Olefin polymerization comprising group 5 transition metal...

Details Olefin polymerization comprising group 5 transition metal... Olefin polymerization comprising group 5 transition metal...

1998-10-23

2001-05-15

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S169200, C526S172000

Reexamination Certificate

active

06232416

ABSTRACT:

TECHNICAL FIELD
This invention relates to organometallic compounds comprising a Group 15 polyanionic ancillary ligand covalently bound to a Group 5 metal center, particularly those suitable for catalysis of olefin polymerization.
BACKGROUND OF THE INVENTION
Coordination polymerization of olefinically unsaturated monomers is well known and has led to the great proliferation of thermoplastic compositions of matter from olefins, such as polyethylene, polypropylene, and ethylene propylene rubber. Early pioneers utilized the early transition metal compounds, particularly those of the Group 4 metals, with such activators as aluminum alkyl compounds. Later developments extended this work to bulky ancillary ligand-containing (e.g., &eegr;5-cyclopentadienyl) transition metal compounds (“metallocenes”) with activators such as alkyl alumoxanes. Representative work addressing polymer molecular weight effects of substituted mono and bis metallocene compounds is described in EP-A 0 129 368 and its counterpart U.S. Pat. No. 5,324,800. Hetero-atom containing monocyclopentadienyl metallocene compounds are described in U.S. Pat. No. 5,057,475 and silicon bridged biscyclopentadienyl metallocene catalysts are described in U.S. Pat. No. 5,017,714. Recent developments have shown the effectiveness of ionic catalysts comprised of activated metallocene cations stabilized by compatible noncoordinating anions, see for example U.S. Pat. Nos. 5,278,119 and 5,384,299 and WO 92/00333. Each of which is incorporated by reference for purposes of U.S. patent practice.
Transition metal polymerization catalyst systems from Group 5-10 metals wherein the active transition metal center is in a high oxidation state and stabilized by low coordination number polyanionic ancillary ligand systems are described in U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No. 5,504,049. Suitable low coordination number polyanionic ancillary ligands include both bulky imides and carbolides. Such are said to be suitable alone or in combination with conventional monoanionic ancillary ligands, such as cyclopentadienyl derivatives. Examples 2 and 8 illustrate Group 5 metal catalyst compounds comprising, respectively, (cyclopentadienyl)vanadium(p-tolylimido)dichloride and (cyclopentadienyl)niobium(2,6-diisopropyl-phenylimido)di-methyl. Olefin polymerization catalysts from Group 5 or 6 metal imido complexes are also described in EP 0 641 804. The Group 5 metal complexes include one imido ligand and a monoanionic organic group containing a cyclopentadienyl nucleus. Example 1 illustrates the preparation of (cyclopentadienyl)vanadium(p-tolylimido)dichloride and the Tables on pages 7-9 illustrate polymerization using it. These documents are incorporated by reference for purposes of U.S. patent practice.
Effective olefin polymerization catalysts based upon vanadium alkyl complexes in which the metal center is stabilized in its highest oxidation state are elusive since there are no well established procedures for the synthesis of such compounds. Difficulties associated with the synthesis of vanadium alkyls in which the metal center is stabilized in its highest oxidation state are well documented. See for example, Buijink, J. J. Organomet. Chem 1995, 497, 161-170, Devore, D. D. J. Am. Chem. Soc., 1987, 109, 7408-7416 and other references well known to those skilled in the art.
It would therefore be desirable to provide vanadium alkyl complexes in which the vanadium metal center is stabilized in its highest oxidation state by (a) a low coordination number polyanionic ligand and (b) and suitable additional ancillary ligands.
INVENTION DISCLOSURE
This invention is directed to Group 5 metal compounds, preferably vanadium, suitable for activation as polymerization catalysts and characterized by comprising one polyanionic ancillary ligand and three single or multidentate uninegative ligands, excluding cyclopentadienyl ligands. The polyanionic ancillary ligand will comprise a Group 15 element covalently bound to the Group 5 metal and the uninegative ligands will comprise Group 14-16 elements as single or multidentate ligands bound to the Group 5 metal. The invention includes a polymerization process characterized by comprising contacting one or more monomers polymerizable by coordination or carbocationic polymerization under suitable polymerization conditions with these catalyst compositions.
BEST MODE AND EXAMPLES OF THE INVENTION
The invention Group 5 metal compounds described above can be generically represented by the following symbols:
[RJ]MR′
3
,  (1)
and
[(RJ)Y
n
(X)]MR′
2
  (2)
where M is a Group 5 metal; J is a Group 15 heteroatom ligand covalently bound to M; R is a substituted or unsubstituted aryl, hydrocarbyl or organometalloid group covalently bound to J, preferably substituted or unsubstituted aryl or alicyclic hydrocarbyl; each R′ is, independently, a uninegative ligand, e.g., substituted or unsubstituted aryl, substituted or unsubstituted linear or cyclic hydrocarbyl, silyl, hydride or substituted or unsubstituted organometalloid group, additionally any two R′ maybe joined to form a metallocycle; X is a univalent single or multidentate ancillary ligand comprising at least one Group 14-16 element covalently bound to M; and, Y is an optional covalent bridging group linking R and X, comprising at least one Group 14-16 element, n=1 when X is covalently linked to R and n=0 when X is not covalently linked to R. The term “substituted” means that one or more hydrogen atoms on the hydrocarbyl, aryl or organometalloid group is replaced by a C
1
-C
20
hydrocarbyl radical or any of an aryl radical, a halide radical, a phosphido radical, an alkoxide or aryloxide radical (preferably having from one twenty carbon atoms), or any other radical containing a Lewis acidic or basic functionality.
The Group 5 metal compounds of the invention having one polyanionic ancillary ligand and three univalent single or multidentate ligands can be represented by the figures below:
wherein each of the labeled substituents are as defined above. Suitable single dentate ligands X include those in the group consisting of aryloxides or alkoxides [—OR
1
], siloxides [—OSiR
1
3
], thiols [—SR
1
], amides [—NR
1
2
], and phosphides [—PR
1
2
], where R
1
can be any member within the group defined above for R′. Suitable multidentate ligands are represented by the bidentate carboxylates [—O
2
CR
1
], carboxythiolates [—S
2
CR
1
], triflates [—O
3
SR
1
], acetylacetates [&eegr;
2
—R
1
COCR
1
COR
1
], amidates [&eegr;
2
—R
1
NCR
1
NR
1
], Group 15 or 16 ortho-substituted pyridines (illustration (a)), Group 15 or 16 substituted hydrocarbyls (illustration (b)), Group 15 or 16 substituted aryls (illustration (c)),
where x=0-6, each x is selected independently, and E is independently a Group 15 element (in which case z may be 1 or 2) or a Group 16 element (in which case z may be 0 or 1).
In addition, multidentate ligands such as shown in illustration (d) may be used
Representative (1) and (2) compounds include the following.
Representative (2) compounds include the following.
wherein E is either a Group 15 element (in which case z=1) or a Group 16 element (in which case z=0); x, R′ is defined as above.
The catalyst compounds of the invention may be prepared in high yields using the following techniques. For vanadium, for example, the synthesis can begin with a reaction between vanadium oxytrichloride and a suitable organic molecule such as an isocyanate, an amine, or an alkali metal salt of an amine (See Scheme 1).
Further chemical modifications can be made through ligand exchange reactions such as metathesis. (See Scheme 2).
For instance, treatment of an arylimido-group (V) trialkyl complex with one equivalent of a protic reagent such as an amine or an alcohol, leads to elimination of one equivalent of alkane along with ligation of an amido group to form compound

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