Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-09-04
2002-08-27
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S010000, C528S009000
Reexamination Certificate
active
06441210
ABSTRACT:
The invention is related to a metal complex containing one or more silsesquioxane ligands. Metal complexes containing one or more silsesquioxane ligands are for instance known from FEHER F. J. et al., ‘Olefin Polymerization by Vanadium-Containing Polyhedral Oligometallasilsesquioxanes’, J. Am. Chem. Soc., 1991, 113, p. 3618-3619.
In this article a vanadium complex is described containing one silsesquioxane ligand. It is reported that this complex is active in the polymerisation of ethylene when it is activated with an aluminum containing co-catalyst.
It is now surprisingly discovered that metal complexes containing a new type of silsesquioxane ligand are also active in olefin polymerisation. The metal complex according to the invention has the formula
Z
y
(MA
x
B
q
)
b
(I),
wherein
Z is a silsesquioxane according to the formula
R
7−l
Si
7
O
12
YD
1+l
(II),
M is a metal from groups 3-6 of the Periodic System of the Elements and the lanthanides,
A is a monoanionic ligand bound to the metal,
B is a &pgr;-bound ligand,
y represents the number of silsesquioxane ligands and is 1-10,
b represents the number of metal groups and is 1-20,
q is 0,1 or 2,
x is the number of substituents A bound to the metal; the value of x depends on the metal used and is equal to the valency of the metal minus 1, 2, 3 or 4,
R is a substituent bound to Si,
Y is an atom from group 13 or 14 of the Periodic System of the Elements,
D is a group, directly bound to Y or Si with one atom from group 15 or 16 of the Periodic System of the Elements and l determines the amount of substituents R and atoms D and is equal to 0, 1, 2 or 3.
A further advantage of the metal complex according to the invention is that polyolefins having a narrow molecular weight distribution can be produced by using these metal complexes.
An other advantage of the metal complex according to the invention is that the metal complexes supported on a carrier material are active in the polymerisation of olefins without the presence of a scavenger.
From Braunstein P et al.: Journal of Organometallic Chemistry, vol. 551, no. 1-2, Jan. 30, 1998 (1998-01-30), page 125-131, metal complexes of the transition metals Ru and Os with thiol-substituted silsesquioxanes are known in which a C-containing spacer between the silsesquioxane and the metal-containing part is always present.
In the following the various components of the metal complex according to the invention will be discussed in more detail.
a) The Silsesquioxane Ligand Z
The silsesquioxane ligand Z is a ligand according to the formula
R
7−l
Si
7
O
12
YD
1+l
(II),
wherein
R is a substituent bound to Si,
Y is an atom from group 13 or 14 of the Periodic System of the Elements,
D is a group, directly bound to Y or Si with one atom from group 15 or 16 of the Periodic System of the Elements and
l determines the amount of substituents R and atoms D and is equal to 0, 1, 2 or 3.
The silsesquioxane ligand has a cubic structure with all but one Si atom and one atom Y at the corner positions and oxygen atoms connecting the Si and Y atoms. The oxygen atoms are located at the sides of the cubic structure.
A substituent R or an atom D is bound to each Si atom and an atom D is bound to the atom Y. The silsesquioxane ligand can contain 7-4 substituents R and 1-4 groups D.
The silsesquioxane ligand can be represented by the following structure:
In the metal complex according to the invention the silsesquioxane ligand is bound via one atom D to one metal atom. This means that a maximum of 4 metal atoms can be connected via a D atom to the silsesquioxane ligand.
In the metal complex according to the invention 1-10 silsesquioxane ligands can be present (represented by y in formula I).
Y is preferably 1.
R is a substituent bound to Si in the silsesquioxane ligand Z. The R groups can be the same or different and can for instance be hydrogen or an alkyl, aryl or silyl group. R is preferably cyclopentyl, cyclohexyl, cycloheptyl or hydrogen.
Y is an atom from group 13 or 14 of the Periodic System of the Elements and can, for instance, be C, Si, Ge, Sn, B or Al.
D is a group, directly bound to Y or Si with one atom from group 15 or 16 of the Periodic System of the Elements. D can, for instance, be O, S, NR
1
, PR
1
, N═ or P═, wherein R
1
is chosen from hydrogen, alkyl, aryl, silyl or stannyl groups.
Preferably the metal complex according to the invention contains silsesquioxane ligands according to the formula R
7
Si
7
O
12
YD. These silsesquioxane ligands can only be bound to one metal M with one atom D. In the silsesquioxane ligands Y is preferably Si.
Most preferably the metal complex according to the invention contains a silsesquioxane ligand according to the formula (RSi)
7
O
12
SiO. This ligand is bound to the metal M via the oxygen atom.
b) The Metal M
The metals in the complex are chosen from groups 3-6 of the Periodic Table of the Elements and the lanthanides (see the new IUPAC notation to be found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990). The metal atoms present in the metal complex according to the invention can be the same or different. In the metal complex according to the invention 1-20 metal atoms can be present (represented by b in formula I). Preferably b is 1.
Preferably M is a metal out of group 4 of the Periodic Table of the Elements.
c) The Mono-anionic Ligand A
The mono-anionic ligand A is bound to the metal. The ligands A can be the same or different and can, for example, be a hydrocarbon ligand containing 1-20 carbon atoms (such as alkyl, aryl, aralkyl, and the like). Examples of such hydrocarbon ligands are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl, and p-tolyl. A ligand A may also be a ligand which in addition to, or instead of, carbon and/or hydrogen contains one or more hetero atoms from groups 14-17 of the Periodic System of the Elements, a hetero atom not being bound directly to the Cp. Thus a ligand may be an N-, O-, and Cl-, or Si-containing group. Examples of ligands containing a hetero atom are trialkylsilyl, triarylsilyl, sulfide, diaryl amido, dialkyl amido, alkoxy or aryloxy groups.
A is preferably an alkyl- or aryl group.
The number of substituents A (represented by x in formula I) depends on the metal used and is equal to the valency of the metal minus 1, 2, 3 or 4. x is preferably 2.
d) The &pgr;-bonded Ligand B
The &pgr;-bonded ligand is bound to the metal M. The ligands B can be the same or different and can, for example, be an allyl, a cyclopentadienyl, an indenyl, a fluorenyl ligand or a boratabenzene ligand. The above mentioned ligands can be substituted with various substituents. For example with alkyl or aryl substituents containing 1-10 carbon atoms. The ligand B is preferably a substituted or non-substituted cyclopentadienyl ligand. The number of substituents B (represented by q in formula I) and is 0, 1 or 2 per metal atom present in the metal complex. q is preferably 1.
The metal complex according to the invention is preferably a metal complex according to the formula ZMA
x
B, wherein Z, M, A and B have the meaning as defined above and x is the number of substituents A bound to the metal; the value of x depends on the metal used and is equal to the valency of the metal minus 2.
The metal complex according to the invention can be supported on a carrier material. Examples of suitable carrier materials are any finely divided solid porous support material, including, but not limited to, MgCl
2
, Zeolites, mineral clays, inorganic oxides such as, for instance, talc, silica, alumina, silica-alumina, meso-porous silica, meso-porous alumosilica, meso-porous alumophospates, inorganic hydroxides, phosphates, sulphates, or resinous support materials such as polyolefins, including polystyrene, or mixtures thereof. These carriers may be used as such or modified, for example by silanes and/or aluminium alkyles and/or aluminoxane compounds.
Preferably the carrier material has a specific surface area of at least 10 m
2
per gram and a pore volume
Abbenhuis Hendrikus C. L.
Duchateau Robbert
Thiele Sven K. H.
Van Santen Rutger A.
Van Tol Maurits F. H.
DSM N.V.
Pillsbury & Winthrop LLP
Shaver Paul F.
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