Catalyst for the production of olefin polymers

Details Catalyst for the production of olefin polymers Catalyst for the production of olefin polymers

1999-12-08

2001-11-20

Wilson, Donald R. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S127000, C526S147000, C526S170000, C526S171000, C526S151000, C526S141000, C526S348000, C526S943000, C502S155000, C502S123000, C502S117000

Reexamination Certificate

active

06320005

ABSTRACT:

The invention relates to a family of novel heteroatom-containing catalyst precursors useful for the polymerization of olefins, such as ethylene, higher alpha-olefins, dienes, and mixtures thereof.
BACKGROUND
A variety of metallocenes and other single site-like catalysts have been developed to prepare olefin polymers. Metallocenes are organometallic coordination complexes containing one or more &pgr;-bonded moieties (i.e., cyclopentadienyl groups) in association with a metal atom. Catalyst compositions containing metallocenes and other single site-like catalysts are highly useful in the preparation of polyolefins, producing relatively homogeneous copolymers at excellent polymerization rates while allowing one to tailor closely the final properties of the polymer as desired.
Recently, work relating to certain nitrogen-containing, single site-like catalyst precursors has been published. PCT Application No. WO 96/23101 relates to di(imine) metal complexes that are transition metal complexes of bidentate ligands selected from the group consisting of:
wherein said transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd;
R
2
and R
5
are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R
3
and R
4
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R
3
and R
4
taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
R
44
is hydrocarbyl or substituted hydrocarbyl, and R
28
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R
44
and R
28
taken together form a ring;
R
45
is hydrocarbyl or substituted hydrocarbyl, and R
29
is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R
45
and R
29
taken together form a ring;
each R
30
is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R
30
taken together form a ring;
each R
31
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
46
and R
47
are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R
48
and R
49
are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
R
20
and R
23
are independently hydrocarbyl or substituted hydrocarbyl;
R
21
and R
22
are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and
n is 2 or
3; and provided that:
said transition metal also has bonded to it a ligand that may be displaced by or added to the olefin monomer being polymerized; and
when the transition metal is Pd, said bidentate ligand is (V), (VII) or (VIII).
Similarly, PCT Application No. WO 97/02298 relates to a process for the polymerization of an olefin, comprising contacting a polymerizable monomer consisting essentially of ethylene, a norbornene or a styrene, with a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group consisting of:
Ar
1
Qn (III); R
8
R
10
N—CR
4
R
5
(CR
6
R
7
)
m
—NR
8
R
10
(V);
 R
8
S—CR
4
R
5
(CR
6
R
7
)
m
—SR
8
  (XXXVII);
wherein:
X is a noncoordinating anion;
Ar
1
is an aromatic moiety with n free valencies, or diphenylmethyl;
each Q is —NR
2
R
43
or —CR
9
═NR
3
;
R
43
is hydrogen or alkyl;
n is 1 or 2;
E is 2-thienyl or 2-furyl;
each R
2
is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
each R
9
is independently hydrogen or hydrocarbyl; and
each R
3
is independently a monovalent aromatic moiety;
m is 1, 2 or 3;
each R
4
, R
5
, R
6
, and R
7
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R
8
is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
each R
10
is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Ar
2
is an aryl moiety;
R
12
, R
13
, and R
14
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R
11
and R
15
are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E
S
is about −0.4 or less;
each R
16
and R
17
is independently hydrogen or acyl containing 1 to 20 carbon atoms;
Ar
3
is an aryl moiety;
R
18
and R
19
are each independently hydrogen or hydrocarbyl;
Ar
4
is an aryl moiety;
Ar
5
and Ar
6
are each independently hydrocarbyl;
Ar
7
and Ar
8
are each independently an aryl moiety;
Ar
9
and Ar
10
are each independently an aryl moiety or —CO
2
R
25
, wherein R
25
is alkyl containing 1 to 20 carbon atoms;
Ar
11
is an aryl moiety;
R
41
is hydrogen or hydrocarbyl;
R
42
is hydrocarbyl or —C(O)—NR
41
—Ar
11
;
R
44
is aryl;
R
22
and R
23
are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and
R
24
is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
PCT Application No. WO 96/33202 relates to a transition metal catalyst containing a pyridine or quinoline moiety and having the formula:
each R is independently selected from hydrogen or C
1
to C
6
alkyl, each R′ is independently selected from C
1
to C
6
alkyl, C
1
to C
6
alkoxy, C
6
to C
16
aryl, halogen, or CF
3
, M is titanium, zirconium, or hafnium, each X is independently selected from halogen, C
1
to C
6
alkyl, C
1
to C
6
alkoxy, or
L is X, cyclopentadienyl, C
1
to C
6
alkyl substituted cyclopentadienyl, indenyl, fluorenyl, or
“m” is 0 to 4, and “n” is 1 to 4.
Similarly, Fuhrmann et al.,
Inorg. Chem.,
35:6742-6745 (1996) discloses certain Group 4 metal complexes containing amine, amido, and aminopyridinato ligands such as:
wherein TMS is trimethylsilyl.
An olefin polymerization catalyst composition is described herein having good polymerization activity and productivity. The catalyst composition comprises a heteroatom-containing catalyst precursor having the formula:
A
q
ML
n
wherein each A has the formula:
M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements;
each L is a monovalent, bivalent, or trivalent anion;
X and Y are each heteroatoms;
Cyclo is a cyclic moiety;
each R
1
is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R
1
groups may be joined to form a cyclic moiety;
each R
2
is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R
2
groups may be joined to form a cyclic moiety;
Q is a bridging group;
each m is independently an integer from 0 to 5;
n is an integer from 1 to 4;
q is 1 or 2;
and when q is 2, the A groups are optionally connected by a bridging group Z.
The catalyst precursor may be conveniently prepared by reacting an organometal compound with a heteroatom-containing ligand of the formula:
wherein X, Y, Q, Cyclo, R
1
, R
2
, and m have the meanings stated above.
SUMMARY OF THE INVENTION
The invention provides a catalyst precursor of the formula:
A
q
ML
n
wherein each A has the formula:
M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements;
each L is a monovalent, bivalent, or trivalent anion;
X and Y are each heteroatoms;
Cyclo is a cyclic moiety;
each R
1
is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R
1
groups may be joined to form a cyclic moiety;
each R
2
is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R
2
groups may be joined to form a cyclic moiety;
Q is a bridging group;
each m is independently an integer from 0 to

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