Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-01-15
2001-07-31
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...
C526S134000, C526S161000, C526S943000, C526S348600, C502S104000, C502S152000, C502S155000, C556S007000, C556S011000, C556S012000, C556S013000, C556S053000
Reexamination Certificate
active
06268444
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. application Ser. No. 545,403. filed Jul. 3, 1990 (EP-A-416,815); U.S. application Ser. No. 547,718, filed Jul. 3, 1990 (EP-A-468,651); U.S. application Ser. No. 702,475, filed May 20, 1991 (EP-A-514,828); U.S. application Ser. No. 876,268, filed May 1, 1992. (EP-A-520,732) and U.S. application Ser. No. 8,003, filed Jan. 21, 1993 (WO 93/19104), as well as U.S. Pat. Nos. 5,055,438, 5,057,475, 5,096,867, 5,064,802, 5,132,380, and WO 95/00526. The teachings of all of the foregoing patents or the corresponding U.S. patent applications are hereby incorporated by reference.
U.S. Pat. Nos. 5,350,817 and 5,304,614 disclose zirconium complexes with bridged-metallocene ligands, 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 fluorene 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 useful for the formation of isotactic polypropylene and polyethylene.
R. Leino; H. J. K. Luttikhedde; P. Lehmus; C.-E. Wilen; R. Sjoholm; A. Lehtonen; J. Seppala; J. H. Nasman
Macromolecules,
1997, 30, 3477-3488 disclose C
2
-bridged bis-indenyl metallocenes with oxygen in the 2-position of the indenyl group, and I. M. Lee; W. J. Gauthier; J. M. Ball; B. Iyengar: S. Collins
Organometallics,
1992, 11, 2115-2122 discloses C
2
-bridged bis-indenyl metallocenes with oxygen in the 5,6-positions of the indenyl group, while N. Piccolravazzi; P. Pino; G. Consiglio; A. Sironi; M. Moret
Organometallics,
1990, 9, 3098-3105 discloses non-bridged bis-indenyl metallocenes with oxygen in the 4 and 7 positions of the indenyl group.
It has been thought that heteroatom-substitution, as opposed to carbon or H-substitution, on any position of the indenyl system of a metallocene complex, when used in an olefin polymerization catalyst, renders the catalyst less active, that is, there is lower catalyst productivity for polymerizations with &agr;-olefins, and the polymer produced has lower molecular weight with lower tacticity. It has been suggested that the diminished activity of this broad class of catalysts is due to interaction of the heteroatom lone pair electrons with the Lewis acid cocatalyst polymerization activator, resulting in a more electronically deactivated Cp ring which is also more sterically hindered. SEE P. Foster; M. D. Rausch; J. C. W. Chien. J.
Organometallic Chem.
1996, 519, 269-272.
Disclosure of random heteroatom substitution in mono-Cp metallocenes is found in EP-A-416,815, WO 95107942, WO 96/13529. U.S. Patent Nos. 5,096,867 and 5,621,126 and related cases.
Up to now it has been thought that heteroatom substitution in metallocene complexes for use as olefin polymerization catalysts would have disadvantages due to unwanted interactions of the lone pair electrons of the heteroatom either with the transition metal atom of the same or a different metallocene molecule, or with other components of the catalyst system.
Numerous improvements in various metallocene complexes used as olefin polymerization catalysts have been made. 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 and which is &pgr;-bonded to one cyclopentadienyl group (Cp) which is a cyclic, delocalized. &pgr;-bound ligand group having 5 substituents: R
A
; (R
B
)
j
-T where j is zero, 1 or 2: R
C
; R
D
and Z; where R
A
, R
B
, R
C
and R
D
are R groups; and where
T is a heteroatom which is covalently bonded to the Cp ring, and to R
B
when j is 1 or 2,and when j is 0, T is F, Cl, Br, or I; when j is 1, T is 0 or S, or N or P and R
B
has a double bond to T; when j is 2, T is N or P; and where
R
B
independently each occurrence is hydrogen, or, is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each R
B
optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbyl amino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms, and each of R
A
, R
C
and R
D
is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl hydrocarbylsilylhydrocarbyl, each R
A
, R
C
or R
D
optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl,)phosphino, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms; or, optionally, two or more of R
A
, R
B
, R
C
and R
D
are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which independently each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both Cp and M via &sgr;-bonds, where Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen;
X is an anionic or dianionic ligand group having tip to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, &pgr;-bound ligand groups;
X′ independently each occurrence is
Klosin Jerzy
Kruper, Jr. William J.
Nickias Peter N.
Patton Jasson T.
Wilson David R.
Dow Chemical Company
Harlan R.
Wu David W.
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