Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2001-05-31

2003-01-14

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...

C526S170000, C526S171000, C526S161000, C526S164000, C526S169000, C526S169100

Reexamination Certificate

active

06506861

ABSTRACT:

FIELD OF THE INVENTION
Selected transition metal complexes of iminocarboxylate and iminoamido ligands, sometimes in the presence of certain cocatalysts, are catalysts for the (co)polymerization of olefins such as ethylene, &agr;-olefins, and certain polar olefins such as olefinic esters. Preferred transition metals include nickel, titanium and zirconium. Also described are certain “Zwitterionic” transition metal complexes as polymerization catalysts for making polar copolymers.
TECHNICAL BACKGROUND
Olefins may be polymerized by a variety of transition metal containing catalysts, for example metallocene and Ziegler-Natta type catalysts. More recently, late transition metal containing polymerization catalysts have also been discovered, and among them are nickel and other transition metal containing catalysts in which the metal atom is complexed to a monoanionic and presumed bidentate ligand, see for instance WO9842664, WO9842665, U.S. Pat. Nos. 6,060,569, 6,174,975 and S. D. Ittel, et al.,
Chem. Rev.
, vol. 100, p. 1169-1203 (2000) (and references cited therein). S. Y. Desjardins, et al.,
J. Organometal. Chem
., vol. 515, p. 233-243 (1996), ibid., vol. 544, p. 163-174 (1997), describe the oligomerization/polymerization of ethylene using nickel complexes of certain pyridine carboxylates.
U.S. Pat. No. 6,174,976 describes the use of certain neutral nickel complexes of ligands containing imino and carboxylate groups to polymerize hydrocarbon monoolefins.
In the following references, Zwitterionic nickel catalysts based on phosphine carboxylate ligands were utilized to carry out ethylene oligomerizations; however, polar monomers were not incorporated in any of the oligomers made with these systems: Komon, Z. J. A., et. al.,
J. Am. Chem. Soc.,
122, 1830-1831 (2000); Komon, Z. J. A., et. al.,
J. Am. Chem. Soc.,
122, 12379-12380 (2000).
Zwitterionic systems have been proposed in U.S. Pat. Nos. 6,103,658 and 6,200,925, but no polar monomers were incorporated in any of the polymers made with these systems.
All of the above publications are incorporated by reference herein for all purposes as if fully set forth.
None of these publications describes the complexes disclosed herein. Since polyolefins are important commercial materials, new catalysts for their manufacture are constantly being sought.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of olefins, comprising the step of contacting, under olefin polymerizing conditions, a monomer component comprising one or more of an olefin of the formula H
2
C=CHR
4
, a norbornene, a styrene, a cyclopentene or a polar olefin, especially an olefin of the formula H
2
C=CHR
4
or a polar olefin of the formula H
2
C=CHR
5
CO
2
R
6
, with a transition metal complex of a ligand of the formula
wherein:
Y is oxo, NR
12
or PR
12
z is O, NR
13
, S or PR
13
;
each of R
1
, R
2
and R
3
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
n is 0 or 1;
R
4
is hydrogen, alkyl or substituted alkyl;
R
5
is a covalent bond, alkylene or substituted alkylene;
R
6
is hydrogen, a metal cation, hydrocarbyl or substituted hydrocarbyl;
each R
12
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
each R
13
is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
and provided that any two of R
1
, R
2
and R
3
geminal or vicinal to one another taken together may form a ring.
In the above mentioned process, the transition metal complex of (I) may in and of itself be an active catalyst, or may be “activated” by contact with a cocatalyst/activator as further described below.
The present invention also concerns the ligand of the formula (I), transition metal complexes thereof, and polymerization catalyst components comprising these transition metal complexes.
This invention also concerns a process for the manufacture of a polar copolymer, wherein one or more hydrocarbon olefins, one or more polar olefins, and a polymerization catalyst system having a transition metal complex component containing a transition metal of groups 6-11 or a lanthanide metal, are contacted under polymerizing conditions to form said polar copolymer, wherein the transition metal complex component comprises a Zwitterionic complex.
These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed description. It is to be appreciated that certain features of the invention which are, for clarity, described below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.
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 (and alkyl groups) herein contain 1 to about 30 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below). The substituent groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. 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 chains or rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the heteroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.
By “(inert) functional group” herein is meant a group, other than 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 deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include, for example, halo (fluoro, chloro, bromo and iodo), ether such as —OR
22
wherein R
22
is hydrocarbyl or substituted hydrocarbyl, silyl, substituted silyl, thioether and tertiary amino. In cases in which the functional group may be near a transition metal atom, the functional group alone should not coordinate to the metal atom more strongly than the groups in those compounds that are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
By a “cocatalyst” or a “catalyst activator” is meant one or more compounds that react with a transition metal compound to form an activated catalyst species. One such catalyst activator is an “alkyl aluminum compound” which, herein, is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as, for example, alkoxide, hydride and halogen may also be bound to aluminum atoms in the compound.
By “neutral Lewis base” is meant a compound, that is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, thioethers, olefins and organic nitrites.
By “neutral Lewis acid” is meant a compound, that is not an ion, which can act as a Lewis acid. Examples of such compounds include boranes, alkylaluminum compounds, aluminum halides and antimony [V] halides.
By “cationic Lewis acid” is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations.
By an “empty coordination site” is meant a potential coordination site on a transition

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