Living Ring-Expansion Polymerization of Thiirane with Cyclic Monocarbamothioates

Abstract

We synthesized two kinds of monocarbamothioates TZO­(R) containing a thiazolidin-2-one (TZO) skeleton and TZD­(R) containing a thiazolidine-2,4-dione (TZD) skeleton. In the reaction of TZO­(R) and phenoxypropyrenesulfide (PPS) using tetrabutylammonium chloride (TBAC) as a catalyst in 1-methyl-2-pyrrolidinone at 60 °C, anionic ring-opening polymerization of PPS proceeded to give the corresponding linear polysulfides, polyPPS, with M n = 75 860–206 700 (M w/M n = 1.54–1.73) in high yield. In contrast, in the reaction of TZD­(R) and PPS, the continuous insertion reaction of PPS into TZD­(R), i.e., living ring-expansion polymerization, occurred to afford cyclic polysulfides TZD­(R)-c-poly­(PPS) n with M n = 1870–33 420 (M w/M n = 1.07–1.26) in high yield. The ring size could be controlled by the feed ratio of TZD­(R)/PPS in the range of 1/5–1/100.

Green synthesis of well-defined linear poly(hydroxyl thioether) direct from epoxide in water

“…The conversion of epoxide to episulfide with appropriate sulfo reagent in ethanol or water has been known for decades, 24,25 and AROP of episulfide initiated by thiolate 26 or thiol/1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) 27 can lead to the formation of various architectures of polythioether. 28,29 Whether AROP can be performed in water and how to merge the O-S ER with AROP for green synthesis of polythioether direct from epoxide are challenging subjects. Aiming at this purpose, a representative hydroxyl-containing monomer, 2-[4-(hydroxymethyl)phenoxymethyl] epoxide ( pHMPE), was deliberately designed, which should exhibit different behavior from the common compound 2-( phenoxymethyl) epoxide (PME) without hydroxyl groups 28 in the classical O-S ER procedure with potassium thiocyanate (KSCN).…”

Repairable, Recyclable, and Regenerable Macrocycle Organic Polymer†

“…Note that MOPs are inherently different from conventional porous polymers in terms of the network topology, structure tunability, pore size adjustability, healing ability, [ 28 ] recyclability, [ 29 ] and self‐growing ability. [ 30 ] This work opens a new door for designing and constructing novel organic frameworks that offer unique characteristics not easily accessible with conventional MOFs/COFs.…”

Efficient synthesis of trefoil-shaped tricyclic polymers by a ROMP-based blocking-cyclization technique

“…[1][2][3][4] Cyclic polymers are a kind of topological polymer without chain ends, 5,6 and exhibit unique physical properties, such as smaller hydrodynamic volume, lower viscosity, and higher glass transition temperature, compared with their linear polymer counterparts. [7][8][9][10] Consequently, cyclic polymers have attractive application potential in the fields of drug delivery, coatings, and electronic devices. [11][12][13][14][15] Multicyclic polymers with multiple ring units are a kind of cyclic polymer with complex topological structures, and can be divided into three basic types namely fused, bridged, and spiro (such as eight-, trefoil-, and quatrefoil-shaped) cyclic polymers.…”