Dinuclear complexes and polymerization catalysts therefrom

Details Dinuclear complexes and polymerization catalysts therefrom Dinuclear complexes and polymerization catalysts therefrom

1999-01-20

2001-05-22

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S001000, C556S012000, C556S043000, C556S053000, C556S054000, C556S058000, C534S015000, C502S103000, C502S117000, C526S160000, C526S943000

Reexamination Certificate

active

06235917

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to certain Group 3, 4 or Lanthanide metal complexes possessing two metal centers and to polymerization catalysts obtained therefrom. In one form this invention relates to such metal complexes per se. In another embodiment of the claimed invention, the complexes can be activated to form catalysts for the polymerization of olefins. Also included in the invention are processes for preparing such complexes and methods of using the catalysts in addition polymerizations.
Biscyclopentadienyl Group 4 transition metal complexes in which the metal is in the +4, +3 or +2 formal oxidation state, and olefin polymerization catalysts formed from such by combination with an activating agent, for example, alumoxane or ammonium borate, are well known in the art. Thus, U.S. Pat. No. 3,242,099 describes the formation of olefin polymerization catalysts by the combination of biscyclopentadienyl metal dihalides with alumoxane. U.S. Pat. No. 5,198,401 discloses tetravalent biscyclopentadienyl Group 4 transition metal complexes and olefin polymerization catalysts obtained by converting such complexes into cationic forms in combination with a non-coordinating anion. Particularly preferred catalysts are obtained by the combination of ammonium borate salts with the biscyclopentadienyl titanium, zirconium or hafnium complexes. Among the many suitable complexes disclosed are bis(cyclopentadienyl)zirconium complexes containing a diene ligand attached to the transition metal through &sgr;-bonds where the transition metal is in its highest formal oxidation state. R. Mülhaupt, et al.,
J. Organomet. Chem.,
460,191 (1993), reported on the use of certain binuclear zirconocene derivatives of dicyclopentadienyl-1,4-benzene as catalysts for propylene polymerization.
Constrained geometry metal complexes, including titanium complexes, and methods for their preparation are disclosed in U.S. application Ser. No. 545,403, filed Jul. 3,1990 (EP-A-416,815); U.S. Pat. Nos. 5,064,802, 5,374,696, 5,055,438, 5,057,475, 5,096,867, and 5,470,993.
Metal complexes of the constrained geometry type containing two metal centers joined by means of a dianionic ligand separate from and unconnected to the ligand groups in such complexes that contain delocalized &pgr;-electrons, are previously taught, but not exemplified, in U.S. Pat. No. 5,055,438.
SUMMARY OF THE INVENTION
The present invention relates to dinuclear metal complexes corresponding to the formula:
wherein:
M and M′ are independently Group 3, 4, 5, 6, or Lanthanide metals;
L, L′, W, and W′, independently, are divalent groups having up to 50 nonhydrogen atoms and containing an aromatic &pgr;-system through which the group is bound to M, said L and W also being bound to Z, and said L′ and W′ also being bound to Z′;
Z and Z′ independently are trivalent moieties comprising boron or a member of Group 14 of the Periodic Table of the Elements, and optionally also comprising nitrogen, phosphorus, sulfur or oxygen, said Z and Z′ having up to 20 atoms not counting hydrogen;
X and T independently each occurrence are anionic ligand groups having up to 40 atoms exclusive of the class of ligands containing an aromatic &pgr;-system through which the group is bound to M or M′, or optionally two X groups or two T groups together form a C
4-40
conjugated or nonconjugated diene optionally substituted with one or more hydrocarbyl, silyl, halocarbyl, or halohydrocarbyl groups;
X′ and T′ independently each occurrence are neutral ligating compound having up to 20 atoms other than neutral diene compounds;
Q is a divalent anionic ligand group bound to both Z and Z′, said Q having up to 20 nonhydrogen atoms;
w and w′ are independently 0 or 1;
x and t are independently integers from 0 to 3, selected to provide charge balance; and
x′ and t′ are independently numbers from 0 to 3.
Additionally according to the present invention there is provided a composition of matter useful as an addition polymerization catalyst comprising:
1) at least one dinuclear metal complex (I) as previously disclosed, and
2) one or more activating cocatalysts,
the molar ratio of 1) to 2) being from 1:10,000 to 100:1, or
the reaction product formed by converting 1) to an active catalyst by use of an activating technique.
Further additionally according to the present invention there is provided a process for polymerization of one or more addition polymerizable monomers comprising contacting said monomer or a mixture of said monomers with a catalyst comprising the aforementioned composition of matter.
The invented catalyst compositions allow the preparation of mixtures of polymers from a single monomer or mixture of monomers thereby forming directly a polymer blend in the reactor. This result is accentuated where different metals, different metal valencies or different ligand groups attached to the two metal centers are employed. Alternatively, the invention allows for increased incorporation of long chain branching in a polymer formed from a single monomer, especially ethylene, or a mixture of monomers, due to selection of one metal center adapted to forming oligomeric products terminated by vinyl functionality in combination with a second metal center adapted to form high molecular weight polymers or adapted to long chain &agr;-olefin incorporation into a polymer.
DETAILED DESCRIPTION
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
In all of the forgoing and succeeding embodiments of the invention, desirably, when w and w′ are both 1, two X and two T groups together are a diene or substituted diene. Further preferred compounds correspond to the formula:
wherein
Z, Z′, M, M′, X, X′, T, T′, w, w′, x, x′, t, and t′ are as previously defined;
Cp and Cp′, independently are cyclic C
5
R′
4
groups bound to Z or Z′ respectively and bound to M or M′ respectively by means of delocalized &pgr;-electrons, wherein R′, independently each occurrence, is hydrogen, hydrocarbyl, silyl, halo, fluorohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, N,N-di(hydrocarbylsilyl)amino, N-hydrocarbyl-N-silylamino, N,N-di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylsulfido; or hydrocarbyloxy-substituted hydrocarbyl, said R′ having up to 20 nonhydrogen atoms, and optionally, two such R′ substituents may be joined together thereby causing Cp or Cp′ to have a fused ring structure; and
Q is a linear or cyclic hydrocarbylene, or silane group or a nitrogen, oxygen, or halo substituted derivative thereof, said Q having up to 20 nonhydrogen atoms.
More preferred metal coordination complexes according to the present invention correspond to the formula:
wherein:
R′ each occurrence is hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, halohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, di(hydrocarbylsilyl)amino, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylsulfido; or hydrocarbyloxy-substituted hydrocarbyl, said R′ having up to 20 nonhydrogen atoms, and optionally, two R′ groups together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring thereby forming a fused ring structure, or R′ in one occurrence per cyclopentadienyl system is a covalent bond to Q;
Z″ independently each occurrence is a trivalent group selected from SiR*, CR*, SiR*SiR*
2
, CR*CR*
2
, CR*SiR*
2
, CR*
2
SiR*, or GeR*; wherein R* each occurrence is independently hydrogen, hydrocarbyl, silyl, halogenated alkyl, or halogenated aryl, said R* having up to 12 non-hydrogen atoms;
Z′″ independently each

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