Polymerization of ethylene

Details Polymerization of ethylene Polymerization of ethylene

1999-11-18

2001-05-15

Wilson, Donald R. (Department: 1713)

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

Organic compounds

Heavy metal containing

C556S021000, C556S139000, C526S132000, C526S172000, C526S352000

Reexamination Certificate

active

06232483

ABSTRACT:

FIELD OF THE INVENTION
Polymerization of ethylene using as catalysts novel nickel complexes in which the nickel is coordinated to selected phosphorous substituted aryl sulfonamide ligands is described.
TECHNICAL BACKGROUND
Polymers of ethylene are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyethylene (PE) being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, etc. In most cases, ethylene is polymerized using a catalyst, often a transition metal compound or complex. These catalysts vary in cost per unit weight of PE produced, the structure of the polymer produced, the possible need to remove the catalyst from the PE, the toxicity of the catalyst, etc. Due to the commercial importance of polymerizing ethylene, new polymerization catalysts are constantly being sought.
P. Braunstein, et al., J. Chem. Soc., Dalton Trans., 1996, p. 3571-3574 report the use of nickel complexes having certain phosphorous-nitrogen ligands as oligomerization catalysts for ethylene. Sulfonamides are not mentioned.
European Patent Application 454,231 discloses certain types of neutral phosphorous ligands in nickel complexes as being useful in olefin polymerizations. Ligands containing sulfonamides are not disclosed.
SUMMARY OF THE INVENTION
This invention concerns a first process for the polymerization of ethylene, comprising, contacting, at a temperature of about −20° C. to about +200° C., ethylene, optionally a Lewis acid, and a compound of the formula
wherein:
R
1
, R
2
, R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
5
and R
6
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar
1
, Ar
2
and Ar
3
are each independently hydrocarbyl or substituted hydrocarbyl; and
L
1
is a neutral monodentate ligand and L
2
is a monoanionic monodentate ligand, or L
1
and L
2
taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may be displaced by said ethylene or add to said ethylene.
This invention also concerns a second process for the polymerization of ethylene, comprising contacting, at a temperature of about −20° C. to about +200° C., a Ni [II] complex of a monoanionic bidentate ligand of the formula
with ethylene and optionally a Lewis acid, wherein:
R
1
, R
2
, R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
5
and R
6
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar
1
is aryl or substituted aryl;
Ar
2
and Ar
3
are each hydrocarbyl or substituted hydrocarbyl;
and provided that a Ni [II] atom also has bonded to it a ligand that may be displaced by said ethylene or add to said ethylene.
Also described herein is a compound of the formula
wherein:
R
1
, R
2
, R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
5
and R
6
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
1
is aryl or substituted aryl; and
Ar
2
and Ar
3
are each independently hydrocarbyl or substituted hydrocarbyl.
This invention concerns a compound of the formula
wherein:
R
1
, R
2
, R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
5
and R
6
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar
1
is aryl or substituted aryl;
Ar
2
and Ar
3
are each independently hydrocarbyl or substituted hydrocarbyl; and
L
1
is a neutral monodentate ligand and L
2
is a monoanionic monodentate ligand, or L
1
and L
2
taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may be displaced by said ethylene or add to said ethylene.
DETAILS OF THE INVENTION
Herein, certain terms are used. Some of them are:
A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. 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 hydrocarbyl group which 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 “substituted” are heteroaromatic rings.
By “(inert) functional group” herein is meant a group other hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as—OR
7
wherein R
7
is hydrocarbyl or substituted hydrocarbyl, nitro and perfluorohydrocarbyl (contains only fluorine and carbon). In cases in which the functional group may be near a nickel atom the functional group should not coordinate to the metal atom more strongly than the groups in compounds which are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
By a “polymerization process” herein (and the polymers made therein) is meant a process which produces a polymer with a degree of polymerization (DP) of about 5 or more, preferably about 10 or more (except where otherwise noted) By “DP” is meant the average number of repeat (monomer) units in the polymer.
By “aryl” herein is meant a monovalent radical whose free valence is to a carbon atom of an aromatic ring, preferably a ring carbon atom of a carbocyclic ring. The aryl radical may contain one ring or may contain 2 or more fused rings, such as 9-anthracenyl or 1-naphthyl.
By “substituted aryl” herein is meant an aryl radical substituted with one or more groups that do not interfere with the synthesis of the compound or the resulting polymerization. Suitable substituents include alkyl, aryl such as phenyl, halo, alkoxy, nitro and perfluorohydrocarbyl.
By a “monoanionic ligand” is meant a ligand with one negative charge.
By a “neutral Ligand” is meant is ligand that is not charged.
Compounds useful herein as ligands include (II) and (IV), as described above. The ligands are made from the corresponding sulfonamides. Sulfonamides (II) can be made by reacting an arylsulfonyl chloride with an appropriate aromatic amine (see Experiments B to E). The resulting sulfonamide is then lithiated as with n-butyl lithium and reacted with an appropriate diarylchlorophosphine (see Examples 1 to 5). The sulfonamides corresponding to the ligand (IV) wherein n is 1 can be made by reacting methanesulfonyl chloride with an appropriate amine to form the sulfonamide, and then metalating the sulfonamide with n-butyl lithium and reacting with an appropriate diarylchlorophosphine.
For compounds wherein n is 2 or 3 the following synthesis applicable:
Cl(CH
2
)
2-3
SO
2
Cl+Ar′NH
2
→Cl(CH
2
)
2-3
SO
2
NHAr′
Cl(CH
2
)
2-3
SO
2
NHAr′+Ar
2
PNa→Ar
2
P(CH
2
)
2-3
SO
2
NHAr′
A reaction similar to the second reaction is described in European Patent Application 280,380.
Nickel complexes of the various phosphinosulfonamides can be made by a variety of methods. Bis(1,4-cyclooctadiene)Ni [0] may be reacted with the phosphinosulfonamide to form a complex useful as an oligomerization catalysts (see Example 6). The compound (N,N,N′N′-tetramethylethylenediamine)NiMe
2
may be reacted with the phosphinosulfonamide to form an active catalyst (see Examples 7 and 8).
Ligands to which eth

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