Initiator, anionic cationic

Polymerization Reactions. The polymerization of butadiene with itself and with other monomers represents its largest commercial use. The commercially most important polymers are styrene—butadiene mbber (SBR), polybutadiene (BR), styrene—butadiene latex (SBL), acrylonittile—butadiene—styrene polymer (ABS), and nittile mbber (NR). The reaction mechanisms are free-radical, anionic, cationic, or coordinate, depending on the nature of the initiators or catalysts (194—196). 

Addition polymerization is employed primarily with substituted or unsuhstituted olefins and conjugated diolefins. Addition polymerization initiators are free radicals, anions, cations, and coordination compounds. In addition polymerization, a chain grows simply hy adding monomer molecules to a propagating chain. The first step is to add a free radical, a cationic or an anionic initiator (I ) to the monomer. For example, in ethylene polymerization (with a special catalyst), the chain grows hy attaching the ethylene units one after another until the polymer terminates. This type of addition produces a linear polymer ... 

We have used different anionic, cationic, and metathesis initiators but after the reaction of the initiator with one monomer molecule (initiation, kj) no subsequent propagation was observed ... 

Generally speaking, a monomer with electron-releasing groups will be more rapidly polymerized by cationic initiators. Anionic initiators polymerize olefins with electron-withdrawing groups more rapidly. A more sensitive test of the nature of the reaction is the behavior of a mixture of two such monomers in copolymerization in which they compete for the intermediate. This will be discussed in more detail in Chapter XII on polar versus radical mechanisms. 

Although PS is largely commercially produced using free radical polymerization, it can be produced by all four major techniques—anionic, cationic, free radical, and coordination-type systems. All of the tactic forms can be formed employing these systems. The most important of the tactic forms is syndiotactic polystyrene (sPS). Metallocene-produced sPS is a semicrystalline material with a of 270°C. It was initially produced by Dow in 1997 under the trade name Questra. It has good chemical and solvent resistance in contrast to regular PS that has generally poor chemical and solvent resistance because of the presence of voids that are exploited by the solvents and chemicals. 

Strongly electrophilic or nucleophilic monomers will polymerize exclusively by anionic or cationic mechanisms. However, monomers that are neither strongly electrophilic nor nucleophilic generally polymerize by ionic and free radical processes. The contrast between anionic, cationic, and free radical methods of addition copolymerization is clearly illustrated by the results of copolymerization utilizing the three modes of initiation (Figure 7.1). Such results illustrate the variations of reactivities and copolymer composition that are possible from employing the different initiation modes. The free radical tie-line resides near the middle since free radical polymerizations are less dependent on the electronic nature of the comonomers relative to the ionic modes of chain propagation. 

Carbonyl monomers can be polymerized by acidic initiators, although their reactivity is lower than in anionic polymerization. Protonic acids such as hydrochloric and acetic acids and Lewis acids of the metal halide type are effective in initiating the cationic polymerization of carbonyl monomers. The initiation and propagation steps in polymerizations initiated with protonic acids can be pictured as... 

Depending on the nature of the active center, chain-growth reactions are subdivided into radicalic, ionic (anionic, cationic), or transition-metal mediated (coordinative, insertion) polymerizations. Accordingly, they can be induced by different initiators or catalysts. Whether a monomer polymerizes via any of these chain-growth reactions - radical, ionic, coordinative - depends on its con-... 

Keywords Anionic Cationic Initiator Nanoparticles Surface initiated polymerization... 

According to the studies of monomers in the organic glass matrices mentioned so far, the ion radicals formed from solute monomers relate their radiation-induced ionic polymerization to the primary effect of ionizing radiations on matter. It is concievable that the initiating species in the anionic polymerization (caxbanions) are formed by the addition of the monomer molecules to the anion radicals which result from electron transfer from the matrices to the solute monomer. The formation of the cation radicals is necessary also to initiate the cationic polymerization. 

Another type of ionic species was proposed by Uelzmann (92). Uelzmann suggested that from trialkylaluminum and titanium tetrachloride, TiClg)+ and (R3A1C1) caused cationic initiation on the titanium followed by an anionic propagation on the aluminum ion. Bestian and co-workers (70) proposed similar cationic intermediates which propagate by anionic shifts. These steps are the opposite of the anionic initiation and cationic propagation proposed in this review for the butene-1 polymerization. 

Initiators -for acrylamide [ACRYLAMIDE POLYMERS] (Vol 1) -anionic initiators [INITIATORS - ANIONIC INITIATORS] (Voll4) -cationic initiators [INITIATORS - CATIONIC INITIATORS] (Vol 14) -in emulsion polymerization [LATEX TECHNOLOGY] (Vol 15) -for fluorocarbon elastomers [ELASTOMERS, SYNTHETIC - FLUOROCARBON ELASTOMERS] (Vol 8) -Free-radical initiators [INITIATORS - FREE-RADICAL INITIATORS] (Voll4) -organohthium compounds as [LITHIUM AND LITHIUM COMPOUNDS] (Vol 15) -peroxides as [PEROXIDES AND PEROXIDE COMPOUNDS - INORGANIC PEROXIDES] (Vol 18) -for propylene oxide [PROPYLENE OXIDE] (Vol 20) -for PUR polyols [POLYETHERS - PROPYLENE OXIDE POLYMERS] (Vol 19) -of suspension polymerization [ACRYLIC ESTER POLYMERS - SURVEY] (Vol 1)... 

Azobisnitriles are efficient sources of free radicals for vinyl polymerizations and chain reactions, e.g., chlorinations. See also Initiators (Free-Radical) Initiators (Anionic) and Initiators (Cationic). These compounds decompose in a variety of solvenls al nearly first-order rates to give free radicals with no evidence of induced chain decomposition, They can be used in bulk, solution, and suspension polymerizations and because no oxygenated residues are produced, they are suitable for use in pigmented or dyed systems that may be susceptible to oxidative degradation. 

Free-radical initiators, Anionic initiators, Cationic initiators,... 

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