Catalyst Transfer Polymerization
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Catalyst Transfer Polymerization
Catalyst transfer polymerization (CTP), or Catalyst Transfer Polycondensation, is a type of living chain-growth polymerization that is used for synthesizing conjugated polymers. Benefits to using CTP over other methods are low polydispersity and control over number average molecular weight in the resulting polymers. Very few monomers have been demonstrated to undergo CTP. History The first reports of CTP came simultaneously from the labs of Yokozawa and McCullough in 2004, with the recognition that polythiophene can be synthesized with low dispersity and with control over molecular weight. This recognition sparked interest in polymerization mechanism so that it could be expanded to other monomers. Few polymers can be synthesized via CTP, so most conjugated polymers are synthesized via step-growth using palladium catalyzed cross-coupling reactions. Characteristics CTP is exclusively performed on arene monomers to give conjugated polymers. The polymers obtained from CTP are o ...
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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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Suzuki Coupling
The Suzuki reaction is an organic reaction, classified as a cross-coupling reaction, where the coupling partners are a boronic acid and an organohalide and the catalyst is a palladium(0) complex. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their contribution to the discovery and development of palladium-catalyzed cross-couplings in organic synthesis. This reaction is also known as the Suzuki–Miyaura reaction or simply as the Suzuki coupling. It is widely used to synthesize poly olefins, styrenes, and substituted biphenyls. Several reviews have been published describing advancements and the development of the Suzuki reaction. The general scheme for the Suzuki reaction is shown below, where a carbon-carbon single bond is formed by coupling a halide (R1-X) with an organoboron species (R2-BY2) using a palladium catalyst and a base. Reaction mechanism The mechanism of the Suzuki rea ...
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Polyphenylene
Poly(''p''-phenylene) (PPP) is made of repeating ''p''-phenylene units, which act as the precursor to a conducting polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that Electrical conductance, conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage ... of the rigid-rod polymer family. The synthesis of PPP has proven challenging, but has been accomplished through excess polycondensation with the Suzuki coupling method. Early efforts typically produced black, insoluble powders that were difficult to characterize. For example, a 1962 paper reports "The solid glowed red-hot in a Bunsen flame, with no evidence of flame formation, and disappeared only slowly." (J. Polym. Sci. (1960), 47, 45) Initially, the chemical and thermal stability of the material drove interest in its synthesis. It was used in rocket nozzles and some fabrics requiring high thermal stability. ...
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Polythiophene
Polythiophenes (PTs) are polymerized thiophenes, a sulfur heterocyclic compound, heterocycle. The parent PT is an insoluble colored solid with the formula (C4H2S)n. The rings are linked through the 2- and 5-positions. Poly(alkylthiophene)s have Alkyl, alkyl substituents at the 3- or 4-position(s). They are also colored solids, but tend to be soluble in organic solvents. PTs become Conductive polymer, conductive when oxidized. The electrical resistivity and conductivity, electrical conductivity results from the Delocalized electron, delocalization of electrons along the polymer backbone. Conductivity however is not the only interesting property resulting from electron delocalization. The optical properties of these materials respond to environmental stimuli, with dramatic color shifts in response to changes in solvent, temperature, Electric potential, applied potential, and binding to other molecules. Changes in both color and conductivity are induced by the same mechanism, tw ...
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Nuclear Magnetic Resonance Spectroscopy
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic field and the NMR signal is produced by excitation of the nuclei sample with radio waves into nuclear magnetic resonance, which is detected with sensitive radio receivers. The intramolecular magnetic field around an atom in a molecule changes the resonance frequency, thus giving access to details of the electronic structure of a molecule and its individual functional groups. As the fields are unique or highly characteristic to individual compounds, in modern organic chemistry practice, NMR spectroscopy is the definitive method to identify monomolecular organic compounds. The principle of NMR usually involves three sequential steps: # The alignment (polarization) of the magnetic nuclear spins in an applied, constant magnetic field B0. # The ...
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Matrix-assisted Laser Desorption/ionization
In mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) is an ionization technique that uses a laser energy absorbing matrix to create ions from large molecules with minimal fragmentation. It has been applied to the analysis of biomolecules ( biopolymers such as DNA, proteins, peptides and carbohydrates) and various organic molecules (such as polymers, dendrimers and other macromolecules), which tend to be fragile and fragment when ionized by more conventional ionization methods. It is similar in character to electrospray ionization (ESI) in that both techniques are relatively soft (low fragmentation) ways of obtaining ions of large molecules in the gas phase, though MALDI typically produces far fewer multi-charged ions. MALDI methodology is a three-step process. First, the sample is mixed with a suitable matrix material and applied to a metal plate. Second, a pulsed laser irradiates the sample, triggering ablation and desorption of the sample and matrix materi ...
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Gel Permeation Chromatography
Gel permeation chromatography (GPC) is a type of size-exclusion chromatography (SEC), that separates analytes on the basis of size, typically in organic solvents. The technique is often used for the analysis of polymers. As a technique, SEC was first developed in 1955 by Lathe and Ruthven.Lathe, G.H.; Ruthven, C.R.J. The Separation of Substance and '1956', ''62'', 665–674. The term ''gel permeation chromatography'' can be traced back to J.C. Moore of the Dow Chemical Company who investigated the technique in 1964. The proprietary column technology was licensed to Waters Corporation, who subsequently commercialized this technology in 1964.Moore, J.C. Gel permeation chromatography. I. A new method for molecular weight distribution of high polymers. ''J. Polym. Sci.'', 1964, ''2'', 835-84 GPC systems and consumables are now also available from a number of manufacturers. It is often necessary to separate polymers, both to analyze them as well as to purify the desired product. When cha ...
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Propagation Copy
Propagation can refer to: *Chain propagation in a chemical reaction mechanism * Crack propagation, the growth of a crack during the fracture of materials *Propaganda, non-objective information used to further an agenda *Reproduction, and other forms of multiplication or increase ** Plant propagation, the production of more plants **Propagation of schema, in artificial reproduction * Software propagation, the distribution of free software * Wave propagation, the motion of a wave ** Radio propagation, the application of wave propagation to radio communications ;In music * ''Propagation'' (album) *"Propagation", a song by Lower Dens from the album ''Nootropics Nootropics ( , or ) (colloquial: smart drugs and cognitive enhancers, similar to adaptogens) are a wide range of natural or synthetic supplements or drugs and other substances that are claimed to improve cognitive function or to promote rela ...
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Stille Coupling
The Stille reaction is a chemical reaction widely used in organic synthesis. The reaction involves the coupling of two organic groups, one of which is carried as an organotin compound (also known as organostannanes). A variety of organic electrophiles provide the other coupling partner. The Stille reaction is one of many palladium-catalyzed coupling reactions.Hartwig, J. F. ''Organotransition Metal Chemistry, from Bonding to Catalysis''; University Science Books: New York, 2010. Stille, J. K. '' Angew. Chem. Int. Ed. Engl.'' 1986, ''25'', 508–524.ReviewFarina, V.; Krishnamurthy, V.; Scott, W. J. ''Org. React.'' 1998, ''50'', 1–652.Review : + \ \ce \ \overbrace^ + \!-\! :*\!,\ : Allyl, alkenyl, aryl, benzyl,acyl :*: halides (Cl, Br, I), pseudohalides (, OPO(OR)2), OAc The R1 group attached to the trialkyltin is normally sp2-hybridized, including vinyl, and aryl groups. These organostannanes are also stable to both air and moisture, and many of these reagents either are com ...
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Negishi Coupling
The Negishi coupling is a widely employed transition metal catalyzed cross-coupling reaction. The reaction couples organic halides or triflates with organozinc compounds, forming carbon-carbon bonds (C-C) in the process. A palladium (0) species is generally utilized as the metal catalyst, though nickel is sometimes used. A variety of nickel catalysts in either Ni0 or NiII oxidation state can be employed in Negishi cross couplings such as Ni(PPh3)4, Ni(acac)2, Ni(COD)2 etc. : :* The leaving group X is usually chloride, bromide, or iodide, but triflate and acetyloxy groups are feasible as well. X = Cl usually leads to slow reactions. :* The organic residue R = alkenyl, aryl, allyl, alkynyl or propargyl. :* The halide X' in the organozinc compound can be chloride, bromine or iodine and the organic residue R' is alkenyl, aryl, allyl, alkyl, benzyl, homoallyl, and homopropargyl. :* The metal M in the catalyst is nickel or palladium :* The ligand L in the catalyst can be triphenylp ...
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Chain-growth Polymerization
Chain-growth polymerization (American English, AE) or chain-growth polymerisation (British English, BE) is a polymerization technique where Unsaturated compound, unsaturated monomer molecules add onto the active site on a growing polymer chain one at a time. There are a limited number of these active sites at any moment during the polymerization which gives this method its key characteristics. Introduction In 1953, Paul Flory first classified polymerization as "step-growth polymerization" and "chain-growth polymerization". IUPAC recommends to further simplify "chain-growth polymerization" to "chain polymerization". It is a kind of polymerization where an active center (free radical or ion) is formed, and a plurality of monomers can be polymerized together in a short period of time to form a macromolecule having a large molecular weight. In addition to the regenerated active sites of each monomer unit, polymer growth will only occur at one (or possibly more) endpoint. Many comm ...
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