Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-05-10
2002-07-16
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S155000, C526S127000, C526S131000, C526S135000, C526S160000, C526S943000, C526S161000, C526S348600, C556S007000, C556S011000, C556S051000, C556S053000
Reexamination Certificate
active
06420299
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to boron-substituted derivatives of cyclopentadienes (Cp) and metal complexes thereof which find utility as olefin polymerization catalyst components.
BACKGROUND
Constrained geometry complexes (CGC) and methods for their preparation are disclosed in U.S. Pat. No. 5,703,187, U.S. Pat. No. 5,064,802, 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, as well as EP-A-514,828, WO 95/00526, and elsewhere. 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. Organometaic Chem
. 1996, 519, 269-272 disclose non-bridged and Si-bridged ansa bis-indenyl complexes in which the 5 membered ring of the indenyl group is substituted with a dimethylamino substituent. The complexes were disclosed as useful components of catalysts for use in the formation of polyethylene and isotactic polypropylene.
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. Additional pertinent disclosure may be found in
Organometallics
, 1966, 15, pp 58-67
, J. Organomet. Chem
., 1998, 567, pp 127-131
; Organometallics
, 1997, 16, pp 4995-5005
; Organometallics
, 1996, 15, pp 2393-2398
; Organometallics
, 1996, 15, pp 5524-5535
; J. C. S. Chem. Commun
., 1995, pp 2081-2082; WO 97/15581, and
Chimia
, 1995, 49, pg 501.
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
The present invention provides novel boron-substituted derivatives of cyclopentadienes corresponding to the formula:
where, R
A
independently each occurrence is hydrogen or R
B
;
R
B
is BR
C
2
, or a hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, BR
C
2
-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, di(hydrocarbyl)amino, hydrocarbadiylamino, or hydrocarbyloxy group, each R
B
having from 1 to 80 atoms not counting hydrogen, and optionally two R
B
groups may be covalently linked to form one or more fused rings; and
R
C
independently each occurrence is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dihydrocarbylamino-substituted hydrocarbyl, hydrocarbadiylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, or R
D
;
R
D
independently each occurrence is a dihydrocarbylamino or a hydrocarbyloxy group having from 1 to 20 nonhydrogen atoms, and optionally two R
D
groups on a single boron together form a hydrocarbadiylamino-, hydrocarbadiyloxy, hydrocarbadiyldiamino-, or hydrocarbadiyldioxy-group having both valences bound to boron; with the proviso that in at least one occurrence R
A
is selected from BR
C
2
, a BR
C
2
-substituted hydrocarbyl group, and joined derivatives thereof, wherein at least one R
C
is R
D
.
This invention also provides derivatives of the aforementioned complexes in the form of:
(A) a Group 1 metal salt derivative;
(B) a Grignard derivative: or
(C) a monosilylated anion or disilylated dianion derivative.
Within the scope of this aspect of the invention is the use of one of the foregoing derivatives for synthesis to produce a metal complex of this invention, or, more specifically, the use of one of these derivatives 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 ligands derived from one or more of the foregoing derivatives.
The present invention further provides metal complexes corresponding to the formula:
wherein M is a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides,
Z is a divalent moiety 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 ligand group having up to 60 atoms not counting hydrogen, and optionally 2 X groups together form a divalent anionic ligand group;
X′ independently each occurrence is a neutral Lewis base ligand having up to 20 atoms;
p is a number from 0 to 5, and is two less than the formal oxidation state of M;
q is zero, 1 or 2;
E is silicon or carbon,
R
F
independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R
F
having up to 30 carbon or silicon atoms, and
x is 1 to 8, or optionally (R
F
2
E)
x
is —T′Z′— or —(T′Z′)
2
—, wherein, T′ independently each occurrence is boron or aluminum, and Z′ independently each occurrence is:
R
1
is independently each occurrence hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group, or a trihydrocarbylsilylhydrocarbyl group, said R
1
groups containing up to 20 atoms not counting hydrogen, and two such R
1
groups may optionally be joined together to form a ring structure; and
R
5
is R
1
or N(R
1
)
2
.
The above metal complexes may exist as isolated crystals optionally in pure form or as a mixture (including as a mixture with other complexes), in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or chelated derivative thereof.
Also, according to the present invention, there is provided a catalyst composition for olefin polymerization prepared from catalyst system components comprising:
(A) a metal complex of one or more of the aforementioned Formulae II, III, or IV; 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 a catalyst composition for olefin polymerization prepared from catalyst system components comprising:
(A) a metal complex of one or more of the aforementioned metal complexes of Formulae II, III, or IV; and
(B) a 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 reverse moleculararchitecture.
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
Green D. Patrick
Kruper, Jr. William J.
Timmers Francis J.
Dow Global Technologies Inc.
Harlan R.
Wu David W.
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