Claims
- 1. The process for the manufacture of a catalytic solid, comprising:
- a) mixing at least one magnesium compound chosen from the group consisting of Mg oxide and compounds of formulae MgX.sub.n (O--R).sub.2-n, and at least one transition metal compound selected from the group consisting of compounds of formulae MY.sub.x (O--R').sub.t-x and M'O.sub.y (O--R").sub.s-2y in which
- X denotes a halogen
- each of M and M' denotes a transition metal chosen from the group consisting of the elements of groups IVB and VB of the Periodic Table, the valency of which is at least equal to 4
- Y denotes a halogen or a group (O--R'")
- each of R, R', R" and R'" denotes an alkyl, aryl or cycloalkyl group containing up to 20 carbon atoms
- O.ltoreq.n.ltoreq.2
- O.ltoreq.x.ltoreq.t, t being equal to the valency of M
- O.ltoreq.y.ltoreq.s/2, being equal to the valency of M', to obtain a solution comprising a complex of said at least one magnesium compound with said at least one transition metal compound,
- b) reducing and halogenating the solution of the complex thus obtained by contacting it with a reducing-halogenating agent, in order to precipitate a catalytic solid, comprising an amorphous coprecipitate of a halogen compound of a transition metal M or M' in the trivalent state, a halogen compound of a transition metal M" in the trivalent state, and a magnesium halide, and
- c) isolating the precipitated catalytic solid thus obtained from the solution,
- wherein the reducing-halogenating agent consists essentially of at least one complex of empirical formula M"(A)Al.sub.2 Cl.sub.8 in which
- M" denotes a transition metal of group IVB of the Periodic Table, and
- A denotes an aromatic hydrocarbon.
- 2. The process according to claim 1, wherein the compound of transition metal M or M', the magnesium compound and the complex [M"(A)Al.sub.2 (X', X").sub.8 ]M"(A)Al.sub.2 Cl.sub.8 are used in quantities such that the molar ratio (M or M')/Mg is from 1 to 20 and that the molar ratio M"/(M or M') is from 0.3 to 1.
- 3. The process according to claim 1, wherein the at least one magnesium compound is mixed with the at least one transition metal compound in at least one organic solvent selected from the group consisting of toluene and hexane and the complex M"(A)Al.sub.2 Cl.sub.8 is used in the form of a solution in toluene.
- 4. The process according to claim 1, wherein at least one magnesium compound is mixed with the at least one transition metal compound at a temperature of 50.degree. to 135.degree. C.
- 5. The process according to claim 1, including treating the precipitated catalytic solid at a temperature of at least 40.degree. C. and lower than the solvent boiling point and for a period of approximately from 0.5 to 12 hours.
- 6. The process according to claim 1, wherein the catalytic solid is subjected to washing with an organic liquid chosen from the group consisting of aliphatic hydrocarbons.
- 7. The process according to claim 6, including washing the precipitated catalytic solid after treatment at a temperature of at least 40.degree. C. and lower than the solvent boiling point for a period of approximately 0.5 to 12 hours.
- 8. The process according to claim 1, wherein the reducing-halogenating agent is chosen from the group consisting of those corresponding to the empirical formula Ti(toluene)Al.sub.2 Cl.sub.8 and Zr(toluene)Al.sub.2 Cl.sub.8.
- 9. The process according to claim 1, wherein the reducing-halogenating agent is deposited on an inorganic support.
- 10. The process according to claim 9, wherein in order to deposit the reducing-halogenating agent on the inorganic support, the inorganic support is impregnated with a solution of the reducing-halogenating agent in a diluent chosen from aromatic hydrocarbons.
- 11. The process according to claim 9, wherein the inorganic support is dehydroxylated silica.
- 12. The process according to claim 1, wherein the compound corresponding to one of the formulae MY.sub.x (O--R').sub.t-x and M'O.sub.y (O--R").sub.s-2y is selected from the group consisting of those in which M or M' is Ti, V or Zr.
- 13. The process according to claim 12, wherein the compound MY.sub.x (O--R').sub.t-X is selected from the group consisting of titanium tetrabutylate and vanadium tetrabutylate.
- 14. The process according to claim 1, wherein the compound MgX.sub.n (O--R).sub.2-n is a magnesium dialcoholate which is used in a quantity such that the molar ratio (M or M')/Mg is from 1 to 2.
- 15. The process according to claim 14, wherein, after the isolation of the precipitated catalytic solid from the reaction mixture, the said catalytic solid is treated with titanium tetrahalide in which the halogen is identical with that of the reducing-halogenating agent used.
- 16. The process according to claim 15, wherein the precipitated catalytic solid is treated with titanium tetrachloride.
- 17. The process according to claim 15, wherein, after the treatment with titanium tetrahalide, the catalytic solid is subjected to washing with an organic liquid chosen from the group consisting of aliphatic hydrocarbons.
- 18. The process according to claim 6, wherein the organic washing liquid is hexane.
- 19. The process according to claim 1, wherein the magnesium compound is chosen from the group consisting of magnesium dichloride and magnesium diethylate.
- 20. The process according to claims 13, wherein, in the case where the compound MY.sub.x (O--R').sub.t-x is titanium tetrabutylate and the magnesium compound is magnesium dichloride, a molar ratio Ti(O--C.sub.4 H.sub.9).sub.4 /MgCl.sub.2 of at least 2 is used.
- 21. The process according to claims 13, wherein, in the case where the compound MY.sub.x (O--R').sub.t-x is vanadium tetrabutylate and the magnesium compound is magnesium dichloride, a molar ratio V(O--C.sub.4 H.sub.9).sub.4 /MgCl.sub.2 of 2 to 20 is used.
- 22. The process according to claim 1, wherein the reducing-halogenating agent of empirical formula M"(A)Al.sub.2 Cl.sub.8 is prepared by reacting a transition metal tetrachloride M"Cl.sub.4, an aluminium trichloride AlCl.sub.3, an aromatic hydrocarbon A with metallic magnesium suspended in an organic solvent, refluxing the suspension so obtained at a temperature which is equal to or slightly higher than the boiling temperature of the aromatic hydrocarbon for a period varying from 1 to 12 hours, allowing the reaction mixture to cool, separating off any solid fraction comprising an excess of one of the components used, and collecting the solution thus obtained containing the reducing-halogentaing agent, where:
- M" denotes a transition metal of group IVB of the Periodic Table.
- 23. A catalytic solid manufactured by the process of claim 1 comprising a coprecipitate of a magnesium halide and of halides of at least two different transition metals selected from groups IVB and VB of the Periodic Table, in which at least 90% by weight has an amorphous structure.
- 24. The catalytic solid according to claim 23, having a content of transition metals of 5 to 30% of the weight of the catalytic solid, a magnesium content of 0.5% to 20% of the weight of the catalytic solid, and an aluminium content of 0.5 to 10% of the weight of the catalytic solid.
- 25. The catalytic solid according to claim 23, wherein the transition metals are in a molar ratio of 1 to 4.
- 26. The catalytic solid according to claim 23, wherein the halides of the two transition metals are chlorides.
- 27. A process for the polymerisation of at least one olefin, according to which a catalytic solid in accordance with claim 23 is contacted with said at least one olefin.
- 28. The process according to claim 27, wherein the olefin is ethylene.
Priority Claims (1)
Number |
Date |
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09200532 |
Jun 1992 |
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Parent Case Info
This application is a continuation, of application Ser. No. 08/072,943, Filed Jun 8, 1993, now abandoned.
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Continuations (1)
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Number |
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Parent |
72943 |
Jun 1993 |
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