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

Polythioesters Prepared by Ring‐Opening Polymerization of Cyclic Thioesters and Related Monomers

“…The methodology was successfully extended to the preparation of higher, renewable linear poly(ester‐ alt ‐thioether)s made with epoxides bearing different side chains, and bio‐based N ‐acetylhomocysteine thiolactone (NHTL), by using 2‐ tert ‐butylimino‐2‐diethylamino‐1,3‐dimethylperhydro‐1,3,2‐diazaphosphorine (BEMP) ‐BnOH as initiating system in THF (Scheme 18). [28b,c] …”

Recent advances in the ring-opening polymerization of sulfur-containing monomers

“…This methodology was later extended for the preparation of renewable poly(ester- alt -thioether)s using bio-based thiolactone monomer M3b and various functionalized epoxides. 29,30…”

“…This methodology was later extended for the preparation of renewable poly(ester-alt-thioether)s using bio-based thiolactone monomer M3b and various functionalized epoxides. 29,30 In 2015, Kiesewetter et al described the thiol-initiated organocatalytic ROP of M1 to obtain polymers with broad molecular weight distributions (Đ = 1.4-1.7) but with unsatisfactory M n values generally lower than 33.0 kg mol −1 due to transthioesterification side reactions. 31 The suppression of such undesired trans-thioesterification was later reported achievable using fused or bridged-ring thiolactone monomers.…”

Thiolactone chemistry, a versatile platform for macromolecular engineering

“…Despite the presence of a weakly acidic amide group in the structure of commercially-available bio-based N -acetyl homocysteine thiolactone, the use of benzyl alcohol-BEMP as initiating system allowed its alternating copolymerization with various epoxides. 122 Well-defined copolymers were synthesized. It is noteworthy, that these NHTL-based copolymers have significantly higher T g compared to similar structures prepared with γ-thiobutyrolactone.…”

“…Recent papers reported the use of monomers based on renewable compounds. 122,125 In addition, the design of self-immolative polymers is currently a very active field of polymer science. [160][161][162] Thioesters can be cleaved under mild conditions and did not induce side-reactions.…”