Cationic polymerization structure-reactivity

The formation of high molecular products during the cationic polymerization depends on whether the propagation reaction, consisting of the interaction of the cationic chain end as a reactive intermediate with the monomer, reproduces the reactive intermediate (see Eq. (1)). For this reason the monomer functions as the agent and as the substrate when in the form of the cation. This means, however, the interaction between the monomer and the cationic chain end is a function of the monomer structure itself when all other conditiones remain the same. 

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 ... 

These various structures show characteristic differences of the reactivity during the propagation step. When one observes cationic polymerizations, the propagation via free ions takes place from 10 to 100 times faster than that via ion pairs 1-2). This ratio should be valid for anions from Lewis acids as well as those from protic acids. 

Structure and Reactivity Relationships in the Photoinitiated Cationic Polymerization of 3,4-Epoxy cyclohexylmethyl-3, 4 -epoxy cyclohexane... 

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. 

Ledwith, A. and D. C. Sherrington, Reactivity and Mechanism in Cationic Polymerization, Chap. 9 in Reactivity, Mechanism and Structure in Polymer Chemistry, A. D. Jenkins and A. Ledwith, eds., Wiley-Interscience, New York, 1974. 

Cationic polymerizations induced by thermally and photochemically latent N-benzyl and IV-alkoxy pyridinium salts, respectively, are reviewed. IV-Benzyl pyridinium salts with a wide range of substituents of phenyl, benzylic carbon and pyridine moiety act as thermally latent catalysts to initiate the cationic polymerization of various monomers. Their initiation activities were evaluated with the emphasis on the structure-activity relationship. The mechanisms of photoinitiation by direct and indirect sensitization of IV-alkoxy pyridinium salts are presented. The indirect action can be based on electron transfer reactions between pyridinium salt and (a) photochemically generated free radicals, (b) photoexcited sensitizer, and (c) electron rich compounds in the photoexcited charge transfer complexes. IV-Alkoxy pyridinium salts also participate in ascorbate assisted redox reactions to generate reactive species capable of initiating cationic polymerization. The application of pyridinium salts to the synthesis of block copolymers of monomers polymerizable with different mechanisms are described. 

Contact and solvent-separated ion pairs can be distinguished in anionic systems the interionic distance of the former is usually 1-3 A, which increases to 4 or even 7 A in solvent-separated ion pairs [21]. There is apparently no further minimum in the potential energy diagram. The reactivity of solvent-separated ion pairs and free ions in anionic systems are similar, being a few orders of magnitude more reactive than contact ion pairs. In contrast, contact ion pairs in cationic systems are separated by 4-6 A, and therefore resemble the solvent-separated species of anionic systems in terms of structure, as well as their relative reactivity and ability to dissociate. The existence of solvent-separated ion pairs in cationic polymerization is questionable and has not yet been proven spectroscopically. 

Several conclusions have to be drawn. The first is related to the obvious gap between the empiricism and even archaism of most of industrial cationic polymerization processes and the level of fundamental science devoted for decades to these reactions. Previous chapters in this volume clearly illustrate the situation. This feature was pointed out in the early book of Kennedy and Marechal [1], and the explanation based on the very favorable price/performances characteristics of the products is still realistic. Nevertheless it is noteworthy that recent improvements or new processes based on more scientific approaches led to a better control of the polymerization, of polymer structure, and to high-performance commercial products which will increasingly occupy the market. This is the case for the recently marketed reactive BF3-based polybutenes with high content of exomethylenic chain ends, for the strongly developing pure monomer hydrocarbon resins ( + 8% in 1994), or for the new benzyl halide-based halobutyl rubber, and it is revealing that these products represent the three families of cationically prepared industrial polymers... 

Simple organic substances and oligomers have often been used to elucidate reaction mechanisms, reactivities of fimctional groups, and structural characteristics of polymers. However, only a limited amount of model studies have been carried out in the field of cationic polymerization. 

Development of the elucidation of the catalytic reaction mechanism and the structure-reactivity relationships proceeded much more slowly. By the mid-1960s Wilke [17], Porri [18], and Dolgoplosk [19] had already shown that allyl-transition metal complexes can catalyze the butadiene polymerization stereoselectively and quite probably represent the real catalysts. In particular the allylnickel(II) complexes [Ni(C3Hs)X]2 (X = I [20], CF3CO2 [21]) and more recently the cationic complexes [Ni(C3H5)L2]PFe, with L = P(OPh)3, etc. [22, 23], were also used to explore the catalytic reaction mechanism. 

J. V. Crivello and U. Varlemann, Structure and Reactivity Relationships in the Photo-initiated Cationic Polymerization of 3,4-Epoxycyclohexylmethyl-3, 4 - Epoxycyclohexane Carboxylate. In Photopolymerization, Vol. 673, A. B. Scranton and C. N. Bowman, Eds., American Chemical Society, Washington D.C., 1997, p. 82. 

A novel well-defined macromonomer of epoxy end-functionalized poly(V -capro-lactone) (PCL) was synthesized and its reactivity in photoinitiated cationic polymerization was examined [28]. PCL macromonomer as the comonomer allowed a rather simple incorporation of PCL side chains into poly(cyclohexene oxide) (PCHO) backbone. This way PCHO-g-PCL copolymer with random sequences of the structure shown in Scheme 13.16 is formed. 

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