Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-01-17
2002-09-24
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S012000, C526S160000, C526S943000, C502S103000, C502S117000
Reexamination Certificate
active
06455719
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to constrained geometry complexes of group 4 metals and dienes characterized by high olefin polymerization activity, to ligands of such complexes and to methods for the production of such complexes and ligands.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 5,470,993 describes the synthesis of constrained geometry group 4 metal diene complexes by contacting a reduced form of a group 4 metal tetrjhalide, a diene and an appropriate dianion ligand of the desired metal complex.
The diene complexes may have the formula which appears at lines 20-34 of Column 5 of U.S. Pat. No. 6,015,916 as follows:
The corresponding dihalo ligand may have the formula also set forth in U.S. Pat. No. 6,015,916 (see Formula II of claim
1
):
The ligand may be any corresponding dihalo compound in which the chlorine substituents are replaced by bromine, iodine or fluorine and in which the “t-bu” substituent is replaced by any alkyl group.
U.S. Pat. No. 6,015,916 describes the synthesis of similar complexes by treatment of a dihalo ligand of a metallocene compound with an alkali metal alkyl and a diene. The specification of U.S. Pat. No. 6,015,916 is, by express reference, incorporated herein and made a part of this specification.
German Application DE 197 39 946 A1 describes a metallocene synthesis in which an appropriate ligand is converted to a metallocene by treatment with an adduct of Formula (I)
M
1
X
n
D
a
(I)
in which M
1
denotes a metal of groups 3, 4, 5 or 6 or the periodic system of elements (PSE) or an element of the group of lanthanides or actinides, preferably titanium, zirconium, or hafnium, by special preference zirconium; X is the same or different, being halogen, a C
1-10
-alkoxy, C
6-10
-aryloxy, C
1-10
-alkylsulfonate such as mnesylate, triflate, nonaflate, a C
6-10
-arylsulfonate such as tosylate, benzene sulfonate, a C
1-10
-alkylcarboxylate such as acetate, formate, oxalate, or a 1,3-dlcarbonylate such as acetylacetonate or a fluorinated 1,3-dicarbonylate; n is an integer and equals 2, 3, 4, 5 or 6 and corresponds to the oxidation number of the metal M
1
; a is an integer or a fraction number and 0<a≦4; and D is a linear, cyclic, or branched oligoether or polyether containing at least two oxygen atoms or an oligoether or polyether containing at least two sulfur atoms.
There is a need for group 4(II) diene complexes of high catalytic activity in which these disadvantages are reduced or eliminated and for dihalo ligands of such complexes.
Accordingly, it is an object of this invention to provide novel cyclopentadienyl group 4 metal diene complexes and dihalo ligands or such complexes which provide uniquely active olefil polymerization catalysts.
It is a related object of the invention to provide cyclopentadienyl group 4 metal diene complex single site polymerization catalysts and catalyst compositions of low impurity content such that the single site functionality thereof is not significantly impaired.
It is a specific object of the invention to provide a magnesium-free cyclopentadienyl group 4 metal diene complex metallocene.
DEFINITIONS
The following expressions have the meaning set forth:
(1) Cyclopentadienyl group means cyclopentadienyl, tetraalkylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
(2) The expressions group 4(II) and group 4(III) mean a group 4 metal of valence 2(II) or 3(III).
(3) A Group 4(II) metallocene compound is a compound comprised of a group 4(II) metal bonded to one or more cyclopontadienyl groups.
(4) A Group 4(II) metallocene ligand is a chemical precursor which contains a cyclopentadienyl or substituted cyclopentadienyl group from which a group 4(II) metllocone may be synthesized.
(5) Constrained geometry compound or catalyst (CGC) means a catalyst in which the metal center is contained in a ring structure and covalently bonded to a cyclic group via a delocalized n-system and covalently bonded via a sigma-bond to another atom, e.g., carbon, nitrogen, oxygen. A small ring size induces constraint about the metal atom center. For titanium-containing CGCs, the incorporated titanium atom can be in the +4, +3, or +2 formal oxidation state. See EP application 90309496.9, WO 95/00526 and U.S. Pat. No. 5,470,993.
(6) CpSA ligand means (t-butylamino) (tetramethylcyclopentadienyl) dimethylsilane.
(7) (CpSA)
2−
means doubly-deprotonated CPSA ligand.
(8) (CpSA)
2−
TiCl
2
means [(t-butylarido) (tetramethylcyclopentadienyl)dimethylsilane] titanium dichloride.
(9) Activity means generally the quantity of polymer produced under standard conditions by a defined amount of catalyst per unit time.
CATALYTIC ACTIVITY DETERMINATION
As used in this application, catalyst efficiency or activity is based on ethylene consumption in a batch reactor under standard conditions for temperature, solvent, monomer quantities, hydrogen quantities, monomer pressure and run time.
The activity of the sample catalyst is reported as the percentage of activity of the sample versus the activity of a standard (“standard activity”). For purposes of this application, the “standard” is the CGC group 4(II) diene complex from Boulder Scientific Company Batch 459-0140 of 1997.
The equation for reporting the sample catalyst activity is as follows:
%
Activity
=
Average
Sample
Activity
Average
Standard
Activity
×
100
=
Sample
Activity
“Average” means the average of two runs with activities which are the same within plus or minus 5%
“PROCESS DESCRIPTION” AND “REACTION” FOR “STANDARD” CGC BSC-1459-4-0140 DATED FEB. 26, 1997
PROCESS DESCRIPTION
This process involves making reactant slurries 1 and 2 in separate vessels and then combining these slurries for the final reaction. Slurry 1 is produced by charging toluene into a vessel and deoxygenating. Then titanium tetrachloride is added, followed by adding n-butyllithium. This addition is very exothermic. The resulting mixture comprising slurry 1 is stirred for 1 hour. This process is illustrated by equation 1):
Slurry 2 is made up as follows: Toluene and CpSA ligand are charged to a reaction vessel. After adjusting the pot temperature to 45-50° C., a solution of isopropylmagnesium chloride in ethyl ether is fed into the reaction vessel resulting in gas evolution. Gentle heating is used as needed in order to end up with a pot temperature of 45-50° C. at the end of the Grignard feed. The reaction mixture is slowly heated and solvents begin to distill along with increased gas evolution. The reaction mixture is heated up to 85-90° C., and this temperature is maintained for 2 hours. After allowing the reaction mixture to cool to 60-65° C., TiCl
3
is fed into the reaction vessel. The reaction mixture is then cooled to 20-25° C. This becomes known as Slurry 2. This process is illustrated by equations 2) and 3):
The agitated Slurry 1 is transferred into the reactor containing the agitated Slurry 2 as quickly as possible resulting in about a temperature increase of about 7-15° C. Methylene chloride is then charged to the reaction vessel, the vessel containing Slurry 1 is then rinsed out with toluene and charged to the Slurry 2 reaction vessel, and this mixture is then agitated for 2 hours. A dark reddish-brown color is noted in the reaction vessel as soon as Slurry 1 is introduced. This reaction is illustrated by equation 4):
Solvents are removed under reduced pressure (60-80 mm Hg) using a rotary vane vacuum pump to about ½ of the starting volume. Toluene is added back, Celite is added, and the mixture is filtered through the large Sparkler filter. Solvents are then distilled to concentrate the product. The remaining crude product solution is then used directly in the next step.
“PROCESS DESCRIPTION” AND “REACTION” FOR CONVERSION OF CGC DICHLORIDE TO A GROUP 4(II) DIENE COMPLEX
PROCESS DESCRIPTION
The crude product from the previous steps of this process, equations 1) to 4) which is still contained in
Gately Daniel A.
Sullivan Jeffrey M.
Boulder Scientific Company
Irons Edward S.
Nazario-Gonzalez Porfirio
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