Complexes of pyridldiimines with vanadium and other...

Details Complexes of pyridldiimines with vanadium and other... Complexes of pyridldiimines with vanadium and other...

2000-08-16

2002-10-01

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...

C526S165000, C526S348000, C502S103000, C502S167000

Reexamination Certificate

active

06458905

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates generally to pyridyldiimine ligands having one of the following structures:
The invention also relates generally to pyridyldiimine metal complexes having one of the following structures:
for example the Group 4b, 5b, and 6b transition metal (M) complexes. The invention also relates to the use of these metal complexes as olefin polymerization or oligomerization catalysts.
Reardon, Damien, et al., Life and Death of an Active Ethylene Polymerization Catalyst, Ligand Involvement in Catalyst Activation and Deactivation. Isolation and Characterization of Two Unprecedented Neutral and Anionic Vanadium(I) Alkyls,
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, dated Sep. 23, 1999, Vol. 121, No. 40, pp. 9318-9325, discloses the complex identified as {2,6-bis[2,6-(I-Pr)
2
PhN═C(Me)]
2
(C
5
H
3
N)}VCl
3
. 1.3(CH
2
Cl
2
). This complex corresponds to Complex I as shown here, in which R
1
, R
5
, R
6
, and R
10
are isopropyl; R
11
-R
12
are methyl; R
2
-R
4
, R
7
-R
9
, and R
13
-R
15
are hydrogen; M is vanadium, X is chloride, and n is 3. The substituents for this species are identified in Table II of this specification as Species 41. This complex is disclosed by Reardon et al. to be a diimine/pyridine ligand complexed with vanadium trichloride.
Reardon et al. states that reaction of this complex with a stoichiometric amount of methyl alumoxane (also known as partially methylated aluminum oxide or PMAO) in toluene resulted in an olefin polymerization catalyst that produced polyethylene having a molecular weight of 67,400 atomic mass units and a high polydispersity. Reardon et al. also identifies the corresponding Ligand I, the substituents for which are identified in the column “Reardon” in Reference Table 1 of this specification.
U.S. Pat. No. 5,714,556, issued Feb. 3, 1998 to Johnson et al., e.g. col. 22, lines 20-25, discloses 2,6-bis[4-trifluoromethyl-PhN═C(Me)]
2
(C
5
H
3
N), which has the structure of Ligand I, in which R
3
and R
8
are —CF
3
; R
11
and R
12
are methyl; and R
1
-R
2
, R
4
-R
7
, R
9
-R
10
, and R
13
-R
15
are hydrogen. See “Johnson” in Reference Table 1. Johnson et al. states that this compound was “ineffective in catalyzing the polymerization of ethylene under the conditions described for Examples 23-66.” Col. 20, lines 25-29.
Britovsek, George J. P., et al., Novel Olefin Polymerization, Catalysts Based on Iron and Cobalt,
CHEM. COMMUN
., 1998 p. 849 (Brit. I), discloses the use of iron and cobalt complexes of these ligands:
2,6-bis[2,6-diisopropyl-PhN═C(methyl)]
2
(C
5
H
3
N)
2,6-bis[2,6-dimethyl-PhN═C(methyl)]
2
(C
5
H
3
N)
2,6-bis[2,4,6-trimethyl-PhN═C(methyl)]
2
(C
5
H
3
N)
2,6-bis[2,4-dimethyl-PhN═C(methyl)]
2
(C
5
H
3
N)
2,6-bis[2,6-dimethyl-PhN═CH]
2
(C
5
H
3
N).
Referring to the structure of Complex I, the R substituents for these compounds are believed to be, respectively, as follows:
R
1
, R
5
, R
6
, and R
10
are isopropyl; R
11
and R
12
are methyl; and R
2
-R
4
, R
7
-R
9
, and R
13
-R
15
are hydrogen (i.e. “Brit.-I-1” in Reference Table 1);
R
1
, R
5
, R
6
, and R
10
-R
12
are methyl; R
2
-R
4
, R
7
-R
9
, and R
13
-R
15
are hydrogen (Brit. I-2 in Reference Table 1);
R
1
, R
3
, R
5
, R
6
, R
8
and R
10
-R
12
are methyl; R
2
, R
4
, R
7
, R
9
, and R
13
-R
15
are hydrogen (Brit. I-3 in Reference Table 1);
R
1
, R
3
, R
6
, R
8
, R
11
, and R
12
are methyl; R
2
, R
4
, R
5
, R
7
, R
9
, R
10
, and R
13
-R
15
are hydrogen (Brit. I-4 in Reference Table 1);
R
1
, R
5
, R
6
, and R
10
are methyl; R
2
-R
4
, R
7
-R
9
, and R
11
-R
15
are hydrogen (Brit. I-5 in Reference Table 1).
Brit. I discusses olefin oligomerization or polymerization using these complexes in MAO-activated catalysts.
Britovsek, George J. P., et al., Iron and Cobalt ethylene Polymerization Catalysts Bearing 2,6-Bis(Imino)Pyridyl Ligands: Synthesis, Structures, and Polymerization Studies,
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
121 (38) 1999, 8728-40 (indicating publication on the web on Jul. 7, 1998) (Brit. II) discloses the production of Brit I-1 Brit I-2, 3, Brit II-3, as identified in Reference Table 1. Brit. II discloses the preparation of these compounds by refluxing the starting aniline and 2-6-diacetyl pyridine in ethanol and glacial acetic acid, and reports a 60% to 80% yield.
Small, Brooke L., et al., Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene,
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, dated Apr. 14, 1998, vol. 120, No. 16, pp. 4049-4050 (Small I), shows iron and cobalt complexes of three ligands in which, respectively:
R
1
, R
5
, R
6
, and R
10
are isopropyl; R
11
and R
12
are methyl; and R
2
-R
4
, R
7
-R
9
, and R
3
-R
15
are hydrogen (Small I-1 in Reference Table 1);
R
1
, R
5
, R
6
, R
10
-R
12
are methyl; and R
2
-R
4
, R
7
-R
9
, and R
13
-R
15
are hydrogen (Small I-2 in Reference Table 1); and
R
1
and R
6
are t-butyl; R
11
-R
12
are methyl; and R
2
-R
5
, R
7
-R
10
, and R
13
-R
15
are hydrogen (Small I-3 in Reference Table 1). These complexes are said to be used as ethylene polymerization catalysts.
Alyea, E. C., et al., Terdentate AWN Donor Ligands Derived From 2,6-Diacetvlpyridine,
SYN. REACT. INORG. METAL
-
ORG. CHEM
., 1974, 4(6), 535-544, describes a method of synthesizing pyridine-bis-(benzylimine) ligands from aniline or benzylamine and 2,6-diacetylpyridine, and their conversion to nickel and zinc complexes. At page 536, Alyea et al. describes one phenyl-substituted 2,6-diacetylpyridine represented by Ligand I (for which R
1
-R
10
and R
13
-R
15
are hydrogen and R
11
-R
12
are methyl: see Alyea 1 in Reference Table 1) and one p-methoxyphenyl ligand represented by Ligand I (for which R
3
and R
8
are methoxy moieties; R
11
-R
12
is methyl, and R
1
-R
2
, R
4
-R
7
, R
9
-R
10
; and R
13
-R
15
are hydrogen: see Alyea 2 in Reference Table 1). The benzyl-substituted ligands and complexes described in Alyea are understood to differ from Ligand I and Complex I by the presence of a methylene linkage between each phenyl moiety and the associated nitrogen atom—they are made from benzylamine or its derivative, instead of from an aniline derivative. These ligands are represented by Ligand II, in which R
16
and R
17
are benzyl (phenylmethyl) moieties, R
18
and R
19
are methyl moieties, and R
20
-R
22
are hydrogens: see Alyea 3 in Reference Table 2.
Small, Brooke L. et al., Iron-Based Catalysts with Exceptionally High Activities and Selectivities for Oligomerization of Ethylene to Linear &agr;-Olefins,
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
120 1998, 7143-7144 (Small II), discloses iron complexes with ligands of Complex I in which, for respective compounds:
R
1
R
6
, R
11
and R
12
are methyl and R
2
-R
5
, R
7
-R
10
, and R
13
-R
15
are hydrogen: see Small II-1 in Reference Table 1;
R
1
and R
6
are ethyl; R
11
and R
12
are methyl; and R
2
-R
5
, R
7
-R
10
, and R
13
-R
15
are hydrogen: see Small II-2 in Reference Table 1; and
R
1
and R
6
are isopropyl; R
11
and R
12
are methyl; and R
2
-R
5
, R
7
-R
10
, and R
13
-R
15
are hydrogen: see Small I-3 in Reference Table 1.
Small II reports that “by reducing the steric bulk of these pyridinebisimine ligands the resulting iron catalysts oligomerize ethylene to linear &agr;-olefins with exceptionally high turnover frequencies . . . and selectivities.” Specifically, the steric bulk at R
1
and R
6
is being reduced. The ligands are said to be synthesized by reacting an excess of the aniline analog and 2,6-diacetylpyridine in methylene chloride or methyl alcohol, in the presence of formic acid for 40 hours, then working up the product. Yields of 55-67% are reported.
U.S. Pat. No. 5,817,651, issued Oct. 9, 1998 (D'Ambra et al.) discloses the preparation of 3-[(1-phenylimino)ethyl]pyridine by reacting 3-acetyl pyridine and aniline in a toluene solvent, in the presence of glacial acetic acid (Preparation 10). The reaction is refluxed for three days, collecting

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