Patent EA-003246-B1 (EA)
Title: Organometallic composition, catalytic composition active in the (co)polymerization of a-olefins, method for preparation the same and fluorinated organic compound
Inventor: SOMMMAZZI ANNA
IPC: C07F3/00
Filed: 1999-06-14
Abstract: 1. An organometallic composition, suitable as an activator of a metallocene complex of a metal of group 4 to form a (co) polymerization catalyst of alpha-olefins, characterized in that it comprises the reaction product between: (A) a fluorinated organic compound, comprising at least one di-unsaturated cycle with 5 or 6 carbon atoms, having the following formula (I): wherein: each Ri group (i being an integer from 1 to 7) is a substituent of the di-unsaturated cycle independently selected from hydrogen, fluorine and a fluorinated or non-fluorinated, aliphatic or aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally joined to a different Ri hydrocarbyl group to form a further cycle, on the condition that at least two, preferably at least three, of the groups R1, R2, R3 R4 or R5 are independently selected from the group consisting of: fluorine, or a fluorinated alkyl group having the formula -CF(R9R10), wherein each R9 or R10 group can have any of the above meanings of the Ri groups and at least one of them is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl ArF as defined below, or a fluorinated vinyl group VF as defined below, or a fluorinated aryl group ArF- substituted on the aromatic ring with at least two groups selected from fluorine, a -CF(R9R10) group as defined above or a different ArF group, or a fluorinated vinyl group Vr substituted on at least two positions of the double bond with groups selected from fluorine, a -CF(R9R10) group or an ArF group as defined above; the R8 group is hydrogen, -OH or together with said R5 group, it forms a carbonyl oxygen; and "m" can have the values of 0 or 1; (B) an organometallic compound having the following formula (II): M'RnX(p-n) (II) wherein: M' is a metal of group 2 or 13 of the periodic table of elements; each R is independently hydrocarbyl group, having from 1 to 10 carbon atoms; each X is a halogen atom; "p" is the valence of M' and is equal to 2 for group 2 and 3 for group 13, "n" is a decimal number ranging from 1 to p. 2. The organometallic composition according to claim 1, wherein said M' in formula (II) is Mg or Al and said X is chlorine or bromine. 3. The composition according to any of claims 1 or 2, wherein, in said formula (II), M' is Al, "p" = "n" = 3. 4. The composition according to any of the previous claims, wherein "m" in formula (I) is equal to zero. 5. The composition according to any of the previous claims, wherein, R5 in formula (I) is selected from fluorine or ArF. 6. The composition according to any of the previous claims, wherein, R8 in formula (I) is hydrogen. 7. The composition according to any of the previous claims from 1 to 5, wherein R8 in formula (I) is the -OH hydroxy group. 8. The composition according to any of the previous claims, wherein said fluorinated di-unsaturated compound has the following formula (IV): wherein: R5 and R8 have the same meaning as defined for formula (I); "y" and "z" independently have integer values ranging from 1 to 4, extremes included; the groups R11 and R12 are independently substituents of hydrogen atoms of the respective aromatic ring in one or more of the four positions available on each one, and are selected from fluorine or a fluorinated or non-fluorinated, aliphatic or aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally joined to a different R11 or R12 hydrocarbyl group, respectively, to form another cycle, on the condition that at least 3, preferably at least 4, of the groups R5, R11 and R12 are independently selected from the group consisting of: fluorine, or a fluorinated alkyl group having the formula -CF(R9R10) wherein each R9 or R10 group can have any of the above meanings of Ri groups and at least one of these is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl ArF- as defined below, or a fluorinated vinyl group VF as defined below, or a fluorinated aryl ArF substituted on the aromatic ring with at least two groups selected from fluorine, a -CF(RsRio) group as defined above or a different Arr group, or a fluorinated vinyl group VF substituted on at least two positions of the double bond with groups selected from fluorine, a -CF(R9R10) group as defined above or another ArF group ArF. 9. The composition according to claim 8, wherein, in formula (IV), all the eight R11 and R12 are equal to each other and are trifluoromethyl, or, preferably, fluorine. 10. The composition according to any of the previous claims, wherein components (A) and (B) are in such a quantity that the ratio between M' in the organometallic compound having formula (II) and said di-unsaturated cyclic compound having formula (I) or (IV) ranges from 0.1 to 100, preferably from 1 to 10. 11. A catalytic composition active in the (co)polymerization of a-olefins comprising the following components in contact with each other: (i) the organometallic composition according to any of the previous claims from 1 to 10, (ii) a metallocene complex of a metal M of group 4 of the periodic table, comprising at least one cyclopentadienyl group, optionally substituted, penta-apto ((<5>-) coordinated to said metal. 12. The catalytic composition according to claim 11, wherein said components (i) and (ii) are in such a quantity that the molar ratio (A)/(M), wherein (M) are the moles of metal in component (ii) and (A) the moles of di-unsaturated compound in the organometallic composition (i), ranges from 0.5 to 50, preferably from 1 to 10. 13. The catalytic composition according to any of the previous claims 11 or 12, wherein said metallocene complex (ii) has the following formula (III): wherein: - M represents a metal selected from Ti, Zr or Hf; - each RA independently represents a group of an anionic nature bound to the metal M, different from cyclopentadienyl or substituted cyclopentadienyl; - "w" is an index which can have integer values 1 or 2 depending on whether the valence of M is 3 or 4; - A represents an anionic ligand having from 5 to 30 carbon atoms; - R8 regardless of the nature of the other substituents, can have any of the meanings previously specified for the ligand A and for the group RA, and can also be connected with said group A by means of a divalent organic group having from 1 to 15 carbon atoms, to form a so-called "bridged" metallocene complex. 14. The catalytic composition according to any of the previous claims from 11 to 13, wherein, in said metallocene complex having formula (III), the groups RA and RB are independently selected from hydride, chloride, bromide, a hydrocarbyl or halogenated hydrocarbyl radical, different from cyclopentadienyl, having from 1 to 30, preferably from 1 to 10, carbon atoms, a phosphonate, sulfonate or carbonate group, an alkoxy, carboxy or aryloxy group having from 1 to 20, preferably from 1 to 10, carbon atoms, an amide group, an organic group having from 1 to 20, preferably from 1 to 10, carbon atoms, bound to the metal M with an amide nitrogen atom, an organic group having from 1 to 20, preferably from 1 to 10, carbon atoms, bound to the metal M with a silicon atom. 15. The catalytic composition according to any of the previous claims from 11 to 13, wherein said metallocene complex having formula (III) is a bis-cyclopentadienyl complex having the following formula (V): wherein: M represents a metal selected from titanium, zirconium or hafnium; each A' or A'' independently represents an organic group containing an h<5>-cyclopentadienyl ring of an anionic nature, coordinated to the metal M; each R' or R'' independently represents a group of an anionic nature s-bound to the metal M, selected from hydride, chloride, bromide, a C1.-C20 alkyl or alkylaryl group, a C3-C20 alkylsilyl group, a C5-C20 cycloalkyl group, a C6-C20 aryl or arylalkyl group, a C6-C20 alkoxyl or thioalkoxyl group, a C2-C20 carboxylate or carbamate group, a C2-C20 dialkylamide group and a C4-C20 alkylsilylamide group. 16. The catalytic composition according to the previous claim 15, wherein, in said metallocene complex having formula (V), the groups A' and A'' are cyclopentadienyl, indenyl, or fluorenyl, and their homologous products, wherein one or more carbon atoms of the molecular skeleton are substituted with a linear or branched, alkyl, aryl or alkylsilyl radical having from 1 to 10 carbon atoms, preferably methyl. 17. A method for the preparation of the catalytic composition according to any of the claims from 11 to 16, comprising putting components (i) and (ii) as previously defined in claim 11, in contact with each other, so that the ratio (A) / (M), wherein (M) are the moles of metallocene complex having formula (III) and (A) the moles of fluorinated compound having formula (I), ranges from 0.5 to 50, preferably from 1 to 10. 18. The method according to the previous claim 17, wherein said components (i) and (ii) are put in contact and reacted with each other in an inert diluent and at temperatures ranging from room temperature up to 150 degree C, for times varying from 1 to 30 minutes. 19. The method according to any of the previous claims 17 or 18, wherein said metallocene complex in component (ii) consists of a complex having formula (III) wherein RA and RB are both different from alkyl, or a complex having formula (V) wherein R' and R'' are both different from alkyl, comprising the step of reacting said metallocene complex with a quantity of said organometallic compound having formula (II) sufficient to effect the alkylation of said metallocene complex. 20. The method according to claim 19, wherein the metal M' in the compound having formula (II) is Mg or, preferably, Al and the atomic ratio M'/M ranges from 3 to 10. 21. A process for the (co) polymerization of one or more cx-olefins, both in continuous and batch, in one or more steps in suitable reactors, at low (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa) pressure at temperatures ranging from 20 to 240 degree C, optionally in the presence of an inert d