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
2000-12-04
2002-08-13
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S154000, C502S155000, C502S167000
Reexamination Certificate
active
06432862
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 iron or cobalt 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, branching, 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 containing iron or cobalt, are especially useful in polymerizing ethylene and propylene, see for instance U.S. patent applications Ser. No. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No. 5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No. 6,150,482) (“equivalents” of World Patent Applications 98/27124 and 98/30612). It is also known that blends of distinct polymers, that vary for instance in molecular weight, molecular weight distribution, crystallinity, and/or branching, may have advantageous properties compared to “single” polymers. For instance it is known that polymers with broad or bimodal molecular weight distributions may often be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Also, 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.
Various reports of “simultaneous” oligomerization and polymerization of ethylene to form (in most cases) branched polyethylenes have appeared in the literature, see for instance World Patent Application 90/15085, U.S. Pat. Nos. 5,753,785, 5,856,610, 5,686,542, 5,137,994, and 5,071,927, C. Denger, et al,. Makromol. Chem. Rapid Commun., vol. 12, p. 697-701 (1991), and E. A. Benham, et al., Polymer Engineering and Science, vol. 28, p. 1469-1472 (1988). None of these references specifically describes any of the processes herein or any of the branched homopolyethylenes claimed herein.
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 is a Fe or Co complex of a ligand of the formula:
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;
(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 process for the polymerization of olefins, comprising, contacting under polymerizing conditions:
(a) a first active polymerization catalyst for said olefins which is a Fe or Co complex of a ligand of the formula:
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;
(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;
and provided that:
one or both of said first olefin and said second olefin is ethylene;
one of said first polymerization catalysts and said second polymerization catalyst produces an oligomer of the formula R
60
CH═CH
2
from said ethylene, wherein R
60
is n-alkyl; and
a branched polyolefin is a product of said polymerization process.
This invention also concerns a polymerization catalyst component, comprising:
(a) a first active polymerization catalyst for said olefins which is a Fe or Co complex of a ligand of the formula:
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;
(b) a second active polymerization catalyst for said olefins which contains one or more transition metals;
(c) a catalyst support; and
(d) optionally one or more polymerization catalyst activators for one or both of (a) and (b).
Also described herein is a polyolefin containing at least 2 ethyl branches, at least 2 hexyl or longer branches and at least one butyl branch per 1000 methylene groups, and provided that said polyolefin has fewer than 5 methyl branches per 1000 methylene groups.
This invention also includes a polyolefin, containing about 20 to about 150 branches of the formula —(CH
2
CH
2
)
n
H wherein n is an integer of 1 to 100, provided that said polyolefin has less than about 20 methyl branches per 1000 methylene groups.
DETAILS OF THE INVENTION
In the polymerization processes and catalyst compositions described herein certain groups may be present. By hydrocarbyl is meant a univalent radical containing only carbon and hydrogen. By substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more (types of) substitutents that does not interfere with the operation of the polymerization catalyst system. Suitable substituents in some polymerizations may include some or all of halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. Preferred substituents are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide. Which substitutents are useful in which polymerizations may in some cases be determined by reference to U.S. patent applications Ser. No. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No. 5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No. 6,150,482) (and their corresponding World Patent Applications), both of which are hereby included by reference. By an aryl moiety is meant a univalent group whose free valence is to a carbon atom of an aromatic ring. The aryl moiety may contain one or more aromatic ring and may be substituted by inert groups. By phenyl is meant the C
6
H
5
— radical, and a phenyl moiety or substituted phenyl is a radical in which one or more of the hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl). Preferred substituents for substituted phenyl include those listed above for substituted hydrocarbyl, plus hydrocarbyl. If not otherwise stated, hydrocarbyl, substituted hydrocarbyl and all other groups containing carbon atoms, such as alkyl, preferably contain 1 to 20 carbon atoms.
By a polymerization catalyst activator is meant a compound that reacts with a transition metal compound to form an active polymerization catalyst. A preferred polymerization catalyst activator is an alkylaluminum compound, that is a compound which has one or more alkyl groups bound to an aluminum atom.
By
E. I. du Pont de Nemours and Company
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