WO1999048929A1

WO1999048929A1 - Prepolymerized catalyst components for the polymerization of olefins

Info

Publication number: WO1999048929A1
Application number: PCT/EP1999/001804
Authority: WO
Inventors: Gabriele Govoni; Mario Sacchetti; Gianni Vitale
Original assignee: Montell Technology Company B.V.
Priority date: 1998-03-23
Filing date: 1999-03-18
Publication date: 1999-09-30
Also published as: EP1418186B1; TR199902842T1; NO995726D0; NO995726L; ES2232127T3; EP1418186A2; ZA997682B; AR018165A1; JP4782256B2; KR20010012657A; EP1418186A3; JP2002500697A; AU3415099A; CN100406476C; EP0984988B1; DE69921918T2; CN1262693A; MY128259A; ATE509962T1; ID23021A

Abstract

The invention provides new prepolymerized catalyst components for the (co)polymerisation of olefins CH2=CHR, wherein R is hydrogen or a C1-C12 alkyl group, characterized by comprising a solid catalyst component, comprising Ti, Mg, halogen and an electron donor compound, being capable of yielding, under standard polymerization conditions, a propylene homopolymer having an insolubility in xylene at 25 °C higher than 90 %, which is prepolymerized with ethylene to such an extent that the amount of the ethylene prepolymer is up to 100g per g of said solid catalyst component. These such catalyst components allow to obtain a high catalyst activity, a high isotactic index and are not affected by aging.

Description

"PREPOLYMERIZED CATALYST COMPONENTS FOR THE POLYMERIZATION

OF OLEFINS"

The present invention relates to catalyst components for the polymerization of olefins

CH₂=CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms,

the catalysts obtained therefrom and their use in the polymerization of said olefins.

In particular the catalyst components of the present invention are very suitable for the

preparation of crystalline propylene (co)polymers by using gas-phase, slurry or bulk

(co)polymerization processes.

High-yield catalyst components for the polymerization of olefins and in particular for

propylene are known in the art. They are generally obtained by supporting, on a

magnesium dihalide, a titanium compound and an electron donor compound as a selectivity control agent. Said catalyst components are then used together with an aluminum alkyl and,

optionally, another electron donor (external) compound in the stereospecific polymerization of propylene. Depending on the type of electron donor used the stereoregularity of the

polymer can vary. However, the stereospecific catalysts of interest should be able to give

polypropylene (co)polymers having isotactic index, expressed in terms of xylene

insolubility, of higher than 90% .

Said catalyst components, and the catalysts obtained therefrom, are largely used in the

plants for the (co)polymerization of propylene both operating in liquid phase (slurry or

bulk) and in gas-phase. However, the use of the catalyst components as such is not

completely satisfactory. Indeed, problems such as formation of polymers with irregular

morphology and in particular of fines, low bulk density and low catalyst activity are

experienced when plants operate with catalyst components as such. In order to solve these problems, an additional prepolymerization line may be included, in

which the catalyst is prepolymerized under controlled conditions, so as to obtain

prepolymerized catalysts having good morphology. After prepolymerization, the catalysts

also increase their resistance in such a way that the tendency to break under polymerization

conditions is decreased. As a consequence, also the formation of fines is reduced.

Moreover also the activity of the catalyst and the bulk density of the final polymers results

to be improved. The use of this additional line, however, makes the plant operations and

design more complex and costly; in certain cases it is therefore desirable to avoid it. One of the alternative solutions is that of supplying the plants directly with a

prepolymerized catalyst which can be prepared in another facility. This solution requires

the preparation of a prepolymerized catalyst meeting certain requirements such as easy preparation and handling, easy stocking operability, absence or minimal reduction of activity with time (aging) preferably coupled with a basic high activity.

USP 5,641,721 discloses a method for preparing a prepolymerized catalyst comprising (i) the preparation of a procatalyst composition by depositing a transition metal compound on a

suitable support, (ii) mixing said procatalyst composition with a viscous substance and then

prepolymerizing said procatalyst composition with a monomer in the presence of said

viscous substance. The viscous substance has a viscosity of from 1000 to 15000 cP while

the monomer used is propylene. Albeit it is alleged that the catalyst activity is unchanged

after 5 months, it appears that the selectivity is decreased. Moreover, the prepolymerization

in such a viscous substance makes the preparation of the prepolymerized catalyst complex

and, in addition, leads to a low catalyst activity. It has now surprisingly been found that by carrying out the prepolymerization with a

specific monomer it is possible to obtain a catalyst for the polymerization of olefins which

has a high catalyst activity, a high isotactic index and which is not affected by aging.

It is therefore an object of the present invention a prepolymerized catalyst component for

the (co)polymerization of olefins CH₂=CHR, wherein R is hydrogen or a C1-C12 alkyl

group, characterized by comprising a solid catalyst component, comprising Ti, Mg,

halogen and an electron donor compound, being capable of yielding, under standard

polymerization conditions, a propylene homopolymer having an insolubility in xylene at 25 °C higher than 90% , which is prepolymerized with ethylene to such an extent that the

amount of the ethylene prepolymer is up to lOOg per g of said solid catalyst component.

Preferably the amount of ethylene polymer is less than 15 g and more preferably said

amount is less than 5 g per g of solid catalyst component.

In particular, the catalyst components comprise a titanium compound, having at least a Ti-

halogen bond and the above mentioned electron donor compound supported on a Mg halide.

The magnesium halides, preferably MgCl₂, in active form used as a support for Ziegler-

Natta catalysts, are widely known from the patent literature. Patents USP 4,298,718 and

USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta

catalysis. It is known from these patents that the magnesium dihalides in active form used

as support or co-support in components of catalysts for the polymerization of olefins are

characterized by X-ray spectra in which the most intense diffraction line that appears in the

spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose

maximum intensity is displaced towards lower angles relative to that of the more intense

line. The preferred titanium compounds used in the catalyst component of the present invention

are TiCl₄ and TiCl₃; furthermore, also Ti-haloalcoholates of formula Ti(OR)_n._yX_y, where n is the valence of titanium and y is a number between 1 and n, can be used.

The internal electron-donor compound may be selected from esters, ethers, amines and

ketones. It is preferably selected from alkyl, cycloalkyl or aryl esters of monocarboxylic

acids, for example benzoic acid, or polycarboxylic acids, for example phthalic or malonic

acid, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms.

Moreover, it can be also selected from 1,3-diethers of formula (I):

R¹¹ R¹

VIII

(I)

VII

wherein R¹, R", R"¹, R^1V, R^v and R^VI equal or different to each other, are hydrogen or

hydrocarbon radicals having from 1 to 18 carbon atoms, and R^vπ and R^vm, equal or different from each other, have the same meaning of R'-R^VI except that they cannot be

hydrogen; one or more of the R'-R^vιπ groups can be linked to form a cycle. Particularly

preferred are the 1,3-diethers in which R^vπ and R^VI" are selected from C_rC₄ alkyl radicals.

Examples of preferred electron-donor compounds are methyl benzoate, ethyl benzoate,

diisobutyl phthalate and 9,9-bis(methoxymethyl)fluorene. As explained above, however,

the internal electron donor compound must be selected in such a way to have a final solid

catalyst component capable of producing, under the standard polymerization test disclosed below, a propylene homopolymer having an insolubility in xylene at 25 °C higher than

90% .

The preparation of the solid catalyst component can be carried out according to several

methods. According to one of these methods, the magnesium dichloride in an anhydrous

state, the titanium compound and the electron donor compound of formula (I) are milled

together under conditions in which activation of the magnesium dichloride occurs. The so

obtained product can be treated one or more times with an excess of TiCl₄ at a temperature

between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared. According to a further method, the product obtained by co-

milling the magnesium chloride in an anhydrous state, the titanium compound and the

electron donor compound is treated with halogenated hydrocarbons such as 1,2- dichloroethane, chlorobenzene, dichloromethane etc. The treatment is carried out for a time

between 1 and 4 hours and at temperature of from 40 °C to the boiling point of the halogenated hydrocarbon. The product obtained is then generally washed with inert

hydrocarbon solvents such as hexane.

According to another method, magnesium dichloride is preactivated according to well

known methods and then treated with an excess of TiCl₄ at a temperature of about 80 to

135 °C in the presence of the electron donor compound. The treatment with TiCl₄ is

repeated and the solid is washed with hexane in order to eliminate any non-reacted TiCl₄.

A further method comprises the reaction between magnesium alcoholates or

chloroalcoholates (in particular chloroalcoholates prepared according to U.S. 4,220,554)

and an excess of TiCl₄ in the presence of an electron donor compound (I) at a temperature

of about 80 to 120°C. Particularly preferred are the solid catalyst component prepared by reacting a titanium compound of formula Ti(OR)n-yXy, where n is the valence of titanium and y is a number

between 1 and n, preferably TiCl₄, with an adduct of formula MgCl₂-»pROH, where p is a

number between 0,1 and 6 and R is a hydrocarbon radical having 1-18 carbon atoms. The

adduct can be suitably prepared in spherical form by mixing alcohol and magnesium

chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating

under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the

emulsion is quickly quenched, thereby causing the solidification of the adduct in form of

spherical particles. Examples of spherical adducts prepared according to this procedure are

described in USP 4,399,054. The so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-

130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0.1 and 2.5. The dealcoholated adduct is then suspended

in cold TiCl₄ (generally 0°C); the mixture is heated up to 80-130°C and kept at this

temperature for 0.5-2 hours. The treatment with TiCl₄ can be carried out one or more

times. The internal electron donor compound can be added during the treatment with TiCl₄.

The treatment with the electron donor compound can be repeated one or more times.

The preparation of catalyst components in spherical form is described for example in

European Patent Applications EP-A-395083.

The solid catalyst components obtained according to the above method show a surface area

(by B.E.T. method) generally between 20 and 500 m²/g and preferably between 50 and 400

m²/g, and more preferably between 100 and 400 m²/g; a total porosity (by B.E.T. method)

higher than 0.2 cm³/g preferably between 0.2. and 0.6 cmVg and more preferably from 0.3 to 0.5 cmVg. The porosity (Hg method) due to pores with radius up to lO.OOOA generally ranges from 0.3 to 1.5 cm³/g, preferably from 0.45 to 1 cm³/g.

A further method to prepare the solid catalyst component of the invention comprises

halogenating magnesium dihydrocarbyloxide compounds, such as magnesium dialkoxide or

diary loxide, with solution of TiCl₄ in aromatic hydrocarbon (such as toluene, xylene etc.)

at temperatures between 80 and 130°C. The treatment with TiCl₄ in aromatic hydrocarbon

solution can be repeated one or more times, and the internal electron donor compound is

added during one or more of these treatments. In any of these preparation methods, the desired internal electron donor compound can be added as such or, in an alternative way, it

can be obtained in situ by using an appropriate precursor capable to be transformed in the

desired electron donor compound by means, for example, of known chemical reactions such as esterification, transesterification etc. Generally, the internal electron donor

compound is used in molar ratio with respect to the MgCl₂ of from 0.01 to 1 preferably

from 0.05 to 0.5.

As explained above the prepolymerized catalyst component can be obtained by

prepolymerizing the solid catalyst component together with ethylene. The

prepolymerization is normally carried out in the presence of an Al-alkyl compound.

The alkyl-Al compound (B) is preferably chosen among the trialkyl aluminum compounds

such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-

hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of

trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum

sesquichlorides such as AlEt₂Cl and Al₂Et₃Cl₃. It has been found particularly advantageous to carry out said prepolymerization using low

amounts of alkyl-Al compound. In particular said amount can be such as to have an Al/Ti

molar ratio from 0.0001 to 50, preferably from 0.001 to 10 and more preferably from 0.01

to 1.

Moreover, it has also been found advantageous to carry out said prepolymerization in the

absence of an external donor compound.

The prepolymerization can be carried out in liquid phase, (slurry or solution) or in gas-

phase at temperatures generally lower than 80°C, preferably between -20 and 50°C.

Furthermore, it is preferably carried out in a liquid diluent in particular selected from

liquid hydrocarbons. Among them, pentane, hexane and heptane are preferred.

As explained the so obtained prepolymerized catalyst components can be used in the polymerization of olefins, and in particular of propylene, allowing to obtain high activity

and polymers with high stereoregularity, high bulk density and very good morphology thus

showing their particular suitability for the liquid (bulk or slurry) and gas-phase processes.

In addition, as it is shown in the examples, aging problems are solved since the activity of

the catalyst remains unaltered or even improved in some cases, after several months of

time. Accordingly, the catalyst components of the invention are particularly suitable for the

use in liquid or gas-phase olefin polymerization plants operating without a

prepolymerization line.

In particular, said olefin polymerization processes can be carried out in the presence of a

catalyst comprising (A) the prepolymerized catalyst component; (B) an Al-alkyl compound

of the type described above and optionally (C) one or more electron donor (external)

compound.

8 This latter can be of the same type or it can be different from the internal donor described

above. Suitable external electron donor compounds include silicon compounds, ethers,

esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethyl piperidine,

ketones and the 1 ,3-diethers of the general formula (I) given above.

Another class of preferred external donor compounds is that of silicon compounds of formula

R_a ⁵R_b ⁶Si(OR⁷)_c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum

(a+b+c) is 4; R⁵, R⁶, and R⁷, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms

optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a

is 1, b is 1, c is 2, at least one of R³ and R⁶ is selected from branched alkyl, cycloalkyl or aryl

groups with 3-10 carbon atoms optionally containing heteroatoms and R⁷ is a C,-C₁₀ alkyl

group, in particular methyl. Examples of such preferred silicon compounds are

methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane,

dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and

l,l,l,trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane. Moreover, are also preferred the

silicon compounds in which a is 0, c is 3, R⁶ is a branched alkyl or cycloalkyl group, optionally

containing heteroatoms, and R⁷ is methyl. Examples of such preferred silicon compounds are

cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.

In particular when esters of monocarboxylic acids, for example benzoates are used as

internal donors also the external donor compound is selected from this class p-ethoxy-ethyl

benzoate being the most preferred. In addition, a mixture of this donor with another one

and in particular one selected from the class of silicon compounds can be used. In this case

methylcyclohexyldimethoxysilane and dicyclopentyldimethoxysilane are most preferred. The electron donor compound (C) is used in such an amount to give a molar ratio between the

organoaluminum compound and said electron donor compound of from 0.1 to 500, preferably

from 1 to 300 and more preferably from 3 to 100.

The above described polymerization process can be carried out under the polymerization

conditions generally known in the art. Accordingly, the polymerization is generally carried

out at temperature of from 20 to 120°C, preferably of from 40 to 80°C. When the

polymerization is carried out in gas-phase the operating pressure is generally between 0.5 and

10 MPa, preferably between 1 and 5 MPa. In the bulk polymerization the operating pressure

is generally between 1 and 6 MPa preferably between 1.5 and 4 MPa. In any of the polymerization processes used (liquid or gas-phase polymerization) the catalyst

forming components (A), (B) and optionally (C), can be pre-contacted before adding them to the polymerization reactor. Said pre-contacting step can be carried out in the absence of polymerizable olefin or optionally in the presence of said olefin in an amount up to 3 g per g

of solid catalyst component. The catalyst forming components can be contacted with a liquid

inert hydrocarbon solvent such as propane, n-hexane, or n-heptane at a temperature below

about 60 °C and preferably from about 0°C to 30 °C for a time period of from 10 seconds to

60 minutes.

When a gas-phase polymerization process is used, it can be carried out according to known

techniques operating in ore or more reactors having a fluidized or mechanically agitated bed.

Inert fluids such as nitrogen, or low hydrocarbons like propane, can be used both as a

fluidization aid and in order to improve the thermal exchange within the reactors. In addition,

also techniques increasing the removal of the reaction heat comprising the introduction of

liquids, optionally in mixture with gas, into the reactors, can be used. Preferably the liquids

10 are fresh or make-up monomers. Such techniques are disclosed for example in EP-A-89691,

EP-A-241947, USP 5,352,749, WO94/28032 and EPA-695313.

The following examples are given in order better illustrate the invention without limiting it.

EXAMPLES

Characterization

Determination of X.I.

2.5 g of polymer were dissolved in 250 ml of o-xylene under stirring at 135EC for 30

minutes, then the solution was cooled to 25 °C and after 30 minutes the insoluble polymer was

filtered. The resulting solution was evaporated in nitrogen flow and the residue was dried and

weighed to determine the percentage of soluble polymer and then, by difference, the X.I. % .

General procedure for the standard propylene polymerization test

A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst-

feeding system, monomer feeding lines and thermostatting jacket, was used. The reactor was

charged with 0.01 g of solid catalyst component and with TEAL, and cyclohexyl-methyl

dimethoxy silane in such amounts to give an Al/Donor molar ratio of 20. Moreover, 3.2 1 of

propylene, and 1.5 1 of hydrogen were added. The system was heated to 70°C over 10 min.

under stirring, and maintained under these conditions for 120 min. At the end of the

polymerization, the polymer was recovered by removing any unreacted monomers and was

dried under vacuum.

Determination of Melt Index

ASTM D 1238 condition "L"

Examples 1-2 and comparison example 3

Preparation of Solid Catalyst Component

11 Into a 500 ml four-necked round flask, purged with nitrogen, 250 ml of TiC14 were

introduced at 0°C. While stirring, 10 g of microspheroidal MgCl₂»C₂H₅OH containing

about 54% weight of alcohol were added. The flask was heated to 40 °C and 6 mmoles of

diisobutylphthalate were thereupon added. The temperature was raised to 100°C and

maintained for two hours, then the stirring was discontinued, the solid product was allowed to settle and the supernatant liquid was siphoned off.

The treatment with TiCl₄ was repeated and the solid obtained was washed six times with

anhydrous hexane (6 x 100 ml) at 60°C and then dried under vacuum: The characteristics

of the catalyst components and the results of the propylene polymerization test procedure are reported in table 1. Ethylene Prepolymerization

The catalyst components prepared according to the above procedure were prepolymerized with ethylene under the conditions reported in table 2. In comparison example 4 prepolymerization was not carried out. Propylene Polymerization

The prepolymerized catalyst obtained was then used in the polymerization of propylene

carried out in a bulk pilot polymerization plant under the following conditions:

Al/Cat (weight ratio): 8

Al/Donor (weight ratio): 6

Donor/cat (weight ratio): 1.3

Time (min.): 80

Temperature (°C): 70

The results are shown in table 3.

12 Example 4-5 and comparison example 6

Preparation of the catalyst component

The catalyst components were prepared according to the procedure of example 1 but using

ethyl benzoate instead of dusobutylphthalate. The characteristics of the catalyst components

and the results of the propylene polymerization test procedure are reported in table 1.

Ethylene Prepolymerization

The catalyst components prepared according to the above procedure were prepolymerized

with ethylene under the conditions reported in table 2. In comparison example 6

prepolymerization was not carried out.

Propylene Polymerization

The catalyst components obtained were then used in the polymerization of propylene which

was carried out in a bulk pilot polymerization plant under the following conditions:

Al/Cat (weight ratio): 4.6

Al/Donor (weight ratio): 1.4

Donor/cat (weight ratio) : 3.2

Time (min.): 80

Temperature (°C): 70

using p-ethoxy-ethylbenzoate as external donor The results are shown in table 3.

Example 7 and comparison example 8

The catalyst components were prepared according to the procedure of example 4 but using

9,9-bis(methoxymethyl)-fluorene instead of ethyl benzoate. The characteristics of the

catalyst components and the results of the propylene polymerization test procedure are

reported in table 1.

13 Ethylene Prepolymerization

with ethylene under the conditions reported in table 2. In comparison example 8

prepolymerization was not carried out.

Propylene Polymerization

Al/Cat (weight ratio) : 13.7

Time (min.): 80

Temperature (°C): 70

without using an external donor The results are shown in table 3.

Evaluation of aging properties

The catalyst components prepared according to the examples 4 and 5 were tested for the

polymerization of propylene in order to evaluate their aging properties. A first test was

carried out after the prepolymerization and a further test was carried out after 120 days. All

the tests were carried out according to the general standard procedure but using p-ethoxy-

ethylbenzoate as external donor in an amount such as to give an Al/donor molar ratio of

1.8. The results are reported in table 4.

14 TABLE 1

Solid catalyst components

Example Ti (%) Mg (%) Donor(%) Xil.Ins.(%)

1 3 18.8 9.6 98.1

2 3.1 18.9 9.5 97.9

comp 3 3 18.9 9.4 98.1

4 4.3 17 13.5 95.9

5 3.4 17.5 13.8 95.6

comp.6 4.1 17.1 13.3 96

7 4.1 15.5 17.2 97

comp.8

15 TABLE 2

Prepolymerized catalyst components

Prepolymerization conditions

Example Al/cat (wt) Cat/C2- Time (min.) Temp.(°C)

1 0.004 1 300 20

2 0.004 1 300 20

comp.3 - - - -

4 0.005 1 300 20

5 0.01 1 300 20

comp.6 - - - -

7 0.005 1 300 20

Comp.8 - - - -

16 TABLE 3

Polymerization results with the prepolymerized catalyst components

Example Yield Xil. Ins. Bulk Density MIL

1 23 96 0.47 1.3

2 24 96 0.48 1.2

comp.3 16 95 0.32 1.4

4 28 95.5 0.43 1.6

5 30 95 0.42 2

comp.6 20 94 0.3 3

7 78 96.3 0.43 1

Comp.8 55 95 0.32 1

TABLE 4

Example Aging (days) Yield kg/g Xil.Ins (%) Bulk density

4 0 38.6 94.4 0.38

4 120 41.4 94.6 0.41

5 0 35.3 94.3 0.385

5 120 36.1 95 0.40

17

Claims

1. A prepolymerized catalyst component for the polymerization of olefins CH₂ = CHR,

wherein R is hydrogen or a C,-C₁₂ alkyl group, characterized by comprising a solid

catalyst component comprising Mg, Ti, halogen and an electron donor compound and

being capable of yielding under standard propylene polymerization conditions a

propylene homopolymer having an insolubility in xylene at 25 ┬░C higher than 90% ,

said solid catalyst component being prepolymerized with ethylene to such an extent

that the amount of the ethylene prepolymer is up to lOOg per g of solid catalyst

component.

2. Catalyst component according to claim 1 in which the amount of ethylene polymer is

less than 15 g per g of solid catalyst component.

3. Catalyst component according to claim 2 in which the amount of ethylene is less than

5 g per g of solid catalyst component.

4. Catalyst component according to claim 1 in which the solid catalyst component

comprises a titanium compound having at least a Ti-halogen bond and an electron donor

compound supported on a Mg halide in active form.

5. Prepolymerized catalyst component according to any of the preceding claims

characterized in that the solid catalyst component is obtained by reacting a titanium

compound of formula Ti(OR)n-yXy, where n is the valence of titanium and y is a

number between 1 and n, with an adduct of formula MgCl₂*pROH, where p is a

number between 0,1 and 6 and R is a hydrocarbon radical having 1-18 carbon atoms.

6. Catalyst component according to any of claims 5 in which the titanium compound is

TiCl₄.

18

7. Catalyst component according to claim 1 in which the internal electron-donor

compound is selected from esters, ethers, amines and ketones.

8. Catalyst component according to claim 6 in which said internal donor is selected from

alkyl, cycloalkyl or aryl esters of monocarboxylic acids, the said alkyl, cycloalkyl or

aryl groups having from 1 to 18 carbon atoms.

9. Catalyst component according to claim 6 in which the internal donor is selected from

the group consisting of ethyl benzoate and diisobutyl phthalate.

10. Catalyst component according to claim 6 in which the internal donor is selected from

1,3-diethers of formula (I):

R¹¹ R¹

_R╧Ç╬╣ -ORΓäó¹

(I) R^IV/ -OR

R _Rv╬╣

wherein R¹, R", R¹", R^IV, R^v and R^V1 equal or different to each other, are hydrogen or

hydrocarbon radicals having from 1 to 18 carbon atoms, and R^v╧Ç and R^VI", equal or

different from each other, have the same meaning of R'-R^V1 except that they cannot be

hydrogen; one or more of the R'-R ¹ groups can be linked to form a cycle.

11. Catalyst component according to claim 9 in which R^v" and R^vm are selected from C,-

C₄ alkyl radicals and the groups R^╧Ç╬╣ and R^IV are linked to form a cycle.

12. Process for the preparation of the prepolymerized catalyst component according one

of the claims 1-11 carried out by prepolymerizing ethylene in the presence of a solid

19 catalyst component comprising Mg, Ti, halogen and an electron donor compound,

and of an Al-alkyl compound.

13. Process according to claim 12 in which the alkyl-Al compound is chosen among

trialkyl aluminum compounds and alkylaluminum halides.

14. Process according to claim 13 in which the alkyl-Al compound is selected from

triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum,

tri-n-octylaluminum .

15. Process according to any of the claims 12-14 in which the prepolymerization is

carried out using amounts of alkyl-Al compound such as to have an Al/Ti. molar ratio

from to 0.0001 to 50.

16. Process according to claim 15 in which the Al/Ti molar ratio is from to 0.001 to 10.

17. Process according to claim 16 in which the Al/Ti molar ratio is from 0.01 to 1.

18. Process according to claim 12 in which the prepolymerization is carried out in liquid diluent selected from liquid hydrocarbons.

19. Catalyst for the polymerization of olefins CH₂=CHR, wherein R is hydrogen or a

hydrocarbon radical having 1-12 carbon atoms comprising a prepolymerized catalyst

component according to any of the claims 1-11 an aluminum alkyl compound and,

optionally, one or more electron donor compounds.

20. Catalyst according to claim 19 in which a benzoate is used both as internal and

external donor.

21. Catalyst according to claim 20 in which a mixture of a benzoate and a silicon

compounds are used as external donors.

20

22. Catalyst according to claim 20 in which ethyl benzoate is the internal donor, and p-

ethoxy ethylbenzoate is the external donor.

23. Catalyst according to claim 21 in which ethyl benzoate is the internal donor, and the

external donor comprises a mixture p-ethoxy ethylbenzoate and

dicyclopentyldimethoxysilane .

24. Process for the polymerization of olefins CH₂ = CHR, wherein R is hydrogen or a

hydrocarbon radical having 1-12 carbon atoms carried out in the presence of a

catalyst comprising (A) the prepolymerized catalyst component according to one of

the claims 1-11; (B) an Al-alkyl compound and, optionally, (C) of an external donor

compound.

25. Process according to claim 24 in which the catalyst forming components (A), (B) and

optionally (C), are pre-contacted before adding them to the polymerization reactor.

26. Process according to claim 24 in which the olefin is propylene.

27. Process according to claim 24 in which the external electron donor is selected from

silicon compounds, ethers, esters, amines, heterocyclic compounds, ketones and the

1,3-diethers of the general formula (I).

28. Process according to claim 27 in which the external donor is selected from silicon

compounds of formula R_a ⁵R_b ⁶Si(OR⁷)_c, where a and b are integer from 0 to 2, c is an

integer from 1 to 3 and the sum (a+b+c) is 4; R⁵, R⁶, and R⁷, are alkyl, cycloalkyl or aryl

radicals with 1-18 carbon atoms optionally containing heteroatoms.

29. Process according to claim 21 in which a is 1 , b is 1, c is 2, at least one of R⁵ and R⁶

is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms and

R⁷ is a C_J-C_JO alkyl group.

21