Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-04-11
2002-03-12
Henderson, Christopher (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S134000
Reexamination Certificate
active
06355748
ABSTRACT:
The present invention provides a catalyst composition for the polymerization of olefins, which comprises the reaction product of a spirocycle, a complex of an atom selected from Groups 3-14 and the Lanthanides, and an activating cocatalyst.
BACKGROUND OF THE INVENTION
In the field of single-site polymerization of olefins, typical catalyst compositions comprise organometallic catalysts such as metallocenes contacted with activating cocatalysts such as alumoxanes. The synthesis and isolation of metallocenes can be difficult due to their air and moisture sensitivity. Yields are often poor with more complex kinds of catalysts. Thus, catalyst cost can be substantial. Moreover, it is difficult to change substantially the rates and product properties of these catalysts once they have been made, since the ligand of the catalyst exerts overwhelming control over the catalyst composition properties. Thus, such catalysts are not especially amenable to processes using a variety of conditions or producing a variety of products.
Catalyst compositions that can be assembled at the site of the reactor are advantageous in terms of cost because isolation and purification is avoided. Moreover, catalysts previously considered non-isolable or catalysts that could not even be made in impure form can be readily made by self-assembly. Self-assembled catalyst compositions can also be extremely versatile. Catalyst composition properties can be tuned by adjusting the various components of the catalyst composition.
U.S. Pat. Nos. 5,378,567 and 5,451,555 to Tajima et al. relate to catalyst compositions for the homopolymerization or copolymerization of olefins. The catalyst compositions comprise a first compound of the formula Me
1
(OR
1
)
p
R
2
q
X
1
4-p-q
, wherein Me
1
is Ti, Zr, or Hf, a second compound of the formula Me
2
(OR
3
)
m
R
4
n
X
2
z-m-n
, wherein Me
2
is a Group I-III metal, and a third compound that is an organocyclic compound having two or more conjugated double bonds. A variety of organocyclic compounds are described in these patents, none of which are spirocycles.
Similarly, U.S. Pat. No. 5,331,071 to Kataoka et al. describes a process for the polymerization of olefinic hydrocarbons carried out in the presence of a catalyst component derived from reacting a compound of the formula M
e
1
R
1
n
X
1
4-n
, wherein Me
1
is Ti, Zr, or Hf, a compound of the formula Me
2
R
2
m
X
2
z-m
, wherein Me
2
is a Group I-III metal, an organocyclic compound having two or more conjugated double bonds, and an inert carrier, along with a modified organoaluminum compound having Al—O—Al bonds. Again, a variety of organocyclic compounds are described, none of which are spirocycles.
Derwent Abstract 96-088466/10 for DE 4434640 relates to the in situ production of a bridged metallocene catalyst by reacting a cyclopentadiene with a base, a bridging reagent, and a metal compound. The resulting stereorigid catalyst may be used for the polymerization of olefins.
Applicant has now discovered a self-assembled catalyst composition that may be easily and cost effectively made. The catalyst composition comprises the reaction product of a spirocycle, a complex of an atom selected from Groups 3-14 and the Lanthanides, and an activating cocatalyst. The catalyst composition may contain a solvent as well, and is preferably used in unsupported, liquid form. Isolation of the catalyst composition or intermediates thereto is not required. Combinations of different spirocycles, complexes of an atom selected from Groups 3-14 and the Lanthanides, and activating cocatalysts can lead to versatile catalyst compositions that can be altered on-stream to match product and process requirements. Conditions used during catalyst composition formation such as temperature and concentrations of the reactants also can be used to control the properties of the resulting catalyst composition and polymer product.
SUMMARY OF THE INVENTION
The invention provides a catalyst composition comprising the reaction product of:
a) a spirocycle of the formula:
including oligomers thereof,
wherein each R
1
, R
2
, R
3
, R
4
, and R
5
is independently hydrogen, hydrocarbyl, or a heteroatom-containing group; and any two or more R groups may be joined to form a ring;
b) a complex of the formula [L
m
MX
n
]
r
wherein each L is a neutral ligand, M is an atom selected from Groups 3 to 14 and the Lanthanides, each X is an anionic group, m is an integer of 0 or greater, n is an integer of 0 or greater; and r is an integer of 1 or greater; and
c) an activating cocatalyst.
The invention also provides a process for the polymerization of olefins, which comprises contacting under polymerization conditions olefin with the above catalyst composition.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst composition comprises the reaction product of at least one spirocycle, at least one complex of an atom selected from Groups 3-14 and the Lanthanides, and at least one activating cocatalyst.
The spirocycle has the formula:
wherein each R
1
, R
2
, R
3
, R
4
and R
5
, is independently hydrogen; hydrocarbyl such as alkyl, aryl, alkenyl, or alkynyl; or a heteroatom-containing group such as alkoxy, aryloxy, amino, halo, a silicon atom, or silicon-containing group. A heteroatom-containing group is any group containing at least one atom that is not carbon or hydrogen. Preferably, any hydrocarbyl group contains from 1 to 50 carbon atoms. Similarly, any alkoxy or aryloxy group preferably contains from 1 to 50 carbon atoms. Any two or more R groups may be joined to form a ring. In the case of R
1
through R
4
, two adjacent R groups may comprise one or more arene rings fused to the cyclopentadiene ring.
Furthermore, two or more such spirocycle moieties can be linked by one or more linking groups such as hydrocarbyls or heteroatom-containing groups to form a dimer or other oligomer. As used herein, an oligomer of a spirocycle means two or more spirocycles linked together by such linking groups.
Examples of spirocycles include include 1,1-diphenylspiro[2.4]hepta-4,6-diene, 1-phenylspiro[2.4]hepta-4,6-diene, 1,1-dimethylspiro [2.4]hepta-4,6-diene, 1-methylspiro[2.4]hepta-4,6-diene, 1,1,2,2-tetraphenylspiro[2.4]hepta-4,6-diene, 5-methylspiro[2.4]hepta-4,6-diene, 5-phenylspiro[2.4]hepta-4,6-diene and spiro[2.4]hepta-4,6-diene.
Preferred spirocycles contain at least one cyclopentadiene ring that is spiro-fused to a second 3 or 4-member ring (n=2 or 3), especially a three-membered ring. Most preferred are the following spirocycles:
The spirocycle may be made in any manner. One useful synthesis method from common precursors is described in to Kawase, T; Kurata, H; Fujino, S.-i.; Ekinaka, T.; Oda, M.
Tetrahedron Letters
, 7201, 1992. Spirocycles are also commercially available from many sources, including Fluka Chemicals.
For example, 4,5-Benzo-1,1-[2.4]hepta-4,6-diene may be synthesized by lithium reduction of 1-(diphenylmethylene)indene (synthesized by the method of Baizer, J. J.; Anderson, J. D.
J. Organic Chem
. 1965, 30, 1348-51) to give the dilithio salt, followed by addition of methylene chloride to make the spirocycle.
The complex of an atom selected from Groups 3-14 and the Lanthanides has the formula [L
m
MX
n
]
r
. Each L is the same or different neutral ligand, such as Et
2
O, tetrahydrofuran, Et
3
N, or pyridine.
M is an atom selected from Groups 3 to 14 of the Periodic Table and the Lanthanides. Preferably, M is an element selected from Groups 3 to 6 and the Lanthanides. More preferably, M is a Group 4 element.
Each X is the same or different anionic group, such as halide, alkoxide, amide, hydrocarbyl, acetylacetonate, carboxylate, carbamate, amidate, or aluminate anion such as tetramethylaluminate or tetrachloroaluminate.
The letter m is an integer of 0 or greater, the letter n is an integer of 0 or greater; and the letter r is an integer of 1 or greater Examples of the complex of an atom selected from Groups 3-14 and the Lanthanides include titanium (IV) chl
Henderson Christopher
Union Carbide Chemicals & Plastics Technology Corporation
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