Patent EA-002597-B1 (EA)
Title: Vanadium composition complex, its production, catalyst system for the (co)polymerization of alpha-olefins and process for making thereof
Inventor: MASI FRANCESCO
IPC: C07C57/52
Filed: 1999-11-02
Abstract: 1. A Vanadium complex having general formula (I) "(I)" (RCOO)nVXpLm wherein R is a monofunctional hydrocarbon radical having from 1 to 20 carbon atoms and from 1 to 6 halogen atoms, selected from chlorine and bromine; X is chlorine or bromine; L is an electron donor; p+n = 3, 4 or 5; n is greater than or equal to 1; m is between 0 and 3. 2. The Vanadium complex according to claim 1, wherein R is a monofunctional hydrocarbyl radical containing from 1 to 6 chlorine atoms. 3. The Vanadium complex according to claim 1, wherein X is chlorine. 4. The complex according to claim 1, wherein n+p = 3. 5. The complex according to claim 1, wherein R-COO is    wherein R1, R2, R3, R4 and R5, the same or different, are selected from H, Cl or Br, alkyls, cycloalkyls, aryls, arylalkyls, alkylaryls or alkyls, cycloalkyls, aryls, arylalkyls, alkylaryls containing chlorine or bromine, with the proviso that at least one of the R1-R5 residues is selected from chlorine or bromine, or an alkyl, cycloalkyl aryl, arylalkyl, alkylaryl group containing chlorine or bromine; q varies from 0 to 10. 6. The complex according to claim 1, wherein R-COO is    wherein R1, R2, R3, R4 have the meaning defined above, r and s vary independently from 0 to 5, with the restriction that r + s are less than or equal to 5. 7. The complex according to claim 1, wherein R-COO is    wherein: Z, R1, R2, R3, R4, R5, R6, the same or different, are selected from H, Cl, Br, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, alkyls, cycloalkyls, aryls, arylalkyls, alkylaryls containing chlorine or bromine, with the proviso that at least one of the Z and R1-R6 residues is chlorine or bromine or an alkyl, cycloalkyl aryl, arylalkyl, alkylaryl group containing chlorine or bromine; t and u independently vary from 0 to 10, preferably from 0 to 2. 8. A process for the preparation of the Vanadium complexes having general formula (I) which comprises: a) reaction of a Tallium (Tl) salt having the general formula RCOOTl, wherein R has the meaning defined above, with a Vanadium halide, preferably VCl3 in an aliphatic or aromatic, ether or chlorinated, hydrocarbon solvent, alone or in a mixture, preferably selected from THF and dimethoxyethane, at temperatures ranging from 0 to 50 degree C, preferably from 15 to 30 degree C, for a time ranging from 30 minutes to 6 hours, preferably from 1 to 4 hours; b) separation, preferably filtration, of the Tl halide formed by the reaction; c) isolation of the Vanadium complex. 9. A catalytic system for the (co)polymerization of alpha -olefins consisting of: (a) Vanadium complex having general formula (I); (b) organo Aluminum derivative having general formula (II) AlRnXm, wherein R is a C1-C20 alkyl group, X is chlorine or bromine, and n+m= 3, with the exclusion of the compound having n= 0; c) optionally a reactivator 10. The catalytic system according to claim 9 wherein X is chlorine. 11. The catalytic system according to claim 9 wherein the reactivator (c) is a chlorinated compound. 12. The catalytic system according to claim 9 wherein the Vanadium complex (I) has general formula (Ia) (CCl3(-CH2)nCOO)3V, wherein n is between 0 and 2. 13. The catalytic system according to claim 13, wherein the organo Aluminum derivative (II) has the general formula AlR3, wherein R is a C1-C20 alkyl group. 14. The catalytic system according to claim 14, wherein R is isobutyl. 15. The catalytic system according to claim 14, wherein the reactivator is absent. 16. A process for the (co)polymerization of alpha-olefins in liquid phase, at low or medium pressure, at a temperature ranging from -5 degree C to 75 degree C, characterized in that the above (co)polymerization is carried out in the presence of the catalytic system according to claim 9.