Facile Synthesis of Well‐Defined Branched Sulfur‐Containing Copolymers: One‐Pot Copolymerization of Carbonyl Sulfide and Epoxide

Abstract

Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well‐defined branched poly(monothiocarbonate)s in a “grafting through” manner by copolymerizing carbonyl sulfide (COS) with epichlorohydrin (ECH), where the side‐chain forms in situ. The lengths of the side‐chains are tunable based on reaction temperatures. More importantly, enhancement in thermal properties of the branched copolymer was observed, as the Tg value increased by 22 °C, compared to the linear analogues. When chiral ECH was utilized, semicrystalline branched poly(monothiocarbonate)s were accessible with a Tm value of 112 °C, which is 40 °C higher than that of the corresponding linear poly(monothiocarbonate)s. The strategy presented herein for synthesizing branched polymers provides efficient and concise access to topological polymers.

Cooperative taming of CS2/oxetane copolymerisation: Consequences of main-chain sulfuration on polymer properties and catalysis

“…[18][19][20][21][22] Taking this methodology to the arena of sulfurated polymers, ROCOP of carbonyl sulfide COS with epoxides or oxetane represents a well-established route to selectively yield poly(monothiocarbonates) (Figure 1(a)). [23][24][25][26][27][28][29] Yet this ROCOP requires specialised steel reactor setups to safely handle highly toxic, flammable and gaseous carbonyl sulfide as well as commercial access to high purity COS (which is for example currently not the case in Europe) limiting the utility of this ROCOP in standard research laboratories. Using the liquid heavier homologue CS2 is substantially simpler as it can be employed as a cosolvent and in principle allows access to copolymers with even higher sulfur ranks.…”

Toward high-performance stereo- and sequence-defined block copolymers via site-monomer specific recognition of chiral three-site organocatalyst

“…[42][43][44][45] ROCOP of PO/COS, first reported by our group in 2013, 46 has been demonstrated to be a facile route to produce polythiocarbonates with approving optical and mechanical properties. [47][48][49] Block copolymers bearing PLA and polythiocarbonate fragments promise to integrate the superior properties of each block. In addition, there are several stereo-, regio-, and chemoselective regulation in ROP of rac-LA 50 and ROCOP of PO/COS.…”