Olefin polymerization catalysts, their production and use

Details Olefin polymerization catalysts, their production and use Olefin polymerization catalysts, their production and use

1999-02-10

2001-12-25

Wu, David W. (Department: 1755)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C526S348000, C526S111000, C526S135000, C502S155000, C502S117000, C502S158000, C502S162000, C502S156000

Reexamination Certificate

active

06333389

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a new family of olefin polymerization catalysts based upon phenoxide complexes of transition metals.
BACKGROUND OF THE INVENTION
The intense commercialization of metallocene polyolefin catalysts (metallocene being cyclopentadienyl based transition metal catalyst compounds) 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 will be more economical due to the relative ease of synthesis of a variety of substituted analogs.
Anionic, multidentate heteroatom ligands have received the most attention in non-metallocene polyolefins catalysis. Notable classes of bidentate anionic ligands which form active polymerization catalysts include N—N
−
and N—O
−
ligand sets. Examples of these types of non-metallocene catalysts include amidopyridines (Kempe, R., “Aminopyridinato Ligands—New Directions and Limitations”, 80
th
Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, Jun. 1-4, 1997. Kempe, R. et al,
Inorg. Chem
. 1996 vol 35 6742.) Likewise, recent reports by Jordan et al. of polyolefin catalysts based on hydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F.,
Organometallics
1997, 16, 3282) have been interesting even though the catalytic activities of Jordan's hydroxyquinoline catalysts is low.
European Patent Application 0 803 520 discloses polymerization catalysts containing beta-diketiminate ligands. Other recent non-metallocene olefin polymerization catalysts include U.S. Pat. No. 4,057,565 which discloses 2-dialkylaminobenzyl and 2-dialkylaminomethylphenyl derivatives of selected transition metals and WO 96/08498 which discloses group 4 metal complexes containing a bridged non-aromatic, anionic dienyl ligand group.
U.S. Pat. No. 5,637,660 discloses bidentate pyridine based transition metal catalysts.
Further Grubbs et al in Organometallics, Vol 17, 1988 page 3149-3151 disclose that nickel (II) salicylaldiminato complexes combined with B(C
6
F
5
)
3
polymerized ethylene. (49,500 Mw, Mw/Mn 6.8, and 35 branches per 1000 C's).
Ethylenebis(salicylideneiminato)zirconium dichloride combined with methyl alumoxane deposited on a support and unsupported versions were used to polymerize ethylene by Repo et al in Macromolecules 1997, 30, 171-175.
Further EP 241,560 A1 discloses alkoxide ligands in transition metal catalyst systems.
EP 0 874 005 A1 discloses phenoxide compounds with an imine substituent for use as a polymerization catalyst.
Thus there is a need in the art for new novel olefin polymerization catalysts.
SUMMARY OF THE INVENTION
This invention relates to a catalyst system comprising an activator and one or more heteroatom substituted phenoxide group 3 to 10 or lanthanide transition metal compounds wherein the metal is bound to the oxygen of the phenoxide group and provided that:
a) if more than one heteroatom substituted phenoxide is present it is not bridged to the other heteroatom substituted phenoxide,
b) if the metal is a group 4 metal then the carbon ortho to the carbon bound to the oxygen of the phenoxide may not be bound to an aldehyde or an ester, and
c) the carbon ortho to the carbon bound to the oxygen of the phenoxide may not be bound to the C
1
carbon in a group represented by the formula:
wherein R
6
and R
7
are independently hydrogen, halogen, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, an sulfur containing group, a phosphorus containing group, a silicon containing group, a germanium containing group, or a tin containing group. The activator is preferably one or more of aluminum alkyl, an alumoxane, a modified alumoxane, a non-coordinating anion, or a borane.
This invention further relates to a novel olefin polymerization systems comprising an activator and one or more catalysts represented by the of the following formulae:
wherein R
1
to R
5
may be independently hydrogen, a heteroatom containing group or a C
1
to C
100
group provided that one of R
2
to R
5
is a group containing a heteroatom (R
5
and/or R
1
also may or may not be bound to the metal M), and further provided that the R
4
and R
5
groups do not form pyridine in the first formula if M is a group 4 metal and the R
4
and R
5
groups do not form pyridine in at least one ring of the second formula if M is a group 4 metal, O is oxygen, M is a group 3 to 10 transition metal or lanthanide metal, n is the valence state of M, Q is an anionic ligand or a bond to an R group containing a heteroatom which may be any of R
1
to R
5
, and further provided that if M is a group 4 metal then R
5
may not be an aldehyde or an ester, and further provided that if M is nickel then R
5
may not be an imine. Any two or more R groups may form a ring structure. Provided however that neither R
1
nor R
5
may be a group represented by the formula
wherein R
6
and R
7
are independently hydrogen, halogen, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, an sulfur containing group, a phosphorus containing group, a silicon containing group, a germanium containing group, or a tin containing group, and R
6
and R
7
may be bonded to each other to form a ring. The activator is preferably an aluminum alkyl, an alumoxane, a modified alumoxane, a non-coordinating anion, a borane or a combination thereof.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to a novel olefin polymerization system comprising an activator and one or more catalysts represented by the following formulae:
wherein R
1
is hydrogen or a C
4
to C
100
group, preferably a tertiary alkyl group, preferably a C
4
to C
20
alkyl group, preferably a C
4
to C
20
tertiary alkyl group, preferably a neutral C
4
to C
100
group and may or may not also be bound to M, and at least one of R
2
to R
5
is a group containing a heteroatom, the rest of R
2
to R
5
are independently hydrogen or a C
1
to C
100
group, preferably a C
4
to C
20
alkyl group (preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl) and any of R
2
to R
5
also may or may not be bound to M, provided that in the first formula if M is a group 4 metal then the R
4
and R
5
groups do not form pyridine and in the second formula if M is a group 4 metal the R
4
and R
5
groups do not form pyridine in at least one ring, and further provided that if M is a group 4 metal then R
5
may not be an aldehyde or an ester, and further provided that if M is nickel then R
5
may not be an imine, further provided that neither R
1
nor R
5
may be a group represented by the formula
wherein R
6
and R
7
are independently hydrogen, halogen, a hydrocarbon group, a heterocyclic compound residue, an oxygen containing group, a nitrogen containing group, a boron containing group, an sulfur containing group, a phosphorus containing group, a silicon containing group, a germanium containing group, or a tin containing group, and R
6
and R
7
may be bonded to each other to form a ring;
O is oxygen, M is a group 3 to group 10 transition metal or lanthanide metal, preferably a group 4 metal, preferably Ti, Zr or Hf. n is the valence state of the metal M, preferably 2, 3, 4, or 5, Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, or a bond to an R group containing a heteroatom which may be any of R
1
to R
5
. A heteroatom containing group may be any heteroatom or a heteroatom bound to carbon silica or another heteroatom. Preferred heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium. Particularly preferred heteroatoms include nitrog

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