Cationic polymerization compared with

The prevalence of investigations devoted to P-pinene stems from the relative simplicity of its cationic polymerization, compared with the more complex behavior of a-pinene. 

The reactivity of I in photoinitiated cationic polymerization is due to several factors associated with the structure of this monomer. Most importantly, the presence of the ester groups in I which can interact with oxiranium ions generated at either of the two epoxide groups both intra- and intermolecularly produces dioxacarbenium ions of reduced activity in the propagation reaction. Taking this into account, a series of diepoxides were prepared which did not possess ester groups. Some of these monomers show enhanced reactivity as measured by RTIR in photoinitiated cationic polymerization compared to I. 

The generally lower stereospecificity in cationic polymerizations compared to anionic polymerizations has been attributed by Natta (188) to be due to more easily dissociated ion pairs, large gegen-ions having several equal atoms (e. g., chloride) available for coordination with the carbonium ion, and to isomerization reactions. Therefore, just as was discussed previously for anionic polymerizations, cationic polymeriza-... 

Biswas and Sinha Ray [35] subsequently reported that direct interaction of MMT with PY led only to ca. 5% yield of PPY in 3 h while ANI could not be polymerized by MMT. Such a trend is possibly not surprising since NVC is relatively more susceptible to cationic polymerization compared to the latter monomers. 

Cationic polymerization with Lewis acids yields resinous homopolymers containing cycHc stmctures and reduced unsaturation (58—60). Polymerization with triethyl aluminum and titanium tetrachloride gave a product thought to have a cycHc ladder stmcture (61). Anionic polymeriza tion with lithium metal initiators gave a low yield of a mbbery product. The material had good freeze resistance compared with conventional polychloroprene (62). 

Sulfate radical anion may be converted to the hydroxyl radical in aqueous solution. Evidence for this pathway under polymerization conditions is the formation of a proportion of hydroxy end groups in some polymerizations. However, the hydrolysis of sulfate radical anion at neutral pi I is slow (k— 107 M"1 s 1) compared with the rale of reaction with most monomers (Ar=l08-109 M 1 s 1, Table 3.7)440 under typical reaction conditions. Thus, hydrolysis should only be competitive with addition when the monomer concentration is very low. The formation of hydroxy end groups in polymerizations initiated by sulfate radical anion can also be accounted for by the hydration of an intermediate radical cation or by the hydrolysis of an initially formed sulfate adduct either during the polymerization or subsequently. 

When one compares the brutto polymerization rate constants, a measure of the reactivity of monomers during cationic homopolymerizations is obtained. It was found for p-substituted styrenes that lg kBr increased parallel to the reactivity, which the monomers show versus a constant acceptor 93). The reactivity graduation of the cationic chain ends is apparently overcomed by the structural influence on the monomers during the entire process of the cationic polymerization. The quantitative treatment of the substituent influences with the assistance of the LFE principle leads to the following Hammett-type equations for the brutto polymerization rate constants ... 

When the statements above are compared with the cationic polymerization, an essential difference can be determined (see Table 12). 

Polymeric cationic retarders that contain up to several hundred cationic groups per molecule have been proposed [45-47]. The early types [45,46] were described as quaternised polyamines (section 9.5) of relative molecular mass 1000-20 000, as compared with 300-500 for conventional quaternary ammonium compounds. Polyacrylamides of molecular mass 2500-780 000 have been evaluated more recently [47]. 

Applying these methodologies monomers such as isobutylene, vinyl ethers, styrene and styrenic derivatives, oxazolines, N-vinyl carbazole, etc. can be efficiently polymerized leading to well-defined structures. Compared to anionic polymerization cationic polymerization requires less demanding experimental conditions and can be applied at room temperature or higher in many cases, and a wide variety of monomers with pendant functional groups can be used. Despite the recent developments in cationic polymerization the method cannot be used with the same success for the synthesis of well-defined complex copolymeric architectures. 

Under free radical conditions, we found that the bulk polymerization of 4-allyloxystyrene gave an insoluble crosslinked polymer with AIBN. Similar results were previously reported for the polymerization with benzoyl peroxide (8). The cationic polymerization of /7-alkoxystyrene monomers have been shown to proceed at rates that are comparable to vinyl ethers (12,13). As expected from these studies, we found that alkenyloxystyrene monomers also have a high degree of cationic reac-... 

The chain transfer constant for an additive or solvent in the polymerization can be determined. This value can then be compared with the transfer constants for the same substance in the polymerization of the same monomer by known radical, cationic, and anionic initiators. 

---