Organocatalytic ring-opening polymerization of thionolactones: anything O can do, S can do better

Abstract

Organocatalysts facilitate the synthesis of polythionolactones; oxidative crosslinking yields a degradable polymer foam.

Sustainable and degradable plastics

“…This is in sharp contrast to the commonly observed non-polymerizability of such non-strained five-membered rings at ambient conditions, and to the organocatalytic ROP of larger thionolactones which affords polythionolactones without S/O scrambling. 9 Remarkably, the recovered polythioesters display absolute number-average molar mass (Mn,SEC) up to 178.5 kg/mol with relatively narrow dispersity (Đ = Mw/Mn < 1.6), while previously reported values, following another approach, did not exceed 6.3 kg/mol (50% yield).…”

One-Step Synthesis of Sequence-Controlled Polyester-block-Poly(ester-alt-thioester) by Chemoselective Multicomponent Polymerization

“…The microphase separation of the polyester and polythioester blocks enables materials that combine the properties of the respective homopolymers to furnish a new set of functionalities. 20,21 Typically, sequential monomer addition or the macroinitiator method involving multiple steps have been typically used in the synthesis of polythioester BCPs. 22−29 As one of pioneers for polythioesters, Lu and Ren et al reported the copolymerization of carbonyl sulfide (COS) with epoxide and synthesized ABA triblock copolymer containing the "hard" semicrystalline poly(ethylene monothiocarbonate) and the "soft" amorphous poly(propylene monothiocarbonate) by stepwise addition of epoxides.…”

“…Polyesters and their copolymers represent one family of ecofriendly polymeric materials for many important applications in drug delivery, nanolithography, sustainable plastics, solid electrolytes, or electrode binders. − Subtle modification of the oxygen atoms in polyester with sulfur atoms can lead to significant changes in polymer properties, such as refractive index, − dynamic and responsive behaviors, − heavy-metal coordination abilities, − and chemical recyclability. − The integration of polyesters and polythioesters into a block copolymer (BCP) allows for fine-tuning of physicochemical properties. The microphase separation of the polyester and polythioester blocks enables materials that combine the properties of the respective homopolymers to furnish a new set of functionalities. , …”

Synthesis of Poly(thioester sulfonamide)s via the Ring‐Opening Copolymerization of Cyclic Thioanhydride with N‐Sulfonyl Aziridine Using Mild Phosphazene Base

“…Therefore, the synthesis and application of polythioesters have been increasingly reported. [25][26][27][28][29][30][31][32][33][34][35] If substitution of ester groups of poly(ester amide)s with thioester groups, novel poly(thioester amide)s would be obtained. Furthermore, the new poly(thioester amide)s are expected to have new/enhanced properties and become a promising polymeric material.…”