Cationic mechanism, chain polymerization

In the coordinated cationic mechanism the polymerization is initiated by a proton formed by interaction of the catalyst-active hydrogen-containing compounds. The metal atom coordinates the monomer and the growing polymer chain, thus leading to some degree of stereospecificity during the polymerization. 

In the presence of Lewis bases and acids, epoxy resins undergo homopolymerization resulting in polyether chains. Depending on whether Lewis bases or acids are used, the polymerization proceeds via an anionic or cationic mechanism. Catalytic polymerization of monoepoxides results in linear polymers, whereas diepoxides give a crosslinked network. 

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. 

Analogous principles should apply to ionically propagated polymerizations. The terminus of the growing chain, whether cation or anion, can be expected to exhibit preferential addition to one or the other carbon of the vinyl group. Poly isobutylene, normally prepared by cationic polymerization, possesses the head-to-tail structure, as already mentioned. Polystyrenes prepared by cationic or anionic polymerization are not noticeably different from free-radical-poly-merized products of the same molecular weights, which fact indicates a similar chain structure irrespective of the method of synthesis. In the polymerization of 1,3-dienes, however, the structure and arrangement of the units depends markedly on the chain-propagating mechanism (see Sec. 2b). 

Chain gro tvth polymerization begins when a reactive species and a monomer react to form an active site. There are four principal mechanisms of chain growth polymerization free radical, anionic, cationic, and coordination polymerization. The names of the first three refer to the chemical nature of the active group at the growing end of the monomer. The last type, coordination polymerization, encompasses reactions in which polymers are manufactured in the presence of a catalyst. Coordination polymerization may occur via a free radical, anionic, or cationic reaction. The catalyst acts to increase the speed of the reaction and to provide improved control of the process. 

Chain-reaction mechanisms differ according to the nature of the reactive intermediate in the propagation steps, such as free radicals, ions, or coordination compounds. These give rise to radical-addition polymerization, ionic-addition (cationic or anionic) polymerization, etc. In Example 7-4 below, we use a simple model for radical-addition polymerization. 

It appeared to us that the only reasonable non-ionic reaction product of an acid and an olefin would be an ester, and for this reason we put forward the idea that this is the active species in the pseudo-cationic polymerizations. Of course, the idea of an ester in this role has a respectable ancestry which has been discussed in this new context [6]. The ester mechanism of polymerization will be discussed in sub-section 3.3. It must be understood that our conclusion concerning the non-ionic nature of the chain-carriers in the pseudocationic polymerizations is quite independent of our view that the chain-carriers are esters this is at present merely an hypothesis to explain our factual conclusion. 

The proposed structures are consistent with the polyaddition mechanism of cationic ring-opening polymerization of ECH in conjunction with a modifier (18). The polymer chain propagates simultaneously at both ends of the difunctional modifier through polyaddition of monomers. Consequently, one unit of modifier is incorporated into the polymer chain and the functionality of the... 

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. ... 

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. 

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... 

In addition to post-functionalizing polymers by bonding the macrocycle to the preformed polymer backbone, macrocycles can be incorporated into polymer matrices by direct polymerization of the macrocycle, either by a step-growth mechanism or a chain-growth mechanism. [46] Polymeric crown ether stationary phases were pioneered by Blasius et al. [34, 59-62] These resins were used to separate both cations (including protonated amines) with a common anion, and anions with a common cation in high... 

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... 

There are essentially two different mechanisms that UV curing may occur by — free radical or cationic. Free radical polymerization is the most predominantly used route and will be discussed first. The chain reaction that occurs consists of at least four steps ... 

The results show that the presence of bulky substituent on a polymer chain may effectively inhibit the termination proceeding by this mechanism. The results presented at this point may be summarized as follows chain transfer to polymer is a general feature of cationic ring-opening polymerization although for different systems the contribution of this reaction may vary only in some systems this process results in termination (These systems involve, e.g., cyclic amines (3- and 4-membered) and cyclic sulfides (3- and 4-membered) and the contribution of the reaction is reduced for substituted chains. 

This characteristic feature of cationic polymerization of THF allows the important synthetic application of this process for preparation of oli-godiols used in polyurethane technology and in manufacturing of block copolymers with polyesters and polyamides (cf., Section IV.A). On the other hand, the cationic polymerization of THF not affected by contribution of chain transfer to polymer is a suitable model system for studying the mechanism and kinetics of cationic ring-opening polymerization. 

Substitution of proton on the nitrogen with alkyl group, as in the case of aziridines, simplifies the mechanism of polymerization. In the polymerization of 1-methylazetidine, termination due to the chain transfer to polymers is still detectable [176], Further substitution at carbon atoms reduces the extent of chain transfer to polymer and in the cationic polymerization of 1,3,3-trimethylazetidine the concentration of active species, quaternary azetidinium ions ... 

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]. 

Cyclic phosphates polymerize by both cationic and anionic mechanisms. Anionic polymerization is the method of choice for preparation of high molecular weight polymers because in cationic polymerization the reaction of exocyclic ester group leads to chain transfer ... 

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