Substituted polycyclic cyclopentadienes and method for their preparation
AssigneePolimeri Europa S.p.A.
InventorsPaolo Biagini, Diego Vigliarolo, Giampietro Borsotti, Roberto Santi
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Abstract
New polycyclic cyclopentadiene compounds having the formula (II) wherein the various substituents and symbols R1, R2, R3, R4, R5, R6, R7, Z1 and Z2 and “n” have the meaning specified in the description. These compounds can form metallocene complexes with transition metals, which have shown unusual properties in the (co)polymerization of ethylene and alpha-olefins in general.
Claims33
A polycyclic cyclopentadienyl compound having the following formula (II):
- 34
- wherein:
- each of the symbols R1, R2, R3, R4, R5, R6, R7, Z1 and Z2 independently represents hydrogen or an organic substituent having from 1 to 15 carbon atoms, and in addition, any one of said R or Z groups can be a divalent organic group further bound to another organic group having from 5 to 20 carbon atoms and comprising a cyclopentadienyl group, and
- “n” has any of the integer values from 1 to 10 extremes included;
- or a mixture of said compounds having formula (II).
The compound according to any of the previous claims, wherein, in formula (II), the symbols R1, R2, R3, R4, Z1 and Z2 all represent hydrogen and at least one of the symbols R5, R6, or R7, independently represent methyl or ethyl, preferably methyl.
The compound according to any of the previous claims, wherein, in formula (II), one of the groups R5, R6 or R7, preferably R5 or R7, is a divalent hydrocarbon or silane group having from 2 to 6 carbon atoms, further bound to a second cyclopentadienyl group having from 5 to 20 carbon atoms, preferably selected from cyclopentadienyl, indenyl, fluorenyl and homologous groups thereof.
The complex according to any of the previous claims from 7 to 11, wherein a group selected from said Z′ and Z″ in formula (X) is further covalently bound with the polycyclic cyclopentadienyl group deriving from the compounds having formula (II), bound, in the same formula (X), to the metal Mv, by means of a divalent hydrocarbon or silane having from 1 to 15, preferably from 2 to 6, carbon atoms, to form a so-called “bridged” structure.
A catalyst for the (co)polymerization of ethylene and other α-olefins comprising the following two components in contact with each other, or the product of their reaction:
- (i) at least one metallocene complex according to any of the previous claims from 7 to 17, on the condition that the metal Mv in the complex having formula (X) is a metal of groups 4 to 6 of the periodic table;
- (ii) a co-catalyst consisting of at least one organometallic compound of an element M′ different from carbon and selected from elements of groups 2, 12, 13 or 14 of the periodic table as defined above.
The catalyst according to any of the previous claims, wherein said component (ii) is a polymeric aluminoxane, preferably methylaluminoxane.
The catalyst according to any of the claims from 18 to 20, wherein said component (ii) consists of at least one compound or a mixture of organometallic compounds of M′ capable of reacting with the complex in component (i) by extracting therefrom a σ-bound group to form on the one hand, at least one neutral compound and on the other hand, an ionic compound consisting of a metallocene cation containing the metal Mv or Mq, and of an organic non-coordinating anion containing the metal M′, whose negative charge is delocalized on a multicentric structure.
The catalyst according to any of the previous claims from 23 to 25, wherein said component (ii) consists of an ionic-ionizing compound selected from the group of compounds having one of the following formulae:
- [(RC)xNH4−x]+[B(RD)4]−;
- B(RD)3;
- [Ph3C]+[B(RD)4]−;
- [(RC)3PH]+[B(RD)4]−;
- [Li]+[B(RD)4]−;
- [Li]+[Al(RD)4]−;
- wherein the deponent “x” is an integer ranging from 0 to 3;
- each RC group independently represents an alkyl or aryl radical having from 1 to 10 carbon atoms and each RD group independently represents an aryl radical partially or totally fluorinated, having from 6 to 20 carbon atoms.
The catalyst according to any of the previous claims from 24 to 26, wherein said component (ii) comprises, in addition to said ionic-ionizing compound, an aluminum trialkyl or an alkylaluminum halide represented by the following formula
- AlR9mX3−m
- wherein:
- R4 is a linear or branched C1-C8 alkyl group, or one of their mixtures,
- X is a halogen, preferably chlorine or bromine, and
- “m” is a decimal number ranging from 1 to 3 extremes included;
- with a ratio between Mv or Mq in component (i) and Al in the aluminum alkyl ranging from 1/10 to 1/1,000, preferably from 1/100 to 1/500.
A process for the (co)polymerization of α-olefins, both in continuous and batchwise, in one or more steps, 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° C., optionally in the presence of an inert diluent, characterized in that at least one α-olefin is put in contact, under the above conditions, with a catalyst according to one of the previous claims from 18 to 27.
The process according to any of the previous claims from 28 to 31, characterized in that it is carried out in solution or in suspension in a suitable inert liquid medium, consisting of an aliphatic or cycloaliphatic hydrocarbon having from 3 to 15 carbon atoms, or a mixture of these.
The process according to any of the previous claims from 28 to 32, characterized in that the concentration, in the polymerization mixture, either of the metal Mv of the complex having formula (X), or Mq of the complex having formula (XI), forming component (i) of said catalyst, ranges from 10−5 to 10−8 moles/liter.
Dependencies are inferred from the claim text.