Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1994-01-19
1995-12-26
Nagumo, Mark
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526129, 526154, 526123, 526351, 526352, 5261242, 5261245, 502152, C08F 452, C08F 1006, C08F 1002
Patent
active
054789010
DESCRIPTION:
BRIEF SUMMARY
This invention relates to the polymerisation of olefins, in particular 1-olefins such as ethylene and/or propylene, using as catalysts pi-arene complexes of lanthanide metals and to supported pi-arene complexes of lanthanide metals which are especially suitable as catalysts in such polymerisations.
Pi-complexes of aromatic compounds (arenes) and lanthanide metals in which the atoms of the lanthanides are in the zero valence state are known, for example, from published European Patent Specification No. 0295829 A which describes a range of such compounds and their use in chemical vapour deposition techniques.
The present invention is based on our discovery that pi-arene complexes of lanthanide metals carried on supports, particularly inorganic oxide or halide supports, are active as olefin polymerisation catalysts.
Accordingly, the present invention provides an olefin polymerisation catalyst comprising a pi-arene complex of one or more lanthanide metals carried on or reacted onto the surface of a solid support.
The invention includes a method of polymerising at least one olefin monomer which comprises bringing the olefin monomer(s) into contact with a catalytic amount of an olefin polymerisation catalyst comprising a pi-arene complex of one or more lanthanide metals carried on or reacted onto the surface of a solid support, thereby bringing about polymerisation of the olefin monomer(s).
The invention further includes the use of an olefin polymerisation catalyst comprising a pi-arene complex of one or more lanthanide metals carried on or reacted onto the surface of a solid support, as a catalyst in the polymerisation or copolymerisation of olefins.
The pi-arene complexes of lanthanide metals used in this invention are materials in which occupied pi-orbitals (bonding or antibonding) of an arene molecule interact with the available outer orbitals of a lanthanide metal atom. Most usually the arene is a carbocylic, typically a benzenoid, arene compound.
Particularly useful arenes include hydrocarbyl substituted benzenes in which there can be one or more, for example two or three, such hydrocarbyl substituents. Suitable benzenoid arene compounds can be selected from those of the formulae (Ia): ##STR1## where
R.sub.1 is a hydrocarbyl group;
R.sub.2 and R.sub.3 are each independently a hydrogen atom or a hydrocarbyl group; and
R.sub.4 is a hydrogen atom or, when R.sub.2 and R.sub.3 are both hydrogen atoms, a hydrocarbyl group.
Thus arenes of the formula I(a) include monohydrocarbyl substituted, 1,3- and 1,4-di-hydrocarbyl substituted and 1,3,5-trihydrocarbyl substituted benzenes. Further suitable arenes include compounds selected from those of the formula (Ib): ##STR2## where
each R.sub.5 is a hydrocarbyl group;
n is 0, 1 or 2; and
A is a group of one of the formulae: ##STR3## where
R.sub.6 is a hydrocarbyl group;
m is 0, 1 or 2; and
l is 0 or 1.
In particular, arenes of the formula (Ib) include naphthalene and hydrocarbyl substituted naphthalenes.
Hydrocarbyl substituents in the arenes of the pi-complexes, used in this invention are particularly alkyl groups typically C.sub.1 to C.sub.10, more usually C.sub.1 to C.sub.6, alkyl groups e.g. methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl and tert-butyl groups. Particularly suitable arenes include toluene and 1,3,5-tri-tert-butyl benzene (TTBB).
Most usually, the pi-complex will be a 2:1 (molecular) arene:lanthanide complex. We believe that such complexes exist primarily as arene:lanthanide:arene `sandwich` compounds. In such 2:1 pi-complexes the lanthanide metal atom is (formally) in the zeroth valence state. It is certain such complexes that form the subject matter of EP 0295829 A referred to above. Accordingly, the 2:1 complexes will typically have the formula (II):
each An is independently a molecule of an arene, particularly one of
Ld is an atom of a lanthanide metal.
The lanthanide metal used in the complex can be any lanthanide metal from lanthanum (La), Atomic No 57) to Lutetium (Lu, atomic No 71) in the Periodic Table. Particularly suitable complexes incl
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Jones Peter J. V.
Segal John A.
Whyman Robin
BASF - Aktiengesellschaft
Nagumo Mark
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