Di- and tri-heteroatom substituted indenyl metal complexes

Details Di- and tri-heteroatom substituted indenyl metal complexes Di- and tri-heteroatom substituted indenyl metal complexes

2001-09-07

2003-04-29

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...

C526S160000, C526S170000, C526S172000, C556S011000, C556S051000, C556S052000, C502S103000

Reexamination Certificate

active

06555634

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes and to olefin polymerization catalysts derived therefrom that are particularly suitable for use in a polymerization process for preparing polymers by polymerization of &agr;-olefins and mixtures of &agr;-olefins.
BACKGROUND
Constrained geometry metal complexes and methods for their preparation are disclosed in U.S. Pat. No. 5,703,187; U.S. Pat. No. 5,321,106; U.S. Pat. No. 5,721,185; U.S. Pat. No. 5,374,696; U.S. Pat. No. 5,055,438; U.S. Pat. No. 5,057,475; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,064,802; U.S. Pat. No. 5,132,380; U.S. Pat. No. 5,470,993, as well as EP-A-514,828, and elsewhere.
U.S. Pat. Nos. 5,350,817 and 5,304,614 disclose bridged zirconocene complexes, wherein two indenyl groups are covalently linked together by a bridge containing carbon or silicon, which are useful for the polymerization of propylene.
EP-A-577,581 discloses unsymmetrical bis-Cp metallocenes containing a fluorenyl ligand with heteroatom substituents.
E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief; W. Roll; O. Weyland; B. Dorerer; H.-H. Brintzinger
J. Organometallic Chem
. 1996, 520, 63-68, and H. Plenio; D. Birth
J. Organometallic Chem
. 1996, 519, 269-272 disclose systems in which the cyclopentadienyl ring of the indenyl is substituted with a dimethylamino group in non-bridged and Si-bridged bis-indenyl complexes useful for the formation of isotactic polypropylene and polyethylene.
Disclosure of random heteroatom substitution in mono-Cp metallocenes is found in EP-A-416,815, WO 95/07942, WO 96/13529, and U.S. Pat. No. 5,096,867 and U.S. Pat. No. 5,621,126. Specific heteroatom substitution of the 3- and 2-position of indenyl complexes of group 4 metals was disclosed in WO98/06727 and WO/98/06728 respectively. The foregoing specifically substituted metal complexes have produced improved catalyst results, however, problems still remain with catalyst efficiency and deactivation of the catalyst under high temperature polymerization conditions. It would be advantageous to be able to produce polyolefins with higher molecular weights. It would also be advantageous to be able to improve other physical characteristics of the polymers produced by altering the substitution around the cyclopentadienyl group of the metallocene complexes used in olefin polymerization catalyst systems.
SUMMARY OF THE INVENTION
According to the present invention there are provided metal complexes corresponding to the formula:
where M is a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the +2, +3 or +4 formal oxidation state,
R
A
independently each occurrence is hydrogen, R
B
or TR
B
j
, with the proviso that in at least two but not more than three occurrences R
A
is TR
B
j
,
j is 1 or 2, and when j is 1, T is oxygen or sulfur and when j is 2, T is nitrogen or phosphorus,
R
B
independently each occurrence is a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, or two R
B
groups are joined together forming a divalent ligand group;
Z is a divalent moiety bound to the substituted indenyl group and bound to M by either covalent or coordinate/covalent bonds, comprising boron or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen;
X is an anionic or dianionic ligand group having up to 60 atoms (including ligands that are cyclic, delocalized, &pgr;-bound ligand groups);
X′ independently each occurrence is a Lewis base ligand having up to 20 atoms;
p is a number from 0 to 5, (when each X is an anionic ligand, p is two less than the formal oxidation state of M, when some or all X groups are dianionic ligand groups each dianionic X group accounts for two valencies and p is correspondingly reduced in value); and
q is zero, 1 or 2.
Certain of the metal complexes wherein the metal is a Group 3 or lanthanide metal are catalytically active for polymerization of olefins without addition of an activator or cocatalyst. Preferably however a cocatalyst is present. Accordingly, in one embodiment according to the present invention, there is provided a catalyst composition for olefin polymerization comprising:
(A) a catalyst component comprising a metal complex as previously defined; and
(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1:10,000 to 100:1; or optionally catalyst component (A) is activated by use of an activating technique.
Another embodiment of this invention is a catalyst composition for olefin polymerization comprising:
(A) a catalyst component comprising a metal complex as previously defined; and
(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1:10,000 to 100:1 wherein the metal complex is in the form of a radical cation.
Further according to the present invention there is provided a process for the polymerization of olefins comprising contacting one or more C
2-20
&agr;-olefins under polymerization conditions with one of the aforementioned catalyst compositions.
A preferred process of this invention is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more C
2-20
&agr;-olefins under polymerization conditions with one of the aforementioned catalyst compositions at a temperature from 100° C. to 250° C.
Within the scope of this invention are the polyolefin products produced by the aforementioned processes. Preferred products have long chain branching and/or reverse molecular architecture.
This invention also provides a cyclopentadienyl-containing ligand of one of the aforementioned metal complexes where the ligand is in the form of:
(A) a free acid with 2 protons capable of being deprotonated;
(B) a dilithium, disodium or dipotassium salt;
(C) a magnesium salt: or
(D) a mono or disilylated dianion.
Within the scope of this aspect of the invention is the use of one of these ligands for synthesis to produce a metal complex of this invention, or, more specifically, the use of one of these ligands for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, and from 1 to 4 of the ligands.
The present catalysts and processes result in the highly efficient production of high molecular weight olefin polymers over a wide range of polymerization conditions, and especially at elevated temperatures. They are especially useful for the solution or bulk polymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), ethylene/styrene (ES polymers), propylene and ethylene/propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbornene, 1,4-hexadiene or similar nonconjugated diene. The use of elevated temperatures dramatically increases the productivity of such processes due to the fact that increased polymer solubility at elevated temperatures allows the use of increased conversions (higher concentration of polymer product) without exceeding solution viscosity limitations of the polymerization equipment. In addition, the use of higher polymerization temperatures results in a reduction of energy costs needed to devolatilize the reaction product.
The catalysts of this invention may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase. The catalyst may be prepolymerized with one or more olefin monomers in situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolymerized catalyst prior to the primary polymerization process.
DETAILED DESCRIPTION
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, publ

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