Preparation of polymerization catalysts

Details Preparation of polymerization catalysts Preparation of polymerization catalysts

2000-12-18

2003-02-11

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S018000, C556S021000, C556S042000, C556S051000, C556S057000, C502S103000, C502S120000, C526S139000, C526S140000, C526S141000, C526S142000

Reexamination Certificate

active

06518444

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a method to synthesize Group 15 containing metal polymerization catalyst compounds. More specifically, this invention relates to a method to synthesize Group 15 containing ligands, and especially arylamine ligands, for use in the preparation of Group 15 containing metal polymerization catalyst compounds.
BACKGROUND OF THE INVENTION
The commercialization of metallocene polyolefin catalysts (metallocene being cyclopentadienyl based transition metal catalyst compounds) has led to widespread interest in the design and preparation of other catalysts and catalyst systems, particularly for use in economical gas and slurry phase processes.
Anionic, multidentate heteroatom ligands have received attention in polyolefins catalysis. Notable classes of bidentate anionic ligands which form active polymerization catalysts include N—N
−
and N—O
−
ligand sets. Examples of these types catalysts include amidopyridines. (Kempe, R., “Aminopyridinato Ligands—New Directions and Limitations”, 80
th
Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, Jun. 1-4, 1997; Kempe, R. et al.,
Inorg. Chem
. 1996 vol. 35 6742.) Likewise, recent reports by Jordan et al. disclose polyolefin catalysts based on hydroxyquinolines. (Bei, X.; Swenson, D. C.; Jordan, R. F.,
Organometallics
1997, 16, 3282).
U.S. Pat. No. 5,576,460 to Buchwald et al. discloses two synthesis routes to preparing arylamine compounds. The first route includes reacting a metal amide comprising a metal selected from the group consisting of tin, boron, zinc, magnesium, indium and silicon, with an aromatic compound comprising an activated substituent in the presence of a transition metal catalyst to form an arylamine. The second route utilizes an amine rather than a metal amide. The '460 patent teaches that this reaction be conducted at a temperature of less than about 120° C. and is drawn to the use of the arylamine as an intermediate in pharmaceutical and agricultural applications.
U.S. Pat. No. 5,929,281 to Nishiyama et al. discloses the preparation of a heterocyclic aromatic amines in the presence of a catalyst system comprising a palladium compound and a tertiary phosphine and the preparation of arylamines in the presence of a catalyst system comprising a palladium compound and a trialkylphosphine.
U.S. Pat. No. 3,914,311 to Coulson discloses a low temperature method of preparing an arylamine by the reaction of an amine with an aromatic compound having a displaceable activated substituent at temperatures as low as 25° C. in the presence of nickel catalyst and a base.
Boger et al in “Palladium (O) Mediated &bgr;-Carboline Synthesis: Preparation of the CDE Ring System of Lavendamycin” 25 Tetrahedron Letters, No. 30, pp. 3175-78 (1984) discloses low temperature preparation of arylamines by reacting an amine with an aromatic compound containing an activated substituent at 80° C. or 100° C. in the presence of a palladium catalyst and a base.
There is a need in the art for new methods to synthesize anionic, multidentate heteroatom ligands for use in polymerization catalyst systems.
SUMMARY OF THE INVENTION
The present invention relates to a method to synthesize a Group 15 containing metal polymerization catalyst. In another respect the invention relates to an efficient high temperature synthesis of Group 15 containing ligands, especially arylamine ligands, for use in preparing polymerization catalysts and catalyst systems.
Specifically, the arylamine is prepared by reacting an amine and an aromatic compound having suitable leaving groups at a temperature above 120° C. and preferably above 130° C.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
The present invention provides a method to synthesis a Group 15 containing metal polymerization catalyst compound defined below. Generally, the method includes a new efficient high temperature preparation of the Group 15 atom containing ligand.
Group 15 Containing Metal Polymerization Catalyst Compound
The Group 15 containing metal polymerization catalyst compounds, which may be prepared by the method of the present invention, generally include a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group. The Group 15 atoms of the catalyst compound are also bound to a Group 15 or 16 atom through another group which may be a C
1
to C
20
hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also be bound to nothing or a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
In another embodiment, the Group 15 containing metal catalyst compound, prepared by the method of the present invention is represented by the formulae:
wherein:
M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, preferably a Group 4, 5, or 6 metal, and more preferably a Group 4 metal, and most preferably zirconium, titanium or hafnium;
each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl;
y is 0 or 1 (when y is 0 group L′ is absent);
n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4;
m is the formal charge of the YLZ or the YL′Z ligand, preferably 0, −1, −2 or −3, and more preferably −2;
L is a Group 15 or 16 element, preferably nitrogen;
L′ is a Group 15 or 16 element or Group 14 containing group, preferably carbon, silicon or germanium;
Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen;
Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen;
R
1
and R
2
are independently a C
1
to C
20
hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, preferably a C
2
to C
20
alkyl, aryl or aralkyl group, more preferably a linear, branched or cyclic C
2
to C
20
alkyl group, most preferably a C
2
to C
6
hydrocarbon group;
R
3
is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R
3
is absent, hydrogen or an alkyl group, and most preferably hydrogen;
R
4
and R
5
are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms, and even more preferably a C
1
to C
20
hydrocarbon group, a C
1
to C
20
aryl group or a C
1
to C
20
aralkyl group, or a heteroatom containing group, for example PR
3
, where R is an alkyl group, R
1
and R
2
may be interconnected to each other, and/or R
4
and R
5
may be interconnected to each other;
R
6
and R
7
are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent; and
R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, a heteroatom containing group.
By “formal charge of the YLZ or YL′Z ligand”, it is meant the charge of the entire ligand absent the metal and the leaving groups X.
By “R
1
and R
2
may also be interconnected” it is meant that R
1
and R
2
may be directly bound to each other or may be bound to each other through other groups. By “R
4
an

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