Controlling polymer stereochemistry in ring-opening polymerization: a decade of advances shaping the future of biodegradable polyesters

Abstract

In this review, we describe recent developments in biodegradable polymer synthesis with a focus on the use of discrete complexes and organocatalysts as active initiators for the stereocontrolled ring-opening polymerization of cyclic esters.

(+)‐Limonene‐Lactam: Synthesis of a Sustainable Monomer for Ring‐Opening Polymerization to Novel, Biobased Polyamides

“…For this purpose, we will also consider lactam polymerizations in solution which seems to be promising after first attempts in THF. Copolymerizations with other lactams to, e.g., PA-co-PAs, and with lactones [48] to PEAs are under further investigation also with regards to kinetics and the different monomer reactivities. Incorporated double bonds of 4 enable functionalization of the resulting PA, leading to its tunability.…”

Synthesis of Benzoxazine Functionalized Amine‐Bridged Bis(phenolato) Rare Earth Complexes and Their Application in Ring‐Opening Polymerization of rac‐Lactide

“…Stereoregular PLAs are crystalline polymers with a high melting point, whereas atactic PLA is amorphous and brittle. Therefore, extensive efforts have been focused on the synthesis of stereoregular PLAs, [ 4‐5 ] and a variety of catalysts/initiators have been applied in the controlled ROP of rac ‐LA, including organocatalysts, [ 6‐8 ] main group metal, [ 9‐17 ] transition metal, [ 18‐20 ] and rare earth metal complexes. [ 21‐23 ] Among them, rare earth metal complexes have attracted intensive attention due to their high activity, high stereoselectivity, and good controllability for polymerization under mild conditions.…”

Advancing the Development of Recyclable Aromatic Polyesters by Functionalization and Stereocomplexation

“…Functionalities and tacticities of polymer chains have a significant influence on the physical and mechanical properties of polymeric materials [20–27] . As a synthetic toolbox, both direct polymerization of functionalized monomers and postpolymerization modification have been devoted to introducing diverse functionalities into polymers, enabling the fine‐tuning and improvement of the thermal and mechanical properties of the pristine polymer [20] .…”

“…Functionalities and tacticities of polymer chains have a significant influence on the physical and mechanical properties of polymeric materials. [20][21][22][23][24][25][26][27] As a synthetic toolbox, both direct polymerization of functionalized monomers and postpolymerization modification have been devoted to introducing diverse functionalities into polymers, enabling the fine-tuning and improvement of the thermal and mechanical properties of the pristine polymer. [20] Additionally, significant efforts have focused on synthesizing stereoregular polymers towards high-performance materials, [28][29][30][31][32][33] such as ROP of enantiopure monomers to isotactic polymers.…”