The present invention relates to metal coordination complexes having constrained geometry. The invention also relates to certain novel addition polymerization catalysts comprising such metal complexes having constrained geometry. Furthermore, the invention relates to methods for the polymerization of addition polymerizable monomers and to the resulting polymers.
Because of the unique exposure of the active metal site of the metal coordination complexes having constrained geometry, catalysts resulting therefrom have unique properties. Under certain conditions, the catalysts of the invention are capable of preparing novel olefin polymers having previously unknown properties due to their unique facile abilities to polymerize xcex1-olefins, diolefins, hindered vinylidene aliphatic monomers, vinylidene aromatic monomers and mixtures thereof.
Numerous metal coordination complexes are known in the art including such complexes involving monocyclopentadienyl groups and substituted monocyclopentadienyl groups. The present metal coordination complexes differ from those previously known in the art due to the fact that the metal is bound to a delocalized substituted xcfx80-bonded moiety in a manner so as to induce a constrained geometry about the metal. Preferably the metal is bound to a cyclopentadienyl, substituted cyclopentadienyl or similar group by both a xcex75-bond and a bridging linkage including other ligands of the metal. The complexes also preferably include metals having useful catalytic properties.
Also previously known in the art are transition metal coordination complexes known as tucked complexes. Such complexes are described in Organometallics 6, 232-241 (1987).
In U.S. Ser. No. 8,800, filed Jan. 30, 1987 (published in equivalent form as EP 277,004) there are disclosed certain bis(cyclopentadienyl) metal compounds formed by reacting a bis(cyclopentadienyl) metal complex with salts of Bronsted acids containing a noncoordinating compatible anion. The reference discloses the fact that such complexes are usefully employed as catalysts in the polymerization of olefins. For the teachings contained therein U.S. Ser. No. 8,800 and EP 277,004 are herein incorporated in their entirety by reference thereto.
Previous attempts to prepare copolymers of vinylidene aromatic monomers and xcex1-olefins, in particular copolymers of styrene and ethylene, have either failed to obtain substantial incorporation of the vinylidene aromatic monomer or else have achieved polymers of low molecular weight. In Polymer Bulletin, 20, 237-241 (1988) there is disclosed a random copolymer of styrene and ethylene containing 1 mole percent styrene incorporated therein. The reported polymer yield was 8.3xc3x9710xe2x88x924 grams of polymer per micromole titanium employed.
It has now been discovered that previously known addition polymerization catalysts are incapable of high activity and polymerization of numerous monomers because they lack constrained geometry.
It would be desirable if there were provided novel complexes of groups 3 (other than scandium), 4-10 and the lanthamides having constrained geometry.
Additionally it would be desirable if there were provided novel catalysts for addition polymerizations comprising novel complexes of groups 3 (other than scandium), 4-10 and the lanthamides having constrained geometry.
Furthermore, it would desirable if there were provided a process for the preparation of polymers of addition polymerizable monomers using novel catalysts comprising complexes of groups 3 (other than scandium), 4-10 and the lanthamides having constrained geometry.
Finally, it would be desirable if there were provided novel polymers of addition polymerizable monomers that may be prepared by an addition polymerization process using catalysts comprising novel complexes of groups 3 (other than scandium), 4-10 and the lanthamides having constrained geometry.
In one aspect the present invention relates to a metal coordination complex having constrained geometry. More particularly it relates to such coordination complexes that are usefully employed in combination with activating cocatalyst compounds or mixtures of compounds to form a catalytic system usefully employed in the polymerization of addition polymerizable monomers, especially ethylenically unsaturated monomers.
In another aspect the present invention relates to a process for preparing certain components of the above metal coordination complexes having constrained geometry and to the precursor compounds necessary therefor.
In yet another aspect the present invention relates to a process for preparing addition polymers, especially homopolymers and copolymers of olefins, diolefins, hindered aliphatic vinyl monomers, vinylidene aromatic monomers and mixtures of the foregoing and to the resulting polymer products.
According to the present invention there is provided a metal coordination complex comprising a metal of group 3 (other than scandium), 4-10 or the lanthamide series of the periodic table of the elements and a delocalized _-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal between the centroid of the delocalized, substituted xcfx80-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar xcfx80-bonded moiety lacking in such constrain-inducing substituent, and provided further that for such complexes comprising more than one delocalized, substituted xcfx80-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted xcfx80-bonded moiety.
In addition there is provided a metal coordination complex corresponding to the formula: 
wherein:
M is a metal of group 3 (other than scandium), 4-10, or the lanthamide series of the periodic table of the elements;
Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an xcex75 bonding mode to M;
Z is a moiety comprising boron, or a member of group 14 of the periodic table of the elements, and optionally sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z together form a fused ring system;
X independently each occurrence is an anionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms;
n is 0, 1, 2, 3, or 4 depending on the valence of M; and
Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, optionally Y and Z together form a fused ring system.
There is also provided according to the present invention a process for preparing a metal coordination complex corresponding to the foregoing formula I comprising the steps of:
A) contacting a metal compound of the formula MXn+2 or a coordinated adduct thereof with a dianionic salt compound corresponding to the formula:
(L+x)y(Cp*-Z-Y)xe2x88x922xe2x80x83xe2x80x83(II) 
or 
((LXxe2x80x3)+x)y(Cp*-Z-Y)xe2x88x922xe2x80x83xe2x80x83(III) 
wherein:
L is a metal of group 1 or 2 of the periodic table of the elements,
Xxe2x80x3 is fluoro, chloro, bromo, or iodo,
x and y are either 1 or 2 and the product of x and y equals 2, and
M, X, Cp, R, and Y are as previously defined; and
B) recovering the resulting product.
Further there is provided a process for preparing a metal coordination complex corresponding to the foregoing formula I comprising the steps of:
A) contacting a metal compound of the formula MXn+1 or a coordinated adduct thereof with a dianionic salt compound corresponding to the formulas II or III;
B) oxidizing the metal to a higher oxidation state by contacting the reaction product of step A) with a noninterfering oxidizing agent; and
C) recovering the resulting product.
There is also provided a catalyst useful in addition polymerizations comprising the following components:
a) a metal coordination complex comprising a metal of group 3 (other than scandium), 4-10 or the lanthamide series of the periodic table of the elements and a delocalized xcfx80-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal between the centroid of the delocalized, substituted xcfx80-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar xcfx80-bonded moiety lacking in such constrain-inducing substituent, and provided further that for such complexes comprising more than one delocalized, substituted xcfx80-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted xcfx80-bonded moiety; and
b) an activating cocatalyst.
In a further embodiment of the present invention there is provided a catalyst useful in addition polymerizations comprising the following components:
a) a metal coordination complex corresponding to the formula I, and
b) an activating cocatalyst.
Even further according to the present invention there is provided a polymerization process comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst comprising:
a) a metal coordination complex comprising a metal of group 3 (other than scandium), 4-10 or the lanthamide series of the periodic table of the elements and a delocalized xcfx80-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal between the centroid of the delocalized, substituted xcfx80-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar xcfx80-bonded moiety lacking in such constrain-inducing substituent, and provided further that for such complexes comprising more than one delocalized, substituted xcfx80-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted xcfx80-bonded moiety; and
b) an activating cocatalyst.
Further according to the present invention there is provided an addition polymerization process comprising the steps of;
A) contacting a mixture comprising one or more addition polymerizable monomers under polymerization conditions in the presence of a catalyst comprising a metal coordination complex corresponding to the formula I and an activating cocatalyst; and
B) recovering the resulting polymer.
Further still according to the present invention there is provided a polymer comprising in interpolymerized form one or more addition polymerizable monomers prepared by contacting an addition polymerizable monomer or mixture thereof under addition polymerization conditions with a catalyst comprising:
a) a metal coordination complex comprising a metal of group 3 (other than scandium), 4-10 or the lanthamide series of the periodic table of the elements and a delocalized xcfx80-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at, the metal between the centroid of the delocalized, substituted xcfx80-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar xcfx80-bonded moiety lacking in such constrain-inducing substituent, and provided further that for such complexes comprising more than one delocalized, substituted xcfx80-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted xcfx80-bonded moiety; and
b) an activating cocatalyst.
In a still further embodiment of the present invention there is provided a polymer comprising in polymerized form one or more addition polymerizable monomers prepared by contacting an addition polymerizable monomer or mixture thereof under addition polymerization conditions with a catalyst comprising the following components:
a) a metal coordination complex corresponding to the formula I and an activating cocatalyst.
In still further embodiments there are provided ElPE polymers which are highly elastic, interpolymers of ethylene and one or more olefins other than ethylene.
In addition there are provided pseudo-random interpolymers of an xcex1-olefin, particularly ethylene and a vinylidene aromatic monomer, a hindered aliphatic vinylidene monomer, or a mixture thereof.
The complexes of the invention are usefully employed as catalysts for addition polymerization processes to prepare polymers that are useful as molded articles, films for packaging applications, and foams for cushioning applications; and in the modification of synthetic and naturally occuring resins. The complexes may also be used as catalysts for hydrogenations, catalytic cracking processes, and in other industrial applications.