The precise synthesis of poly(thioester)s with diverse structures is still a significant challenge in the polymeric materials field. Herein, we report a novel approach to the synthesis of well‐defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts. Both the cation and anion have strong effects on the copolymerization. [PPN]OAc ([PPN]=bis(triphenylphosphine)iminium) with a bulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with a completely alternating structure, controlled molecular weight, and narrow polydispersity. The poly(thioester) obtained from succinic thioanhydride and propylene sulfide is a typical semicrystalline material, possessing a high refractive index of up to 1.78. Because it uses readily available monomers, this method is expected to open up a new route to poly(thioester)s with diverse structures and properties.
The precise synthesis of poly(thioester)s with diverse structures is still as ignificant challenge in the polymeric materials field. Herein, we report an ovel approacht ot he synthesis of well-defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts.B oth the cation and anion have strong effects on the copolymerization.[PPN]OAc ([PPN] = bis(triphenylphosphine)iminium) with abulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with ac ompletely alternating structure,controlled molecular weight, and narrow polydispersity.T he poly(thioester) obtained from succinic thioanhydride and propylene sulfide is atypical semicrystalline material, possessing ah igh refractive index of up to 1.78. Because it uses readily available monomers,t his method is expected to open up an ew route to poly(thioester)s with diverse structures and properties. Scheme 1. Comparison of synthetic routes to aliphatic poly(thioester)s.
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