Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From sulfur-containing reactant
Reexamination Certificate
2000-03-31
2002-03-26
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From sulfur-containing reactant
C528S384000, C528S394000, C528S398000, C528S422000, C528S487000, C502S155000, C502S168000, C502S200000, C502S208000, C502S216000
Reexamination Certificate
active
06362309
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to new compositions that provide useful catalysts for polymerizations.
BACKGROUND OF THE INVENTION
Ancillary (or spectator) ligand-metal coordination complexes (e.g., organometallic complexes) and compositions are useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents and drugs. Ancillary ligand-metal coordination complexes of this type can be prepared by combining an ancillary ligand with a suitable metal compound or metal precursor in a suitable solvent at a suitable temperature. The ancillary ligand contains functional groups that bind to the metal center(s), remain associated with the metal center(s), and therefore provide an opportunity to modify the steric, electronic and chemical properties of the active metal center(s) of the complex.
Certain known ancillary ligand-metal complexes and compositions are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilylation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, carbon-halogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions and other transformations.
One example of the use of these types of ancillary ligand-metal complexes and compositions is in the field of polymerization catalysis. In connection with single site catalysis, the ancillary ligand offers opportunities to modify the electronic and/or steric environment surrounding an active metal center. This allows the ancillary ligand to create possibly different polymers. Certain polymerization catalysts are known. See U.S. Pat. No. 4,336,360, EP Application No. 0 343 734 and Japanese Kokai Patent 09-255713, each of which is incorporated herein by reference. Likewise EP 343,734 discloses catalysts compositions for use in producing polyketone polymers, preferably polymers of carbon monoxide. The catalysts compositions are based upon a palladium compound, an anion of an acid having a pKa less than 2 and a compound represented by the formula R
1
R
2
M
1
—R—M
2
—R
3
, where R
1
and R
2
are aryl groups, M
1
is P or As, M
2
is S or Se, R
3
is a hydrocarbyl group and R is a bridging group having at least two carbons.
It is always a desire to discover new catalysts that will catalyze or assist in catalysis of reactions differently from known systems. This invention provides new catalyst compositions that may catalyze polymerization reactions differently, including more efficiently and selectively than known systems.
SUMMARY OF THE INVENTION
The invention disclosed herein is a new catalyst comprising metal-ligand complexes or compositions of metal precursors and ligands that catalyze polymerization and copolymerization reactions, particularly with monomers that are olefins, diolefins or otherwise acetylenically unsaturated. These compositions may also polymerize monomers that have polar functionalities in homopolymerizations or copolymerizations. The new catalyst compositions are prepared by combining a suitable ligand with a suitable metal precursor and, optionally, a suitable activator. The ligands of the composition are characterized by the general formula:
wherein each R
1
, R
2
, and R
3
is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R
1
and R
2
are joined together in a ring structure and/or R
1
or R
2
is joined together with X in a ring structure; also optionally, R
3
and X are joined in a ring structure; E is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony (provided however that when E=N, X is not a benzylic group bound to N through the CH
2
of the benzylic group); and X is a covalent bridging moiety. Suitable metal precursors are characterized by the formula: M(L)
n
where L represents any neutral or charged ligand capable of stabilizing the metal precursor, M represents any transition metal and n is a number from 0-6, provided however that when E=P and R
3
=H, then X cannot be R
1
R
2
C—CR
3
R
4
or R1C=CR2, where R
1
—R
4
are as defined above. Suitable activators are known to those skilled in the art.
For catalysis, the ligands can be included in a composition including a suitable metal, where the said composition has catalytic properties. Also, the ligands can be coordinated with a metal precursor to form metal-ligand complexes, which may be catalysts. Depending on the groups chosen for X, E, R
1
, R
2
, and R
3
in the ligand (e.g., prior to reaction with the metal precursor), the metal-ligand complexes can be characterized by one of many different general formulas depending on how the ligand attaches to or coordinates with the metal.
Thus, in another aspect of the invention, a polymerization process is disclosed for monomers. The polymerization process involves contacting one or more monomers to the catalyst compositions or to the coordination complexes of this invention under polymerization conditions. The catalyst compositions or the coordination complexes may be active catalysts themselves or make be activated with a known activating technique or compound. The polymerization process can be continuous, batch or semi-batch and can be homogeneous or heterogeneous.
Further aspects of this invention will be evident to those of skill in the art upon review of this specification.
DETAILED DESCRIPTION OF THE INVENTION
The inventions disclosed herein are metal complexes and compositions, which are useful as catalysts for chemical reactions, especially polymerization reactions.
As used herein, the phrase “characterized by the formula” is not intended to be limiting and is used in the same way that “comprising” is commonly used. The term “independently selected” is used herein to indicate that the R groups, e.g., R
1
, R
2
, R
3
, R
4
, and R
5
can be identical or different (e.g. R
1
, R
2
, R
3
, R
4
, and R
5
may all be substituted alkyls or R
1
and R
2
may be a substituted alkyl and R
3
may be an aryl, etc.). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. The terms “compound” and “complex” are generally used interchangeably in this specification, but those of skill in the art may recognize certain compounds as complexes and vice versa. For the purposes of illustration, representative certain groups are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.
The term “alkyl” is used herein to refer to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc. In particular embodiments, alkyls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
“Substituted alkyl” refers to an alkyl as just described in which one or more hydrogen atom to any carbon of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, and combinations thereof Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
The term “heteroalkyl” refers to an alkyl as described above in which one or more hydrogen atoms to any carbon of the alkyl is replaced by a heteroatom selected from the group consisting of N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. The bond between the carbon atom and the heteroatom may be saturated or unsaturated. Thus, an alkyl substituted with a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl
Boussie Thomas
Hall Keith Anthony
Hillhouse Gregory
Lund Cheryl
Murphy Vince
Symyx Technologies Inc.
Truong Duc
LandOfFree
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