Cationic polymerization of seven‐membered cyclic monothiocarbonate 1,3‐dioxepan‐2‐thione

Abstract

The cationic ring-opening polymerization of a seven-membered cyclic monothiocarbonate, 1,3-dioxepan-2-thione, produced a soluble polymer through the selective isomerization of thiocarbonyl to a carbonyl group {O[SC(CAO)O(CH 2 ) 4 ] n O}. The molecular weights of the polymer could be controlled by the feed ratio of the monomer to the initiators or the conversion of the monomer during the polymerization, although some termination reactions occurred after the complete consumption of the monomer. EXPERIMENTAL MaterialsDichloromethane and pyridine were dried over CaH 2 and distilled under a nitrogen atmosphere.

Ring‐opening polymerization of trimethylene carbonate by poly(ethylene glycol) in the presence of HCl·Et2O as a monomer activator

“…The biomedical suitability of PTMC, due to its moderate biodegradability and the weak inflammatory effect of its degraded products, has been previously reported 2–4. Various organometallic catalysts such as zinc, tin, and alkali metal compounds have been used for the conventional ring‐opening polymerization (ROP) of 1,3‐dioxan‐2‐one [trimethylene carbonate (TMC)] 5–10…”

Polymeric nano-micelles as drug carrier using polyethylene glycol and polytrimethylene carbonate linear and star-shaped block copolymer

“…Endo et al and our group investigated the ROP of ester monomer with an alcohol as an initiator in the presence of HCl AE Et 2 O as monomer activator [8][9][10][11][12][13][14][15]. Thus, this method may be considered as a candidate to easily give PEG and PTMC block copolymers.…”

Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity

“…Organocatalysts have been extensively used for ring‐opening polymerization (ROP) and upcycling polytetrahydrofuran, with the catalytic characteristics depending greatly on the basicity, Lewis acididity and molecular structures of the catalysts [14–16] . The traditional synthesis of sulfur‐containing polymers often includes the condensation of thiols with phosgene and ring‐opening polymerization of cyclic thiocarbonates derived from thiols and phosgene, and copolymerization of the epoxides or episulfides with carbon disulfide (CS 2 ) [17–20] . However, these procedures frequently need hazardous chemicals, labor‐intensive pre‐synthesis of starting materials, or the generation of complex units due to an oxygen/sulfur exchange reaction (O/S ER) that may produce a combination of COS, CO 2 , and episulfides in the system.…”

“…[14][15][16] The traditional synthesis of sulfur-containing polymers often includes the condensation of thiols with phosgene and ring-opening polymerization of cyclic thiocarbonates derived from thiols and phosgene, and copolymerization of the epoxides or episulfides with carbon disulfide (CS 2 ). [17][18][19][20] However, these procedures frequently need hazardous chemicals, labor-intensive pre-synthesis of starting materials, or the generation of complex units due to an oxygen/sulfur exchange reaction (O/S ER) that may produce a combination of COS, CO 2 , and episulfides in the system. The mutual copolymerization of the resulting mixture generated complex repeating units in the main chain.…”