RU2141974C1 - Component of catalyst for preparing elastomeric ethylene-propylene copolymers - Google Patents

Abstract

FIELD: polymerization catalysts. SUBSTANCE: solid component of catalyst for preparing basically amorphous ethylene- propylene copolymers essentially contains titanium compound applied on solid substance basically consisting of magnesium halide. The component is prepared as follows. Solution basically consisting of organoaluminum compound dissolved in aliphatic hydrocarbons is mixed with solution prepared by (i) dissolving magnesium halide in solvent mixture in presence of aluminum trihalide, (ii) treating solution thus obtained with tetravalent titanium compound of general formula Ti(OR)_4-nX_n wherein R is aliphatic, cycloaliphatic, and aromatic C₁-C₂₀-hydrocarbon radical, X is halogen atom, and n integer from 0 to 4, and (iii) optionally subjecting solution to additional treatment with electron-donor compound selected from group including carboxylic acid esters, alkyl- or alkylaryl ethers (simultaneously with or after previous treatment). Resulting solid catalyst component is then separated from combined solution and optionally purified. Method is distinguished by that above-mentioned solvent mixture is a mixture of hydrocarbyl halides or aromatic hydrocarbons. EFFECT: increased productivity of catalyst. 7 cl, 5 tbl, 22 ex

Description

 The invention relates to a solid component of a Cycller-Natta type catalyst suitable for the synthesis of high purity elastomeric copolymers.

 The use of these components in the synthesis of elastomeric copolymers of ethylene with propylene makes it possible to obtain predominantly amorphous polymers of high purity.

 It is known that predominantly amorphous polymers of ethylene with propylene can be advantageously obtained using catalysts of the Cycller-Natta type, as described by G. Natta, G. Mazzanti et al Journal Polimer Science Vol. 51 (1961), p. 411 and Fr A-2, 027457.

These catalysts contain at least two components:
a) a salt of a transition metal from group IV to VIII of the periodic system;
b) an organometallic metal compound of group 1 to group IV of the periodic system.

 In order to obtain copolymers having a low degree of crystallinity, a narrow distribution of molecular weight and composition, it is more preferable to use a vanadium compound as a transition metal salt: in this case, the complete catalytic system includes the third component (c), which can increase the polymerization rate, expressed as kg of polymer obtained per gram of vanadium for an hour.

 In particular, type “a” components are used, which are vanadium salts with a valency of 3 to 5, such as, for example, vanadium halides, vanadium halides, vanadium or vanadyl alcoholates, and vanadium acetylacetonate.

 Preferred type b components are organometallic aluminum compounds, such as aluminum trialkylates, aluminum alkyl halides.

Components of type "c" are, in most cases, organohalogen compounds such as chloralanes or chloroesters, such as, for example, CHCl ₃ , CCl ₄ , ethyl trichloroacetate or n-butyl perchlorocrotonate.

 To obtain ethylene-propylene elastomeric copolymers, both solution polymerization and suspension polymerization are used.

 Solution polymerization is characterized in that both the monomers and polymers are dissolved in a hydrocarbon medium, while suspension polymerization is carried out in a medium in which the elastomer is practically insoluble.

This latter method typically includes liquid propylene as a suspending medium and has significant economic advantages over solution polymerization, in particular:
i) high polymer concentrations in the reactor can be used without significantly increasing the viscosity of the reaction medium;
ii) solvents and suspending agents that are not polymerized are used, the recycling of which results in energy consumption;
iii) the heat of reaction can be very effectively removed by evaporation of the liquid monomers and their subsequent condensation before loading into the reactor.

For a suspension process with a reaction temperature not exceeding 50 ^° C., a particularly favorable catalyst system comprises vanadium triacetylacetonate (component "a"), aluminum diethyl monochloride (component "b") and n-butyl perchlorocrotonate (component "c"); With this system, a wide range of copolymers with satisfactory mechanical and elastic properties can be obtained for use in various fields, both as raw and vulcanized polymers.

 However, catalysts based on vanadium salts have the disadvantage of having low productivity.

 In addition, if the method does not include the final washing step, then significant amounts of catalyst residues, in particular chlorinated compounds resulting from the reaction of the vanadium salt with the organometallic catalyst component, may be present in the polymer.

 Catalysts suitable for copolymerization of ethylene with propylene and having a higher productivity than that obtained using systems containing vanadium compounds are described in US-A-3789036, US-A-4013823, US-4331561, GB-A-2099836 , GB-A-1293814, EP-A-301894.

The catalysts described in the above documents preferably contain the following components:
A) a solid product obtained by introducing a titanium compound of the formula Ti (OR) _n X _4-n (where R is an aliphatic, cycloaliphatic or aromatic radical with the number of carbon atoms from 1 to 20, X represents a halogen atom, and n is an integer between 0 and 4) in contact with a magnesium compound selected from halides, alkoxy halides or MgCl ₂ adducts and alcohols;
B) at least one organometallic aluminum compound of the formula (Al (Z _3-m ) X _m or Al ₂ Z _t X _p , where Z is an alkyl group, X is halogen, m is an integer between 0 and 2, t and p are integers between 1 and 5 at p + t = 6.

Examples of compounds of type (B) that can be used together with component (A) for the synthesis of polyolefins are: Al (C ₂ H ₅ ) ₂ Cl, Al (iso-C ₄ H ₉ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ , etc.

Examples of magnesium compounds suitable for preparing the solid component (A) are MgCl ₂ , MgCl (OC ₄ O ₉ ), MgCl ₂ • m (n-HOC ₄ H ₉ ).

An example of a compound of type (A) is described in Italian patent application IT-A-MI 91 A001935. This compound may be represented by the formula;
M ₁ Mg _(0.3-20) X _(2-60) Al _(0-6) (P-COO) _(0.1-3) ,
where M may be Ti, v, Zr or H _f ; X is halogen; R represents a hydrocarbon radical containing at least 4 carbon atoms.

 According to the procedure described in the above application, (2-ethylene hexanoate) titanium chloride is taken as a titanium compound and (2-ethylene hexanoate) magnesium chloride is taken as a magnesium compound.

 A variety of very effective methods are known for preparing the active solid compound (A) used in the polymerization of ethylene and α-olefins.

Some of them include, for example, treatment with a titanium compound of a solid support having a high specific surface area and comprising a magnesium compound; for example, EP-A-202550 describes a method for producing a solid catalytic component (A) having high performance in the synthesis of polyolefins, which involves grinding MgCl ₂ with ethylene benzoate and further processing the solid product thus obtained with an excess of TiCl ₄ .

According to US-A-4843049, the solid component (A) can be obtained, for example, in the following way:
a) spray drying an ethanolic solution of MgCl ₂ to obtain a solid granular substrate;
b) treating the Ti substrate (n-OC ₄ H ₉ ) in n-decane;
c) addition of Al (C ₂ H ₅ ) ₂ Cl.

 A critical stage of the above method is the preparation of a magnesium-based support, especially in the operations necessary to obtain a sufficiently high specific surface for the absorption of a titanium compound: this stage is usually expensive and technologically very difficult.

Alternative methods that simplify the preparation of the media consist of:
(a) treating a previously prepared solution of a magnesium compound with a titanium compound,
(b) isolating the solid product (A) by treatment with a suitable precipitant.

According to the example of JP 56004608, the solid catalyst component (A) is prepared by adding butanol to a solution of MgCl ₂ and titanium tetrabutyl oxide in heptane and then adding ClAlCl ₃ , TiCl ₄ and methylhydro polysiloxane.

IT-A-19473/84 discloses the preparation of a solid component (A) by reacting a titanium compound (i) dissolved in a hydrocarbon (such as Ti (OC ₄ H ₉ ) ₄ dissolved in anhydrous n-hexane) with a liquid complex (ii) of total formulas MX ₂ n (AlRX ₂ ) pAlX ₃ (where, for example: M is Mg, X is chlorine, R is a C ₂ H ₅ radical; "n" and "p" are integers ranging from 1 to 4 and from 0 to 1 (respectively) and the subsequent addition of electron-donating compound (iii), such as, for example, n-butyl ether or anisole.

 Throughout the method, the isolation of the solid product (A) occurs immediately after the reaction between components (i) and (ii) without the use of additional precipitants.

JP-A-158871 describes that component (A can be obtained by contacting TiCl ₄ with a solid product obtained by precipitating from a solution of anhydrous MgCl ₂ in propyl chloride in the presence of AlCl ₃ .

In accordance with the present invention, the deposition of a titanium compound on solid crystalline MgCl ₂ can advantageously be carried out according to a new simplified method.

The present invention relates to a catalyst component for the synthesis of predominantly amorphous, elastomeric ethylene-propylene copolymers containing a titanium compound supported on a solid consisting mainly of MgCl ₂ ; the catalyst component of the invention is a product of a process that includes:
i) the interaction of the solution (I), mainly containing an organometallic aluminum compound dissolved in aliphatic hydrocarbons, with a solution (II) obtained by the following steps:
a) dissolving anhydrous magnesium halide in a mixture of solvents selected from halogenated hydrocarbons and aromatic hydrocarbons and corresponding mixtures in the presence of aluminum trihalide;
b) treating the solution obtained in step (a) with a tetravalent titanium compound of the general formula Ti (OR) _4-n = X _n , where R is an aliphatic cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 20 carbon atoms, X is halogen and n represents an integer from 0 to 4;
c) a possible treatment with an electron-donor compound selected from the group of carboxylic acid esters and alkyl or aryl or arylalkyl esters simultaneously with or after treatment with a titanium compound of step (b);
ii) recovering and possibly purifying the solid catalyst component thus obtained.

Preferably, solution (II) is obtained by treating anhydrous MgCl ₂ and AlCl ₃ with a mixture of 1,2-dichloroethane and toluene or a mixture of n-butyl chloride and 1,2-dichloroethane at a temperature of from 10 to 90 ^° C. and subsequent addition after cooling to a temperature of from 10 to 40 ^° C. TiCl ₄ , Ti (O-n-C ₄ H ₉ ) ₄ or TiCl (OC ₄ H ₉ ) ₃ and an electron-donor compound from the group of ethers or esters, preferably ethyl benzoate, dibutyl ether or anisole.

In both cases, the ingredients react in the following molar ratios:
AlCl ₃ / MgCl ₂ from 1 to 5; 1,2-dichloroethane (or n-butyl chloride) / AlCl ₃ not less than 0.1; MgCl ₂ / Ti from 0.5 to 5; 1,2-dichloroethane / toluene from 0.05 to 5; electron donor compound / Ti no more than 5.

The concentration of MgCl ₂ in a solvent mixture (1,2-dichloroethane plus toluene or n-butyl chloride and 1,2-dichloroethane) is preferably from 1 to 7 g / 100 ml; the temperature at which the interaction between the ingredients occurs, is from 10 to 90 ^o C and the reaction time is between 0.5 and 8 hours.

Solution (1) consists essentially of an organometallic aluminum compound of the general formula Al (Z _3-m ) X _m or Al ₂ Z _t X _p , where Z is an alkyl group, X is halogen, m is an integer from 1 to 3, t and p are integers between 1 and 5 at p + t = 6 dissolved in a hydrocarbon solvent at a concentration of 5 to 15 g / l.

The molar ratio between alkyl aluminum (I) and titanium (II) is preferably from 3 to 20. The mixing temperature of the two solutions is from 30 to 60 ^o C.

 The interaction of solutions (I) and (II) causes the formation of a solid product (A), which can be isolated and washed by conventional methods.

The deposition of the catalytic component can also be performed by photopolymerization of ethylene or propylene, in both cases in a hydrocarbon solution or suspension of a liquid monomer in the presence of one or more aluminum alkylates, preferably Al (C ₂ H ₅ ) ₃ , Al (iso-C ₄ H ₉ ) ₃ or mixtures thereof; the concentration of aluminum alkylate before prepolymerization is preferably from 1 to 10 g / l; the molar ratio between aluminum alkylate and titanium preferably leaves from 2 to 25; the weight ratio between the prepolymer and the solid product dissolved in solution (II) containing AlCl ₃ , MgCl ₂ and a titanium compound is preferably from 1 to 10.

 Alternatively, liquid (I) and liquid (II) can be introduced directly into the polymerization reactor; in this case, the catalytic component is formed in situ in the reactor.

 Preferably, solution (II) is mixed in advance with a solution (I) of an organometallic aluminum compound in a hydrocarbon; in this case, a catalytic solid product is formed immediately before the polymerization editor without any operations to isolate the solid product (A).

 The invention is illustrated by the following examples.

 The preparation of polymers is carried out in a 3 liter autoclave using the following procedure.

Purification with propylene containing triisobutylaluminum in 5% w / v, followed by washing with pure propylene. 1.8 liters of clean polymerization grade propylene with room temperature are fed into the autoclave at 23 ^° C, then the temperature is raised to the polymerization temperature in the autoclave and gaseous hydrogen and ethylene are introduced into the autoclave in a predetermined ratio so that the required partial pressure.

 The catalyst is prepared as follows.

 A solution of alkylaluminum in hexane with a concentration of 2 to 4% w / v (component "B") is obtained in a glass funnel in a nitrogen atmosphere; 50% of this solution is poured into a 50 ml glass flask with a nitrogen atmosphere, equipped with a bottom valve, into which the solid component “A” is immediately added in the form of a suspension in hexane or directly the amount of liquid (II).

 The catalytic suspension thus obtained is poured into a steel cylinder placed above the autoclave, filling is completed by washing the flask with the remaining 50% solution containing an organometallic compound. The contents of the cylinder are then immediately and quickly fed to the autoclave using excess nitrogen pressure.

 The pressure of the autoclave is kept constant during the experiment by feeding ethylene from a cylinder with a controlled weight. At the end of the experiment, the remaining monomers are degassed and the autoclave is emptied.

 Finally, the polymer is homogenized with a roller mixer and its characteristics are determined.

 Examples 1 and 2 relate to catalysts prepared by a method comprising dissolving magnesium chloride in a mixture of 1,2-dichloroethane and toluene, while in examples 6 to 22 this dissolution is carried out in a mixture of 1,2-dichloroethane and n-butyl chloride.

 In particular, for the synthesis of ethylene-propylene copolymers, solid catalytic components are used containing respectively: titanium tetrabutylate (examples 1 and 2) and titanium tetrabutylate together with anisole (examples 3 and 5).

 In examples 6, 7 and 8, liquid catalyst components are introduced directly into the polymerization reactor without prior isolation of the solid product, and they are the precursors of the solid catalysts described in examples 9-16; they respectively contain titanium tetrabutylate, titanium tetrachloride, tri-iso-propylate (chlorine) titanium.

 Examples 9 to 16 relate to solid catalysts for prepolymerization, examples 17 to 22 relate to solid catalysts containing titanium tetrabutylates.

 Examples 1 and 2.

 Dissolution of magnesium chloride in 1,2-dichloroethane and toluene.

The following products are sequentially charged into a 250 ml flat-bottomed flask equipped with a stirrer, reflux condenser and anhydrous nitrogen supply unit: 44.2 g of anhydrous AlCl ₃ , 10.5 g of anhydrous floccule MgCl ₂ , 142 ml of toluene and 17 , 3 ml of 1,2-dichloroethane, which are dehydrated on molecular sieves. Then the suspension is heated and the mixture of liquids is brought to a boil in 1 hour and boiled for 2 hours.

 During treatment, acid gas evolution is observed. At the end of the reaction, a dark brown solution is obtained which, when filtered, leaves only traces of a solid.

 The solution is characterized by the following molar ratio: Al / Mg = 3, 1,2-dichloroethane / Mg = 2, toluene / Mg = 12.

 Obtaining a liquid product (II).

In a 100 ml test tube with a magnetic stirrer and a nitrogen transmission device, 50 ml of a solution of MgCl ₂ in 1,2-dichloroethane plus toluene, prepared as described above, 30 ml of anhydrous 1,2-dichloroethanol and 7.15 ml of titanium tetrabutylate, dissolved in 10 ml of 1,2-dichloroethane; After the titanium compound is added, heat is generated.

 The resulting solution is characterized by a molar ratio Mg / Ti = 1.5; CHIBA / Ti = 6.

 Obtaining a precipitate of a solid catalytic component containing titanium tetrabutylate.

 In a pear-shaped flask with a stirrer, reflux condenser and a nitrogen transmission device, 250 ml of 10% w / v are charged. a solution of triisobutylaluminum (TIBA) in hexane; then 87 ml of the liquid product (P) obtained as described above is charged over 1 minute.

After adding the liquid product (P), heat is generated and the dark solid product immediately forms. The mixture is heated in 30 minutes to 50 ^o C and then left with stirring for 2 hours, filtered on a porous filter in a nitrogen atmosphere, the precipitate is washed 3 times with anhydrous hexane at room temperature, dried in vacuum and obtain 7.4 g of a solid product with the following analytical composition:
The total content of Ti = 11.7%, Mg = 7.85%, Al = 2.7%, Cl = 55.35%, (O-n-C ₄ H ₉ ) groups = 0.9.

 The effect of the catalyst in the polymerization process is evaluated under the conditions shown in table 1.

 Examples 3 and 5.

 Obtaining a precipitate of a solid catalytic component containing titanium tetra-n-butylate and anisole.

The following substances are loaded sequentially with stirring into a 100 ml test tube with a mechanical stirrer and a nitrogen feed device:
- 70 ml of a solution of MgCl ₂ in 1,2-dichloroethane and toluene, obtained as described in examples 1 and 2;
- 30 ml of anhydrous 1,2-dichloroethane;
- 9.54 g of anisole dissolved in 10 ml of 1,2-dichloroethane (in 15 minutes);
- 10 g of titanium tetra-n-butylate dissolved in 10 ml of 1,2-dichloroethane (in 15 minutes).

 The mixture was incubated for 1.5 hours at room temperature, then loaded in 30 seconds into a 1-liter flask equipped with a stirrer, a refrigerator, a nitrogen supply device and containing 350 ml of 10% w / v. TIBA solution in hexane.

After the addition of the liquid product (P), heat is released and the dark solution is immediately formed. The mixture is heated to 50 ^° C. in 30 minutes, left under stirring for 2 hours, filtered through a porous filter under nitrogen atmosphere, the precipitate is washed 3 times with anhydrous hexane at room temperature, dried under vacuum for 2 hours at 55 ^° C. and 11 g of a solid product are obtained with the following analytical composition:
The total content of Ti = 10.3%; Ti ³⁺ = 10%; Mg = 8.65%; Al = 1.4%; Cl = 52.8%; (O-n-C ₄ H ₉ ) group = 3.3%; anisole = 2.8%
Example 6

Dissolution of magnesium chloride in 1,2-dichloroethane: in a 250 ml flask with a flat bottom and a water sludge, equipped with a stirrer, reflux condenser and a nitrogen supply, the following products are loaded in order: 14.9 g of anhydrous AlCl ₃ , 3.55 g anhydrous flake-like MgCl ₂ and 74 ml of 1,2-dichloroethane dehydrated on molecular sieves; then 12 ml of n-butyl chloride are added in 15 minutes at room temperature. When an alkyl halide is added, acid gas evolution is observed.

The suspension is then heated 1.5 hours to a temperature of 80 ^o C and left by itself for 1.5 hours.

 At the end of the reaction, a dark brown solution is obtained which, when filtered, leaves only traces of a solid product.

 The solution is characterized by the following molar ratios: Al / Mg = 3, Al / n-butyl chloride = 1.

Obtaining a liquid catalytic component containing titanium tetra-n-butylate: in a 50 ml tube with a magnetic stirrer and a nitrogen supply, load 25 ml of a solution of MgCl ₂ in 1,2-dichloroethane obtained as described above; after the titanium compound is added, heat evolution is observed. The resulting solution is characterized by a molar ratio Mg / Ti = 4.

 Example 7

A liquid catalyst component containing titanium tetrachloride is prepared using the same procedure as in Example 6, using TiCl ₄ as the titanium compound.

 Example 8

 A liquid catalytic product containing triisopropyl titanium chloride is prepared using the same procedure as in Example 6 using triisopropyl titanium chloride as the titanium compound.

 Examples 9-11.

Preparation by prepolymerization of a solid catalyst component containing titanium tetra-n-butylate:
In a 500 ml temperature-controlled flask equipped with a reflux condenser, 150 ml of anhydrous hexane, 4.5 g of triisobutylaluminium (10% solution in hexane) and 13 ml of a solution containing titanium tetra-n-butylate obtained as described in Example 6 are charged; then the temperature with stirring is brought to 50 ^o C; at a constant pressure of 75 mm H, ethylene of the polymerization grade is introduced and the prepolymerization lasts 3.5 hours.

 Then the liquid part is removed by decantation, the polymer is washed 3 times with anhydrous hexane, the solid product is dried in vacuum and 2.4 g of powder are obtained.

 Examples 12-14.

Preparation by prepolymerization of a solid catalyst component containing titanium tetrachloride:
The same procedure is used as in examples 9-11 when using a solution containing titanium tetrachloride obtained as described in example 7.

 Examples 15-16.

 Preparation by prepolymerization of a solid catalyst component containing triisopropyl titanium chloride.

 The same procedure is used as in example 9-11 when using a solution containing triisopropyl titanium chloride obtained as described in example 8.

 Examples 17-19.

 Obtaining a precipitate of a solid catalytic component containing titanium tetra-n-butylate.

In a 100 ml test tube equipped with a magnetic stirrer and a nitrogen supply, 50 ml of a solution of MgCl ₂ in 1.2-dichloroethane prepared as described in Example 6 and 2.1 g of titanium tetra-n-butylate (molar ratio MgTi / = 3,5); after adding a titanium compound, the solution leaves for 2 hours at the same temperature; the liquid product thus obtained is quickly fed into a 500 ml thermostatic flask equipped with a reflux condenser, a magnetic stirrer and a nitrogen supply device and containing 184 ml of 10% by weight. a solution of triisobutylaluminum (TIBA) in hexane; the molar ratio is thus 15.

After mixing, heat is generated and an immediate dark solution is formed. Then the suspension is heated for 1.5 hours to 50 ^o C, the precipitate is filtered off, washed 3 times with anhydrous hexane.

The solid product is dried in vacuum, it has the following analytical composition: total Ti content = 7.55%; Mg = 12%; Al = 2.45%; Cl = 57.55%; (O-n-C ₄ H ₉ ) group: less than 0.1%.

 Example 20-22.

 Obtaining a precipitate of a solid catalytic component containing titanium tetra-n-butylate.

 The same procedure is used as described in examples 17-19, but the amounts of the titanium compound and TIBA are changed in such a way as to obtain a molar ratio of Mg / Ti to 1.5 and a molar ratio of TIBA / Ti to 6.3.

The solid product is dried in vacuum, it has the following analytical composition: total Ti content = 10.85%; Ti ⁺³ = 10.65%; Mg = 6.75%; Al = 2.5%; Cl = 46.6%; (O-n-C ₄ H ₉ ) group = 0.93%
Table 1 shows the copolymerization conditions of ethylene with propylene for all catalysts and also the polymerization yields.

 Comparison between the results of polymerization tests with the products of examples 3, 4 and 5 and with the products of examples 1 and 2 shows that the introduction of anisole as the electron-donating compound in the preparation of the catalyst component “A” gives a significant increase in yield at the same initial ethylene / propylene molar ratio.

 Examples 1 and 2 show that an increase in the partial pressure of hydrogen reduces catalytic activity, even if it is associated with an increase in ethylene concentration; on the contrary, if component "A" contains anisole, a simultaneous increase in the concentrations of hydrogen and ethylene causes an increase in yield.

 Examples 6, 7 and 8 show that a solid component containing titanium compounds on a support and having high catalytic activity can be formed in situ in a polymerization reactor by direct loading of solution (II).

 As shown in examples 9-16, the prepolymerization of liquid components described in examples 6-8 makes it possible to obtain high catalytic activity.

 A comparison of examples 17-19 with examples 20 and 21 shows that an increase in the titanium content in the solid component causes a decrease in the catalytic yield calculated from titanium.

 A comparison between Example 21 and Example 22 shows that a significant increase in the productivity of the catalyst system occurs with an increase in the polymerization temperature.

 Physical and mechanical analysis and physical and mechanical characteristics.

 For the obtained polymers, the following tests are carried out.

 - The propylene content is determined by the IR spectra of the polymers in the films of 0.2 mm thickness using a Perkin-Elmer spectrophotometer model 1760 GT1P.

The method consists in measuring the ratio between the absorption bands at 4390 and 4255 cm ^-1 using calibration curves constructed for standard polymers.

 - Characteristic viscosity.

The measurements are carried out in o-dichlorobenzene at 135 ^o C using a Ubbelode viscometer; measure the flow time of the solvent and polymer solutions with increasing polymer concentration.

 An extrapolation of the dependence of viscosity on the inverse concentration to zero gives the characteristic viscosity.

 - Molecular mass distribution.

These analyzes are performed by gel permeation chromatography in o-dichlorobenzene at 135 ^° C. using an AIC / GPC 150 "WATERS" apparatus with a refractometer and a system of 10 micron PI GEI columns with porosities of 10 ³ , 10 ⁴ , 10 ⁵ , 10 ⁶ angstroms.

 The calibration curves used for the calculation are obtained using standard monodispersed polystyrene samples using the Mark-Houwink equation, valid for linear polyethylene and polypropylene; molecular weights are adjusted according to the composition according to the Scholt equation (Th. G. Scholte, N. L. J. Meigerink et al .: J. Appl. Poly, Sci, 1084, 29, 3763-3782).

 The results of these analyzes are shown in table 2.

The values of M _w / M _n obtained for the liquid components of examples 6-8 are lower or at least very close to the values obtained for all other catalytic components in the examples and, in particular, for the corresponding catalysts obtained by prepolymerization (examples 9-16 )

Comparison of the results in relation to examples 1-6 with the results in relation to examples 17-22 shows that various methods of dissolving magnesium chloride or the introduction of anisole together with a titanium compound give the synthesis of copolymers of the same type, characterized by high polydispersity and M _w / M _n values from 10 to thirty.

 - Vulcanization and obtaining samples to obtain physical and mechanical characteristics.

 The vulcanization of the mixtures is carried out using the formulations shown in table 3.

- The degree of vulcanization of the copolymers is determined according to ASTM D2084-86 on a MDR 100-S rheometer at a temperature of 160 ^o C with a rotor oscillation frequency of 50 min ^-1 , a deformation angle of 0.2 ^o , a gap of 0.2 mm.

 The following measurements are made: the time required to achieve 2% of the maximum torque (t 02); the time required to reach 90% of maximum torque (t 90); maximum vulcanization rate.

 - Mechanical characteristics of vulcanized copolymers.

Characteristics of vulcanized copolymers are measured according to ASTM methods shown in table 4, using samples of plates molded on a press at 165 ^o C for 40 minutes and at 18 MPa.

 Table 5 shows the results of measurements of physical and mechanical characteristics for the obtained copolymers before and after vulcanization.

 These results show that all catalysts give easily crosslinkable copolymers with good mechanical and elastic properties.

Claims (7)

1. The solid component of the catalyst for producing elastomeric ethylene-propylene, mainly amorphous, copolymers, mainly containing a titanium compound supported on a solid, mainly consisting of magnesium halide, which is the product of a method consisting in: i) mixing solution (I), mainly consisting of an organometallic aluminum compound dissolved in aliphatic hydrocarbons with a solution (II) obtained by the following steps: a) dissolving anhydrous magnesium halide in cm Solvent B in the presence of an aluminum trihalide; b) treating solution (a) with a tetravalent titanium compound of the general formula Ti (OR) _4-n X _n , where R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 20 carbon atoms, X is a halogen and n represents an integer from 0 to 4; c) a possible treatment with an electron-donor compound selected from the group of carboxylic acid esters, alkyl or alkylaryl ethers, simultaneously with or after treatment with a titanium compound of step (b); ii) isolating and possibly purifying the solid catalyst component thus obtained, characterized in that, in step (a), a mixture of solvents selected from halogenated hydrocarbons or aromatic hydrocarbons and corresponding mixtures is used as a solvent mixture. 2. The component according to claim 1, characterized in that the solution (II) is obtained by treating anhydrous MgCl ₂ and AlCl ₃ with a mixture of 1,2-dichloroethane and toluene or a mixture of n-butyl chloride and 1,2-dichloroethane at a temperature of from 10 to 90 ^o With the subsequent addition after cooling to a temperature of from 10 to 40 ^o With a titanium compound selected from TiCl ₄ , Ti (O-n-C ₄ H ₉ ) ₄ , TiCl (O-n-C ₄ H ₉ ) ₃ . 3. The component according to claim 1, characterized in that upon receipt of the solution (II) the ingredients are taken in the following molar ratios: AlCl ₃ / MgCl ₂ from 1 to 5; n-butyl chloride / AlCl ₃ not less than 0.1; MgCl ₂ / Ti from 0.5 to 5. 4. The component according to claim 1, characterized in that upon receipt of the solution (II) the ingredients are taken in the following molar ratios: AlCl ₃ / MgCl ₂ from 1 to 5; 1,2-dichloroethane / AlCl ₃ not less than 0.1; MgCl ₂ / Ti from 0.5 to 5.  5. The component according to claim 1, characterized in that the interaction between the solution (I) and the solution (II) occurs directly in the polymerization reactor and in the contact phase, the molar ratio between the organometallic aluminum compound and the titanium compound being from 3 to 20. 6. The component according to claim 2, characterized in that it was obtained by prepolymerization with ethylene, propylene or a mixture thereof in the presence of aluminum alkylates with a molar ratio of aluminum / Ti from 2 to 25, and the weight ratio between the prepolymer and the solid product consisting of MgCl ₂ / AlCl ₃ and titanium compounds dissolved in solution (II), is from 1 to 10. 7. The component according to claims 1 to 6, characterized in that it is used in the polymerization process in suspension without extraction of catalytic residues at the end of the process to obtain elastomeric ethylene-propylene copolymers characterized by a polymer content of from 20 to 55 wt.%, Mooney viscosity (MLI + 4.125) from 10 to 80 and a ratio of M _w / M _n between 8 and 30.

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