Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-11-17
2003-02-04
Wu, David W. (Department: 1713)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S009000, C556S007000, C556S013000, C556S051000, C556S052000, C502S103000, C526S943000, C526S090000, C526S160000, C526S172000, C526S161000, C526S170000
Reexamination Certificate
active
06515155
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes, polymerization catalysts derived therefrom, and the resulting polymerization processes using the same. More particularly, such metal complexes are characterized by a nitrogen containing aliphatic or cycloaliphatic moiety that is substituted with one or more aryl groups, an aryl-substituted silane bridging group, or one or more Group 14 organometalloid substituents on the metal.
BACKGROUND
EP-A-923,589, which is equivalent to WO98/06727, published Feb. 19, 1998, disclosed Group 4 metal complexes containing a heteroatom substituent at the 3-position of the cyclopentadienyl, especially indenyl, ligand groups. Particular heteroatom containing substituents included dihydrocarbylamino substituents including dimethylamino, diethylamino, methylethylamino, methylphenylamino, dipropylamino, dibutylamino, piperidinyl, morpholinyl, pyrrolidinyl, hexahydro-1H-azepin-1-yl, hexahydro-1(2H)-azocinyl, octahydro-1H-azonin-1-yl, and octahydro-1(2H)-azecinyl.
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-A416,815, WO 95/07942, WO 96/13529, and USP's 5,096,867 and 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.
Despite the advance in the art, particular higher use temperature, obtained by such prior art metal complexes as were disclosed in the foregoing reference, there remains a desire for improved metal complexes capable of even further increase in use temperature that are still capable of forming catalyst compositions useful in producing polymers having high molecular weights and, for ethylene/higher &agr;-olefin copolymers, high incorporation of comonomer. The subject compositions of this invention show unexpected improvement in these desirable features.
SUMMARY OF THE INVENTION
According to the present invention there are provided metal complexes corresponding to the formula:
where M is a Group 4 metal that is in the +2, +3 or +4 formal oxidation state;
R
A
independently each occurrence is hydrogen, or a hydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy, hydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl group of from 1 to 80 atoms, not counting hydrogen, or further optionally, two or more R
A
groups from the same or different metal complexes or R
A
and R
B′
from the same or different metal complexes may be covalently linked together;
R
B′
independently each occurrence is hydrogen, or a hydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy, hydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl group of from 1 to 80 atoms, not counting hydrogen, and optionally, two or more R
B′
groups from different metal complex or R
B′
and an R
A
from the same or a different metal complex may be covalently linked together;
Z is a divalent moiety, bound to M via a covalent or coordinate/covalent bond, 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 exclusive of the class of ligands that are cyclic, delocalized, r-bound ligand groups;
X′ independently each occurrence is a neutral ligand having up to 40 atoms;
p is zero, 1 or 2, and is two less than the formal oxidation state of M when X is an anionic ligand, and when X is a dianionic ligand group, p is 1; and
q is zero, 1 or 2;
with the proviso that one or more of the following conditions A), B) or C), is true:
A) R
B′
corresponds to the formula N(R
B
)
2
, wherein R
B
each occurrence is aralkyl, or two R
B
groups together form a divalent hydrocarbon moiety or a halo- or silyl-substituted derivative thereof, said group containing from 4 to 40 atoms not counting hydrogen, and comprising at least one aromatic substituent, A
R
;
B) Z is (R
D
)
2
Si—Y—, wherein R
D
independently each occurrence is C
6-20
aryl or two R
D
groups together are C
6-20
arylene; and
Y is bonded to M and is selected from the group consisting of —O—, —S—, —NRE—, and —PRE—; wherein, R
E
independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R
E
having up to 20 nonhydrogen atoms; or
C) X in at least one occurrence is selected from the group consisting of tri(hydrocarbyl)silylhydrocarbyl, tri(hydrocarbyl)germylhydrocarbyl, and mixtures thereof, or two X groups together are a divalent ligand group of the formula (ER′
2
)
x′
wherein E is silicon, germanium or carbon, but in at least one occurrence is silicon or germanium, and R′ independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′ having up to 30 carbon or silicon atoms, and x′ is an integer from 1 to 8.
The above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a Lewis base, especially a dihydrocarbylether, cyclic aliphatic ether, trihydrocarbylamine, trihydrocarbylphosphine, or halogenated derivative thereof, or as a polymeric or crosslinked polymeric product, wherein one or more R
A
groups are polymerized with one another or copolymerized with an ethylenically unsaturated comomomer.
Also, according to the present invention, there is provided a catalyst composition, useful, inter alia, for the polymerization of addition polymerizable monomers, comprising the following components or the reaction product thereof:
(A) one or more metal complexes of formula (I); and
(B) an activating cocatalyst, wherein the molar ratio of (A) to (B) is from 1 :10,000 to 100:1.
Another embodiment of this invention is the foregoing catalyst composition wherein the metal complex is in the form of a radical cation.
Further according to the present invention there is provided a polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with one of the aforementioned catalyst compositions.
A preferred process of this invention is a high temperature solution polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with one of the aforementioned catalyst systems at a temperature from 50° C. to 250° C., preferably from 150° C. to 250° C., most preferably from 175° C. to 220° C. Within the scope of this invention are the polymeric products produced by the aforementioned processes.
This invention also includes the precursor of the delocalized electron containing, cyclic moiety of the metal complex of formula (I), said precursor corresponding to the formula:
wherein, Y′ is —OR
C
, —SR
C
, —NR
C
R
E
, —PR
C
R
E
;
R
A
and R
E
are as previously defined;
R
B′
independently each occurrence is hydrogen, or a hydrocarbyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbylamino, hydrocarbyloxy, hydrocarbylsilyl, or tri
Klosin Jerzy
Kruper, Jr. William J.
Nickias Peter N.
Roof Gordon R.
Soto Jorge
Dow Global TEchnologies Inc.
Lee Rip A.
Wu David W.
LandOfFree
Substituted group 4 metal complexes, catalysts and olefin... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Substituted group 4 metal complexes, catalysts and olefin..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Substituted group 4 metal complexes, catalysts and olefin... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3139935