EP0702701A1

EP0702701A1 - Method for polymerising or copolymerising propylene in liquid propylene, solid catalytic component, and method for making same

Info

Publication number: EP0702701A1
Application number: EP95908995A
Authority: EP
Inventors: Corinne Gomez-Journaud; Jean-Michel Brusson; Roger Spitz
Original assignee: Appryl SNC
Current assignee: Appryl SNC
Priority date: 1994-02-18
Filing date: 1995-02-08
Publication date: 1996-03-27
Also published as: JPH08509263A; CA2160806A1; KR960701907A; CN1123552A; WO1995022568A1; NO954122L; NO954122D0; FI954937A; FI954937A0

Abstract

A method for polymerising or copolymerising propylene in liquid propylene in the presence of a cocatalyst and a solid catalytic component prepared by contacting (a) a solid compound containing magnesium, halogen and transition metal atoms, with (b) an organic aluminium derivative, and (c) a dialkoxysilane of formula R?1R2Si(OR3)(OR4¿), wherein R?3 and R4¿ are hydrocarbon groupings containing 1-12 carbon atoms and preferably methyl or ethyl groupings, and R?1 and R2¿ are hydrocarbon groupings, where one or both of R?1 and R2¿ contains at least three carbon atoms. A novel solid catalytic component for polymerising olefins, and a method for making same, are also disclosed.

Description

POLYMERIZATION PROCESS OR D: POLYMERIZATION

PROPYLENE IN THE PROP. -i- E LIQUID, SOLID CATALYTIC COMPONENT AND PROCESS FOR PRODUCING THE SAME

MANUFACTURING

* * * * * * * * * * * TECHNICAL AREA

The present application relates to a process for the polymerization of propylene in liquid propylene or for the copolymerization of propylene with an alpha-olefin in liquid propylene in the presence of a cocatalystur and of a solid catalytic component containing magnesium atoms, halogen, aluminum, a transition metal and silicon.

The present application also relates to new solid catalytic components, in particular usable in the preceding process, as well as their manufacturing process.

PRIOR ART The polymerization of propylene can be carried out either in suspension, or in the gas phase, or in liquid propylene. Generally, this polymerization is carried out in the presence of a cocatalyst, which is usually an organic derivative of aluminum, in the presence of a solid catalytic component containing atoms of magnesium, halogen, aluminum, a metal of transition and possibly also containing an internal electron donor, and in the presence of an external electron donor, in other words of an electron donor not incorporated in the solid catalytic component, the role of this electron donor external being to raise the isotacticity index of the synthesized polypropylene. Polypropylenes with a high isotacticity index have improved mechanical properties, in particular in terms of their rigidity.

It has already been attempted to incorporate an alkoxysilane into a solid catalytic component in order to avoid having to introduce an external electron donor to the polymerization. US Patent 4,442,276 describes such components containing a trialkoxysilane. These components make it possible, with relatively modest productivity, to obtain polymers having high isotacticity indices by polymerization of propylene in suspension. The Applicant has discovered that in the polymerization of propylene in liquid propylene, these components do not lead to polymers with high indices of isotacticity. The document EP0582943 describes the polymerization of propylene in the presence of a solid component containing silicon and titanium at a rate of 0.5 to 100 moles of silicon per gram of atom of titanium, which corresponds to 24 to 4800 moles of silicon per mole of titanium. The insertion of silicon in the solid component is produced after prepolymerization of propylene on the other ingredients of the component. It is essential not to wash this component before using it in polymerization.

Document EP0501741 describes the polymerization of propylene in suspension between 150 and 300 ° C in the presence on the one hand of a solid component containing titanium and a silane and on the other hand of an organic derivative of aluminum, the ratio Al / Ti molar which cannot be greater than 1.

STATEMENT OF THE INVENTION

The Applicant has discovered that an alkoxysilane incorporated into a catalytic component exhibits, when said catalytic component is used in a process for the polymerization of propylene in liquid propylene, unpredictable behavior in terms of the isotacticity index of the polymer obtained as well as in terms of the productivity of the polymerization.

In fact, an alkoxysilane incorporated into a solid catalytic component will not have the same influence depending on whether this solid catalytic component is used in a process for the polymerization of propylene in liquid propylene or in a process for the polymerization of propylene in suspension. In addition, in the polymerization of propylene in liquid propylene, the influence of an alkoxysilane incorporated into a solid catalytic component does not appear to be able to be easily extrapolated from the observation of its influence when the same alkoxysilane is present in polymerization in as an external electron donor, that is to say not incorporated into the solid catalytic component.

It has now been found that a particular selection of alkoxysilanes could be incorporated into a solid catalytic component containing magnesium, halogen, aluminum and transition metal atoms, and possibly containing an internal electron donor, said solid catalytic component leading, in polymerization of propylene in liquid propylene, to polymers with high indices of isotacticity with generally good productivity, without an external electron donor necessarily having to be present in the polymerization medium.

It is possible to incorporate a much smaller quantity of these aikoxysilanes in the solid catalytic components considered than it would be necessary to introduce them into the polymerization medium outside of the solid catalytic component if these aikoxysilanes were to play their conventional role of external electron donor.

The role of the alkoxysilane in the present invention should not be assimilated to that of a conventional internal electron donor, the latter being always incorporated in solid catalytic component before or at the same time as the tm -.r-ion metal.

The invention conceives of a process for the polymerization of propylene in liquid propylene or for the copolymerization of propylene in liquid propylene with ethylene or an alpha-olefin containing from four to twelve carbon atoms, in the presence of a cocatalyst and a solid catalytic component obtained by bringing a into contact. a solid compound (a) containing magnesium, halogen and transition metal atoms, b. an organic aluminum derivative (b), c. a dialkoxysilane (c) of formula R ¹ R2si (OR ³ ) (OR ⁴ ) in which R3 and R ^ which may be identical or different represent hydrocarbon groups containing from 1 to 12 carbon atoms and preferably methyl or ethyl groups, R ^* 1 and R2, which may be identical or different, represent hydrocarbon groups, R ^" ! Being saturated and containing at least three carbon atoms. R1 and R2 may each contain from 1 to 20 carbon atoms.

For a given R2 group, preferably, the carbon atom of R1 linked to silicon is linked to two carbon atoms. For a given group R1, preferably R2 is saturated and contains at least three carbon atoms. More preferably, R2 is saturated and its carbon atom linked to silicon is linked to two carbon atoms.

The halogen contained in the solid compound (a) is preferably chlorine. The transition metal contained in the solid compound (a) can be zirconium, hafnium, vanadium or, preferably, titanium.

The solid compound (a) may be a catalytic component of the type

Ziegler-Natta. A catalytic component of the Ziegler-Natta type is generally in the form of a complex containing at least Mg, Ti and Cl, the titanium being in chlorinated form of Ti ^ιv and / or Ti '"and optionally contains a donor d 'electrons.

A Ziegler-Natta type catalytic component is usually the result of the combination of at least one magnesium compound, a titanium compound, chlorine and possibly an electron donor as well as any other compound which can be used in this type of component. . The magnesium compound is usually chosen from the compounds of formula Mg (OR) _n Cl2-n in which R represents hydrogen or a linear or cyclic hydrocarbon radical and n represents an integer ranging from 0 to 2. The titanium compound is usually chosen from the chlorinated compounds of titanium of formula Ti- (OR) _x Cl4_ _x in which R represents an aliphatic or aromatic hydrocarbon radical containing from one to fourteen carbon atoms, or represents COR ^' ' with Ri representing an aliphatic or aromatic hydrocarbon radical containing from one to fourteen atoms of carbon, and x represents an integer ranging from 0 to 3.

The chlorine present in the Ziegler-Natta type catalytic component can come directly from the titanium compound and / or the magnesium compound. It can also come from an independent chlorinating agent such as hydrochloric acid or an organic chloride such as butyl chloride. The electron donor possibly contained in the catalytic component of the Ziegler-Natta type is a liquid or solid organic compound known to enter into the composition of these catalytic components. The electron donor can be a mono or polyfunctional compound advantageously chosen from aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, acrylic derivatives, in particular alkyl acrylates or alkyl methacrylates and siianans. Particularly suitable as electron donors are compounds such as methyl paratoluate, ethyl benzoate, ethyl or butyl acetate, ethyl ether, ethyl para-anisate, dibutylphthalate, dioctylphthalate, diisobutylphthalate, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone, vinyl acetate, methyl methacrylate.

The organic aluminum derivative (b) may be a derivative of formula R ¹ R ² R ³ AI in which R ¹ , R ² and R ³ , which may be identical or different, each represent either a hydrogen atom, either a halogen atom or an alkyl group containing from 1 to 20 carbon atoms, at least one of R1, R2 or R ³ representing an alkyl group. As an example of a suitable compound, mention may be made of ethyl aluminum dichloride or dibromide or dihydride, isobutyl aluminum dichloride or dibromide or dihydride, diethyl aluminum chloride or bromide or hydride, di-aluminum chloride or bromide or hydride n propylaluminium, chloride or bromide or hydride of diisobutylaluminium.

The organic aluminum derivative can also be an aluminoxane. linear, of formula

R

I

R2 AI-0- (AI-0) _n -AI R2, or cyclic of formula

R representing for these two formulas an alkyl radical comprising from one to six carbon atoms, and n being a whole integer from 2 to 40, preferably from 10 to 20. The aluminoxane may contain? S groups R of different nature. Preferably, the groups R all represent methyl groups.

Preferably to the abovementioned compounds, a trialkylaluminum such as tri-n-hexylaluminum, triisobutylaluminum, trimethylaluminum or triethylaluminum is used, the latter compound being particularly preferred.

Preferably, prepolymerization is not carried out before bringing ingredients (a), (b) and (c) into contact.

The contact between the compounds (a), (b) and (c) is preferably carried out in the presence of an H hydrocarbon, which is preferably a saturated aliphatic or saturated alicyclic hydrocarbon such as hexane, heptane or cyciohexane. Compounds (b) and (c) can be added pure to a suspension of (a) in an H hydrocarbon or can be added in the form of solutions, a solution of (b) in an H hydrocarbon on the one hand and a solution of (c) in a hydrocarbon H on the other hand, to a suspension of (a) in a hydrocarbon H. The suspension of (a) in hydrocarbon H preferably contains sufficient hydrocarbon H so that said suspension can _-ιre agitated without attrition of (a).

Generally, the total amount of hydrocarbon H finally present with the mixture of (a), (b) and (-.,. Is less than 100 liters per kg of solid compound (a).

(B) is generally introduced in an amount such that the molar ratio [AI] / [M], that is to say aluminum supplied by (b) on the transition metal M supplied by (a) 0.5 to 100 and preferably 1 to 50 in the suspension mixture of (a), (b) and (c). We generally introduce (c) in an amount such that the molar ratio

[Si] / [M], that is to say silicon supplied by (c) on the transition metal M supplied by (a) ranges from 0.5 to 20 and preferably from 1 to 10 in the mixture suspended from (a), (b) and (c).

Preferably, in order to obtain a good compromise between the isotacticity index of the polymers and the productivity of these polymers, the compounds (b) and (c) are first brought into contact, which are then brought into contact with the compound (a). Preferably, to do this, a solution of (b) and (c) is first prepared in an H hydrocarbon, then the solution of (b) and (c) is mixed with a suspension of (a) in a hydrocarbon H. The suspension of (a) in hydrocarbon H preferably contains sufficient hydrocarbon H so that said suspension can be stirred without attrition of (a).

The solid catalytic component obtained by contacting (a), (b) and (c) can then be filtered and washed with an H hydrocarbon and dried. Washing of the solid component is recommended in particular when it is desired to store it before engaging it in polymerization. This washing is favorable to its stability.

The implementation of the process for the polymerization or copolymerization of propylene in liquid propylene according to the invention requires the introduction into the polymerization medium of a cocatalyst which can be chosen from the list of compounds of formula R ¹ R2R ³ AI previously described for the choice of the organic aluminum derivative (b) in an amount such that the molar ratio of the cocatalyst to the transition metal M contained in the solid catalytic component ranges from 100 to 3000. Generally, the cocatalyst is present in the medium of polymerization at a rate of 0.5 to 10 millimoles of cocatalyst per liter of liquid propylene. The polymerization or copolymerization of propylene in liquid propylene can be carried out continuously or batchwise at temperatures up to the critical temperature, that is to say approximately 92 ° C., and at pressures which can be between atmospheric pressure and critical pressure.

In the case where the process according to the invention is used for the copolymerization of propylene with ethylene or an alpha-olefin containing from four to twelve carbon atoms, it is preferred to adjust the amounts of monomers so that the final polymer contains between 85 and 100% by weight of polymerized propylene.

The polymerization in liquid propylene can be carried out in the presence of a chain transfer agent so as to control the melt index of the polymer or copolymer to be produced.

The preferred chain transfer agent is hydrogen which is introduced in an amount of 0.01% to 5% by mole of the whole olefin (s) and hydrogen.

The polymerization in liquid propylene can be carried out continuously or batchwise in the presence or absence of an inert diluent which can be an aliphatic hydrocarbon such as hexane or an alicyclic hydrocarbon such as cyclohexane. ? ^_ The solid component talytiques obtainable in the manner previously de: -. And for which compounds (b) and (c) are first contacted in,.-Mbles then contacted with the compound (a), are also an object of the present invention. Their manufacturing process is also an object of the present invention. These components can be used in a process for the polymerization of ethylene, propylene, an alpha-olefin containing from four to twelve carbon atoms or a mixture of some of these monomers, whether acts of a liquid phase or gas phase polymerization process, in the presence or absence of an inert diluent. In the case of a liquid phase polymerization process, emulsion or solution polymerization techniques can be used. The inert diluent can be an aliphatic hydrocarbon such as hexane or an alicyclic hydrocarbon such as cyclohexane.

The polymerizations can be carried out continuously or batchwise. The general techniques of these polymerization processes are well known to those skilled in the art. These polymerizations are generally carried out in the presence of a cocatalyst, which can be an organic derivative of aluminum such as one of those listed above and, where appropriate, in the presence of a transfer agent, which can be the hydrogen. WAYS TO IMPLEMENT THE INVENTION

Examples 1, 2, 9 to 19 illustrate the invention. In these examples, the polymerization process according to the invention was carried out without the presence of an external electron donor in the polymerization medium. Examples 4 to 8 and 20 to 22 are comparative examples describing polymerizations in the presence of alkoxysilanes as an external electron donor and in the presence of catalytic components not containing alkoxysilane. Example 3 is comparative and shows that the introduction of phenyltrialkoxysilane into a solid catalytic component does not lead to satisfactory results. However, it leads to good results (comparative example 8), in the same way as dicyclopentyldimethoxysilane (comparative example 6) or cyclohexylmethyldimethoxysiiane (comparative example 7) if it is introduced as an external electron donor.

Example 23 illustrates a process according to the invention in which the compounds (a) and (c) have been brought into contact beforehand before being brought into contact with (b). This example is more particularly to be compared with Example 1 in which (a) and (b) have previously been brought into contact before contact with (c) and with Example 12 in which (b) and (c) have previously was put in contact before contact with (a). Example 24 is comparative and shows that the introduction of diphenyldimethoxysilane into a catalytic component does not lead to good results.

Example 25 is comparative and shows that a polymerization with a molar ratio of the cocatalyst to the titanium contained in the solid component, of 1, does not lead to good results.

In Table 1,% Ti,% Mg,% Al and% Si represent the percentages by weight of titanium, magnesium, aluminum and silicon respectively contained in the solid catalytic components. In Table 1, Si / Ti represents the molar ratio of silicon present in the polymerization medium to the titanium contained in the solid catalytic components, and this, of course, exclusively for the comparative examples involving an alkoxysilane as a donor 'external electrons.

In Table 1, it represents the isotacticity index of the polymers obtained. This index was determined by measuring the heptane index, which is equal to the percentage by weight of polymer insoluble in heptane boiling in the polymer considered. It is measured by extraction of the soluble fraction with boiling heptane for two hours in a Kumagawa type device. In the case of pure polypropylene (homopolymer), the isotacticity index corresponds to the percentage by weight of isotactic polymer contained in the crude polymer.

In the examples, the melt indices were determined by ASTM method D1238, method 2.

The productivity of the polymerizations is expressed in Table 1 in grams of polymer per gram of solid catalytic component introduced into the polymerization.

The meanings of the abbreviations used in the examples are given below:

DCPDMS dicyclopentyldimethoxysilane CHMDMS cyclohexylmethyldimethoxysilane

PTES phenyltriethoxysilane CPHDMS cyclopentylhexyldimethoxysilane iBiPDMS isobutylisopropyldimethoxysilane CPMDMS cyclopentylmethyldimethoxysilane iBCHDMS isobutylcyclohexyldimethoxysilane

DiBDMS diisobutyldimethoxysiiane DPDMS diphenyldimethoxysilane DBP dibutylphthalate TEA triethylaluminium

Example 1 a) Preparation of a support for a catalytic component 30 g of commercial anhydrous MgCl 2 are introduced into a 300 ml nitrogen-purged reactor equipped with mechanical paddle agitation and temperature regulation by double jacket. in the form of grains with an average diameter of approximately 2 mm, 4.5 g of 1-2-4-5-tetramethylbenzene and 200 ml of tetrahydrofuran (THF). The temperature is brought to 60 ° C. and the mixture is left to stir for 16 hours. The solid is then filtered and washed 3 times with 100 ml of hexane at 60 ° C for 15 minutes then dried at 60 ° C, two hours under a stream of nitrogen. 54.2 g of a solid composed of 11.7% by weight of magnesium and 54.3% by weight of THF are recovered. b) Preparation of a catalytic component 6.4 g of the solid obtained in a) is introduced at 50 ° C. Into a 300 ml reactor purged with nitrogen equipped with a stirring rotating at 100 revolutions per minute, 21 ml toluene and 62 ml of pure TiCl4. The temperature is brought to 90 ° C. and 1.05 ml of dibutylphthalate (DBP) is then introduced. The mixture is left stirring for 2 hours. After filtration, a second series of treatments is carried out by introducing 4 ml of TiCl4 and 79 ml of toluene. The temperature is brought to 100 ° C. for 1 hour. Filtration is then carried out and this treatment is repeated with a mixture of TiCl 4 and toluene 4 times under the same conditions. The solid is then washed with 64 ml of hexane at 60 ° C for 10 minutes and then filtered. The solid is resuspended in 200 ml of hexane and the temperature is brought back to 20 ° C. 7.5 ml of a solution of 1 millimole per ml of triethylaluminum (TEA) are then introduced into hexane. 2.5 ml of a 1 millimole solution per ml of dicyclopentyldimethoxysilane (DCPDMS) are then introduced into hexane, this quantity being introduced in four fractions at 15-minute intervals. After the last introduction, it is left to react for an additional 15 minutes. The amounts of TEA and DCPDMS introduced during this treatment comply with the following molar ratios: [AI] / [Ti] = 6 and [Si] / [Ti] = 2, the amount of titanium in the solid being 1.7 % in weight. The solid is then filtered and then washed 4 times with 100 ml of hexane at 20 ° C. The solid is finally dried under a stream of nitrogen at 20 ° C for 2 hours. The catalytic component is in the form of a pulverulent powder of particle size and morphology identical to that described by photo 5, of the patent application whose publication number is FR 2669915. The catalytic component contains 1, 5 % by weight of titanium, 19.4% by weight of magnesium, 1.7% by weight of aluminum and 1.3% by weight of silicon. c) Polymerization in the presence of the catalytic component

Into a 3.5 liter stainless steel reactor, fitted with magnetic stirring and thermal regulation by double jacket, are introduced at 30 ° C, in order: 2.5 NI of hydrogen, 2.4 liters of liquid propylene, 12 millimoles of triethylaluminum.

After stirring for approximately 10 minutes, 20 mg of the catalytic component prepared in b) are injected into the reactor. The temperature is brought in 10 minutes to 70 ° C and maintained for one hour at this value.

The reactor is then cooled and the pressure lowered to atmospheric pressure. 634 grams of a powder with an isotacticity index of 97.7% by weight are recovered. The melt index of the polymer obtained is 2.1 g / 10 min. The other results are collated in Table 1. Example 2

The operation is carried out according to Example 1 except that the DCPDMS solution of Example 1 is replaced by 2.5 ml of a 1 millimole per ml solution of cyclohexylmethyldimethoxysilane (CHMDMS) in hexane during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of this catalytic component is 0.9 NI. The melt index of the polymer obtained is 4.7 g / 10 min. The results are collated in Table 1.

Example 3 The procedure is as in Example 1 except that the solution of

DCPDMS of Example 1 with 2.5 ml of a solution of 1 millimole per ml of phenyltriethoxysilane (PTES) during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of this catalytic component is 0.7 NI. The melt index of the polymer obtained is 10.6 g / 10 min. The results are collated in Table 1.

Example 4 (comparative) a) Preparation of a catalytic component

6.4 g of the solid obtained in a) of example 1, 21 ml of toluene are introduced into a 300 ml nitrogen-purged reactor fitted with stirring rotating at 100 revolutions per minute. 62 ml of pure TiCI4. The temperature is brought to 90 ° C. and 1.05 ml of dibutylphthalate (DBP) is then introduced. The mixture is left stirring for 2 hours. After filtration, a second series is carried out treatments by introducing 4 ml of TiCI4 and 79 ml of toluene. The temperature is raised to 100''J for 1 hour. Filtration is then carried out and this treatment is repeated with a mixture of TiCl 4 and toluene 4 times under the same conditions. The solid is then washed 3 times with 64 ml of hexane at 60 ° C for 10 minutes each time and then filtered. The solid is finally dried under a stream of nitrogen at 60 ° C for 2 hours. The catalytic component is in the form of a powdery powder with a particle size and morphology identical to that described by photo 5 of the patent application, the publication number of which is FR 2669915. The catalytic component contains 2% by weight of titanium and 19.6% by weight of magnesium. b) Polymerization in the presence of the catalytic component In a 3.5 liter stainless steel reactor, fitted with magnetic stirring and thermal regulation by double jacket, the following are introduced at 30 ° C., in the order: 1, 05 NI of hydrogen, 2.4 liters of liquid propylene, 12 millimoles of triethylaluminum and 0.017 millimoles of dicyclopentyldimethoxysiiane (DCPDMS) as an external electron donor. The amount of DCPDMS introduced into the reactor was determined so as to respect the [Si] / [Ti] molar ratio of 2.

After stirring for approximately 10 minutes, 20 mg of the catalytic component, the preparation of which has just been described, are injected into the reactor. The temperature is brought in 10 minutes to 70 ° C and maintained for one hour at this value.

At the end of the reaction, the reactor is cooled to room temperature and the pressure lowered to atmospheric pressure. 700 αrammes of a powder with an isotacticity index of 89.3% by weight are recovered. The melt index of the polymer obtained is 2.8 g / 10 min. The other results are collated in Table 1.

Example 5 (comparative)

Repeat Comparative Example 4 except that no dicyclopentyldimethoxysiiane is introduced during the polymerization and that the amount of hydrogen introduced is 0.4 NI. The melt index of the polymer obtained is 8.1 g / 10 min. The other results are collated in Table 1.

Example 6 (comparative) In an 8 liter stainless steel reactor, fitted with magnetic stirring and thermal regulation by double jacket, the following are introduced at 30 ° C., in order: 3.2 NI of hydrogen, 6 liters of liquid propylene, 30 millimoles of triethylaluminum and 3 millimoles of dicyclopentyldimethoxysiiane (DCPDMS) as an external electron donor.

After stirring for 10 minutes, 40 mg of the catalytic component prepared as in a) of Comparative Example 4 are injected into the reactor. The temperature is brought in 10 minutes to 70 ° C and maintained for one hour at this value.

The reactor is then cooled to room temperature and the pressure lowered to atmospheric pressure. 2150 grams of a powder with an isotacticity index of 97.8% by weight are recovered. The melt index of the polymer obtained is 3.8 g / 10 min. Table 1 groups the other results.

Example 7 (comparative)

Repeat Comparative Example 6 except that the 3 millimoles of DCPDMS are replaced by 3 millimoles of CHMDMS. The amount of hydrogen used in this case is 1.6 NI. The melt index of the polymer obtained is 4.6 g / 10 min. The results are collated in Table 1.

Example 8 (comparative)

Repeat Comparative Example 6 except that the 3 millimoles of DCPDMS are replaced by 3 millimoles of PTES. The amount of hydrogen used in this case is 1.2 NI. The melt index of the polymer obtained is 7.2 g / 10 min. The results are collated in Table 1.

EXAMPLE 9 The procedure is as in Example 1 except that during the preparation of the catalytic component, 15 ml of triethylaluminum at 1 mmol / ml are introduced and no longer only 7.5 ml. In addition, 5 ml of a DCPDMS solution at 1 mmol / ml and no longer 2.5 ml are then introduced, in four times at 15-minute intervals, as in example 1. The amounts of TEA and DCPDMS introduced here respect the molar ratios: [AI] / [Ti] = 12 and [Si] / [Ti] = 4, the amount of titanium on the solid being equal to 1.7% by weight. The melt index of the polymer obtained is 1.4 g / 10 min. The results are collated in Table 1.

Example 10 The procedure is as in Example 1 except that during the preparation of the catalytic component, 30 ml of triethylaluminum at 1 mmol / ml are introduced and no longer only 7.5 ml. In addition, 10 ml of a DCPDMS solution at 1 mmol / ml and not 2.5 ml are then introduced in four times at 15-minute intervals. as in Example 1. The amounts of TEA and DCPDMS introduced here respect the molar ratios: [AI] / [Ti] = 24 and [Si] / [Ti] = 8, the amount of titanium on the solid being equal at 1.7% by weight. The melt index of the polymer obtained is 1.2 g / 10 min. The results are collated in Table 1.

Example 11

The procedure is as in Example 10 except that 10 ml of a 1 mmol / ml solution of CHMDMS are introduced in place of the DCPDMS solution. The melt index of the polymer obtained is 5.3 g / 10 min. The results are collated in Table 1.

Example 12

The procedure is as in Example 1 except that the preparation of the catalytic component is as follows: In a 300 ml nitrogen-purged reactor fitted with stirring rotating at 100 revolutions per minute, the following are introduced at 50 ° C. , 4 g of the solid prepared in a) of Example 1, 21 ml of toluene and 62 ml of pure TiCl4. The temperature is brought to 90 ° C. and 1.05 ml of dibutylphthalate (DBP) is then introduced. The mixture is left stirring for 2 hours. After filtration, a second series of treatments is carried out by introducing 4 ml of TiCl4 and 79 ml of toluene. The temperature is brought to 100 ° C. for 1 hour. Filtration is then carried out and this treatment is repeated 4 times under the same conditions. The solid is then washed with 64 ml of hexane at 60 ° C for 10 minutes and then filtered. The solid thus obtained is resuspended in 200 ml of hexane. At 20 ° C., a mixture is prepared containing 7.5 ml of a solution of triethylaluminum (TEA) at 1 mmol / ml in hexane and 2.5 ml of a solution of dicyclopentyldimethoxysiiane (DCPDMS) at 1 mmol / ml in hexane. The mixture is stirred for 10 minutes at room temperature. The 10 ml of this mixture are then introduced in four batches at intervals of 15 minutes. After the last introduction, it is left to react for an additional 15 minutes. The amounts of TEA and DCPDMS introduced during this treatment comply with the following molar ratios: [AI] / [Ti] = 6 and [Si] / [Ti] = 2, the amount of titanium on the solid being equal to 1, 7% by weight. The solid is then filtered and then washed 4 times with 100 rr of hexane at 20 ° C. The solid is finally dried under a stream of nitrogen at 20 ° C for 2 hours. The catalytic component is in the form of a pulverulent powder with a particle size and morphology identical to that described by photo No. 5 of the patent application whose publication number is FR 2669915. The catalytic component contains 1.8% by weight of titanium, 17.5% by weight of magnesium, 1.5% by weight of aluminum and 1.1% by weight of silicon. The melt index of the polymer obtained is 2.2 g / 10 min. The results are collated in Table 1.

Example 13 The procedure is as in Example 12 except that the mixture of TEA and

DCPDMS is produced with 15 ml of triethylaluminum at 1 mmol / ml and 5 ml of DCPDMS at 1 mmol / ml. The two compounds are left to react for 10 minutes at room temperature. Then the 20 ml of this mixture are introduced four times, in 15-minute intervals. The amounts of TEA and DCPDMS introduced here respect the molar ratios: [AI] / [Ti] = 12 and [Si] / [Ti] = 4, the amount of titanium on the solid being equal to 1.7% by weight . The melt index of the polymer obtained is 1.3 g / 10 min. The results are collated in Table 1.

Example 14

The procedure is as for Example 12 except that the mixture of TEA and DCPDMS is produced with 3.75 ml of triethylaluminum at 1 mmol / ml and 1.25 ml of DCPDMS at 1 mmol / ml. The two compounds are left to react for 10 minutes at room temperature. Then the four ml of this mixture are introduced in four batches at intervals of 15 minutes. The amounts of TEA and DCPDMS introduced here respect the molar ratios: [AI] / [Ti] = 3 and [Si] / [Ti] = 1, the amount of titanium on the solid being equal to 1.7% by weight . The melt index of the polymer obtained is 2g / 10min. The results are collated in Table 1.

Example 15

The procedure is as in Example 1 except that 2.5 ml of a cyclopentyl n-hexyl dimethoxysilane solution (CPHDMS) are introduced in place of the DCPDMS solution during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of the catalytic component thus obtained is 0.9 NI. The melt index of the polymer obtained is 3.2 g / 10 min. The results are collated in Table 1.

Example 16

The procedure is as for Example 1 except that 2.5 ml of a solution of isobutylisopropyldimethoxysiiane (iBiPDMS) are introduced in place of the solution of DCPDMS during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of the component catalytic thus obtained is 1, 2 NI. The melt index of the polymer obtained is 3.6 g / 10 min. The results are collated in Table 1.

Example 17 The procedure is as in Example 1 except that 2.5 ml of a cyclopentylmethyidimethoxysilane solution (CPMDMS) are introduced in place of the DCPDMS solution during the preparation of the catalytic component. The quantity of hydrogen used during the polymerization of the catalytic component thus obtained is 0.7 NI. The melt index of the polymer obtained is 4.8 g / 10 min. The results are collated in Table 1.

Example 18

The procedure is as for Example 1 except that 2.5 ml of an isobutyl cyclohexyl dimethoxysilane solution (iBCHDMS) are introduced in place of the DCPDMS solution during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of the catalytic component thus obtained is 0.9 NI. The melt index of the polymer obtained is 3.7 g / 10 min. The results are collated in Table 1.

Example 19

The procedure is as for Example 1 except that 2.5 ml of a solution of diisobutyldimethoxysilane (DiBDMS) are introduced in place of the solution of DCPDMS during the preparation of the catalytic component. The amount of hydrogen used during the polymerization of the catalytic component thus obtained is 1.2 NI. The melt index of the polymer obtained is 7.2 g / 10 min. The results are collated in Table 1.

Example 20 (comparative) a) Preparation of a support for a catalytic component In a 300 ml nitrogen-purged reactor fitted with mechanical paddle stirring, with temperature control by double jacket, 30 g of MgCl2 anhyd e ^r commercial, 4.5 g of 1-2-4-5- tetramethylbenzene and 200 ml of tetrahydro & nydrofurane (THF). The temperature is brought to 60 ° C. and the mixture is left to stir for 16 hours. The solid is then filtered and washed 3 times with 100 ml of hexane at 60 ° C for 15 minutes then dried at 60 ° C, 2 hours, under a stream of nitrogen. 54.2 g of a solid consisting of 11.7% by weight of magnesium and 54.3% by weight of THF are recovered, the morphology of which is identical to that described in photo No. 3 of the patent application, the publication number of which is FR 2669915. b) Preparation of a catalytic component

6.4 g of the support, the preparation of which has just been described, 21 ml of toluene and 62 g are introduced into a 300 ml nitrogen-purged reactor fitted with a stirrer rotating at 100 revolutions per minute. ml of pure TiCI4. The temperature being brought to 90 ° C., 1.05 ml of dibutylphthalate (DBP) are then introduced and the mixture is left stirring for 2 hours. After filtration, a second series of treatments is carried out by introducing 4 ml of TiCl4 and 79 ml of toluene. The temperature is brought to 100 ° C. for 1 hour. Filtration is then carried out and this treatment is repeated 4 times under the same conditions. The solid is then washed 3 times with 64 ml of hexane at 60 ° C for 10 minutes and then filtered. The solid is finally dried under a stream of nitrogen at 60 ° C for 2 hours. The catalytic component is in the form of a pulverulent powder with a particle size and morphology identical to that described by photo No. 5, of the patent application whose publication number is FR 2669915.

The catalytic component contains 2% by weight of titanium and 19.6% by weight of magnesium. c) Polymerization in the presence of the catalytic component

Into a 3.5 liter stainless steel reactor, fitted with magnetic stirring and thermal regulation by double jacket, are introduced at 30 ° C, in order: 0.9 NI of hydrogen, 2.4 liters of liquid propylene, 12 millimoles of triethylaluminum and 0.017 millimoles of cyclopentyl n-hexyl dimethoxysilane (CPHDMS) as an external electron donor. The quantity of CPHDMS introduced into the reactor was determined so as to respect the [Si] / [Ti] molar ratio of 2.

After stirring for approximately 10 minutes, 20 mg of the catalytic component prepared above are injected into the reactor. The temperature is brought in 10 minutes to 70 ° C and maintained for one hour at this value.

At the end of the reaction, the reactor is cooled and the pressure lowered to atmospheric pressure. 519 grams of a powder with an isotacticity index of 63.1% by weight are recovered. The melt index of the polymer obtained is 24.1 g / 10 min. Table 1 collates the other results.

Example 21 (comparative) The procedure is as for Comparative Example 20 except that 0.017 millimole of isobutylisopropyldimethoxysilane (iBiPDMS) is introduced in place of cyclopentyl n-hexyl dimethoxysilane during the polymerization. The amount of hydrogen used during the polymerization in the presence of the catalytic component thus obtained is 1.2 NI. The melt index of the polymer obtained is 7.1 g / 10 min. The results are collated in Table 1.

Example 22 (comparative) The procedure is as for comparative example 20 except that one introduces

0.017 millimole of isobutyl cyclohexyl dimethoxysilane (iBCHDMS) in place of cyclopentyl n-hexyl dimethoxysilane during the polymerization. The amount of hydrogen used during the polymerization of the catalytic component thus obtained is 0.9 NI. The melt index of the polymer is 10.9 grams / 10 minutes. The results are collated in Table 1.

Example 23 a) Preparation of a catalytic component

6.4 g of the solid obtained in a) of Example 1, 21 ml of toluene are introduced into a 300 ml nitrogen-purged reactor fitted with a stirrer rotating at 100 revolutions per minute. 62 ml of pure TiCl4.

The temperature is brought to 90 ° C. and 1.05 ml of dibutylphthalate (DBP) is then introduced. The mixture is left stirring for two hours. After filtration, a second series of treatments is carried out by introducing 4 ml of TiCl 4 ^and 7 ^μm of toluene. The temperature is brought to 100 ° C. for 1 hour. Filtration is then carried out and this treatment is repeated four times under the same conditions. The solid is then washed with 64 ml of hexane at 60 ° C for 10 minutes and then filtered. The solid is resuspended in 200 ml of hexane. The temperature having dropped to 20 ° C., 2.5 ml of a DCPDMS solution at 1 millimole per ml in hexane is introduced, this quantity being introduced in four fractions at 15-minute intervals. After the latest ^{introduction,} the mixture is stirred for 15 minutes.

7.5 ml of a TEA solution of 1 millimole per ml in hexane are then introduced and the mixture is left stirring for 15 minutes. The amounts of TEA and DCPDMS introduced during this treatment comply with the following molar ratios: [AI] / [Ti] = 6 and [Si] / [Ti] = 2, the amount of titanium in the solid being 1.7 % in weight. The solid is then filtered and then washed 4 times with 100 ml of hexane at 20 ° C. solid is finally dried at 20 ° C for two hours under nitrogen flow. The catalytic component thus obtained is in the form of a powder with a morphology identical to that of photo N ° 5 of the patent application, the publication number of which is FR 2 669 915. This catalytic component contains 1.8% in weight of titanium, 18.3% by weight of magnesium, 1.3% by weight of aluminum, 1% by weight of silicon. b) polymerization in the presence of the catalytic component.

The procedure is as for c) of Example 1 except that the catalytic component is used, the preparation of which has just been described and that 2.4 NI of hydrogen are introduced instead of the 2.5 NI of Example 1. The melt index of the polymer obtained is 2.8 g / 10 min. Table 1 collates the other results.

Example 24 (comparative)

The procedure is as for Example 1 except that for the preparation of the catalytic composition, the 2.5 ml of the DCPDMS solution is replaced by 2.5 ml of a 1 millimole solution per liter of diphenyldimethoxysilane in hexane and except that the amount of hydrogen used in the polymerization is 0.7 NI. The melt index of the polymer obtained is 12.5 g / 10 min. Table 1 collates the other results. EXAMPLE 25 (Comparative) The procedure is as for Example 1 except that 0.048 millimole of triethylaluminum is introduced instead of the 12 millimoles of Example 1 and except that 100 mg of solid catalytic component is introduced into the polymerization with instead of the 20 mg of example 1. Finally, 10 grams of polypropylene are recovered, which corresponds to a productivity of 100 g of polypropylene per gram of solid component.

Solid catalytic component Conditions and results of polymerization

nature of% Ti% Mg% AI% Si Naturedu Si / Ti II Productivity ï * -, UΞS external donor alkoxysilane (g / g)

1 DCPDMS 1.5 19.4 1.7 1.3 97.7 31,700

2 CHMDMS 1.6 19.5 1.7 1.3 93.4 19,900

3 (comparative) PTES 1.8 19 1.4 1.2 87.8 12,600

4 (comparative) 2 19.6 DCPDMS 2 89.3 35,000

5 (comparative) 2 19.6 64.9 15,700

6 (comparative) 2 19.6 DCPDMS 350 97.8 53,700

7 (comparative) 2 19.6 CHMDMS 350 96.8 29,700

8 (comparative) 2 19.6 PTES 350 97.2 20 800

9 DCPDMS 1.6 18.5 1.7 1.6 98.5 26,400

10 DCPDMS 1.6 17.8 1.6 1.7 98.5 27,300

11 CHMDMS 1.6 18.4 1.5 1.8 94.6 16,500

12 DCPDMS 1.8 17.5 1.5 1.1 97.6 37,500

13 DCPDMS 1.8 14 1.5 1.4 98.4 34 200

14 DCPDMS 1.9 17.7 1.2 1 96 38 600

15 CPHDMS 1.6 17.3 2 "1 94.9 15500

16 iBiPDMS 1.8 18.4 1.5 •, 1 94.9 21400

17 CPMDMS 2 18.4 1.6 1.2 90.1 26,300

18 iBCHDMS 1.8 18.4 1.5 0.9 95.1 20,100

19 DiBDMS 1.5 18.8 1.5 1 91.6 30 850

20 (comparative) 2 19.6 CPHDMS 2 63.1 25 950

21 (comparative) 2 19.6 iBiPDMS 2 92.1 36 600

22 (comparative) 2 19.6 iBCHDMS 2 84.9 32800

23 DCPDMS 1.8 18.3 1.3 1 95.8 36 350

24 (comparative) DPDMS 1.9 20.1 1.6 2.0 83.7 21,500

TABLE 1

Claims

1. Process for the polymerization of propylene in liquid propylene or for the copolymerization of propylene in liquid propylene with ethylene or an alpha-olefin containing from four to twelve carbon atoms, in the presence of a cocatalyst and a catalytic component solid obtained after bringing a. a solid compound (a) containing magnesium, halogen and transition metal atoms b. an organic aluminum derivative (b) c. a dialkoxysilane (c) of formula RR ² Si (OR ³ ) (OR ⁴ ) in which R ³ and R 4 which may be identical or different represent hydrocarbon groups, R and R, which may be identical or different, represent hydrocarbon groups, R being saturated and containing at least three carbon atoms, characterized in that no prepolymerization is carried out before bringing into contact between (a), (b) and (c), and in that the molar ratio of the cocatalyst to the transition metal M contained in the solid catalytic component ranges from 100 to 3000.

2. Method according to claim 1 characterized in that the carbon atom bonded to the silicon of R, is bonded to two carbon atoms.

3. Method according to claim 1 or 2 characterized in that the group R is saturated and in that the carbon atom bonded to the silicon of R, is bonded to two carbon atoms.

4. Method according to one of claims 1 to 3 characterized in that (b) and (c) are first contacted together and then contacted with (a).

5. Method according to one of claims 1 to 4 characterized in that (a), (b) and (c) are brought into contact in a hydrocarbon.

6. Method according to one of claims 1 to 5 characterized in that

(b) and (c) are first mixed in solution in a hydrocarbon and then mixed with a suspension of (a) in a hydrocarbon.

7. Method according to claim 5 or 6 characterized in that the hydrocarbon or hydrocarbons are saturated aliphatic or saturated alicyclic.

8. Method according to one of claims 1 to 7 characterized in that the contacting between (a), (b) and (c) is carried out in such a way that the molar ratio of the aluminum provided by (b) on the transition metal supplied by (a) goes from 0.5 to 100 and preferably from 1 to 50.

9. Method according to one of claims 1 to 8 characterized in that the contacting between (a), (b) and (c) is carried out in such a way that the molar ratio of the silicon supplied by (c) to the transition metal supplied by (a) ranges from 0.5 to 20 and preferably from 1 to 10.

10. Method according to one of claims 1 to 9 characterized in that the solid catalytic component is washed with a saturated aliphatic hydrocarbon or saturated alicyclic and optionally dried before the polymerization or copolymerization of propylene.

11. Method according to one of claims 1 to 10 characterized in that the cocatalyst is an organic aluminum derivative of formula RR R3AI in which R1, R2 and R ³ , which may be identical or different, each represents either a hydrogen atom, either a halogen atom or an alkyl group containing from 1 to 20 carbon atoms, at least one of R, R2 or R representing an alkyl group.

12. Method for manufacturing a solid catalytic component containing magnesium, halogen, aluminum atoms, a transition metal and silicon, obtained after contacting a. a solid compound (a) containing magnesium, halogen and met.- transition atoms b. an organic derivative of aluminum (b) c. a dialkoxysilane (c) of formula Rl R ² Si (OR ³ ) (OR ⁴ ) in which R ³ and R, which may be identical or different, represent hydrocarbon groups, R1 and R2, which can be identical or different, represent hydrocarbon groups , R1 being saturated and containing at least three carbon atoms, characterized in that (b) and (c) are first contacted together and then contacted with (a).

13. Method according to claim 12, characterized in that (b) and (c) are first mixed in solution in a hydrocarbon and then mixed with a suspension of (a) in a hydrocarbon.

14. The method of claim 13 characterized in that the hydrocarbon (s) are saturated aliphatic or saturated alicyclic.

15. Method according to one of claims 12 to 14 characterized in that the contacting between (a), (b) and (c) is carried out in such a way that the molar ratio of the aluminum provided by (b) on the transition metal supplied by (a) goes from 0.5 to 100 and preferably from 1 to 50.

16. Method according to one of claims 12 to 15 characterized in that the contacting between (a), (b) and (c) is carried out in such a way that the molar ratio of the silicon supplied by (c) to the transition metal supplied by (a) ranges from 0.5 to 20 and preferably from 1 to 10.

17. Method according to one of claims 12 to 16 characterized in that the carbon atom bonded to the silicon of R is linked to two carbon atoms.

18. Method according to one of claims 12 to 17 characterized in that the group R is saturated and in that the carbon atom bonded to the silicon of R ² , is bonded to two carbon atoms.

19. Solid catalytic component capable of being obtained by the process of one of claims 12 to 18.