Olefin polymerization catalyst system

Details Olefin polymerization catalyst system Olefin polymerization catalyst system

1998-12-18

2001-10-16

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...

C526S172000, C526S348600, C526S352000, C526S901000, C526S348500, C502S153000, C502S167000

Reexamination Certificate

active

06303719

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to olefin polymerization catalysts based upon transition metal compounds comprising bidentate ligands containing pyridine or quinoline moieties combined with activators and an additive.
BACKGROUND OF THE INVENTION
The intense commercialization o f metallocene polyolefin catalysts has led to widespread interest in the design of non-metallocene, homogeneous catalysts. This field is more than an academic curiosity as new, non-metallocene catalysts may provide an easier pathway to currently available products and may also provide product and process opportunities which are beyond the capability of metallocene catalysts. In addition, certain non-cyclopentadienyl ligands may be more economical due to the relative ease of synthesis of a variety of substituted analogs.
Thus there is a need in the art for new novel olefin polymerization catalysts. U.S. Ser. No. 09/103,620 discloses the use of transition metal compounds comprising bidentate ligands containing pyridine or quinoline moieties and mixtures thereof with activators to polymerize olefins. In particular [[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2, 6-Diisopropylphenyl Amido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl is combined with modified methyl alumoxane in the gas phase to produce ethylene hexene copolymers.
We have found that the systems in U.S. Ser. No. 09/103,620 U.S. Pat. No. 6,103,657 can be modified by the direct addition of an additive to produce bimodal products from a single catalyst.
For U.S. purposes the following references are mentioned: U.S. Pat. Nos. 4,845,067; 4,999,327; JP 1126111; U.S. Pat. No. 4,508,842; and UK 1015054.
SUMMARY OF THE INVENTION
This invention relates to an olefin polymerization catalyst system comprising the product of the combination of an activator, an additive and a transition metal compound based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. application Ser. No. 09/103,620 filed Jun 23, 1998, now U.S. Pat. No. 6,103,657 which is herein incorporated by reference. This invention further relates to a process to produce polyolefins using such catalysts. This invention further relates to resins produced by such catalyst system, preferably polyethylene resins, more preferably bimodal high density polyethylene resins.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to olefin polymerization catalyst system comprising an activator, an additive and a transition metal compound based on bidentate ligands containing pyridine or quinoline moieties.
The activator may be any known catalyst activator and in one embodiment is an alkyl aluminum, an alumoxane, a modified alumoxane, a polyalumoxane, a non-coordinating anion, a Lewis acid or a mixture thereof
There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253 and 5,731,451 and European publications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publication WO 94/10180, all of which are herein fully incorporated by reference.
Ionizing compounds (non-coordinating anions) may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound. Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3, 1994, now abandoned all of which are herein fully incorporated by reference. Other activators include those described in PCT publication WO 98/07515 such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate, which is fully incorporated herein by reference. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, PCT publications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference. Also, methods of activation such as using radiation and the like are also contemplated as activators for the purposes of this invention. The additive may be an alkoxy compound. Alkoxy compound is defined to be compounds represented by the formula R═O where R is a C
1
to C
100
group and the oxygen may be bound at any point along the R group. The R group may also contain heteroatoms, in addition to the 1 to 100 carbon atoms. Preferred alkoxy compounds include ketones and aldehydes. Particularly preferred alkoxy compounds include acetone, benzophenone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tertiary butyl ketone, acetophenone, cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl n-propyl ketone, ethyl isopropyl ketone, and the like.
In one embodiment, the transition metal catalyst compound based on bidentate ligands containing pyridine or quinoline moieties is represented by the formula:
((Z)XA
t
(YJ))
q
MQ
n
  (I)
where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y are bonded to M; X and Y are independently carbon or a heteroatom, provided that at least one of X and Y is a heteroatom, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X where Z comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms or a silyl group, an alkyl silyl group such as a trialkyl silyl, preferably Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of X, Y or J, preferably X and J; q is 1 or 2; n is the oxidation state of M minus q if Q is a monovalent anion, n is (the oxidation state of M−q)/2, if Q is a bivalent anion or n is (the oxidation state of M−q)/3 if Q is a trivalent anion., typically n is an integer from 1 to 4 depending on the oxidation state of M. In one embodiment, if X is oxygen or sulfur then Z is optional. In another embodiment, if X is nitrogen or phosphorous then Z is present. In an embodiment, Z is preferably an aryl group, more preferably a substituted aryl group.
In another embodiment, R′m is bound to Z and R″p is bound to J, the R″ groups are independently selected from the group consisting of hydrogen or linear, branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals. Also, two or more R″ groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring. Preferably R″ is hydrogen or an aryl group, most preferably R″ is hydrogen. When R″ is an aryl group and Y is nitrogen, a quinoline group is formed. Optionally, an R″ may be joined to A; m is an integer from 0 to 5, preferably 2;
the R′ groups are independently selected from group consisting of hydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl, alkynyl or aryl radicals. Also, two or more R′ groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring. Preferably R′ is an alkyl group having from 1 to 20 carbon atoms, more preferably R′ is methyl, ethyl, propyl, butyl, pentyl and the like, including isomers thereof, more preferably R′ is a methyl group, or a primary, secondary or tertiary hydrocarbon, including isopropyl, t-butyl and the like, most preferably R′ i

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