Copolymerization of olefins

Details Copolymerization of olefins Copolymerization of olefins

2002-09-20

2004-10-12

Rabago, Roberto (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S169100, C526S171000, C526S172000, C526S134000

Reexamination Certificate

active

06803432

ABSTRACT:

FIELD OF THE INVENTION
Selected iron and cobalt complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines) are catalysts for the copolymerization of ethylene and/or propylene and &agr;-olefins. Novel polymers may be produced.
FIELD OF THE INVENTION
Copolymers of ethylene and/or propylene and &agr;-olefins, such as linear low density polyethylene (LLDPE) are important items of commerce, millions of tons being produced annually. These polymers are used in a myriad of ways, such as for fiber, films, molding resins, etc. In most cases, ethylene and &agr;-olefins are copolymerized using a catalyst, often a transition metal compound or complex. These catalysts may vary in cost per unit weight of polymer produced, the structure of the polymer produced, the possible need to remove the catalyst from the polymer, the toxicity of the catalyst, etc. Due to the commercial importance of copolymerizing ethylene, new polymerization catalysts are constantly being sought.
B. L. Small, et al., J. Am. Chem. Soc., vol. 120, p. 4049-4050 (1998), and G. J. P. Britovsek, et al., J. Chem. Soc., Chem. Commun., p. 849-850 (1998) report the polymerization of ethylene using catalysts containing Fe or Co complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines). Copolymerization of &agr;-olefins and ethylene are not reported.
SUMMARY OF THE INVENTION
This invention concerns a first polymerization process, comprising, contacting, at a temperature of about −100° C. to about +200° C., a compound of the formula:
with one or both of ethylene and propylene, and an olefin of the formula H
2
C═CHR
21
and:
(a) a first compound W, which is a neutral Lewis acid capable of abstracting X
−
an alkyl group or a hydride group from M to form WX
−
, (WR
20
)
−
or WH
−
and which is also capable of transferring an alkyl group or a hydride to M, provided that WX
−
is a weakly coordinating anion; or
(b) a combination of second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X
−
, a hydride or an alkyl group from M to form a weakly coordinating anion;
wherein:
M is Co or Fe;
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of a Fe or Co atom present in (II);
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R
6
and R
7
are aryl or substituted aryl;
R
20
is alkyl; and
R
21
is alkyl.
This invention also concerns a second polymerization process, comprising contacting, at a temperature of about −100° C. to about +200° C., a Co[II], Co[III], Fe[II] or Fe[III] complex of a tridentate ligand of the formula:
with one or both of ethylene and propylene, and an olefin of the formula H
2
C═CHR
21
wherein:
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R
6
and R
7
are aryl or substituted aryl;
R
21
is alkyl;
and provided that a Co[II], Co[III], Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
This invention also concerns a third polymerization process, comprising, contacting, at a temperature of about −100° C. to about +200° C., one or both of ethylene and propylene, an olefin of the formula H
2
C═CHR
21
, and a compound of the formula:
wherein:
M is Co or Fe;
R
1
, R
2
and R
3
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R
4
and R
5
are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R
6
and R
7
are aryl or substituted aryl;
R
21
is alkyl;
T
1
is hydride or alkyl or any other anionic ligand into which ethylene or an &agr;-olefin can insert;
Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site;
Q is a relatively non-coordinating anion;
P is a divalent polyolefin group; and
T
2
is an end group.


REFERENCES:
patent: 4367322 (1983-01-01), Shiga et al.
patent: 5866665 (1999-02-01), Shaffer et al.
patent: 5955555 (1999-09-01), Bennett
patent: 6150482 (2000-11-01), Brookhart et al.
patent: 6451939 (2002-09-01), Britovsek et al.
patent: 0 824 111 (1998-02-01), None
patent: WO 98/27124 (1998-06-01), None
patent: WO 98/30612 (1998-07-01), None
patent: WO 98/38228 (1998-09-01), None
patent: WO 99/12981 (1999-03-01), None
Brooke L. Small, et al. Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene,J. Am. Chem. Soc.,120, 4049-4050, 1998.
George J. P. Britovsek, et al., Novel olefin polymerization catalysts based on iron and cobalt,Chem. Commun.,849-850, 1998.
Invitation to Pay Additional Fees with Communication Relating to the results of the Partial International Search (Annex to Form PCT/ISA/206) dated Nov. 15, 1999.

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