Ring Opening Metathesis Polymerization
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Ring Opening Metathesis Polymerization
Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins (e.g. norbornene or cyclopentene). A variety of heterogeneous and homogeneous catalysts have been developed. Most large-scale commercial processes rely on the former while some fine chemical syntheses rely on the homogeneous catalysts. Catalysts are based on transition metals such as W, Mo, Re, Ru, and Ti. Heterogeneous catalysis and applications : Ring-opening metathesis polymerization of cycloalkenes has been commercialized since the 1970s. Examples of polymers produced on an industrial level through ROMP catalysis are Vestenamer or trans-polyoctenamer, which is the metathetical polymer of cyclooctene. Norsorex or polynorbornene is another important ROMP product on the market. Telene and Metton are polydicyclopentadiene products produced in a side reaction of the polymerization of norbornene. ...
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Olefin Metathesis
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. Catalysts The reaction requires metal catalysts. Most commercially important processes employ heterogeneous catalysts. The heterogeneous catalysts are often prepared by in-situ activation of a metal halides (MClx) using organoaluminium or organotin compounds, e.g. combining MClx–EtAlCl2. A typical catalyst support is alumina. Commercial catalysts are often based on molybdenum and ruthenium. Well-defined organometallic co ...
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Functional Group
In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the rest of the molecule's composition. This enables systematic prediction of chemical reactions and behavior of chemical compounds and the design of chemical synthesis. The reactivity of a functional group can be modified by other functional groups nearby. Functional group interconversion can be used in retrosynthetic analysis to plan organic synthesis. A functional group is a group of atoms in a molecule with distinctive chemical properties, regardless of the other atoms in the molecule. The atoms in a functional group are linked to each other and to the rest of the molecule by covalent bonds. For repeating units of polymers, functional groups attach to their nonpolar core of carbon atoms and thus add chemical character to carbon chains. Fun ...
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Acyclic Diene Metathesis
Acyclic diene metathesis or ADMET (distinguish from ADME) is a special type of olefin metathesis used to polymerize terminal dienes to polyenes: The new double bonds formed can be in cis- or trans-configurations. The exact ratio depends on the identities of the monomer and catalyst. ADMET is a type of step-growth, condensation polymerization. It should be distinguished from ring-opening metathesis polymerization (ROMP), which is a chain-growth, addition polymerization. Whereas ADMET is driven by the release of volatile ethylene gas, ROMP is driven by the relief of ring-strain. While the concept of ADMET had been discussed in the scientific literature since the 1970s, the first successful ADMET polymerization was reported in 1991. In this report, 1,5-hexadiene and 1,9-decadiene were polymerized to 1,4-polybutadiene and poly(octenylene), respectively. The polybutadiene had a weight average molar mass (Mw) of 28,000 with over 70% trans double bonds. The poly(octenylene) had ...
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Dicyclopentadiene
Dicyclopentadiene, abbreviated DCPD, is a chemical compound with formula C10H12. At room temperature, it is a white brittle wax, although lower purity samples can be straw coloured liquids. The pure material smells somewhat of soy wax or camphor, with less pure samples possessing a stronger acrid odor. Its energy density is 10,975 Wh/l. Dicyclopentadiene is a co-produced in large quantities in the steam cracking of naphtha and gas oils to ethylene. The major use is in resins, particularly, unsaturated polyester resins. It is also used in inks, adhesives, and paints. The top seven suppliers worldwide together had an annual capacity in 2001 of 179 kilotonnes (395 million pounds). Synthesis and structure The spontaneous dimerization of cyclopentadiene at room temperature to form dicyclopentadiene proceeds to around 50% conversion over 24 hours and yields the ''endo'' isomer in better than 99:1 ratio as the kinetically favored product (about 150:1 ''endo'':''exo'' at 80 °C). How ...
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Latent Inhibition
Latent inhibition (LI) is a technical term in classical conditioning, where a familiar stimulus takes longer to acquire meaning (as a signal or conditioned stimulus) than a new stimulus. The term originated with Lubow and Moore in 1973. The LI effect is latent in that it is not exhibited in the stimulus pre-exposure phase, but rather in the subsequent test phase. "Inhibition", here, simply connotes that the effect is expressed in terms of relatively poor learning. The LI effect is extremely robust, appearing in both invertebrate (for example, honey bees) and mammalian species that have been tested and across many different learning paradigms, thereby suggesting some adaptive advantages, such as protecting the organism from associating irrelevant stimuli with other, more important, events. Theories The LI effect has received a number of theoretical interpretations. One class of theory holds that inconsequential stimulus pre-exposure results in reduced associability for that stimulu ...
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Metallacyclobutane
In organometallic chemistry, a metallacycle is a derivative of a carbocyclic compound wherein a metal has replaced at least one carbon center; this is to some extent similar to heterocycles. Metallacycles appear frequently as reactive intermediates in catalysis, e.g. olefin metathesis and alkyne trimerization. In organic synthesis, directed ortho metalation is widely used for the functionalization of arene rings via C-H activation. One main effect that metallic atom substitution on a cyclic carbon compound is distorting the geometry due to the large size of typical metals. Nomenclature Typically, metallacycles are cyclic compounds with two metal carbon bonds. Many compounds containing metals in rings are known, for example chelate rings. Usually, such compounds are not classified as metallacycles, but the naming conventions are not rigidly followed. Within the area of coordination chemistry and supramolecular chemistry, examples include metallacrowns, metallacryptands, metallah ...
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Science (journal)
''Science'', also widely referred to as ''Science Magazine'', is the peer-reviewed academic journal of the American Association for the Advancement of Science (AAAS) and one of the world's top academic journals. It was first published in 1880, is currently circulated weekly and has a subscriber base of around 130,000. Because institutional subscriptions and online access serve a larger audience, its estimated readership is over 400,000 people. ''Science'' is based in Washington, D.C., United States, with a second office in Cambridge, UK. Contents The major focus of the journal is publishing important original scientific research and research reviews, but ''Science'' also publishes science-related news, opinions on science policy and other matters of interest to scientists and others who are concerned with the wide implications of science and technology. Unlike most scientific journals, which focus on a specific field, ''Science'' and its rival ''Nature (journal), Nature'' c ...
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Transition Metal Carbene Complex
A transition metal carbene complex is an organometallic compound featuring a divalent organic ligand. The divalent organic ligand coordinated to the metal center is called a carbene. Carbene complexes for almost all transition metals have been reported. Many methods for synthesizing them and reactions utilizing them have been reported. The term carbene ligand is a formalism since many are not derived from carbenes and almost none exhibit the reactivity characteristic of carbenes. Described often as , they represent a class of organic ligands intermediate between alkyls and carbynes . They feature in some catalytic reactions, especially alkene metathesis, and are of value in the preparation of some fine chemicals. Classification Metal carbene complexes are often classified into two types. The Fischer carbenes named after Ernst Otto Fischer feature strong π-acceptors at the metal and being electrophilic at the carbene carbon atom. Schrock carbenes, named after Richard R. Schrock ...
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Ethyl Vinyl Ether
Ethyl vinyl ether is an organic compound with the chemical formula CH3CH2OCH=CH2. It is the simplest enol ether that is liquid at room temperature. It is used as a synthetic building block and a monomer. Preparation and reactions Ethyl vinyl ether is made by reaction of acetylene and ethanol in presence of a base. The alkene portion of the molecule is reactive in many ways. It is prone to polymerization, leading to formation of polyvinyl ethers. Polymerization is typically initiated with Lewis acids such as boron trifluoride. Ethyl vinyl ether participates in many reactions of interest to organic synthesis. With catalytic amounts of acids, ethyl vinyl ether adds to alcohols to give the mixed acetal: :EtOCH=CH2 + ROH → EtOCH(OR)CH3 This alcohol protection reaction is akin to the behavior of dihydropyran. Ethyl vinyl ether also participates in inverse demand [4+2] cycloaddition reactions. Deprotonation with butyl lithium gives the acetyl anion equivalent: :EtOCH=CH2 ...
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Polymer Architecture
Polymer architecture in polymer science relates to the way branching leads to a deviation from a strictly linear polymer chain. Branching may occur randomly or reactions may be designed so that specific architectures are targeted. It is an important microstructural feature. A polymer's architecture affects many of its physical properties including solution viscosity, melt viscosity, solubility in various solvents, glass transition temperature and the size of individual polymer coils in solution. Different polymer architectures Random branching Branches can form when the growing end of a polymer molecule reaches either (a) back around onto itself or (b) onto another polymer chain, both of which, via abstraction of a hydrogen, can create a mid-chain growth site. Branching can be quantified by the branching index. Cross linked polymer An effect related to branching is chemical crosslinking - the formation of covalent bonds between chains. Crosslinking tends to increase Tg and in ...
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Living Polymerization
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 (i.e. they have a very low polydispersity index). 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. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from t ...
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Propagation Constant
The propagation constant of a sinusoidal electromagnetic wave is a measure of the change undergone by the amplitude and phase of the wave as it propagates in a given direction. The quantity being measured can be the voltage, the current in a circuit, or a field vector such as electric field strength or flux density. The propagation constant itself measures the change per unit length, but it is otherwise dimensionless. In the context of two-port networks and their cascades, propagation constant measures the change undergone by the source quantity as it propagates from one port to the next. The propagation constant's value is expressed logarithmically, almost universally to the base '' e'', rather than the more usual base 10 that is used in telecommunications in other situations. The quantity measured, such as voltage, is expressed as a sinusoidal phasor. The phase of the sinusoid varies with distance which results in the propagation constant being a complex number, the imagin ...
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