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
2002-04-15
2004-11-30
Harlan, Robert D. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S152000, C502S320000, C526S161000, C526S160000, C526S943000
Reexamination Certificate
active
06825147
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to Group 4 metal complexes containing an aryl substituted cyclopentadienyl ligand and to polymerization catalysts derived from such complexes that are particularly suitable for use in a polymerization process for preparing homopolymers and copolymers of olefins or diolefins, including copolymers comprising two or more olefins or diolefins such as copolymers comprising a monovinyl aromatic monomer and ethylene.
Constrained geometry metal complexes and methods for their preparation are disclosed in U.S. Pat. No. 5,703,187. This publication also teaches the preparation of certain novel copolymers of ethylene and a hindered vinyl monomer, including monovinyl aromatic monomers, having a pseudo-random incorporation of the hindered vinyl monomer therein. Additional teachings of constrained geometry catalysts may be found in U.S. Pat. Nos. 5,321,106, 5,721,185, 5,374,696, 5,470,993, 5,541,349, and U.S. Pat. No. 5,486,632, WO97/15583, and WO97/19463.
In Table 1 of U.S. Pat. No. 5,723,560 and related patents, tetraphenylcyclopentadienyl-, 3,4-diphenylcyclopentadienyl-, and 2,5-diphenylcyclopentadienyl-ligands are listed. 2- and/or 3-substituted indenyl metal complexes are disclosed in U.S. Pat. No. 6,015,868. 3-Aryl-substituted indenyl metal complexes are disclosed in U.S. Pat. No. 5,866,704. Certain highly active, polyaromatic, metal complexes, especially derivatives of s-indacenyl- and cyclopentaphenanthrenyl-ligand groups are disclosed in U.S. Pat. No. 5,965,756 and U.S. Ser. No. 09/122958, filed Jul. 27, 1998, (WO99/14221, published Mar. 25, 1999) respectively. Despite the advance in the art occasioned by the foregoing metal complexes, improved metal complexes that are capable of producing high styrene content ethylene/styrene interpolymers (ESI) and that are economical to prepare are continually desired. Accordingly, it would be desirable if there were provided metal complexes having acceptable catalytic properties that are also economical to produce.
SUMMARY OF THE INVENTION
According to the present invention there is provided 3-arylcyclopentadienyl-substituted metal complexes corresponding to the formula:
wherein,
Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;
R independently each occurrence is hydrogen, Ar, or a group other than Ar selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40 atoms not counting hydrogen atoms;
M is titanium;
Z′ is SiR
6
2
, CR
6
2
, SiR
6
2
SiR
6
2
, CR
6
2
CR
6
2
, CR
6
═CR
6
, CR
6
2
SIR
6
2
, BR
6
, BR
6
L″, or GeR
6
2
;
Y is —O—, —S—, —NR
5
—, —PR
5
—; —NR
5
2
, or —PR
5
2
;
R
5
, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R
5
having up to 20 atoms other than hydrogen, and optionally two R
5
groups or R
5
together with Y form a ring system;
R
6
, independently each occurrence, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, —NR
5
2
, and combinations thereof, said R
6
having up to 20 non-hydrogen atoms, and optionally, two R
6
groups form a ring system;
L″ is a monodentate or polydentate Lewis base optionally bonded to R
6
;
X is hydrogen or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen;
L independently each occurrence is a neutral ligating compound having up to 20 atoms, other than hydrogen, and optionally L and X are bonded together;
X′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen;
z is 0, 1 or 2;
x is 0, 1, 2, or 3;
l is a number from 0 to 2, and
x′ is 0 or 1.
The above compounds may exist as isolated crystals, as a mixture with other compounds, in the form of a solvated adduct, dissolved in a solvent, especially an organic liquid solvent, or in the form of a dimer.
Also, according to the present invention, there is provided a catalyst for polymerization of one or more addition polymerizable monomers comprising:
A. i) a metal complex of formula I, and
ii) an activating cocatalyst, the molar ratio of i) to ii) being from 1:10,000 to 100:1, or
B. the reaction product formed by converting a metal complex of formula I to an active catalyst by use of the foregoing activating cocatalyst or an activating technique.
Further according to the present invention there is provided a process for the polymerization of one or more addition polymerizable monomers comprising contacting one or more such monomers, especially one or more C
2-20
olefins, including cyclic olefins, under polymerization conditions with a catalyst comprising:
A. i) a metal complex of formula I, and
ii) an activating cocatalyst, the molar ratio of i) to ii) being from 1:10,000 to 100:1, or
B. the reaction product formed by converting a metal complex of formula I to an active catalyst by use of the foregoing activating cocatalyst or an activating technique.
Use of the present catalysts and processes is especially efficient in production of copolymers of two or more olefins, in particular, copolymers of ethylene and a vinylaromatic monomer, such as styrene, and interpolymers of three or more polymerizable monomers, including a vinylaromatic monomer over a wide range of polymerization conditions, and especially at elevated temperatures. They are especially useful for the formation of copolymers of ethylene and vinylaromatic monomers such as styrene (ES polymers), copolymers of ethylene, styrene, and a diene (ESDM polymers), and copolymers of ethylene, propylene and styrene (EPS polymers). Examples of suitable diene monomers include ethylidenenorbornene, 1,4-hexadiene or similar conjugated or nonconjugated dienes.
The catalysts of this invention may also be supported on a solid, particulated support material and used in the polymerization of addition polymerizable monomers, especially olefins, in a slurry or in a gas phase process. The catalyst may be prepolymerized with one or more olefin monomers in situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolymerized catalyst prior to the primary polymerization process. Because the metal complexes do not contain fused aromatic rings, they are especially suited for use in the formation of polymer products having desirable biological response, taste, odor, and organoleptic properties, due to an absence of such polycyclic aromatic functionality.
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patent: 5374696 (1994-12-01), Rosen et al.
patent: 5470933 (1995-11-01), Mignani et al.
patent: 5486632 (1996-01-01), Devore et al.
patent: 5541349 (1996-07-01), Wilson et al.
patent: 5703187 (1997-12-01), Timmers
patent: 5721185 (1998-02-01), LaPointe et al.
patent: 5723560 (1998-03-01), Canich
patent: 5866704 (1999-02-01), Nickias et al.
patent: 5965756 (1999-10-01), McAdon et al.
patent: WO 97/15583 (1997-05-01), None
patent: WO 97/19463 (1997-05-01), None
patent: WO 98/10018 (1998-03-01), None
patent: WO 99/14221 (1999-03-01), None
Polymeric Materials: Science & Engineering 2001, Wlater Kaminsky, p. 84, 31.
Feng Shaoguang S.
Klosin Jerzy
Shankar Ravi B.
Timmers Francis J.
Dow Global Technologies Inc.
Harlan Robert D.
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