Catalysts for olefin polymerizations

Details Catalysts for olefin polymerizations Catalysts for olefin polymerizations

2000-10-13

2002-09-17

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...

C526S169100, C526S171000, C526S172000, C526S308000, C526S281000, C526S346000, C502S117000, C502S155000, C502S167000, C556S148000, C556S150000, C568S305000

Reexamination Certificate

active

06451940

ABSTRACT:

FIELD OF THE INVENTION
This invention concerns new processes for the polymerization of olefins using as a polymerization catalyst a nickel complex of certain 2-aminotropones. Also described are novel compounds that are the complexes and intermediates for making the complexes, as well as processes for producing such compounds.
TECHNICAL BACKGROUND
Polymers of ethylene and other olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc. In most cases, olefins are polymerized using a catalyst, often a transition metal compound or complex. These catalysts vary in cost per unit weight of polymer produced, the structure of the polymer produced, the possible need to remove the catalyst from the polyolefin, the toxicity of the catalyst, etc. Due to the commercial importance of polymerizing olefins, new polymerization catalysts are constantly being sought.
Arylaminotropones are useful as chemical intermediates, for instance in the synthesis of pharmaceuticals and pesticides.
Nickel complexes of various neutral ligands and mono-anionic ligands are known as catalysts for the polymerization of ethylene and other olefins, see for instance (for monoanionic ligands) U.S. Pat. No. 6,060,569, WO9830609 (corresponding to U.S. patent application Ser. No. 09/006536, filed Jan. 13, 1998, now U.S. Pat. No. 6,174,975) and WO9842664, which are incorporated by reference herein for all purposes as if fully set forth. None of these references describe the use of aminotropones as ligands for nickel containing olefin polymerization catalysts.
Anilinotropones, especially 2-anilinotropones, have been made by a variety of methods, see for instance K. Kikuchi,
Bull. Chem. Soc. Jpn
., vol. 51, p. 2338 (1978); T. Nozoe,
Bull. Chem. Soc. Jpn
., vol. 51, p. 2185 (1978); and W. R. Brasen,
J. Am. Chem. Soc
., vol. 83, p. 3125 (1961). The methods described in these references are different from the methods described herein. In addition, yields of the desired 2-anilinotropones are generally lower than reported herein, and/or sterically hindered less basic arylamines are not used in the synthesis thereof.
SUMMARY OF THE INVENTION
One aspect of the present invention concerns a first process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more olefins with an active catalyst comprising a nickel complex of an anion of the formula
wherein:
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that R
2
is attached to said nitrogen atom in (I) by an atom that has at least 2 other atoms that are not hydrogen attached to it; and
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring.
Another aspect of the present invention concerns a second process for the polymerization of olefins, comprising the step of contacting, at a temperature of about −100° C. to about +200° C., one or more olefins with a compound of the formula
wherein:
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that R
2
is attached to said nitrogen atom in (I) by an atom that has at least 2 other atoms that are not hydrogen attached to it;
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring;
L
1
is a monodentate monoanionic ligand into which an olefin molecule may insert between L
1
and the nickel atom, and L
2
is an empty coordination site or a monodentate neutral ligand which may be displaced by an olefin, or L
1
and L
2
taken together are a monoanionic bidentate ligand into which an olefin may insert between said monoanionic bidentate ligand and the nickel atom;
and provided that when L
1
and L
2
taken together are
then a cocatalyst is also present.
In the above-mentioned processes, (II) and/or the nickel complex of (I) may in and of themselves be active catalysts, or may be “activated” by contact with a cocatalyst/activator, as exemplified by the case when L
1
and L
2
taken together are (I).
The present invention also concerns a compound of the formula
wherein:
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that R
2
is attached to said nitrogen atom in (I) by an atom that has at least 2 other atoms that are not hydrogen attached to it; and
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring;
L
1
is a monodentate monoanionic ligand, and L
2
is a monodentate neutral ligand or an empty coordination site, or L
1
and L
2
taken together are a monoanionic bidentate ligand.
Another aspect of the present invention is a process for making 2-arylamino substituted tropones, comprising the step of contacting, in solution at a temperature of about 20° C. to about 150° C., a first compound of the formula
a second compound of the formula HNR
9
R
19
(IV), a palladium compound, a base capable of deprotonating said second compound, and a third compound which is a mono- or diphosphine in which all of the bonds to phosphorous are to carbon atoms, wherein:
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring;
R
8
is a group such that the conjugate acid of —OR
8
has a pKa of <0 in water at 20° C.;
R
19
is hydrocarbyl, substituted hydrocarbyl or hydrogen; and
R
9
is aryl or substituted aryl.
Still another aspect of the present invention is a compound of the formula
wherein:
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring; and
R
11
, R
12
, R
13, R
14
and R
15
are each independently hydrogen, hydrocarbyl substituted hydrocarbyl or a functional group, provided that any two of R
11
, R
12
, R
13
, R
14
and R
15
vicinal to one another taken together may form a ring; provided that:
both of R
11
and R
15
are not hydrogen; and/or
the total of the Hammett a constants for R
11
, R
12
, R
13
,
R
14
and R
15
is about 0.50 or more; and/or
an E
S
for one or both of R
11
and R
15
is −0.10 or less.
A further aspect of the present invention is an anion of the formula
wherein:
R
2
is hydrocarbyl or substituted hydrocarbyl, provided that R
2
is attached to said nitrogen atom in (I) by an atom that has at least 2 other atoms that are not hydrogen attached to it; and
R
3
, R
4
, R
5
, R
6
and R
7
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R
3
, R
4
, R
5
, R
6
and R
7
vicinal to one another may form a ring.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Herein, certain terms are used. Some of them are:
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. As examples of hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydro-carbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “subst

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