Toughening CO -Derived Copolymer Elastomers Through Ionomer Networking.

Utilizing carbon dioxide (CO ) to make polycarbonates through the ring-opening copolymerization (ROCOP) of CO and epoxides valorizes and recycles CO and reduces pollution in polymer manufacturing. Recent developments in catalysis provide access to polycarbonates with well-defined structures and allow for copolymerization with biomass-derived monomers; however, the resulting material properties are underinvestigated. Here, new types of CO -derived thermoplastic elastomers (TPEs) are described together with a generally applicable method to augment tensile mechanical strength and Young's modulus without requiring material re-design.

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

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 %).

Sequence Control from Mixtures: Switchable Polymerization Catalysis and Future Materials Applications.

There is an ever-increasing demand for higher-performing polymeric materials counterbalanced by the need for sustainability throughout the life cycle. Copolymers comprising ester, carbonate, or ether linkages could fulfill some of this demand as their monomer-polymer chemistry is closer to equilibrium, facilitating (bio)degradation and recycling; many monomers are or could be sourced from renewables or waste. Here, an efficient and broadly applicable route to make such copolymers is discussed, a form of switchable polymerization catalysis which exploits a single catalyst, switched between different catalytic cycles, to prepare block sequence selective copolymers from monomer mixtures.

Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization.

Thermoplastic elastomers benefit from high elasticity and straightforward (re)processability; they are widely used across a multitude of sectors. Currently, the majority derive from oil, do not degrade or undergo chemical recycling. Here a new series of ABA triblock polyesters are synthesized and show high-performances as degradable thermoplastic elastomers; their composition is poly(cyclohexene--phthalate)--poly(ε-decalactone)--poly(cyclohexene--phthalate) {PE-PDL-PE}.

Bio-based and Degradable Block Polyester Pressure-Sensitive Adhesives.

A new class of bio-based fully degradable block polyesters are pressure-sensitive adhesives. Bio-derived monomers are efficiently polymerized to make block polyesters with controlled compositions. They show moderate to high peel adhesions (4-13 N cm ) and controllable storage and loss moduli, and they are removed by adhesive failure.

Switchable Catalysis Improves the Properties of CO-Derived Polymers: Poly(cyclohexene carbonate--ε-decalactone--cyclohexene carbonate) Adhesives, Elastomers, and Toughened Plastics.

Carbon dioxide/epoxide copolymerization is an efficient way to add value to waste CO and to reduce pollution in polymer manufacturing. Using this process to make low molar mass polycarbonate polyols is a commercially relevant route to new thermosets and polyurethanes. In contrast, high molar mass polycarbonates, produced from CO, generally under-deliver in terms of properties, and one of the most widely investigated, poly(cyclohexene carbonate), is limited by its low elongation at break and high brittleness.

Easy access to oxygenated block polymers via switchable catalysis.

Oxygenated block polyols are versatile, potentially bio-based and/or degradable materials widely applied in the manufacture of coatings, resins, polyurethanes and other products. Typical preparations involve multistep syntheses and/or macroinitiator approaches. Here, a straightforward and well-controlled one-pot synthesis of ABA triblocks, namely poly(ether-b-ester-b-ether), and ABCBA pentablocks, of the form poly(ester-b-ether-b-ester'-b-ether-b-ester), using a commercial chromium catalyst system is described.