Cobalt Mediated Radical Polymerization
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Cobalt Mediated Radical Polymerization
Cobalt based catalysts, when used in radical polymerization, have several main advantages especially in slowing down the reaction rate, allowing for the synthesis of polymers with peculiar properties. As starting the reaction does need a real radical initiator, the cobalt species is not the only used catalyst, it is a mediator. For this reason this type of reaction is referred to as cobalt mediated radical polymerization. Introduction About half of all commercial polymers are produced by radical polymerization. Radical polymerization (RP) reactions have several advantageous properties: *A wide variety of monomers can be polymerized. *RP reactions are tolerant to various functional groups. *RP reactions allow a large temperature range of operation (–100 to >200 °C). *RP reactions are generally compatibility with several reactions conditions (bulk, solution, (mini)emulsion and suspension). *RP reactions allow a relatively simple reactor set-up, and are hence costs effectiv ...
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Cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, produced by reductive smelting, is a hard, lustrous, silver-gray metal. Cobalt-based blue pigments ( cobalt blue) have been used since ancient times for jewelry and paints, and to impart a distinctive blue tint to glass, but the color was for a long time thought to be due to the known metal bismuth. Miners had long used the name ''kobold ore'' (German for ''goblin ore'') for some of the blue-pigment-producing minerals; they were so named because they were poor in known metals, and gave poisonous arsenic-containing fumes when smelted. In 1735, such ores were found to be reducible to a new metal (the first discovered since ancient times), and this was ultimately named for the ''kobold''. Today, some cobalt is produced specifically from one of ...
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Metal Acetylacetonates
Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion () and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR−). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition ...
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Radical Polymerization
In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks (repeat units). Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Following its generation, the initiating free radical adds (nonradical) monomer units, thereby growing the polymer chain. Free-radical polymerization is a key synthesis route for obtaining a wide variety of different polymers and materials composites. The relatively non-specific nature of free-radical chemical interactions makes this one of the most versatile forms of polymerization available and allows facile reactions of polymeric free-radical chain ends and other chemicals or substrates. In 2001, 40 billion of the 110 billion pounds of polymers produced in the United States were produced by free-radical polymerization. Free-radical polymerization is a type of chain-growth polymeriz ...
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Oxidation State
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. While fully ionic bonds are not found in nature, many bonds exhibit strong ionicity, making oxidation state a useful predictor of charge. The oxidation state of an atom does not represent the "real" formal charge on that atom, or any other actual atomic property. This is particularly true of high oxidation states, where the ionization energy required to produce a multiply positive ion is far greater than the energies available in chemical reactions. Additionally, the oxidation states of atoms in a given compound may vary depending on the choice of electronegativity scale used in their calculation. Thus, the oxidation state of an atom in a compound is purely a formalism. ...
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Degenerative Transfer
Degeneracy, degenerate, or degeneration may refer to: Arts and entertainment * ''Degenerate'' (album), a 2010 album by the British band Trigger the Bloodshed * Degenerate art, a term adopted in the 1920s by the Nazi Party in Germany to describe modern art ** Decadent movement, often associated with degeneracy * Dégénération, a single by Mylène Farmer * ''Degeneration'' (Nordau), an 1892 book by Max Nordau * '' Resident Evil: Degeneration'', a 2008 film * "Degenerate", a song by Blink-182 from the album ''Dude Ranch'' * "Degenerates", a song by A Day to Remember from the album ''You're Welcome'' Science, mathematics, and medicine Mathematics * Degeneracy (mathematics), a limiting case in which a class of object changes its nature so as to belong to another, usually simpler, class * Degeneracy (graph theory), a measure of the sparseness of a graph * Degeneration (algebraic geometry), the act of taking a limit of a family of varieties * Degenerate form, bilinear fo ...
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Catalytic Chain Transfer 1
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage ...
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Chain Transfer
Chain transfer is a polymerization Chemical reaction, reaction by which the activity of a growing polymer chain is transferred to another molecule. :P• + XR' → PX + R'• Chain transfer reactions reduce the average molecular weight of the final polymer. Chain transfer can be either introduced deliberately into a polymerization (by use of a ''chain transfer agent'') or it may be an unavoidable side-reaction with various components of the polymerization. Chain transfer reactions occur in most forms of addition polymerization including radical polymerization, ring-opening polymerization, coordination polymerization, and cationic polymerization, as well as anionic polymerization. Types Chain transfer reactions are usually categorized by the nature of the molecule that reacts with the growing chain. * Transfer to chain transfer agent. Chain transfer agents have at least one weak chemical bond, which therefore facilitates the chain transfer reaction. Common chain transfer age ...
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Termination Reaction
Chain termination is any chemical reaction that ceases the formation of reactive intermediates in a chain propagation step in the course of a polymerization, effectively bringing it to a halt. Mechanisms of termination In polymer chemistry, there are several mechanisms by which a polymerization reaction can terminate depending on the mechanism and circumstances of the reaction. A method of termination that applies to all polymer reactions is the depletion of monomer. In chain growth polymerization, two growing chains can collide head to head causing the growth of both of the chains to stop. In the case of radical or anionic polymerization, chain transfer can occur where the radical at the end of the growing chain can be transferred from the chain to an individual monomer unit causing a new chain to start growing and the previous chain to stop growing. With step-growth polymerization, the reaction can be terminated by adding a monofunctional species containing the same function ...
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Reversible Reaction
A reversible reaction is a reaction in which the conversion of reactants to products and the conversion of products to reactants occur simultaneously. : \mathit aA + \mathit bB \mathit cC + \mathit dD A and B can react to form C and D or, in the reverse reaction, C and D can react to form A and B. This is distinct from a reversible process in thermodynamics. Weak acids and bases undergo reversible reactions. For example, carbonic acid: : H2CO3 (l) + H2O(l) ⇌ HCO3−(aq) + H3O+(aq). The concentrations of reactants and products in an equilibrium mixture are determined by the analytical concentrations of the reagents (A and B or C and D) and the equilibrium constant, ''K''. The magnitude of the equilibrium constant depends on the Gibbs free energy change for the reaction. So, when the free energy change is large (more than about 30 kJ mol−1), the equilibrium constant is large (log K > 3) and the concentrations of the reactants at equilibrium are very small. Such a reac ...
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Free Radical
A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Ailments of unknown cause Biogerontology Biological processes Causes of death Cellular processes Gerontology Life extension Metabolic disorders Metabolism Old age Time in life Wikipedia categories named after diseases and disorders {{CatAutoTOC ...
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Cobalt Mediated Radical Polymerization
Cobalt based catalysts, when used in radical polymerization, have several main advantages especially in slowing down the reaction rate, allowing for the synthesis of polymers with peculiar properties. As starting the reaction does need a real radical initiator, the cobalt species is not the only used catalyst, it is a mediator. For this reason this type of reaction is referred to as cobalt mediated radical polymerization. Introduction About half of all commercial polymers are produced by radical polymerization. Radical polymerization (RP) reactions have several advantageous properties: *A wide variety of monomers can be polymerized. *RP reactions are tolerant to various functional groups. *RP reactions allow a large temperature range of operation (–100 to >200 °C). *RP reactions are generally compatibility with several reactions conditions (bulk, solution, (mini)emulsion and suspension). *RP reactions allow a relatively simple reactor set-up, and are hence costs effectiv ...
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Persistent Radical Effect
The persistent radical effect (PRE) in chemistry describes and explains the selective product formation found in certain free-radical cross-reactions. In these type of reactions, different radicals compete in secondary reactions. The so-called persistent (long-lived) radicals do not self-terminate and only react in cross-couplings. In this way, the cross-coupling products in the product distribution are more prominent. The effect was first described in 1936 by Bachmann & Wiselogle. They heated pentaphenylethane and observed that the main reaction product was the starting product (87%) with only 2% of tetraphenylethane formed. They concluded that the dissociation of pentaphenylethane into triphenylmethyl and diphenylmethyl radicals was reversible and that persistent triphenylmethyl did not self terminate and transient diphenylmethyl did to a certain extent. In 1964, Perkins performed a similar reaction with phenylazotriphenylmethane in benzene. Again, the dimerization product of ...
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