Solid catalyst component, catalyst comprising said solid component, and process for the (co)polymerization of α-olefins

Abstract

A solid catalyst component for the (co)polymerization of -olefins having general formula (I):
Zr.sub.nMAl.sub.xCl.sub.yMg.sub.p(I)
wherein: M represents titanium (Ti), vanadium (V), or mixtures thereof; n is a number ranging from 0.01 to 2; x is a number ranging from 0.1 to 4; y is a number ranging from 5 to 53; p is a number ranging from 0 to 15;
obtained by means of a process comprising putting at least one zirconium arene in contact with at least one metal compound and, optionally, with at least one compound of magnesium. Said solid catalyst component can be advantageously used as a solid component in a catalyst for the (co)polymerization of -olefins. Said catalyst can be advantageously used in a process for the (co)polymerization of -olefins.

Claims

1. A solid catalyst component for the (co)polymerization of -olefins, the solid catalyst component having general formula (I):
Zr.sub.nMAl.sub.xCl.sub.yMg.sub.p(I) wherein: M represents titanium (Ti); n is a number ranging from 0.01 to 2; x is a number ranging from 0.1 to 4; y is a number ranging from 5 to 53; p is a number ranging from 0 to 15; obtained by means of a process which comprises putting the following components in contact: (A) at least one zirconium alkyl-arene having general formula (III) or (IIIa):
Zr(.sup.6-arene).sub.2Al.sub.qX.sub.rR.sub.s(III)
Zr(.sup.6-arene)Al.sub.qX.sub.rR.sub.s(IIIa) wherein: arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C.sub.1-C.sub.6 alkyl groups, or mixtures thereof; X represents chlorine; R represents a linear or branched C.sub.1-C.sub.10 alkyl group; q is a number ranging from 2 to 6; r is a number ranging from 2 to 20; and s is a number ranging from 2 to 6; (B) at least one compound selected from: alkoxides or chloroalkoxides having general formula M(OR.sub.1).sub.tCl.sub.4t wherein M represents titanium, R.sub.1 represents a linear or branched C.sub.1-C.sub.10 alkyl group, t is a number ranging from 1 to 4; carboxylates or chlorocarboxylates having general formula (IV):
M(OOCR.sub.2).sub.tCl.sub.4t(IV) wherein M represents titanium, R.sub.2 represents a linear or branched C.sub.1-C.sub.10 alkyl group, t is a number ranging from 1 to 4; or the carboxylate group OOCR.sub.2 in general formula (IV) is selected from: carboxylate groups having general formula (V): ##STR00009## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5, each independently, represent a hydrogen atom; a halogen atom selected from chlorine, bromine, fluorine, or iodine; a monofunctional hydrocarbyl radical as such or having at least one of its hydrogen atoms substituted with a halogen atom selected from chlorine, bromine, fluorine, or iodine; with the proviso that at least one of the substituents from R.sub.1 to R.sub.5 represents chlorine, bromine, fluorine, or iodine, or a monofunctional hydrocarbyl radical having at least one of its hydrogen atoms substituted with a halogen atom selected from chlorine, bromine, fluorine, or iodine; t and u are numbers ranging from 0 to 10; and optionally, (C) at least one magnesium compound selected from: magnesium dialkyls having general formula MgR.sub.3R.sub.4 wherein R.sub.3 and R.sub.4, each independently, represent a linear or branched C.sub.1-C.sub.10 alkyl group; and complexes of magnesium chloride having general formula MgCl.sub.2L.sub.u wherein L represents tetrahydrofuran (THF), or 1,2-dimethoxyethane (DME); and u is a number ranging from 1 to 4.

2. The solid catalyst component according to claim 1, wherein q is 3 in the case of zirconium alkyl-arene having general formula (III), 2 in the case of zirconium alkyl-arene having general formula (IIIa).

3. The solid catalyst component according to claim 1, wherein r is 9 in the case of zirconium alkyl-arene having general formula (III), 6 in the case of zirconium alkyl-arene having general formula (IIIa).

4. The solid catalyst component according to claim 1, wherein s is 2.

5. The solid catalyst component according to claim 1, wherein compounds (A), (B) and, optionally (C), are used in the following molar ratios (0.5-2):(1):(0-12), respectively.

6. The solid catalyst component according to claim 1, wherein in the zirconium alkyl-arene having general formula (III) or (IIIa), said arene is selected from: benzene, toluene, ortho-xylene, meta-xylene, para-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene (mesitylene), hexamethylbenzene, or mixtures thereof.

7. The solid catalyst component according to claim 1, wherein in the zirconium alkyl-arene having general formula (III) or (IIIa), said group R is selected from: ethyl, butyl, iso-butyl, n-octyl.

8. The solid catalyst component according to claim 1, wherein said alkoxides or chloro-alkoxides having general formula M(OR.sub.1).sub.tCl.sub.4t are selected from: titanium tetra-ethoxide; titanium tetra-propoxide; titanium tetra-n-butoxide; titanium tetra-iso-butoxide; or their relative chlorides; or mixtures thereof.

9. The solid catalyst component according to claim 1, wherein said carboxylates or chloro-carboxylates having general formula (IV) are selected from: titanium tetra-n-decanoate; titanium tetra-n-undecanoate; titanium tetra-isobutyrate; titanium tetra-2-ethyl-hexanoate; titanium tetra-2,2-dimethylpropanoate; titanium tetra-versatate; titanium tetra-3-ethyl-pentanoate; titanium tetra-citronellate; titanium tetra-naphthenate; titanium tetra-2-phenyl-butyrate; or their relative chlorides; or mixtures thereof.

10. The solid catalyst component according to claim 1, wherein said magnesium dialkyls having general formula MgR.sub.3R.sub.4 are selected from: magnesium butyl-octyl [(n-C.sub.4H.sub.9).sub.1,5(n-(C.sub.8H.sub.17).sub.0.5Mg], magnesium ethyl-butyl [(n-C.sub.2H.sub.5)(n-(C.sub.4H.sub.9)Mg], magnesium di-butyl [n-(C.sub.4H.sub.9).sub.2Mg], or mixtures thereof.

11. The solid catalyst component according to claim 1, wherein said magnesium chloride complexes having general formula MgCl.sub.2L.sub.u are selected from: magnesium-tetrahydrofuran chloride complex, magnesium 1,2-dimethoxyethane chloride complex, magnesium-pyrane chloride complexes, magnesium-ether ethyl chloride complexes, magnesium-di-octylether chloride complexes, magnesium-di-butylether chloride complexes, or mixtures thereof.

12. The solid catalyst component according to claim 1, wherein said process comprises putting components (A), (B), and, optionally, (C), in contact with at least one organic chloro-derivative (D) which is selected from: (a) di- or poly-chloroalkanes; (b) alkyl esters of aliphatic carboxylic acids di- or tri-chloro-substituted on the carbon in alpha position with respect to the carboxyl; or (c) monochloro triphenylmethane or dichloro diphenylmethane carrying a carboxyalkyl group in para position of at least one of the phenyl rings.

13. The solid catalyst component according to claim 12, wherein the compounds (A), (B), and, optionally, (C) and (D), are used in the following molar ratios (0.5-2):(1):(0-12):(0-40), respectively.

14. The solid catalyst component according to claim 12, wherein said process comprises putting components (A), (B), and, optionally, (C) and (D), in contact with at least one aluminium alkyl chloride (E) which is selected from those having general formula:
Al(R.sub.13).sub.wCl.sub.3w wherein R.sub.13 represents a linear or branched C.sub.1-C.sub.20 alkyl group; w is 1 or 2.

15. The solid catalyst component according to claim 14, wherein the compounds (A), (B), and, optionally, (C) and (D) and (E), are used in the following molar ratios (0.5-2):(1):(0-12):(0-40):(0-40), respectively.

16. The solid catalyst component of claim 1, wherein the zirconium alkyl-arene has the general formula (III) or (IIIa):
Zr(.sup.6-arene).sub.2Al.sub.qX.sub.rR.sub.s(Ill)
Zr(.sup.6-arene)Al.sub.qX.sub.rR.sub.s(IIIa) wherein: arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C.sub.1-C.sub.6 alkyl groups, or mixtures thereof; X represents a halogen atom selected from chlorine, bromine, fluorine, iodine; R represents a linear or branched C.sub.1-C.sub.10 alkyl group; q is a number ranging from 2 to 6; r is a number ranging from 2 to 20; s is a number ranging from 2 to 6.

17. The solid catalyst component of claim 1, wherein the zirconium alkyl-arene having general formula (III) or (IIIa) is prepared by a process which comprises putting the following components in contact: (i) at least one zirconium arene having general formula (II) or (IIIa):
Zr(.sup.6-arene).sub.2Al.sub.qCl.sub.r(II)
Zr(.sup.6-arene)Al.sub.qCl.sub.r(IIIa) wherein: arene represents a benzene, or a benzene substituted with from 1 to 6 linear or branched C.sub.1-C.sub.6 alkyl groups, or mixtures thereof; X represents a halogen atom selected from chlorine, bromine, fluorine, or iodine; q is a number ranging from 2 to 6; r is a number ranging from 8 to 20; (ii) at least one alkylating agent selected from: metal alkyls having general formula:
M(R.sub.16).sub.b wherein M represents aluminium, magnesium, zinc, or lithium; R.sub.16 represents a linear or branched C.sub.1-C.sub.12 alkyl group; b is 1, 2 or 3; aluminium alkyl chlorides having general formula:
Al(R.sub.13).sub.wCl.sub.3w wherein R.sub.13 represents a linear or branched C.sub.1-C.sub.20 alkyl group; w is 1 or 2.

18. The solid catalyst component of claim 17, wherein the components put into contact to prepare the zirconium alkyl-arene having general formula (III) or (IIIa) is carried out in the presence of an organic solvent at room temperature, or at a temperature equal to about the boiling point of the solvent used or at the reflux temperature of the mixture obtained by putting the above components in contact, for a time ranging from 2 hours to 24 hours.

19. A catalyst for the (co)polymerization of -olefins comprising the solid catalyst component according to claim 1.

20. The catalyst for the (co)polymerization of -olefins according to claim 19, comprising: a solid catalyst component having general formula (I):
Zr.sub.nMAl.sub.xCl.sub.yMg.sub.p (I) wherein: M represents titanium (Ti); n is a number ranging from 0.01 to 2; x is a number ranging from 0.1 to 4; y is a number ranging from 5 to 53; p is a number ranging from 0 to 15; a co-catalyst selected from aluminium alkyls having general formula:
Al(R.sub.13).sub.wCl.sub.3w wherein R.sub.13 represents a linear or branched C.sub.1-C.sub.20 alkyl group; w is 1, 2 or 3.

21. The catalyst for the (co)polymerization of -olefins according to claim 19, wherein in said catalyst the molar ratio between the aluminium present in the co-catalyst and the titanium present in the solid catalyst component having general formula (I) ranges from 0.5 to 200.

Description

EXAMPLES

Reagents and Materials

(1) The reagents and materials used in the following examples of the invention are listed hereunder together with their optional pre-treatments and their manufacturer: zirconium tetrachloride (ZrCl.sub.4) (Aldrich, 99.9%): used as such; anhydrous aluminium trichloride (AlCl.sub.3) (Fluka): used as such; benzene (Aldrich): pure, 99%, distilled on sodium (Na) in an inert atmosphere; mesitylene (Aldrich): pure, 99%, distilled on sodium (Na) in an inert atmosphere; toluene (Aldrich): pure, 99%, distilled on lithium aluminium hydride (LiA1H.sub.4) in an inert atmosphere; aluminium metal (Carlo Erba RPE): powder, used as such; aluminium tri-octyl [Al(octyl).sub.3] (Aldrich): used as such; titanium tetrachloride (TiCl.sub.4) (Fluka): pure, 99%, distilled in an inert atmosphere; vanadium tetrachloride (VCl.sub.4) (Fluka): pure, 99%, used as such; anhydrous magnesium chloride (MgCl.sub.2) (Cezus-Areva): >99%, grade T.202, used as such; complex magnesium-tetrahydrofuran chloride [MgCl.sub.2(THF).sub.2] prepared according to the description of Ochedzan-Siodlak et al. in Magnesium chloride modified with organoaluminium compounds as a support of the zirco-cene catalyst for ethylene polymerization, European Polymer Journal (2004), Vol. 40, pages 839-846; magnesium-1,2-dimethoxyethane [MgCl.sub.2(DME).sub.2] chloride complex prepared according to the description of Neumueller et al. in Crystal structure of MgCl.sub.2(1,2-dimethoxyethane).sub.2, Zeitschrift fr Naturforschung. B (1993), Vol. 48, No. 8, pages 1151-1153; butyl-octyl magnesium [(n-C.sub.4H.sub.9).sub.1,5 (n-(C.sub.8H.sub.17).sub.0,5Mg] (Chemtura): used as such; n-decane: pure, 95%, (SynthesisParma), treated on molecular sieves 4 and 10 , of Grace Davison; n-heptane (Carlo Erba, RPE): anhydryfied by distillation on sodium (Na) in an inert atmosphere; n-pentane (Carlo Erba, RPE): anhydryfied by distillation on sodium (Na) in an inert atmosphere; n-hexane (Carlo Erba, RPE): anhydryfied by distillation on sodium (Na) in an inert atmosphere; tert-butylchloride (Acros): used as such; tri-iso-butyl aluminium (TIBAL) (Chemtura): used as such; ethylene: Rivoira Grade 3.5, purity 99.95%; 1-hexene: 97%, Aldrich, distilled on calcium hydride; di-ethyl-aluminium chloride (DEAC) (Chemtura, pure): used as such; 2,3-dichlorobutane (Acros): used as such; methanol (Acros): acidified by addition of an aqueous solution of hydrochloric acid (HCl) at 37%; tetrahydrofuran (THF) (Carlo ERBA, RPE): anhydryfied by distillation on lithium aluminium hydride (LiA1H.sub.4) in an inert atmosphere.

(2) The analyses and characterization methods listed below were used.

(3) Elemental Analysis

(4) a) Determination of Mg, Al, Zr, Ti and V

(5) For the determination of the weight quantity of the metals Mg, Al, Zr, Ti and V, in the solid catalyst components object of the present invention, an aliquot weighed exactly, operating in a dry-box under a nitrogen flow, of about 30 mg-50 mg of sample, was placed in a platinum crucible of about 30 ml, together with a mixture of 1 ml of hydrofluoric acid (HF) at 40%, 0.25 ml of sulfuric (H.sub.2SO.sub.4) at 96% and 1 ml of nitric acid (HNO.sub.3) at 70%. The crucible was then heated on a plate, increasing the temperature until the appearance of white sulfuric fumes (about 200 C.). The mixture thus obtained was cooled to room temperature, 1 ml of nitric acid (HNO.sub.3) at 70% was added and the mixture was then heated until the appearance of fumes. After repeating the above sequence a further two times, a limpid, almost colourless solution was obtained. 1 ml of nitric acid (HNO.sub.3) and about 15 ml of water were then cold-added and the mixture was then heated to 80 C., for about 30 minutes. The sample thus prepared was diluted with water having a MilliQ purity up to a weight of about 50 g, weighed exactly, to obtain a solution on which analytical, instrumental determination was carried out using an ICP-OES (optical detection plasma) Thermo Optek IRIS Advantage Duo spectrometer, by comparison with solutions at a known concentration. For this purpose, a calibration curve was prepared for each analyte, within the range of 0-10 ppm, measuring solutions having a known titre obtained by weight dilution of certified solutions.

(6) The solution of the sample prepared as described above was diluted again by weight so as to obtain concentrations close to those used as reference, before carrying out spectrophotometric analysis. All the samples were prepared in duplicate. The results were considered acceptable if the single data of the tests in duplicate did not differ by more than 2% relative with respect to their average value.

(7) b) Chlorine Determination

(8) For said purpose, samples of the solid catalyst components object of the present invention, about 30 mg-50 mg, were weighed exactly in 100 ml glasses in a dry-box under a stream of nitrogen. 2 g of sodium carbonate (Na.sub.2CO.sub.2) were added and 50 ml of MillQ water were added, outside the dry-box. It was brought to boiling point on a plate, under magnetic stirring, for about 30 minutes. It was left to cool, diluted H.sub.2SO.sub.4 1/5 was added until the reaction became acid and the mixture was titrated with silver nitrate (AgNO.sub.2) 0.1 N with a potentiometer titrimeter.

(9) UV-Vis Spectroscopy

(10) The UV-Vis analysis was carried out using a Perkin-Elmer -19 double-beam spectrophotometer, with scanning within the range of 300 nm to 850 nm and resolution at 0.5 nm. For said purpose, samples of the solid catalyst components object of the present invention, were dissolved in the appropriate solvent at the desired molar concentration, they were placed in a Suprasil quartz cuvette, filled and stoppered operating under a strictly inert atmosphere (dry-box in an argon atmosphere), and were analyzed in diffused reflectance by means of an integrating sphere. The solutions being examined (about 3 ml) were introduced with the Schlenk technique in an an-hydrified argon or nitrogen atmosphere into cells with an optical path of 1 cm specifically modified with a rota-flow stopcock, to allow the charging of the solution in an inert atmosphere and also to ensure a better seal and consequently minimize degradation phenomena by oxidation and/or hydrolysis.

(11) Characterization of the Polymers and Copolymers

(12) The content of monomeric units deriving from 1-hexene in the ethylene-1-hexene copolymers was determined according to the standard technique ASTM D6645-01.

(13) The Melt Flow Index (MFI), correlated to the weight average molecular weight of the polymer, was determined according to the standard technique ASTM-D1238-10. The following tables indicate the Melt Flow Index (MFI) measured with a weight of 2.16 kg at 190 C., expressed as grams of molten polymer in 10 minutes (g/10 min).

(14) The density (g/cm.sup.3) was determined according to the standard technique ASTM D2839-10.

Example 1

Synthesis of Zr(6-benzene)2(Al3Cl11)

(15) A suspension of aluminium in powder form (5.06 g, 187.5 mmoles) in benzene (430 ml) was treated with fresh sublimed AlCl.sub.3 (8.60 g, 64.5 mmoles) and ZrCl.sub.4 (7.16 g, 30.7 mmoles). The mixture was left at reflux temperature (120 C.) for 24 hours. With the passing of time, the suspension slowly changed colour, from yellow to pink and finally became a dark purple colour. The suspension was filtered under heat, on a G3 filter, and the solid was separated (4.3 g). From ICP elemental analysis, said solid proved to have the following metal content (weight %): Al 82.4%, Zr 2.6%, whereas the Cl content, determined by means of potentiometric titration, was equal to 8.9%. After separation of the solid, the volume of the solution was reduced to about 100 ml by evaporation of the solvent under vacuum. 150 ml of anhydrous n-heptane were added to the residue and the mixture was left under vigorous stirring for about 1 hour and then placed in a refrigerator at about 4 C., for 24 hours. The dark precipitated solid was recovered by rapid filtration of the cold suspension, washed with benzene and dried under vacuum obtaining 10.5 g. From elemental analysis by means of ICP, said solid proved to have the following metal content (weight %): Zr 11.7%, Al 12.8%, whereas the Cl content, determined by means of potentiometric titration, was equal to 55%.

(16) The remaining 20.5% by weight of the above solid substantially consists of organic residue and a minimum part (<0.5% by weight) of impurities, whose nature was not further determined, either in the present example or in the subsequent examples.

(17) UV-Vis analysis (benzene) revealed the following three bands: at 366 nm (weak), at 416 nm (intense), at 492 nm (weak).

Example 2

Synthesis of Zr(Benzene)Al2Cl6(n-octyl)2 and Isolation of the Solid Component

(18) A suspension of ZrCl.sub.4 (527 mg, 2.26 mmoles), Al (92.0 mg, 3.41 mmoles), AlCl.sub.3 (905 mg, 6.79 mmoles) in a benzene/mesitylene mixture (40/10 ml) was heated to reflux temperature for 3 hours. The system was treated with Al(octyl).sub.3 (10.0 ml of solution in n-hexane at 25% w/w, 4.78 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. The volume of the solvent was reduced by evaporation at reduced pressure and 20 ml of cold n-pentane were added. The suspension was left under stirring for 60 hours at about 10 C., the solvent was then removed by evaporation under vacuum. The addition of cold n-pentane was repeated a second time and, after filtration of the precipitate obtained, 640 mg (43%) of a dark brown solid were isolated. Elemental analysis, chlorine, carbon and hydrogen determination carried out on the solid gave the following elemental atomic ratios: C.sub.22H.sub.40ZrAl.sub.2Cl.sub.6.

(19) The determination of the carbon and hydrogen was carried out by means of a Carlo Erba automatic analyzer Mod. 1106.

(20) UV-Vis analysis (dichloroethane) gave the following result: weak band at 524 nm.

(21) The solid was also characterized by means of an IR spectrum (nujol) showing the following bands: 3083 m, 1525 m, 1324 m, 1157 m, 999 vw, 884 m, 880 vw, 788 m, 706 m, 674 w, 550 m, 507 w, 494 w, 438 m, 386 m, 320 w.

Example 3

Preparation of a Solution Containing Zr(Mesitylene)Al2Cl6(n-octyl)2

(22) A suspension of ZrCl.sub.4 (527 mg, 2.26 mmoles), Al (92.0 mg, 3.41 mmoles), AlCl.sub.3 (905 mg, 6.79 mmoles) in mesitylene (40 ml), was heated to reflux temperature for 3 hours. The system was treated with Al(octyl).sub.3 (10.0 ml of solution in n-hexane at 25% w/w, 4.78 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. After filtration, the solution obtained (reaction raw product) can be used as such in the preparation of the solid catalyst component object of the present invention.

(23) UV-Vis analysis (benzene/mesitylene: 4/1) gave the following result: two intense bands at 370 nm and 540 nm.

Example 4

Reaction Between Zr(6-benzene)2(Al3Cl11) Obtained in Example 1 and TiCl4 in a Molar Ratio 1:1 (SYNZrTi1)

(24) A solution of Zr(.sup.6-benzene).sub.2(Al.sub.3Cl.sub.11) (0.99 mmoles) obtained as described in Example 1 in 30 ml of benzene, was treated with TiCl.sub.4 (0.99 mmoles): the rapid formation of a brown solid was observed. After 3 hours of stirring at room temperature and 30 minutes at 60 C., the suspension was filtered, the solid was washed with benzene and dried under vacuum at room temperature obtaining 0.5 g of a solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Zr.sub.1.38TiAl.sub.0.75Cl.sub.10.7 (SYNZrTi1).

Example 5

Reaction Between Zr(6-benzene)2(Al3Cl11) Obtained in Example 1 and TiCl4 in a Molar Ratio 1:2 (SYNZrTi2)

(25) A solution of Zr(.sup.6-benzene).sub.2 (Al.sub.3Cl.sub.11) obtained as described in Example 1 (1.10 mmoles) in 30 ml of benzene, was treated with TiCl.sub.4 (2.21 mmoles): the rapid formation of a brown solid was observed. After 3 hours of stirring at room temperature and 30 minutes at 60 C., the suspension was filtered, the solid was washed with benzene and dried under vacuum at room temperature obtaining 0.89 g of a solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Zr.sub.0.55Ti.sub.1Al.sub.1.21Cl.sub.9 (SYNZrTi2).

Example 6

Reaction Between Zr(6-benzene)2(Al3Cl11) Obtained in Example 1 and VCl4 in a Molar Ratio 1:1

(26) A solution of Zr(.sup.6-benzene).sub.2 (Al.sub.3Cl.sub.11) obtained as described in Example 1 (1.20 mmoles) in 30 ml of benzene, was treated with VCl.sub.4 (1.20 mmoles). The suspension was left under stirring at room temperature for 15 hours and heated to reflux temperature for 5 hours. The solid obtained was filtered and dried at room temperature at reduced pressure obtaining 0.82 g of a solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: ZrVAl.sub.3.1Cl.sub.13.9.

Example 7

Reaction Between Zr(6-benzene)2(Al2Cl11) Obtained in Example 1 and TiCl4 (Molar Ratio Ti/Zr=2:1) in the Presence of MgCl2 (Molar Ratio Mg/Ti=5) at 98 C. (SYNZrTi3)

(27) A solution of Zr(.sup.6-benzene).sub.2(Al.sub.2Cl.sub.11) obtained as described in Example 1 (0.98 mmoles) in 30 ml of benzene, was slowly added dropwise into a suspension of TiCl.sub.4 (1.96 mmoles) in n-heptane (90 ml) to which anhydrous MgCl.sub.2 (9.8 mmoles) had been added. The suspension was heated to reflux temperature for 6 hours obtaining a brown solid which was recovered by filtration, washed with n-heptane and dried under vacuum at room temperature. 1.7 g of a solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.58Al.sub.1.5Mg.sub.4.8Cl.sub.19 (SYNZrTi3).

Example 8

Reaction between Zr(6-benzene)2(Al2Cl11) obtained in Example 1 and TiCl4 (molar ratio Ti/Zr=1:1) in the presence of MgCl2(THF)2 (molar ratio Mg/Ti=10), tert-butylchloride at 98 C. (SYNZrTi4)

(28) A solution of Zr(.sup.6-benzene).sub.2(Al.sub.2Cl.sub.11) obtained as described in Example 1 (2.79 mmoles) in 30 ml of benzene, was slowly added dropwise into a suspension of TiCl.sub.4 (2.79 mmoles) in n-heptane (100 ml) to which MgCl.sub.2(THF).sub.2 (27.9 mmoles) had been added. After leaving the suspension under stirring for 1 hour, a solution of tert-butylchloride (16.8 mmoles) was added. The suspension was then heated to reflux temperature for 6 hours obtaining a brown solid which was recovered by filtration, washed with n-heptane and dried under vacuum at room temperature. 3.6 g of a solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.1Al.sub.3.1Mg.sub.9Cl.sub.27 (SYNZrTi4).

Example 9

Reaction between Zr(6-benzene)2(Al2Cl11) obtained in Example 1 and TiCl4 (molar ratio Ti/Zr=3:1) in the presence of (n-C4H9)1.5(n-C8H17)0.5Mg (molar ratio Mg/Ti=1) and 2,3-dichlorobutane at 60 C. (SYNZrTi5)

(29) A solution in n-heptane (20% w/w) of (n-C.sub.4H.sub.9).sub.1.5(n-C.sub.8H.sub.47).sub.0.5Mg (2.3 mmoles) was added to a solution of Zr(.sup.6-benzene).sub.2(Al.sub.3Cl.sub.11) obtained as described in Example 1 (2.3 mmoles) in 30 ml of benzene, and a solution of TiCl.sub.4 (6.9 mmoles) in n-heptane (35 ml) was slowly added dropwise. After leaving the suspension under stirring for 30 minutes, a solution of 2,3-dichlorobutane (2.3 mmoles) was added. The suspension was then heated to 60 C. for 1 hour obtaining a brown solid which was recovered by filtration, washed with n-heptane and dried under vacuum at room temperature. 2.1 g of a solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.4Al.sub.0.6Mg.sub.0.4Cl.sub.7 (SYNZrTi5)

Example 10

Reaction Between a Solution Containing Zr(Mesitylene)Al2Cl6(n-octyl)2 and TiCl4 (Molar Ratio Ti/Zr=2) (SYNZrTi6)

(30) A suspension of ZrCl.sub.4 (323 mg, 1.39 mmoles), Al (56 mg, 2.08 mmoles), AlCl.sub.3 (555 mg, 4.16 mmoles) in mesitylene (40 ml), was heated to 160 C., for 3 hours. The system was treated with Al(octyl).sub.3 (5.1 ml of solution in n-hexane at 25% w/w, 2.60 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess and was then treated dropwise with TiCl.sub.4 (0.38 ml, 2.81 mmoles) in a solution of n-heptane (20 ml). At the end of the addition, the brown suspension was left under stirring, at room temperature, for 15 hours obtaining 1.01 g of a brown solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.5Al.sub.2Cl.sub.14 (SYNZrTi6).

Example 11

Reaction between a solution containing Zr(mesitylene)Al2Cl6(n-octyl)2 and TiCl4 (molar ratio Ti/Zr=1.3) in the presence of MgCl2(THF)2 (molar ratio Mg/Ti=3.4) at room temperature (SYNZrTi7)

(31) A suspension of ZrCl.sub.4 (380 mg, 1.63 mmoles), Al (66.0 mg, 2.45 mmoles), AlCl.sub.2 (652 mg, 4.89 mmoles) in mesitylene (40 ml), was heated to 160 C., for 3 hours. The system was treated with Al(octyl).sub.3 (5.1 ml of solution in n-hexane at 25% w/w, 2.44 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. After treatment with solid MgCl.sub.2(THF).sub.2 (2.82 g, 11.8 mmoles), the resulting suspension was treated dropwise with TiCl.sub.4 (0.38 ml, 3.47 mmoles) in a solution of n-heptane (20 ml). At the end of the addition, the suspension was left under stirring, at room temperature, for 15 hours obtaining 3.82 g of a greyish-green solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.5Al.sub.0.7Mg.sub.4.14Cl.sub.14.7 (SYNZrTi7).

Example 12

Reaction between a solution containing Zr(mesitylene)Al2Cl6(n-octyl)2 and TiCl4 (molar ratio Ti/Zr=2) in the presence of MgCl2(THF)2 (molar ratio Mg/Ti=3) at 120 C. (SYNZrTi8)

(32) A suspension of ZrCl.sub.4 (223 mg, 0.96 mmoles), Al (39.0 mg, 1.44 mmoles), AlCl.sub.3 (383 mg, 2.87 mmoles) in mesitylene (40 ml), was heated to 160 C., for 3 hours. The system was treated with Al(octyl).sub.3 (3.0 ml of solution in n-hexane at 25% w/w, 1.43 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. After treatment with solid MgCl.sub.2(THF).sub.2 (1.48 g, 6.18 mmoles), the resulting suspension was treated dropwise with TiCl.sub.4 (0.22 mL, 2.01 mmoles) in a solution of n-heptane (20 ml). At the end of the addition, the suspension was heated to 120 C., for 8 hours, obtaining 4.50 g of a grey solid. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.5Mg.sub.4Al.sub.1Cl.sub.10 (SYNZrTi8).

Example 13

Reaction between a solution containing Zr(mesitylene)Al2Cl6(n-octyl)x and TiCl4 (molar ratio Ti/Zr=1) in the presence of MgCl2(DME)2 (molar ratio Mg/Ti=9) and 2,3-dichlorobutane (DCB/Zr=40) at 120 C. (SYNZrTi9)

(33) A suspension of ZrCl.sub.4 (229 mg, 0.983 mmoles), Al (40 mg, 1.48 mmoles), AlCl.sub.2 (400 mg, 3.00 mmoles) in mesitylene (40 ml), was heated to 160 C., for 3 hours. The system was treated with Al(octyl).sub.3 (3.1 ml of solution in n-hexane at 25% w/w, 1.48 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. After treatment with MgCl.sub.2(DME).sub.2 (5.01 g, 18.2 mmoles), the resulting suspension was treated dropwise in order, with TiCl.sub.4 (0.22 ml, 2.01 mmoles) in a solution of n-heptane (10.0 ml) and 2,3-dichlorobutane (4.5 ml, 39.3 mmoles). At the end of the addition, the suspension was heated to 120 C., for 15 hours, obtaining 4.25 g of a grey solid having a homogeneous appearance. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.0.3Mg.sub.7.7Al.sub.1,9Cl.sub.20.5 (SYNZrTi9).

Example 14

Reaction between a solution containing Zr(mesitylene)Al2Cl6(n-octyl)2 and TiCl4 (molar ratio Ti/Zr=1) in the presence of MgCl2(THF)2 (molar ratio Mg/Ti=10) and 2,3-dichlorobutane (DCB/Zr=20) at 120 C. (SYNZrTi10)

(34) A suspension of ZrCl.sub.4 (396 mg, 1.70 mmoles), Al (69.0 mg, 2.56 mmoles), AlCl.sub.3 (680 mg, 5.10 mmoles) in mesitylene (40 ml), was heated to 160 C., for 3 hours. The system was treated with Al(octyl).sub.3 (7.1 ml of solution in n-hexane at 25% w/w, 3.40 mmoles). The solution obtained was filtered on a porous septum to eliminate the aluminium metal in excess. After treatment with MgCl.sub.2(THF).sub.2 (4.06 g, 16.9 mmoles), the resulting suspension was treated dropwise in order, with TiCl.sub.4 (0.19 ml, 1.70 mmoles) in a solution of n-heptane (10.0 ml) and 2,3-dichlorobutane (4.0 ml, 34.9 mmoles). At the end of the addition, the suspension was heated to 120 C., for 15 hours, obtaining 3.74 g of a grey solid having a homogeneous appearance. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.1Mg.sub.11.4Al.sub.1.6Cl.sub.32.3 (SYNZrTi10).

Example 15

Reaction of the Solid Catalyst Component Obtained in Example 10 with MgCl2(THF)2 (Molar Ratio Mg/Ti=10) in n-heptane at Reflux Temperature (SYNZrTi11)

(35) A suspension of MgCl.sub.2(THF).sub.2 (1.48 g, 6.18 mmoles) in n-heptane (50 ml) was treated with a sample of the solid catalyst component obtained as described in Example 10, having a titanium content equal to 10.0% (30.5 mg of Ti, 0.637 mmoles). The suspension was heated to the reflux temperature of the solvent, for 15 hours, obtaining 1.10 g of a grey solid having a homogeneous appearance. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.1Mg.sub.10.6Al.sub.1.2Cl.sub.26 (SYNZrTi11).

Example 16

(Co)Polymerization Tests with the Solid Catalyst Components SYNZrTi1-SYNZrTi5

(36) The tests reported in Table 1 (Tests 1-2), Table 2 (Tests 3-4) and Table 3 (Tests 5-9), were carried out in a Bchi steel autoclave having a volume of 300 ml, equipped with a propeller stirrer and double jacket for thermostat heating. A vacuum-nitrogen flushing was exerted in the autoclave for at least three times and said autoclave was left under vacuum at 100 C.-110 C., for an overall duration of about 2 hours. The autoclave was then cooled to 40 C. and a solution containing 140 ml of n-heptane (130 ml of n-heptane and 10 ml of 1-hexene, in the case of copolymerization) and 0.2 ml (0.75 mmoles) of TIBAL as co-catalyst, was charged, by siphoning through a valve. The temperature inside the autoclave was brought to 65 C. and at that point, a solution containing 10 ml of n-heptane, 0.2 ml (0.75 mmoles) of TIBAL (solution in toluene at 25% w/w) and the solid catalyst component (SYNZrTi1-SYNZrTi5) (Ti=0.015 mmoles) (molar ratio Al/Ti=100), was introduced, again by siphoning. The autoclave was subsequently pressurized with ethylene (0.6 MPa), heated to 80 C., and the whole mixture was left to polymerize at 80 C., for 10 minutes, in a continuous flow of ethylene. The ethylene feeding was then closed, the autoclave was cooled to room temperature, the residual gases were vented and the suspension contained in the autoclave was discharged and poured into ethanol. The polymer was recovered by filtration and dried under vacuum, at 60 C., for a few hours.

Example 17

Polymerization Tests with the Solid Catalyst Components SYNZrTi6, SYNZrTi7, SYNZrTi10, SYNZrTi11

(37) The tests reported in Table 4 (Tests 10-13) were carried out in a steel autoclave having a volume of 150 ml equipped with magnetic stirring and optionally heated in a thermostat-regulated oil bath. The solid catalyst component (SYNZrTi6, SYNZrTi7, SYNZrTi10 and SYNZrTi11) was suspended in 60 ml of n-heptane, a quantity of a solution of TIBAL in toluene at 25% w/w was then added so as to obtain a molar ratio Al/Ti=100, and the resulting mixture was transferred to the autoclave. The autoclave was subsequently pressurized with ethylene (1 MPa) and introduced into the oil bath thermostat-regulated at the desired reaction temperature (80 C.) At the end of the reaction (15 minutes), the ethylene feeding was closed, the autoclave was cooled to room temperature, the residual gases were vented and the suspension contained in the autoclave was discharged and poured into acidified methanol. The polymer precipitated was washed with methanol, filtered and dried under vacuum, at 60 C., for a few hours.

Example 18

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 11(SYNZrTi7)

(38) A vacuum-nitrogen flushing was exerted for at least three times and for an overall duration of about 2 hours in a 5-litre steel autoclave, of the Brignole type, equipped with a burette for the addition of the catalyst, a propeller stirrer and a heating thermoresistance connected to a thermostat for the temperature control. A solution containing 1,900 ml of n-decane, 1.5 ml of a 1 M solution of TIBAL (1.5 mmoles) in n-decane as cocatalyst (molar ratio Al/Ti=23), was then introduced into the autoclave. The temperature inside the autoclave was brought to 190 C., and 86 mg of the solid catalyst component obtained as described in Example 11 (SYNZrTi7) (65 moles of Ti), was introduced by means of a burette, under a slight overpressure of ethylene, as a suspension in about 10 ml of n-decane. The autoclave was pressurized with ethylene, keeping under stirring, until a total pressure was reached in the autoclave equal to 1.5 MPa. At this point, the heating of the thermoresistance was interrupted and a temperature increase due to the exothermicity of the polymerization reaction, was observed. The entity of the enthalpy variation (H) can be directly correlated to the activity of the ethylene converted and proportional to the catalytic activity obtained. The ethylene flow necessary for replacing the ethylene converted into polymer, was also registered by means of ASA flowmeters calibrated with an analog volume meter. The polymerization was continued for 5 minutes, maintaining the system at a constant pressure of 1.5 MPa. At the end, the polymerization reaction was interrupted by the introduction of about 10 ml of ethanol into the autoclave. The autoclave was left to cool to room temperature and, subsequently, the contents of the autoclave was discharged into about 3 litres of ethanol. The polymer was separated by filtration, washed with acetone and dried in an oven under vacuum (about 100 Pa), at 90 C., for about 12 hours. At the end, 37 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 5.

Example 19

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 11 (SYNZrTi7) Using a 1:1 Mixture of TIBAL and DEAC, as co-catalyst

(39) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a mixture of a solution 1 M of TIBAL and 1 M of DEAC with a molar ratio 1:1 (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=28.7), were charged into the autoclave.

(40) The autoclave was heated to a temperature of 160 C., 69.6 mg of the solid catalyst component obtained as described in Example 11 (SYNZrTi7) (52.2 moles Ti), were added, as a suspension in about 15 ml of n-decane, and the polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 10 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 48 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 6.

Example 20

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 12 (SYNZrTi8)

(41) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=30) and, at a starting temperature of 190 C., 41.1 mg of the solid catalyst component obtained as described in Example 12 (SYNZrTi8) (50 moles Ti), as a suspension in about 15 ml of n-decane, were charged into the autoclave. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 28 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index MFI) and the density: the results obtained are reported in Table 5.

Example 21

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 14 (SYNZrTi10)

(42) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=30 and, at a starting temperature of 190 C., 73.2 mg of the solid catalyst component obtained as described in Example 14 (SYNZrTi10) (50 moles Ti), as a suspension in about 15 ml of n-decane), were charged into the autoclave. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 20 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 5.

Example 22

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 14 (SYNZrTi10)

(43) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=30), were charged into the autoclave. The autoclave was heated to 160 C. and 73.2 mg of the solid catalyst component obtained as described in Example 14 (SYNZrTi10) (50 moles Ti), were added as a suspension in about 15 ml of n-decane. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 40 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 6.

Example 23

Polymerization of ethylene with the solid catalyst component obtained in Example 14 (SYNZrTi10) using a 1:1 mixture of TIBAL and DEAC, as co-catalyst

(44) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a mixture of a solution 1 M of TIBAL and 1 M of DEAC with a molar ratio 1:1 (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=37.5), were charged into the autoclave. The autoclave was heated to a temperature of 160 C., 58.5 mg of the solid catalyst component obtained as described in Example 14 (SYNZrTi10) (40 moles Ti), were added as a suspension in about 15 ml of n-decane, and the polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 10 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 50 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 6.

Example 24

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 14 (SYNZrTi10) Treated with DEAC in a Ratio Al(DEAC)/Ti=20

(45) 278 mg of solid catalyst component obtained as described in Example 14 (SYNZrTi10) (containing 4.79 mg of titanium=0.1 mmoles) and 15 ml of n-decane, were introduced under nitrogen flow, into a 100 ml glass tailed test-tube. 20 ml of a solution 1 M of DEAC in n-decane were subsequently added, under stirring at room temperature, so as to have a molar ratio Al(DEAC)/Ti=20 (Al/Ti=20). The whole mixture was left under stirring, for 60 minutes, at room temperature, obtaining 265 mg of a solid which was filtered, washed with n-decane and dried.

(46) Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.1Zr.sub.1Mg.sub.11.4Al.sub.1.6Cl.sub.32.1 (SYNZrTi10). Said solid was resuspended with about 10 ml of n-decane and kept in suspension for the subsequent polymerization test.

(47) As can be observed from the atomic ratios obtained, the treatment with DEAC does not significantly modify the composition of the solid catalyst component obtained as described in Example 14, even if its activity is considerably increased. This behaviour was observed systematically during various laboratory tests and consequently, in the following examples, the composition of the solid catalyst components thus prepared is considered the same as the solid catalyst components obtained without treatment with DEAC, without proceeding each time with elemental analysis.

(48) The subsequent polymerization reaction was carried out using the same procedure described in Example 18, with the difference that 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane (molar ratio Al/Ti=30 and, at a starting temperature of 190 C., 111.4 mg of the solid catalyst component prepared as described above (40 moles Ti), as a suspension in about 15 ml of n-decane), were charged into the autoclave. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 40 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 7.

Example 25

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 14 (SYNZrTi10) Treated with DEAC in a Ratio Al(DEAC)/Ti=20

(49) The same procedure was adopted as described in Example 24 with the only difference that, after the addition of DEAC at room temperature, the preformed suspension was heated to 60 C. for 60 minutes, before being filtered. As in the previous Example 24, the treatment did not produce any significant variations in the chemical composition of the solid catalyst component obtained as described in Example 14 (SYNZrTi10).

(50) The subsequent polymerization reaction was carried out according to the procedure described in Example 24, but with the addition, however, of 75 g of 1-hexene, together with n-decane.

(51) 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=30) and, at a starting temperature of 190 C., 111.4 mg of the solid catalyst component prepared as described above (40 moles Ti), as a suspension in about 15 ml of n-decane, were charged into the autoclave. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 55 g of copolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 7.

Example 26

Polymerization of Ethylene with the Solid Catalyst Component Obtained in Example 15 (SYNZrTi11)

(52) The same procedure was used as described in Example 18, with the difference that 1.5 ml of a solution 1 M of TIBAL (1.5 mmoles) in n-decane as co-catalyst (molar ratio Al/Ti=30) and, at a starting temperature of 190 C., 102.50 mg of the solid catalyst component obtained as described in Example 15 (SYNZrTi11) (50 moles Ti), as a suspension in about 15 ml of n-decane, were charged into the autoclave. The polymerization reaction was carried out with the same procedure described above in Example 18, for a time of 5 minutes. At the end, the polymer obtained was recovered and treated analogously to what is described above in Example 18. 17 g of polyethylene homopolymer were obtained, which was characterized by measuring the Melt Flow Index (MFI) and the density: the results obtained are reported in Table 5.

Example 27

Reaction Between the Biphasic System (Reaction Raw Product) Containing Zr(6-Toluene)(AlCl4)2 and TiCl4 in a Molar Ratio 1:2 (SYNZrTi12)

(53) A suspension of ZrCl.sub.4 (1.4 g, 6.01 mmoles), aluminium in powder form (1.0 g, 37.1 mmoles) and AlCl.sub.3 (1.75 g, 13.2 mmoles) in toluene (100 ml) was heated to reflux temperature, for 24 hours, obtaining a biphasic system (reaction raw product) consisting of an overlying purple-coloured phase and an underlying very dark purple phase, extremely viscous. Said biphasic system was heated to about 100 C. and filtered under heat. The filter and walls of the reaction container were washed with toluene at boiling point. After filtration, the biphasic system was treated with TiCl.sub.4 (13 mmoles) and the suspension obtained was heated to 50 C.-60 C. for 15 hours. The brown solid precipitated was recovered by filtration of the suspension, after cooling the same to room temperature, and dried at reduced pressure at room temperature. 3.9 g of a solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: Ti.sub.2Zr.sub.1Al.sub.2.5Cl.sub.18 (SYNZrTi12).

Example 28

Reaction Between the Biphasic System (Reaction Raw Product) Containing Zr(6-toluene)(AlCl4)2 and VCl4 in a Molar Ratio 1:1

(54) A suspension of ZrCl.sub.4 (0.70 g, 3.0 mmoles), aluminium in powder form (0.50 g, 18.5 mmoles) and AlCl.sub.3 (0.81 g, 6.07 mmoles) in toluene (100 ml) was heated to reflux temperature, for 24 hours, obtaining a biphasic system (reaction raw product) consisting of an overlying purple-coloured phase and an underlying very dark purple phase, extremely viscous. Said biphasic system was heated to about 50 C.-60 C. and filtered under heat. The filter and walls of the reaction container were washed with toluene at boiling point. After filtration, the biphasic system was treated with VCl.sub.4 (3.1 mmoles) and the suspension obtained was left under stirring, at room temperature, for 15 hours, and heated to reflux temperature for 5 hours. The solid precipitated was recovered by filtration of the suspension, after cooling the same to room temperature, and dried at reduced pressure at room temperature. 0.82 g of a solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: VZrAl.sub.2.2Cl.sub.11.9.

Example 29

Reaction between the Biphasic System (Reaction Raw Product) Containing Zr(6-toluene)(AlCl4)2 and TiCl4 (Molar Ratio Ti/Zr=16) in the Presence of an Excess of Aluminium (SYNZrTi13)

(55) A suspension of ZrCl.sub.4 (0.70 g, 3.0 mmoles), aluminium in powder form (0.30 g, 11.2 mmoles) and AlCl.sub.3 (1.31 g, 9.82 mmoles) in toluene (100 ml) was heated to reflux temperature, for 15 hours, obtaining a biphasic system (reaction raw product) consisting of an overlying purple-coloured phase and an underlying very dark purple phase, extremely viscous. Said biphasic system was treated with TiCl.sub.4 (48 mmoles) in n-heptane (20 ml) and the mixture obtained was heated to reflux temperature for a whole night. The brown solid precipitated was recovered by filtration of the suspension, after cooling the same to room temperature, and dried at reduced pressure at room temperature. 1.5 g of a brown solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: TiZr.sub.0.31Al.sub.0.46Cl.sub.5.5 (SYNZrTi13).

Example 30

Reaction between the Biphasic System (Reaction Raw Product) Containing Zr(6-toluene)(AlCl4)2 and TiCl4 (Molar Ratio Zr/Ti=10) in the Presence of an Excess of Aluminium (SYNZrTi14)

(56) The same procedure was adopted as described above in Example 29, with the difference that the biphasic system obtained was treated with TiCl.sub.4 (30 mmoles) in n-heptane (20 ml) and the mixture obtained was heated to reflux temperature for a whole night. The brown solid precipitated was recovered by filtration of the suspension, after cooling the same to room temperature, and dried at reduced pressure at room temperature. 0.95 g of a brown solid were obtained. Elemental analysis and chlorine determination carried out on the solid obtained gave the following elemental atomic ratios: TiZr.sub.0.12Al.sub.0.2Cl.sub.4 (SYNZrTi14). It should be noted that although the analysis clearly shows the presence of non-reacted aluminium, said solid catalyst component proved to be active in the polymerization of ethylene (see Table 9).

Example 31

Polymerization Tests with the Solid Catalyst Components SYNZrTi12-SYNZrTi14

(57) The tests reported in Table 8 (Tests 1-2) and in Table 9 (Tests 3-6) were carried out in a steel autoclave having a volume of 150 ml equipped with magnetic stirring and optionally heated in a thermostat-regulated oil bath. The solid catalyst component (SYNZrTi12, SYNZrTi13 and SYNZrTi14) was suspended in 10 ml of n-heptane, a quantity of a solution of TIBAL in toluene at 25% w/w was then added so as to obtain a molar ratio Al/Ti=100, and the resulting mixture was transferred to the autoclave. The autoclave was subsequently pressurized with ethylene (0.6 MPa in Tests 1-2; 1 MPa in Tests 3-6) and introduced into the oil bath thermostat-regulated at the desired reaction temperature (80 C.). At the end of the reaction (30 minutes in Tests 1-2; 15 minutes in Tests 3-6), the reaction mixture was discharged from the autoclave and poured into acidified methanol, and the polymer precipitated was washed with methanol and filtered.

(58) TABLE-US-00001 TABLE 1 Polymerization of ethylene and copolymerization of ethylene with 1-hexene with the solid catalyst component SYNZrTi1 CATALYST ACTIVITY ACTIVITY (moles of PE (kg g.sup.1.sub.Ti (kg mol.sup.1.sub.Ti C6* TEST Ti) (g) h.sup.1) h.sup.1) (mol %) 1 15 4.1 34 1632 2 15 6.2 52 2496 5 Co-catalyst = TIBAL; Al/Ti = 100; n-heptane = 150 ml; P.sub.(ethylene) = 0.6 MPa; 1-hexene (C6) = 10 ml; time = 10 min; T = 80 C. *Calculated by means of FT-IR analysis

(59) TABLE-US-00002 TABLE 2 Polymerization of ethylene and copolymerization of ethylene with 1-hexene with the solid catalyst component SYNZrTi2 CATALYST ACTIVITY ACTIVITY (moles of PE (kg g.sup.1.sub.Ti (kg mol.sup.1.sub.Ti C6* TEST Ti) (g) h.sup.1) h.sup.1) (mol %) 3 15 8.6 72 3456 4 15 10.6 88 4224 2.8 Co-catalyst = TIBAL; Al/Ti = 100; n-heptane = 150 ml; P.sub.(ethylene) = 0.6 MPa; 1-hexene (C6) = 10 ml; time = 10 min; T = 80 C. *Calculated by means of FT-IR analysis

(60) TABLE-US-00003 TABLE 3 Polymerization of ethylene and copolymerization of ethylene with 1-hexene with the solid catalyst component SYNZrTi3, SYNZrTi4 and SYNZrTi5. CATALYST ACTIVITY ACTIVITY (moles of PE (kg g.sup.1.sub.Ti (kg mol.sup.1.sub.Ti C6* TEST Ti) (g) h.sup.1) h.sup.1) (mol %) 5 14 14 125 6000 (SYNZrTi3) 6 11 11.9 135 6480 (SYNZrTi4) 7 15 12.8 107 5136 12.5 (SYNZrTi4) 8 13 6 96 4608 (SYNZrTi5) 9 15 10 84 4032 5.8 (SYNZrTi5) Co-catalyst = TIBAL; Al/Ti = 100; n-heptane = 150 ml; P.sub.(ethylene) = 0.6 MPa; 1-hexene (C6) = 10 ml; time = 10 min; T = 80 C. *Calculated by means of FT-IR analysis

(61) TABLE-US-00004 TABLE 4 Polymerization of ethylene with the solid catalyst component SYNZrTi6, SYNZrTi7, SYNZrTi10 and SYNZrTi11. CATALYST PE ACTIVITY TEST (moles of Ti) (g) (kg mol.sup.1.sub.Ti h.sup.1) 10 28.3 9.5 1343 (SYNZrTi6) 11 9.4 7.73 3303 (SYNZrTi7) 12 15.8 8.3 2101 (SYNZrTi10) 13 9.3 4.85 2086 (SYNZrTi11) Co-catalyst = solution of tri-iso-butyl-aluminium (TIBAL) in toluene at 25% w/w; Al/Ti = 100; n-heptane = 60 ml; P.sub.(ethylene) = 1 MPa; time = 15 min; T = 80 C.

(62) TABLE-US-00005 TABLE 5 Polymerization of ethylene with the solid catalyst components obtained in Examples 11, 12, 14 and 15. Ti Al/Ti Activity MFI.sub.(2.16 kg) Density Example Catalyst (mg) (molar) Yield (g) (kg/g.sub.Ti) (g/10 min) (g/cm.sup.3) 18 SYNZrTi7 2.5 23 37 14.8 0.124 0.9305 20 SYNZrTi8 2.4 30 28 11.7 0.048 0.9299 21 SYNZrTi10 2.4 30 20 8.3 0.072 0.9304 26 SYNZrTi11 2.4 30 17 7.1 0.024 0.9309 Co-catalyst = TIBAL; P.sub.(ethylene) = 1.5 MPa; Time = 5 min; T initial = 190 C.

(63) TABLE-US-00006 TABLE 6 Polymerization of ethylene with the solid catalyst components obtained in Examples 11 and 14 Ti Al/Ti Activity MFI.sub.(2.16 kg) Density Example Catalyst (mg) (molar) Yield (g) (kg/g.sub.Ti) (g/10 min) (g/cm.sup.3) 19.sup.(1) SYNZrTi7 3.11 29 48 15.4 0.69 0.9289 22.sup.(2) SYNZrTi10 2.4 30 40 16.6 0.79 0.9278 23.sup.(3) SYNZrTi10 1.92 37.5 50 26 0.98 0.9276 P.sub.(ethylene) = 1.5 MPa; time = 5 min; T initial = 160 C. .sup.(1)and .sup.(3)co-catalyst = TIBAL/DEAC .sup.(2)co-catalyst = TIBAL

(64) TABLE-US-00007 TABLE 7 Ethylene polymerization and ethylene copolymerization with 1-hexene with a catalyst solid component treated with DEAC (Al/Ti = 20) Ti 1-hexene Al/Ti Yield Activity MFI.sub.(2.16 kg) Density Example Catalyst (mg) (g) (molar) (g) (kg/g.sub.Ti) (g/10 min) (g/cm.sup.3) 24 SYNZrTi10 1.92 30 40 20.8 0.17 0.9363 25 SYNZrTi10 1.92 75 30 40 28.6 0.10 0.9223 T initial = 190 C.; .sup.(2)co-catalyst = TIBAL; P.sub.(ethylene) = 1.5 MPa; t = 5 min

(65) TABLE-US-00008 TABLE 8 Polymerization of ethylene with the catalyst solid component SYNZrTi12 Catalyst Ti Al/Ti T PE Activity Test (mg) (mol) (molar) ( C.) (g) (kg mol.sup.1.sub.Ti h.sup.1) 1 7 6.28 50 80 1.11 353 2 5.2 12.9 50 80 4.95 767 Co-catalyst = solution of tri-iso-butyl-aluminium (TIBAL) in toluene at 25% w/w; n-heptane = 60 ml; P.sub.(ethylene) = 0.6 MPa; t = 30 min; T = 80 C.

(66) TABLE-US-00009 TABLE 9 Polymerization of ethylene with the catalyst solid components SYNZrTi13 and SYNZrTi14 Activity Catalyst Ti Al/Ti T PE (kg Test (mg) (mol) (molar) ( C.) (g) mol.sup.1.sub.Ti h.sup.1) 3 12.2 14.8 100 80 3.26 828.8 (SYNZrTi13) 4 16 19.3 50 80 2.96 613.5 (SYNZrTi13) 5 10 35.3 50 80 2.3 130 (SYNZrTi14) 6 6 21.1 50 80 2.73 259 (SYNZrTi14) Co-catalyst = solution of tri-iso-butyl-aluminium (TIBAL) in toluene at 25% w/w; n-heptane = 60 ml; P.sub.(ethylene) = 1 MPa; t = 15 min; T = 80 C.