Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-01-13
2001-01-16
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...
C526S133000, C526S348600, C526S352000, C502S150000, C502S162000
Reexamination Certificate
active
06174975
ABSTRACT:
FIELD OF THE INVENTION
Olefins are polymerized by a catalyst system that includes a nickel[II] complexes of selected monoanionic bidentate ligands. Some of these complexes are also novel.
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.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of an olefin selected from one or more of R
67
CH═CH
2
, cyclopentene, a styrene, a norbornene or H
2
C═CH(CH
2
)
s
CO
2
R
77
, comprising, contacting, at a temperature of about −100° C. to about +200° C., R
67
CH═CH
2
, cyclopentene, a styrene, a norbornene, or H
2
C═CH(CH
2
)
s
CO
2
R
77
, optionally a Lewis acid, and a compound of the formula:
wherein:
Ar
1
, Ar
2
, Ar
4
, Ar
5
, Ar
10
, Ar
11
, Ar
12
and Ar
13
are each independently aryl or substituted aryl;
R
1
and R
2
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
1
and R
2
taken together form a ring, and R
3
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R
1
, R
2
and R
3
taken together form a ring;
A is a &pgr;-allyl or &pgr;-benzyl group;
R
10
and R
15
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
11
, R
12
, R
13
, R
14
, R
16
, R
17
, R
18
, R
19
, R
20
, R
21
, R
30
, R
31
, R
32
, R
33
, R
34
, R
35
R
50
, R
51
, R
52
, R
53
and R
54
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR
27
;
R
22
is hydrocarbyl, substituted hydrocarbyl, —SR
117
, —OR
117
, or —NR
118
2
, R
24
is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R
27
is hydrocarbyl or substituted hydrocarbyl, and provided that R
22
and R
24
or R
24
and R
27
taken together may form a ring;
R
117
is hydrocarbyl or substituted hydrocarbyl;
each R
118
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR
57
and L is CR
55
;
R
55
, R
56
and R
57
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R
55
, R
56
and R
57
taken together form a ring;
R
67
is hydrogen, alkyl or substituted alkyl;
R
77
is hydrocarbyl or substituted hydrocarbyl;
R
78
is hydrocarbyl or substituted hydrocarbyl;
R
79
, R
80
, R
81
, R
82
, R
83
, R
84
, R
85
, R
86
, R
87
, R
88
and R
89
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R
90
, R
91
, R
92
and R
93
are each independently hydrocarbyl or substituted hydrocarbyl;
R
94
and R
95
are each independently hydrocarbyl or substituted hydrocarbyl;
R
96
, R
97
, R
98
, and R
99
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR
108
wherein R
108
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R
100
, R
101
, R
102
, R
103
, R
104
, R
105
, R
106
, and R
107
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R
109
, R
110
, R
111
, R
112
, R
113
, R
114
, R
115
and R
116
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R
28
and R
29
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that when H
2
C═CH(CH
2
)
s
CO
2
R
77
is present, R
67
CH═CH
2
is also present.
This invention also concerns a process for the polymerization of an olefin selected from one or more of R
67
CH═CH
2
, a styrene, a norbornene or H
2
C═CH(CH
2
)
s
CO
2
R
77
, comprising, contacting, at a temperature of about −100° C. to about +200° C., R
67
CH═CH
2
, cyclopentene, a styrene, a norbornene, or H
2
C═CH(CH
2
)
s
CO
2
R
77
, optionally a Lewis acid, and a compound of the formula:
wherein:
L
1
is a neutral monodentate ligand which may be displaced by said olefin, 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 add to said olefin;
Ar
1
, Ar
2
, Ar
4
, Ar
5
, Ar
10
, Ar
11
, Ar
12
and Ar
13
are each independently aryl or substituted aryl;
R
1
and R
2
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
1
and R
2
taken together form a ring, and R
3
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R
1
, R
2
and R
3
taken together form a ring;
A is a &pgr;-allyl or &pgr;-benzyl group;
R
10
and R
15
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
11
, R
12
, R
13
, R
14
, R
16
, R
17
, R
18
, R
19
, R
20
, R
21
, R
30
, R
31
, R
32
, R
33
, R
34
, R
35
R
50
, R
51
, R
52
, R
53
and R
54
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR
27
;
R
22
is hydrocarbyl, substituted hydrocarbyl, —SR
117
, —OR
117
, or —NR
118
2
, R
24
is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R
27
is hydrocarbyl or substituted hydrocarbyl, and provided that R
22
and R
24
or R
24
and R
27
taken together may form a ring;
R
117
is hydrocarbyl or substituted hydrocarbyl;
each R
118
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR
57
and L is CR
55
;
R
55
, R
56
and R
57
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R
55
, R
56
and R
57
taken together form a ring;
R
67
is hydrogen, alkyl or substituted alkyl;
R
77
is hydrocarbyl or substituted hydrocarbyl;
R
78
is hydrocarbyl or substituted hydrocarbyl;
R
79
, R
80
, R
81
, R
82
, R
83
, R
84
, R
85
, R
86
, R
87
, R
88
and R
89
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R
90
, R
91
, R
92
and R
93
are each independently hydrocarbyl or substituted hydrocarbyl;
R
94
and R
95
are each independently hydrocarbyl or substituted hydrocarbyl;
R
96
, R
97
, R
98
, and R
99
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR
108
wherein R
108
is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R
100
, R
101
, R
102
, R
103
, R
104
, R
105
, R
106
, and R
107
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R
109
, R
110
, R
111
, R
112
, R
113
, R
114
, R
115
and R
116
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R
28
and R
29
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that when H
2
C═CH(CH
2
)
s
CO
2
R
77
is present, R
67
CH═CH
2
is also present.
Also described herein is a compound of the formula:
wherein:
L
1
is a neutral monodentate ligand which may be displaced by said olefin, 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 add to said olefin;
Ar
Bennett Alison Margaret Anne
Coughlin Edward Bryan
Feldman Jerald
Hauptman Elisabeth
Ittel Steven Dale
Citron Joel D.
E.I. Du Pont de Nemours and Company
Evans Craig H.
Harlan R.
Lerman Bart E.
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