Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2001-03-07

2003-05-13

Harlan, Robert D. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S167000, C526S172000

Reexamination Certificate

active

06562751

ABSTRACT:

FIELD OF THE INVENTION
Olefins, such as ethylene, are polymerized using as a polymerization catalyst selected transition metal complexes of anionic ligands having three donor atoms that may coordinate to the transition metal.
TECHNICAL BACKGROUND
Polymers of olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used in lubricants and waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc.
Olefins may be polymerized by a variety of transition metal containing catalysts, for example metallocene and Ziegler-Natta type catalysts. More recently, other types of transition metal containing polymerization catalysts have been discovered, in which the transition metal atom is complexed to a neutral or monoanionic ligand. See, for instance, U.S. Pat. No. 5,714,556, U.S. Pat. No. 5,880,241, U.S. Pat. No. 6,060,569, U.S. Pat. No. 6,174,975, WO9842664 and WO9842665, all of which are incorporated by reference herein for all purposes as if fully set forth. Each type of polymerization catalyst has its advantages and disadvantages, and due the commercial importance of polyolefins, new polymerization catalysts are constantly being sought.
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 monomers selected from the group consisting of ethylene and an olefin of the formula H
2
C=CH(CH
2
)
n
H (XXII), and a Cr, Mn, V, Ti, Zr or Hf complex of an anion of the formula (I)
wherein:
R
1
is hydrocarbyl or substituted hydrocarbyl, R
2
is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R
3
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R
1
and R
2
taken together may be ortho-arylene or substituted ortho-arylene, or R
1
, R
2
and R
3
taken together may form one or more rings;
Z is a bridging group of the formula (II), (III) or (IV)
Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
R
4
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R
4
is not present;
R
6
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
3
and R
6
together may form a ring;
R
7
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
3
, R
6
and R
7
together may form an aromatic ring, or R
6
and R
7
taken together may form a ring;
R
8
is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
9
is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
4
and R
9
taken together may be part of a double bond to an imino nitrogen atom, or R
8
and R
9
taken together may form a carbonyl with the carbon to which they are attached, or R
8
and R
9
taken together may form a ring, or R
4
and R
9
taken together may form a ring, or R
4
, R
8
and R
9
taken together may form a ring, or R
6
, R
7
, R
8
and R
9
taken together may form an aromatic ring;
R
10
, R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
10
, R
11
, R
12
and R
13
taken together may be ortho-arylene;
R
14
and R
15
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R
14
and R
15
taken together may form a carbonyl with the carbon to which they are attached, or R
12
, R
13
, R
14
, and R
15
taken together may form an o-arylene group, or R
10
, R
11
, R
12
, R
13
, R
14
and R
15
taken together may form a fused aromatic ring system, or R
13
and R
14
taken together may form a ring;
R
20
and R
21
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R
20
and R
21
taken together may form a ring;
each R
22
is individually hydrocarbyl, oxygen or alkoxy, provided that when R
22
is oxygen, two of R
22
are taken together to form T=O;
n is an integer of 1 or more;
T is phosphorous or sulfur whose oxidation state is 3 or greater; and
x is equal to the oxidation state of T minus 2.
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 monomers selected from the group consisting of ethylene and H
2
C=CH(CH
2
)nH (XXII) with a compound of the formula (V)
wherein:
R
1
, R
2
, R
3
, R
4
, Q, Z (and all R groups associated with Z), M and m are as defined above for (I),
M is Ti, Zr, Hf, V, Mn or Cr;
m is an integer equal to the valence of M minus 2; and
each L
1
is independently a monodentate monoanionic ligand and at least for one of L
1
an ethylene molecule may insert between L
1
and M, and L
2
is a monodentate neutral ligand which may be displaced by ethylene or an empty coordination site, provided that an L
1
and L
2
taken together may be a monoanionic polydentate ligand and at least for one of these monoanionic polydentate ligands ethylene may insert between said monoanionic polydentate ligand and M.
In the above-mentioned processes, (V) and/or the transition metal complex of (I) may in and of themselves be active catalysts, or may be “activated” by contact with a co-catalyst/activator.
The present invention also concerns a compound of the formula (VI)
wherein R
1
, R
2
, R
3
, R
4
, Q, Z (and all R groups associated with Z), M and m are as defined above for (IV),
p is 0 or 1; and
each L
3
is independently a monodentate monoanionic ligand, and L
4
is a monodentate neutral ligand or an empty coordination site, provided that an L
3
and L
4
taken together may be a monoanionic bidentate ligand.
Further aspects of the present invention include, for example, the anion of the formula (I) as defined above, a Ti, Zr, Hf, V, Mn or Cr complex of such anion, and the combination of such complex, (V) and/or (VI) with a co-catalyst.
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 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 that 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
23
wherein R
23
is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a metal atom the functional group should not coordinate to the metal atom more strongly than the groups in those compounds are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
By a “cocatalyst” or “catalyst activator” is meant one or more compounds that r

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