Das Solvosystem Benzoylchlorid, 4. Mitt.: Spektrophotometrische Untersuchungen

Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers

“…Thus, the polymerization rates decreased in the order of FeCl 3 > SnCl 4 > EtAlCl 2 . This order agrees with the ability to extract Cl À from a chloroalkane in the presence of carbonyl groups 14 (see the introduction). For polymerization in the presence of an added base, equilibrium between the dormant and active species is considered to exist, as shown in Scheme 1.…”

Controlled cationic copolymerization of benzaldehyde with isobutyl vinyl ether using base‐assisting system

“…EtAlCl 2 , which prefers a hard base such as a carbonyl compound,28, 29 interacted with the carbonyl group of BzA more than with the chlorine atom of IBVE‐HCl, inducing cyclotrimerization as illustrated in Scheme (B). In contrast, SnCl 4 , FeCl 3 and GaCl 3 , which have more chloride affinity,22, 30 would remove the Cl atom from IBVE‐HCl, generating a carbocation with the structure derived from IBVE for inducing copolymerization. Thus, copolymerization was conducted in toluene at −78 °C using SnCl 4 , FeCl 3 , and GaCl 3 (Table 1, entries 5–7, respectively), which showed different interactions with basic compounds compared to EtAlCl 2 22, 28, 31–34.…”

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

“…According to the book FriedelCrafts and Related Reactions by Olah, 37 SnCl 4 and FeCl 3 , compared with AlCl 3 , have strong affinity for the Cl atom, especially in a carbonyl-containing solvent. 38 In fact, a clue for achieving fast living cationic polymerization was found when the polymerization of the azocontaining monomer using SnCl 4 was examined and the significant acceleration of the reaction was noted. 36 On the basis of these results, the cationic polymerization of IBVE was examined with IBVE-HCl/SnCl 4 (or IBEAEtAlCl 2 /SnCl 4 ) in toluene at 0 8C in the presence of ethyl acetate (Fig.…”

“…37 In addition, FeCl 3 was more reactive than SnCl 4 and AlCl 3 in the formation of carbocations from a chloroalkane in the presence of a carbonyl compound. 38 Thus, FeCl 3 was expected to induce fast living cationic polymerization with an added base, with a rate even higher than that with SnCl 4 . Furthermore, FeCl 3 has advantages for industrial use: it is easy to handle, 48 has low toxicity, and is economical.…”