A Kaminsky catalyst is a catalytic system for alkene polymerization. [1] Kaminsky catalysts are based on metallocenes of group 4 transition metals (Ti, Zr, Hf) activated with methylaluminoxane (MAO). These and other innovations have inspired development of new classes of catalysts that in turn led to commercialization of novel engineering polyolefins. [2]
Prior to Kaminsky, titanium chlorides supported on various materials were widely used (and still are) as heterogeneous catalysts for alkene polymerization. These halides are typically activated by treatment with trimethylaluminium. Kaminsky discovered that titanocene and related complexes emulated some aspects of these Ziegler–Natta catalysts but with low activity. He subsequently found that high activity could be achieved upon activation of these metallocenes with methylaluminoxane (MAO). The MAO serves two roles: (i) alkylation of the metallocene halide and (ii) abstraction of an anionic ligand (chloride or methyl) to give an electrophilic catalyst with a labile coordination site. [1] [3]
Kaminsky's discovery of well-defined, high activity homogeneous catalysts led to many innovations in the design of novel cyclopentadienyl ligands. These innovations include ansa-metallocenes, Cs-symmetric fluorenyl-Cp ligands, [4] constrained geometry catalysts, [5] Some Kaminsky-inspired catalysts use of chiral metallocenes that have bridged cyclopentadienyl rings. These innovations made possible highly stereoselective (or stereoregular) polymerization of α-olefins, some of which have been commercialized. [2]
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:
In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar. Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups.
A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.
A post-metallocene catalyst is a kind of catalyst for the polymerization of olefins, i.e., the industrial production of some of the most common plastics. "Post-metallocene" refers to a class of homogeneous catalysts that are not metallocenes. This area has attracted much attention because the market for polyethylene, polypropylene, and related copolymers is large. There is a corresponding intense market for new processes as indicated by the fact that, in the US alone, 50,000 patents were issued between 1991-2007 on polyethylene and polypropylene.
Methylaluminoxane, commonly called MAO, is a mixture of organoaluminium compounds with the approximate formula (Al(CH3)O)n. It is usually encountered as a solution in (aromatic) solvents, commonly toluene but also xylene, cumene, or mesitylene, Used in large excess, it activates precatalysts for alkene polymerization.
In organic chemistry, olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds. Because of the relative simplicity of olefin metathesis, it often creates fewer undesired by-products and hazardous wastes than alternative organic reactions. For their elucidation of the reaction mechanism and their discovery of a variety of highly active catalysts, Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock were collectively awarded the 2005 Nobel Prize in Chemistry.
Coordination polymerisation is a form of polymerization that is catalyzed by transition metal salts and complexes.
In organometallic chemistry, a "constrained geometry complex" (CGC) is a kind of catalyst used for the production of polyolefins such as polyethylene and polypropylene. The catalyst was one of the first major departures from metallocene-based catalysts and ushered in much innovation in the development of new plastics.
The Cossee–Arlman mechanism in polymer chemistry is the main pathway for the formation of C–C bonds in the polymerization of alkenes. The mechanism features an intermediate coordination complex that contains both the growing polymer chain and the monomer (alkene). These ligands combine within the coordination sphere of the metal to form a polymer chain that is elongated by two carbons.
Organozirconium chemistry is the science of exploring the properties, structure, and reactivity of organozirconium compounds, which are organometallic compounds containing chemical bonds between carbon and zirconium. Organozirconium compounds have been widely studied, in part because they are useful catalysts in Ziegler-Natta polymerization.
Zirconocene dichloride is an organozirconium compound composed of a zirconium central atom, with two cyclopentadienyl and two chloro ligands. It is a colourless diamagnetic solid that is somewhat stable in air.
Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon (C) to vanadium (V) chemical bond. Organovanadium compounds find only minor use as reagents in organic synthesis but are significant for polymer chemistry as catalysts.
Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.
In organometallic chemistry, bent metallocenes are a subset of metallocenes. In bent metallocenes, the ring systems coordinated to the metal are not parallel, but are tilted at an angle. A common example of a bent metallocene is Cp2TiCl2. Several reagents and much research is based on bent metallocenes.
An insertion reaction is a chemical reaction where one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
In polymer chemistry, chain walking (CW) or chain running or chain migration is a mechanism that operates during some alkene polymerization reactions. CW can be also considered as a specific case of intermolecular chain transfer. This reaction gives rise to branched and hyperbranched/dendritic hydrocarbon polymers. This process is also characterized by accurate control of polymer architecture and topology. The extent of CW, displayed in the number of branches formed and positions of branches on the polymers are controlled by the choice of a catalyst. The potential applications of polymers formed by this reaction are diverse, from drug delivery to phase transfer agents, nanomaterials, and catalysis.
Diiminopyridines are a class of diimine ligands. They featuring a pyridine nucleus with imine sidearms appended to the 2,6–positions. The three nitrogen centres bind metals in a tridentate fashion, forming pincer complexes. Diiminopyridines are notable as non-innocent ligand that can assume more than one oxidation state. Complexes of DIPs participate in a range of chemical reactions, including ethylene polymerization, hydrosilylation, and hydrogenation.
Diimines are organic compounds containing two imine (RCH=NR') groups. Common derivatives are 1,2-diketones and 1,3-diimines. These compounds are used as ligands and as precursors to heterocycles. Diimines are prepared by condensation reactions where a dialdehyde or diketone is treated with amine and water is eliminated. Similar methods are used to prepare Schiff bases and oximes.
A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.
Transition metal phosphinimide complexes are metal complexes that contain phosphinimide ligands of the general formula NPR3− (R = organic substituent). Several coordination modes have been observed, including terminal and various bridging geometries. In the terminal bonding mode the M-N=P core is usually linear but some are quite bent. The preferred coordination type varies with the oxidation state and coligands on the metal and the steric and electronic properties of the R groups on phosphorus. Many transition metal phosphinimide complexes have been well-developed and, more recently, main group phosphinimide complexes have been synthesized.
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