolated, ~eighed and summed to the polymer soluble in boilin~ n-heptane, for calculati~n of the isotacticity index (I.I.).
The quantity of catalytic component used and the con-tent of Ti in said component, the molar ratio of the phenyl-triethoxysilane with respect to the triethylaluminum, the yield in polymer with respect to the introduced catalytic component, the isotacticity index (I.I.), the surface area of the solid catalytic component and the inherent viscosity determined in tetralin at 135C, are reported in Table I.

Example 8 was repeated under the same polymerization conditions described in Examples 1-10, but using a solid catalytic component prepared according to Example 7 of pub-lished German patent application 2,643,143 (corresponding to Canadian patent 1,083,561).

The catalytic component showed an X-rays powder spectrum ln which the most intense diffraction line appearing in the spectrum of MgC12 having 1 m2/g of surface area is decreased in relative intensity and broadened to form a halo.
The content of Ti in the solid catalytic component, the quantity of said component, the molar ratio between tri-ethylaluminum and PES, and the results of the polymerization test are reported in Table I.

The solid catalytic component prepared according to Example 11 was suspended in the inert hydrocarbon solvent Isopar G (a mixture of isoparaffinic hydrocarbons boiling in the temperature range of from 158 to 172.5C) and heat--treated at 120C for 24 hours. The catalytic components thus obtai.ned showed an X-rays powder spectrum in which the most intense diffraction line appeared as a sharp line, the half pea]c breadth of which, howe~er, was broadened more than 30% of the corresponding half peak breadth of MgC12 having 1 m /g of s~trface area.
The catalyst component obtained was used under the same polymerization conditions as described in Example 11.
The characteristics of -the solid catalytic component and the results of the polymerization test are reported in Table I.

Example 1 was repeated but using the solid catalytic component prepared according to Example 1 of the afore-mentioned Monte et al published European patent. The X-rays powder spectrum was similar to that of the catalytic component of Example 1.
The results of the polymerization -tests are reported in Table I.

COMPARATIVE EXAMPI,E 3 Example 11 was repeated except that the solid catalytic ca~nent prepared according to Example 7 of published German patent application 2,643,143 was used. The X-rays powder spectrum was similar to that of catalytic component of Example 11.
The results of the polymerization tests have been reported in Table I.

Example 1 was repeated using a solid catalytic com-ponent prepared as follows.
Anh~drous MgC12, an ester, listed in Table II, and ~iCl~ in molar ratio of 1:1 with respect to the ester, were co-ground in a vibrating mill of the type VIBRATOM manufactured by N.V. T~MA'S, Gravenhage, Holland, having a total volume of one 2n liter and containiny 3 kg of stainless s-teel balls of 16 mm diameter.
Grinding was effectecl for 72 hours employing a filliny coefficient equal to 100 g/l of total volume (vacuum), at an interior temperature of the mill of 25C.
Charging of the mill, the grinding and discharging of the mill occurred in a nitrogen atmosphere.
10 g of the co ground productwere contac-ted with 100 ml of 1,2-dichloroethane at 80C for 2 hours. After this period, 1,2-dichloroethane was removed by filtration at 80C

~t r.l~le mark -16-5~

and the residual solid product was repeatedly washed with n-heptane at room temperature until the chlorine ions dis-appeared from the filtrate and then was kept in heptanic suspension.
The catalytic components thus prepared showed an X-rays powder spectrum in which the most intense diffraction line appearing in the spectrum of MgC12 having 1 m2/g of sur-face area was decreased in relative in~ensity and broadened to form a halo.
The type of ester used, the characteristics of the solid catalytic component, and the results of polymerization tests have been reported in Table II.

EXA~IPLES 19-26 -Example 1 was repeated but using a solid catalytic component prepared according to Example 3 of published British Patent 2,029,840.

A solid adduct MgC12.2.5C2H5OH in the form of spherical particles was slowly added to a suspension of an adduct TiCl~-ester using molar ratios Mg/ester of 10 and TiC14/C2H5OH of 10.
The whole was then heated at 100C, kept at said temperature for 2 hours and then filtered at 100C. The result-ing solid product was treated with 110 ml of TiC14 at 120C for 2 hours. After this period, TiC14 was removed by filtration and the solid was washed with n-heptane at temperatures de-creasing from 90C to room temperature until the chlorine ions disappeared from the filtrate and then kept in he~tanic suspension.

The catalytic components thus prepared showed the X-rays spectra similar -to those of the catalytic component of Examples l-10.
The esters used, the characteristics of the sollid catalytic component and the results of the polymerization tests are reported in Table III.

COMPARATIVE EX~MPLE 4 Example l9 was repeated but using the solid catalytic component prepared according to Example 3 of the published British Patent 2,029,840. The X-rays spec-trum of that catalytic component was similar to those of Examples 1-10.
The characteristics of the solid product and the results of the polymerization test are given in Table III.

IS Example 1 was repeated, but using a solid catalytic component prepared according to Example l of published German Patent Application 3,022,638, whe.rein, instead of ethylbenzoate, esters Oe phthalic acid, listed in Table IV, were used and the treatment with TiCl~ was effected at 120C.
~n The X-~rays spectrum of the catalyti.c components was similar to those of Examples l-10.
The type of ester and the ratios are shown in Table IV, together with the working conditions and the results of the polymerization tests.

Example 27 was repeated but using a solid catalytic component prepared accordiny to Example l of published German Patent Application 3,022.,738 (corresponding to published British Application 2,052,534)~

The working conditions and the results of the poly-me.rization test are reported in Table III.

Example 8 was repeated using instead of phenyl-triethoxysilane an equimolecular amount of the alkoxysilanes reported in Table V.
The characteristics of -the ca-talytic components and the results of the polymerization tests are reported in Table , ~s~

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A solid component, to be used in combination with:
(i) an Al-alkyl or -trialkyl compound containing at least two Al atoms linked to each other through an oxygen atom, a nitrogen atom, an SO4 group or an SO3 group; and (ii) a silicon compound containing at least one Si-OR, Si-OCOR or Si-NR2 bond, wherein R
represents a hydrocarbyl radical;
to form catalysts for the polymerization of alpha-olefins, comprising: an anhydrous Mg-dihalide in active form, as essential support; and, supported on said Mg-dihalide, a Ti-halide or Ti-haloalcoholate and an electron-donor compound selected from: diethyl diisobutylmalonate 7 diethyl n-butylmalonate, diethyl-n-dibutylmalonate, diethylphenylmalonate, diethyl-

1,2-cyclohexanedicarboxylate, dioctylsebacate, diisobutyl adipate, di-2-ethyl-hexyl-maleate, diisobutylmaleate, diisobutyl-3,4-furan-dicarboxylate, di-2-ethylhexylfumarate, 2-ethylhexylmonomaleate, diisobutyl-2,3-naphthalen-dicarboxy-late, di-n-propyl, di-n-butyl, diisobutyl, di-n-heptyl, di-2-ethyl-hexyl, di-noctyl, di-neopentil phthalates, mono-butyl and monoisobutyl esters of phthalic acid, ethyl-isobutyl-phthalate, ethyl-n-butyl-phthalate, 2,3-diacetoxy-naphthalene, l,2-diacetoxybenzene, l-methyl-2,3-diacetoxy-benzene, benzoyl-ethylsalicylate, acetyl-methylsalicylate, ethylene-glycol-pivalate, l,4-butanediol-pivalate, benzyl and isobutylpivalate, n-propylpivalate, ethyl diphenylacetate, isobutylmethacrylate, isobutylacrylate, ethyl-benzoylacetate, isobutylpyruvate, isobutyl-trans-3-methoxy-2-butenoate, phenyl-ethylcarbonate and diphenyl carbonate..

2. A solid component as defined in claim 1, wherein said Mg-dihalide is Mg-dichloride or Mg-dibromide and said Ti-halide is a Ti-tetrahalide.

3. A catalyst for the polymerization of alpha-olefins, comprising the reaction product of: components (i) and (ii), as defined in claim 1, and a solid component comprising: an anhydrous Mg-dihalide in active form, as essential support; and, supported on said Mg-dihalide, a Ti-halide or Ti-haloalcoholate and an ester, as an electron-donor, selected from:
(a) mono- and polyesters of saturated polycarboxylic acids, wherein at least one of the esteric carbonyl groups is linked to a tertiary or quaternary carbon atom, or to a linear or branched chain of at least 4 carbon atoms;
(b) mono- and polyesters of unsaturated poly-carboxylic acids, wherein at least two carboxy groups are linked to vicinal double bond-forming carbon atoms, and wherein at least one hydrocarbyl radical, R, of a -COOR group is a branched saturated or unsaturated radical with 3 to 20 carbon atoms, or an aryl or arylalkyl radical with 6 to 20 carbon atoms;
(c) mono- and diesters of aromatic dicarboxylic acids having their COOH groups in ortho position, and wherein at least one hydrocarbyl. radical, R, of a COOR group contains from 3 to 20 carbon atoms, (d) mono- and polyesters of aromatic hydroxy compounds containing at least two hydroxyl groups in ortho position;
(e) esters of aromatic hydroxy acids wherein at least one hydroxyl group is In ortho position to the carboxy group;
(f) esters of saturated or unsaturated carboxylic acids wherein at least one hydrocarbyl radical, R or R', of a R-COOR' group is a saturated or unsaturated branched radical containing from 3 to 20 carbon atoms, or an arylalkyl radical with 7 to 20 carbon atoms, or R is an aryl radical with 3 to 20 carbon atoms and R' is a linear hydrocarbyl radical containing from 3 to 20 carbon atoms; and (g) esters of carbonic acid of general formula CO(OR)2 wherein each R is, independently, a hydrocarbyl radical with 3 to 20 carbon atoms.

4. A catalyst for the polymerization of alpha-olefins, comprising the reaction product of:
(i) an Al-alkyl or -trialkyl compound containing at least two Al atoms linked to each other through an oxygen atom, a nitrogen atom, an SO4 group or an S03 group;

(ii) a silicon compound containing at least one Si-OR, Si-OCOR or Si-NR2 bond, wherein R
represents a hydrocarbyl radical; and (iii) a solid component as defined in claim 1.

5. A catalyst for the polymerization of alpha-olefins, comprising the reaction product of:
(i) an Al-alkyl or -trialkyl compound containing at least two Al atoms linked to each other through an oxygen atom, a nitrogen atom, an SO4 group or an SO3 group;
(ii) a silicon compound containing at least one Si-OR, Si-OCOR or Si-NR2 bond, wherein R
represents a hydrocarbyl radical; and (iii) a solid component as defined in claim 2.

6. A catalyst as defined in claim 3, wherein the silicon compound of component (ii) is a phenyl di- or tri-alkoxysilane, or an alkyl di- or trialkoxysilane.

7. A catalyst as defined in claim 4, wherein the silicon compound of component (ii) is a phenyl di- or tri-alkoxysilane, or an alkyl di- or trialkoxysilane.

A catalyst as defined in claim 5, wherein the silicon compound of component (ii) is a phenyl di- or trialkoxysilane, or an alkyl di- or trialkoxysilane.

9. A process for the polymerization of alpha-olefins of general formula: CH2=CHR, wherein R is an alkyl radical with 1 to 4 carbon atoms or an aryl radical, and mixtures of said olefins with ethylene, characterized in that: the polymerization process is carried out in liquid phase, in the presence or absence of an inert hydrocarbon solvent, or in gas phase, in the presence of a catalyst as defined in claim 3, 4 or 5.

10. A process for the polymerization of alpha-olefins of general formula: CH2=CHR, wherein R is an alkyl radical with 1 to 4 carbon atoms or an aryl radical, and mixtures of said olefins with ethylene characterized in that: the polymerization process is carried out in liquid phase, in the presence or absence of an inert hydrocarbon solvent, or in gas phase, in the presence of a catalyst as defined in claim 6,/ or 8.