Torsional Strain Enabled Ring-Opening Polymerization towards Axially Chiral Semiaromatic Polyesters with Chemical Recyclability.

The development of new chemically recyclable polymers via monomer design would provide a transformative strategy to address the energy crisis and plastic pollution problem. Biaryl-fused cyclic esters were targeted to generate axially chiral polymers, which would impart new material performance. To overcome the non-polymerizability of the biaryl-fused monomer DBO, a cyclic ester Me-DBO installed with dimethyl substitution was prepared to enable its polymerizability via enhancing torsional strain. Impressively, Me-DBO readily went through well-controlled ring-opening polymerization, producing polymer P(Me-DBO) with high glass transition temperature (Tg >100 °C). Intriguingly, mixing these complementary enantiopure polymers containing axial chirality promoted a transformation from amorphous to crystalline material, affording a semicrystalline stereocomplex with a melting transition temperature more than 300 °C. P(Me-DBO) were capable of depolymerizing back to Me-DBO in high efficiency, highlighting an excellent recyclability.

Advancing the Development of Recyclable Aromatic Polyesters by Functionalization and Stereocomplexation.

The development of innovative synthetic polymer systems to overcome the trade-offs between the polymer's depolymerizability and performance properties is in high demand for advanced material applications and sustainable development. In this contribution, we prepared a class of aromatic cyclic esters (M1-M5) from thiosalicylic acid and epoxides by facile one-pot synthesis. Ring-opening polymerization of Ms afforded aromatic polyesters P(M)s with high molecular weights and narrow dispersities. The physical and mechanical properties of P(M)s can be modulated by stereocomplexation and regulation of the side-chain flexibility of the polymers, ultimately achieving high-performance properties such as high thermal stability and crystallinity (Tm up to 209 °C), as well as polyolefin-like high mechanical strength, ductility, and toughness. Furthermore, the functionalizable moieties of P(M)s have driven a wide array of post-polymerization modifications toward access to value-added materials. More importantly, the P(M)s were able to selectively depolymerize into monomers in excellent yields, thus establishing its circular life cycle.

Biobased High-Performance Aromatic-Aliphatic Polyesters with Complete Recyclability.

The development of high-performance recyclable polymers represents a circular plastics economy to address the urgent issues of plastic sustainability. Herein, we design a series of biobased seven-membered-ring esters containing aromatic and aliphatic moieties. Ring-opening polymerization studies showed that they readily polymerize with excellent activity (TOF up to 2.1 × 105 h-1) at room temperature and produce polymers with high molecular weight (Mn up to 438 kg/mol). The variety of functionalities allows us to investigate the substitution effect on polymerizability/recyclability of monomers and properties of polymers (such as Tgs from -1 to 79 °C). Remarkably, a stereocomplexed P(M2) exhibited significantly increased Tm and crystallization rate. More importantly, product P(M)s were capable of depolymerizing into their monomers in solution or bulk with high efficiency, thus establishing their circular life cycle.

Insights into substitution strategy towards thermodynamic and property regulation of chemically recyclable polymers.

The development of chemically recyclable polymers serves as an attractive approach to address the global plastic pollution crisis. Monomer design principle is the key to achieving chemical recycling to monomer. Herein, we provide a systematic investigation to evaluate a range of substitution effects and structure-property relationships in the ɛ-caprolactone (CL) system. Thermodynamic and recyclability studies reveal that the substituent size and position could regulate their ceiling temperatures (Tc). Impressively, M4 equipped with a tert-butyl group displays a Tc of 241 °C. A series of spirocyclic acetal-functionalized CLs prepared by a facile two-step reaction undergo efficient ring-opening polymerization and subsequent depolymerization. The resulting polymers demonstrate various thermal properties and a transformation of the mechanical performance from brittleness to ductility. Notably, the toughness and ductility of P(M13) is comparable to the commodity plastic isotactic polypropylene. This comprehensive study is aimed to provide a guideline to the future monomer design towards chemically recyclable polymers.