Cationic mechanism, chain

Both modes of ionic polymerization are described by the same vocabulary as the corresponding steps in the free-radical mechanism for chain-growth polymerization. However, initiation, propagation, transfer, and termination are quite different than in the free-radical case and, in fact, different in many ways between anionic and cationic mechanisms. Our comments on the ionic mechanisms will touch many of the same points as the free-radical discussion, although in a far more abbreviated form. 

Styrene—butadiene block copolymers are made with anionic chain carriers, and low molecular weight PS is made by a cationic mechanism (110). Analytical standards are available for PS prepared by all four mechanisms (see Initiators). 

The G values are higher than the G values for initial species (ca 2.5), indicating a chain reaction. The much higher yield for the disappearance of a double bond indicates that cyclization occurs more frequently than cross-linking. Katzer and Heusinger concluded from the studies on the influence of dose rate, temperature and additives (air, anthracene and hydroquinone) that the chain proceeds via a cationic mechanism. 

Hence, cation-radical copolymerization leads to the formation of a polymer having a lower molecular weight and polydispersity index than the polymer got by cation-radical polymerization— homocyclobutanation. Nevertheless, copolymerization occnrs nnder very mild conditions and is regio-and stereospecihc (Bauld et al. 1998a). This reaction appears to occnr by a step-growth mechanism, rather than the more efficient cation-radical chain mechanism proposed for poly(cyclobutanation). As the authors concluded, the apparent suppression of the chain mechanism is viewed as an inherent problem with the copolymerization format of cation-radical Diels-Alder polymerization. ... 

The sterically hindered base 2,6-bis(tert-butyl)pyridine does not inhibit cyclization triaryl-amine retards this reaction photosensibilized one-electron oxidation of a diene leads to the same products, which are formed in the presence of ammoniumyl salt. As shown, in majority of cases, only the cation-radical chain mechanism of the diene-diene cyclization is feasible (Bauld et al. 1987). Meanwhile, cyclodimerizations of 2,4-dimethylpenta-l,3-diene (Gassman and Singleton 1984) and l,4-dimethylcyclohexa-l,3- or -1,4-diene (Davies et al. 1985) proceed through both mechanisms. 

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. 

The polymerisation of Cl3P=NSiMe3 initiated by PCI5 is believed to proceed via a cationic mechanism (Scheme 11.11). " " When the reaction is performed in solution, the process is termed living , as no significant chain transfer or chain... 

In contrast with these results, catalytic cracking yields a much higher percentage of branched hydrocarbons. For example, the catalytic cracking of cetane yields 50-60 mol of isobutane and isobutylene per 100 mol of paraffin cracked. Alkenes crack more easily in catalytic cracking than do saturated hydrocarbons. Saturated hydrocarbons tend to crack near the center of the chain. Rapid carbon-carbon double-bond migration, hydrogen transfer to trisubstituted olefinic bonds, and extensive isomerization are characteristic.52 These features are in accord with a carbo-cationic mechanism initiated by hydride abstraction.43,55-62 Hydride is abstracted by the acidic centers of the silica-alumina catalysts or by already formed carbocations ... 

Ethene does not polymerize by the cationic mechanism because it does not have sufficiently effective electron-donating groups to permit easy formation of the intermediate growing-chain cation. 2-Methylpropene has electron-donating alkyl groups and polymerizes much more easily than ethene by this type of mechanism. The usual catalysts for cationic polymerization of 2-methylpropene are sulfuric acid, hydrogen fluoride, or a complex of boron... 

It is now well established that the cation radicals of unsaturated and strained hydrocarbons undergo a variety of isomerization (e.g., Scheme 18) and cycloaddition reactions with much faster rates than those of the corresponding neutral molecules [162-165]. A cation radical chain mechanism analogous to Scheme 17 was reported for one-way photoisomerization of cis-stilbene (c-S) to truws-stilbene (f-S) via photoinduced electron transfer, as shown in Scheme 18 [166], Once c-S + is formed, it is known to isomerize to t-S + [167,168]. The free energy change of electron transfer... 

An analogous cation radical chain process has been proposed for cis to trans isomerization of N-methyl-4-(6-stryl)-pyridinium ions via electron-transfer sensitization by Ru(bpy)-j2+ and metalloporphyrins (145). Quantum yields for isomerization are substantially higher in aqueous anionic micelles versus homogeneous solution due to the higher concentration of cis-styrylpyridinium ions. A radical cation chain mechanism may also account for previous reports of selective cis to trans sensitized photoisomerization of stilbene (25,26). 

The general features of the isomerization are compatible with a free radical cation chain mechanism, featuring electron transfer from unreacted olefin to rearranged radical cation. This chain mechanism was firmly established in several other isomerizations by the observation of quantum yields greater than unity. Thus, the dicyanoanthracene sensitized irradiation of m-stilbene results in nearly quantitative isomerization (> 98%) to the trans-isomer. In this system, the quantum yield increases with increased ds-stilbene concentration, solvent polarity, salt concentration, as well as decreasing light intensity [159]. 

Some monomers are also polymerized by a cationic mechanism in a series of steps not too unlike those of anionic chain-growth. Initiators are often Lewis acids such as AICI3. The polymerization is not quite as straightforward as anionic, because for one thing cationic intermediates are subject to more side reactions. Common monomers that undergo cationic polymerization include styrene, isobutylene, and vinyl acetate. Some commercial products... 

The mechanism of ammonolysis of phosphorus pentachloride is not completely understood. It has been shown (164) that it proceeds in two steps. Initially, the intermediate [C13PNPC13] + [PC16] is formed, probably via PC14NH2 and PC13NH (48, 380). In the second step, this intermediate reacts with NH4C1 to produce cationic phosphazene chains that undergo cyclization by the elimination of [PC14]+ (164, 256). 

Because of the low reduction potential of TCB, the energy content of the radical ion pair resulting from the reaction of triplet excited sensitizer 3TCB and many olefins is insufficient lead to the triplet state of the olefins. In this case the isomerization takes place via a chain radical-cation mechanism [194, 195], The same electron acceptor also induces the electron transfer-sensitized valence isomerization of quadricyclane to norbomadiene [196, 197],... 

Resulting poly(a-hydroxyacids) are important biomaterials used as resorbable sutures and prostheses [196]. The mechanism of polymerization is not well established. Polymerization may be initiated with Lewis acids (SbF3, ZnCl2, SnCl4) however, other typical cationic initiators (e.g, triethyloxonium or triphenylcarbenium salts) fail to initiate polymerization [197]. Thus, it is not clear whether polymerization proceeds by typical cationic mechanism or rather involves the coordination mechanism. The chain transfer to polymer resulting in transesterification was postulated [198,199] and confirmed later by detailed, 3C NMR studies of lactide copolymers [200]. 

This group usually leads to anionic or coordinate polymerization which are not covered by this review. Nevertheless, polymerizations of oxetanes and THF, known to proceed exclusively by a cationic mechanism, have also been induced by various organometallic initiators. In many cases, these initiators lead to higher molecular weight polymers, probably reacting fast and first with impurities that could, if not destroyed, lower the molecular weight by chain transfer. 

Let us imagine a macromolecule growing by a cationic mechanism and having a chain end X, formed upon initiation, and which is much more reactive (rate constant ke) toward a cationic growing end than the heteroatoms along the chain (rate constant kb), e.g. in the case of a polyether ... 

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