Unprecedentedly high active organocatalysts for the copolymerization of carbonyl sulfide and propylene oxide: steric hindrance effect of tertiary amines

Abstract

The copolymerization of carbonyl sulfide (COS) with epoxides has been developed to be a facile method to synthesize well-defined sulfur-containing polymers. This work describes the steric effect of tertiary amines...

Metal‐free terpolymerization of propylene oxide, carbon dioxide, and carbonyl sulfide: A facile route to sulfur‐containing polycarbonates with gradient sequences

“…As a sulfur analog of polycarbonates, polythiocarbonates have been developed to effectively produce from copolymerization of carbonyl sulfide (COS) and epoxides catalyzed by either metal complexes or organocatalysts. 19,[29][30][31][32][33][34][35][36][37] However, in the case of using metal catalysts, the metal residues can cause deep color or toxicity issues which impedes applications of the polymers. 30 With this regard, our group has reported COS/epoxide copolymerization catalyzed by Lewis bases accompanied with triethyl borane (TEB) for the first time.…”

“…15,31 The obtained polythiocarbonates are colorless and highly transparent with a refractive index up to 1.56, suggesting promising application prospects in optical materials. 30,31,33,35 Although, copolymerization of CO 2 (COS) with epoxides have been extensively reported, the report on the incorporation of thiocarbonate unit into polycarbonate is rare. 27,28 Herein, we report the one-pot/one-step terpolymerization of propylene oxide (PO) with CO 2 and COS to synthesize polythiocarbonate-co-polycarbonate (PTC-co-PC) catalyzed by metal-free Lewis pairs (Scheme 1).…”

Biodegradable Copolymers from CO2, Epoxides, and Anhydrides Catalyzed by Organoborane/Tertiary Amine Pairs: High Selectivity and Productivity

“…Nowadays, the development of metal-free catalysts is still in its infancy. Especially, the common and cheap tertiary amines are rarely studied, although TEB/tertiary amine pairs exhibited unprecedentedly high activity for the ROCOP of propylene oxide (PO) and carbonyl sulfide. , Actually, TEB/tertiary amine pairs have also been applied in the ROCOP of PO with succinic anhydride (SA) but displayed poor activity (TOF ≤10 h –1 ) . Delightfully, Zhang and co-workers recently unveiled that the Lewis pairs composed of equivalent TEB and triethylamine (TEA) or N , N , N ′, N ′-tetraethyl ethylenediamine (TEED) were highly selective for the synthesis of perfectly alternating poly­(propylene carbonate) (PPC) with a productivity of 216 g PPC/g catalyst, which was the highest record among the metal-free Lewis pairs for PPC production.…”

The copolymerization of SO2with propylene oxide mediated by organic ammonium salts: a comprehensive study of the main-chain structure, living polymerization character and regioselectivity

“…13 Besides, the transformation of SO 2 into sulfur-containing polymers has turned out to be an efficient approach for SO 2 utilization, [14][15][16][17][18][19][20][21] and has developed quickly because the obtained polymers have revealed excellent properties, including enhanced optical properties, chemical resistance and metal coordination ability. [22][23][24][25][26][27] Polysulfides, a category of sulfur-containing polymers with sulfite (-OS(O)O-) as a repeating unit, have the promising potential of being used in the area of electrolytes. 28 Polysulfides can be obtained from the copolymerization of SO 2 with epoxides.…”

“…13 Besides, the transformation of SO 2 into sulfur-containing polymers has turned out to be an efficient approach for SO 2 utilization, 14–21 and has developed quickly because the obtained polymers have revealed excellent properties, including enhanced optical properties, chemical resistance and metal coordination ability. 22–27…”