First observation of equilibrium polymerization of cyclic sulfite

Substituent Effect on the Anionic Equilibrium Polymerization of Six-Membered Cyclic Carbonates

“…Linear relationships were observed between ln [M 1 ] and 1/ T in the polymerizations of cyclic carbonates as shown in Figure , supporting the equilibrium polymerization. The Δ H ss and Δ S ss values were calculated from the plots as summarized in Table , which were similar to those of the other heterocyclic compounds. 4f,j, The absolute value of Δ H ss and Δ G ss decreased in the order of 1 > 2 > 3 ≥ 4 > 5 . The monomer with higher polymerizability showed a larger |Δ G ss | value.…”

“…The [A]/[B] value was in the order 1 − 3 > 4 , 5 > 6 , which well agreed with the order of the polymerizability. This result suggests that the steric repulsion of substituents on the polymer chain is responsible for the thermodynamic stability of macromolecules, as reported in the polymerization of spiro ortho ester 4h 4 Optimized geometries of polymer models obtained by the PM3 MO method. 5 Heat of Formation ( H f ) of Polymer Models (A) and Cyclic Carbonates (B) Estimated by the PM3 Method polymer model H f of polymer model (A) (kcal/mol)cyclic carbonate H f of cyclic carbonate (B) (kcal/mol)(A)/(B) I −271.8 1 −128.1 2.12 II −297.6 2 −139.3 2.14 III −314.3 3 −147.4 2.13 IV −190.2 4 −103.0 1.85 V −196.3 5 −106.5 1.84 VI −76.9 6 −65.8 1.17 …”

Cationic Polymerization of Seven-Membered Cyclic Sulfites. Substituent Effect on the Polymerization Behavior

“…The polymerization of 7BnCS afforded poly(7BnCS) ( M̄ n = 8700) in 100% conversion with TfOMe in chlorobenzene (5 M) for 17 days (run 15 in Table ). The polymerization of 7BnCS did not show an equilibrium character different from that of 7CS . The polymerization of 7BnCS with BF 3 ·OEt 2 did not afford a cross-linked polymer but rather poly(7BnCS) without gelation even at 60 °C (run 22 in Table ).…”

“…The polymerization of 7BnCS did not show an equilibrium character different from that of 7CS. 8 The polymerization of 7BnCS with BF 3 ‚OEt 2 did not afford a crosslinked polymer but rather poly(7BnCS) without gelation even at 60 °C (run 22 in Table 2). The cationic polymerization proceeded to afford poly(7BnCS) with less active initiator such as MeI and methyl p-toluenesulfonate (TsOMe) at 60 °C (runs 25 and 26 in Table 2).…”

Electrochemical synthesis of cyclic sulfites using diols and sulfur dioxide

“…19 Cyclic sulfites may be polymerized through cationic ring opening. Depending on the ring size of the starting material, the resulting polymer is either a polyoxyethylene 20 or a polysulfite, 21 which are currently being investigated as either biopolymers 20 or biodegradable polymers (Scheme 1a). 22 Due to their exceptional electrochemical stability, cyclic sulfites have found direct application as additives in lithium ion batteries (Scheme 1b).…”