Block Poly(carbonate‐ester) Ionomers as High‐Performance and Recyclable Thermoplastic Elastomers

Abstract

Thermoplastic elastomers based on polyesters/carbonates have the potential to maximize recyclability, degradability and renewable resource use. However, they often underperform and suffer from the familiar trade‐off between strength and extensibility. Herein, we report well‐defined reprocessable poly(ester‐b‐carbonate‐b‐ester) elastomers with impressive tensile strengths (60 MPa), elasticity (>800 %) and recovery (95 %). Plus, the ester/carbonate linkages are fully degradable and enable chemical recycling. The superior performances are attributed to three features: (1) Highly entangled soft segments; (2) Fully reversible strain‐induced crystallization and (3) Precisely placed ZnII‐carboxylates dynamically crosslinking the hard domains. The one‐pot synthesis couples controlled cyclic monomer ring‐opening polymerization and alternating epoxide/anhydride ring‐opening copolymerization. Efficient convresion to ionomers is achieved by reacting vinyl‐epoxides to install ZnII‐carboxylates.

Defect-free acrylic polymers with a near-Poisson distribution prepared via catalyst-free visible-light-driven radical polymerization

“…We first explored the mechanical properties of the conventional PUs without acrylate polyols via uniaxial tensile testing (Figure 5c). As reported in the previous literature, these PUs exhibited elastomer properties, and the "strength-elongation trade-off" relationship, observed in typical elastomers, 32,33 was clearly seen.…”

Biobased Thermoplastic Elastomers Derived from Citronellyl Glycidyl Ether, CO2, and Polylactide

“…38 Williams and co-workers also explored PTMC as a TPE soft block in combination with Zn 2+ -ionomer polyesters, enhancing the mechanical strength of the TPE. 68 Motivated by the lack of low T g polycarbonates, in the current work we introduce poly(citronellyl glycidyl ether carbonate) (PCitroGEC) as a novel, bioderived alternative for the soft block in poly(ester-b-carbonate-b-ester) copolymer TPEs. Sequential catalytic synthesis is explored to obtain a central PCitroGEC block, which is flanked by glassy PLLA end blocks.…”

Recyclable and Degradable Ionic-Substituted Long-Chain Polyesters

“…, sulfonation), which alter the materials’ properties significantly as a result of Coulombic interactions between the ionic moieties. − In case of acid-containing polyethylenes, hydrogen-bond networks emerge and introduce intra- and intermolecular interactions, complementing the van der Waals forces, which are typically decisive for the material properties . The neutralization of the acid groups with different cations leads to ion-containing polymers, which present an important class of materials with physical cross-links that enhance tensile strength or impact the melt viscosity. , Also, an enhanced surface adhesion compared to PE with its low surface free energy can be beneficial . Ionic-substituted polyethylenes can be accessed by free radical copolymerization under high pressure of ethylene and acrylic comonomers, leading to random copolymers with poor control over the microstructure …”