Scope and limitations of ring-opening copolymerization of trimethylene carbonate with substituted γ-thiolactones

Abstract

The reactivity of functional γ-thiolactones has been investigated in Ring Opening Copolymerization with trimethylene carbonate.

Functional Poly(ester-alt-sulfide)s Synthesized by Organo-Catalyzed Anionic Ring-Opening Alternating Copolymerization of Oxiranes and γ-Thiobutyrolactones

“…In 2011, Du Prez and colleagues demonstrated that γ-thiolactones bearing allyl groups can be ring-opened by primary amines releasing a thiol-containing AB monomer, that can be subsequently polymerized by radical (photo) polymerization in a stepwise fashion . And recently, the ring-opening copolymerization of substituted γ-thiolactones with trimethylene carbonate was reported …”

“…20 And recently, the ring-opening copolymerization of substituted γ-thiolactones with trimethylene carbonate was reported. 21 Alternating copolymers have attracted meaningful attention from both academia and industry due to their unique properties compare to random copolymers. Alternating polymerization do open up opportunities for controlling the chain microstructure and the macroscopic properties of polymer materials.…”

Alternating copolymerization of bio-based N-acetylhomocysteine thiolactone and epoxides

“…[26] Destarac and co-workers reported the copolymerization of substituted γ-thiolactones with trimethylene carbonate. [27] In 1998, the alternating ring-opening copolymerization of γ-thiobutyrolactone with epoxides catalyzed by quaternary onium salts was reported by Nishikubo and co-workers. [28] Perfectly alternating poly(ester-alt-sulfide)s were obtained with high dispersities (Ð) and low molar-mass control.…”

Scope and Limitations of Xanthate-Mediated Synthesis of Functional γ-Thiolactones

“…In contrast with lactone monomers, which are widely used for the synthesis of polyesters via ring-opening polymerization (ROP), 1−3 thiolactones have barely been studied in ROP, with only a few attempts being made in both homo- 4−6 and copolymerization with other cyclic monomers. 7−9 Over the last decade, five-membered ring thiolactones (γ-thiolactones) have received renewed interest with the work of Du Prez et al in the field of functional polymer synthesis. They highlighted that amines could readily open γ-thiolactones to generate a thiol that could be further reacted with a reactive double bond in a one-pot procedure.…”

“…In contrast with lactone monomers, which are widely used for the synthesis of polyesters via ring-opening polymerization (ROP), − thiolactones have barely been studied in ROP, with only a few attempts being made in both homo- − and copolymerization with other cyclic monomers. − Over the last decade, five-membered ring thiolactones (γ-thiolactones) have received renewed interest with the work of Du Prez et al in the field of functional polymer synthesis. They highlighted that amines could readily open γ-thiolactones to generate a thiol that could be further reacted with a reactive double bond in a one-pot procedure. , The use of various functionalized homocysteine thiolactones for this so-called amine–thiol–ene conjugation reaction has led to the synthesis of a tremendous amount of complex functional polymers, , some exhibiting sequence-controlled structures. − Although this new reaction in polymer synthesis seems really promising, the modified homocysteine thiolactones available show a relatively limited structural diversity, with the amine group as the only possible substitution site .…”