Metal complex containing one or more silsesquioxane ligands

Details Metal complex containing one or more silsesquioxane ligands Metal complex containing one or more silsesquioxane ligands

2000-12-20

2004-04-20

Lu, Caixia (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S114000, C526S133000, C526S134000, C502S158000, C556S010000

Reexamination Certificate

active

06723806

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.
In this article it is also reported that a metal complex containing two vanadium atoms and two silsesquioxane ligands is not active in the polymerisation of ethylene.
It is now surprisingly discovered that a metal complex with the formula
Z
y
(MA
x
)
b
  (I)
wherein Z is a silsesquioxane ligand according to the formula
(RSiO
1.5
)
m
O
n
B
q
  (II)
which is connected within one corner to one atom M or to two M atoms by one bridging oxygen atom.
M is a metal from groups 3-10 of the Periodic System of the Elements and the lanthanides,
A is a ligand bonded to the metal,
y represents the number of silsesquioxane ligands and is 2-10,
b represents the number of metal groups and is 2-20,
x is the number of ligands A bonded to the metal; the value of depends on the metal used and is equal to the valency of the metal minus 1, 2, 3 or 4,
R is a substituent bonded to each Si,
m is an integer and is equal to 5-19,
n is 1.5 or 3,
B is a group bonded to an oxygen atom that has one bond to Si and
q is 0, 1 or 2
is active in the polymerisation of olefins.
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.
Other advantages of the metal complex according to the invention are that the metal complex is active in the polymerisation of olefins even without the presence of a cocatalyst and that the metal complexes supported on a carrier material are active in the polymerisation of olefins without the presence of a scavenger.
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
(RSiO
1.5
)
m
O
n
B
q
  (II)
wherein
R is a substituent bonded to each Si,
m is an integer and is equal to each Si,
n is 1.5 or 3,
B is a group bonded to an oxygen atom that has one bond to Si and
q is 0, 1 or 2.
The silsesquioxane has a cubic or prismatic (trigonal, hexagonal or pentagonal) structure with a Si atom at each corner and oxygen atoms connecting the Si atoms. The silsesquioxane can, for example, be represented by the following structures:
In the silsesquioxane ligands 1 or 2 of the Si-atoms are not present so that it is at this place bonded to the metal atom or atoms. This place is defined as a “corner”. It is bonded to a metal atom via at least one oxygen atom. In the silsesquioxane ligand, the Si-atom is not present at one or two of the corners of the silsesquioxane polygonal structure. A Si absent corner is defined as the “corner”. The “corner” is bonded to a metal atom via at least one oxygen atom. The oxygen atoms that are not involved in bonding with the metal atom(s) are bonded to a group B. The B groups can be the same or different and can for instance be hydrogen or an alkyl, aryl, silyl, germyl or stannyl group. The silsesquioxane ligands are connected within one corner to one atom M or to two atoms M by one bridging oxygen atom. In the metal complex according to formula I, Z
y
(MA
x
)
b
, y is in the range 2-10, i.e. 2-10 silsesquioxane ligands can be present. In the metal complex according to the invention 2-10 silsesquioxane ligands can be present (represented by y in formula I).
R is a substituent bonded to each Si of 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.
Preferably the metal complex according to the invention contains silsesquioxane ligands according to the formulas
(RSiO
1.5
)
7
O
1.5
, (RSiO
1.5
)
7
O
1.5
B or (RSiO
1.5
)
7
O
1.5
B
2
wherein R is a substituent bonded to each Si and B is a group bonded to an oxygen atom that has one bond to Si. More preferably the metal complex according to the invention contains silsesquioxane ligands according to the formula
(RSiO
1.5
)
7
O
1.5
The silsesquioxane ligands mentioned above are represented by the following structures
b) The metal M
The metals in the complex are chosen from groups 3-10 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 formula I, Z
y
(MA
x
)
b
, b is in the range 2-20, i.e. 2-20 metal atoms can be present. M is preferably chosen from groups 3-6 of the Periodic Table of the Elements. More preferably M is a metal out of group 4 of the Periodic Table of the Elements.
c) The ligand A
The ligand A is bonded to the metal. The ligands A can be the same or different and can, for example, be a hydrocarbon substituent containing 1-20 carbon atoms (such as alkyl, aryl, aralkyl, and the like). Examples of such hydrocarbon substituents are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl, and p-tolyl. 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 a cyclopentadienyl (Cp) group. Thus a ligand A may be an N-, O-, and Cl-, or Si-containing group. Examples of ligands containing a hetero atom are alkoxy, aryloxy or dialkyl amido groups.
A is preferably an alkyl- or aryl group. The number of ligands 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. When the silsesquioxane ligand is bound to the metal with 3 oxygen atoms the number of ligands A on the metal is equal to the valency of the metal minus 3. When the silsesquioxane ligand is bound to the metal with 2 oxygen atoms the number of ligands A on the metal is equal to the valency of the metal minus 2. When the silsesquioxane ligand is bound to the metal with 1 oxygen atom the number of ligands A on the metal is equal to the valency of the metal minus 1.
Preferably the metal complex according to the invention is a bimetallic complex according to the formulas
or
wherein M, A, Z and x have the meaning as defined above.
Most preferably the metal complex according to the invention is a bimetallic complex according to formula
wherein M, A, Z and x have the meaning as defined above.
Within these metal complexes the metals and the silsesquioxane ligands can be bound to each other in several ways. Examples of possible bonding structures are given below. In these structures only a part of the whole silsesquioxane ligand is shown. The rest of the ligand is mentioned Z*.
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 of at least 0.1 ml per

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