Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2002-02-27
2003-09-16
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S150000, C502S162000, C502S152000, C502S154000, C502S155000, C502S117000, C502S167000, C502S168000
Reexamination Certificate
active
06620759
ABSTRACT:
FIELD OF THE INVENTION
Polymers with varied and useful properties may be produced in processes using at least two polymerization catalysts, at least one of which is a selected nickel polymerization catalyst, for the synthesis of polyolefins.
TECHNICAL BACKGROUND
Polyolefins are most often prepared by polymerization processes in which a transition metal containing catalyst system is used. Depending on the process conditions used and the catalyst system chosen, polymers, even those made from the same monomer(s) may have varying properties. Some of the properties which may change are molecular weight and molecular weight distribution, crystallinity, melting point, and glass transition temperature. Except for molecular weight and molecular weight distribution, branching can affect all the other properties mentioned.
It is known that certain transition metal containing polymerization catalysts, especially those containing late transition metals such as nickel, are especially useful in varying the branching in polyolefins made with them, see for instance World Patent Applications 96/23010 and 97/02298, and U.S. patent application Ser. No. 09/006,628, filed Jan. 13, 1998, now U.S. Pat. No. 6,060,569, and Ser. No. 09/006,536, filed Jan. 13, 1998, now U.S. Pat. No. 6,174,975, and World Patent Applications 98/30610 and 98/30609. It is also known that blends of distinct polymers, that vary for instance in the properties listed above, may have advantageous properties compared to “single” polymers. For instance it is known that polymers with broad or bimodal molecular weight distributions may be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Similarly, thermoplastics such as crystalline polymers may often be toughened by blending with elastomeric polymers.
Therefore, methods of producing polymers which inherently produce polymer blends are useful especially if a later separate (and expensive) polymer mixing step can be avoided. However in such polymerizations one should be aware that two different catalysts may interfere with one another, or interact in such a way as to give a single polymer.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of olefins, comprising, contacting under polymerizing conditions:
(a) a first active polymerization catalyst for said olefins which contains a Ni complex of a ligand selected from the group consisting of:
or 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
60
, R
61
, R
62
and R
63
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
64
and R
65
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar
14
, Ar
15
, Ar
16
, Ar
17
, Ar
18
and Ar
19
are each independently hydrocarbyl or substituted hydrocarbyl;
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;
(b) a second active polymerization catalyst for said olefins which contains one or more transition metals;
(c) a least one first olefin capable of being polymerized by said first active polymerization catalyst; and
(d) at least one second olefin capable of being polymerized by said second active polymerization catalyst.
This invention also concerns a polymerization catalyst component, comprising:
(a) a first active polymerization catalyst for said olefins which contains a Ni complex of a ligand selected from the group consisting of:
or 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
18
, 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
60
, R
61
, R
62
and R
63
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
64
and R
65
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 1, 2 or 3;
Ar
14
, Ar
15
, Ar
16
, Ar
17
, Ar
18
and Ar
19
are each independently hydrocarbyl or substituted hydrocarbyl;
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
Citron Joel David
Johnson Lynda Kaye
E. I. du Pont de Nemours and Company
Rabago R.
Wu David W.
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