Toughening CO₂‐Derived Copolymer Elastomers Through Ionomer Networking

Abstract

Utilizing carbon dioxide (CO2) to make polycarbonates through the ring‐opening copolymerization (ROCOP) of CO2 and epoxides valorizes and recycles CO2 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 CO2‐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. These TPEs combine high glass transition temperature (Tg) amorphous blocks comprising CO2‐derived poly(carbonates) (A‐block), with low Tg poly(ε‐decalactone), from castor oil, (B‐block) in ABA structures. The poly(carbonate) blocks are selectively functionalized with metal‐carboxylates where the metals are Na(I), Mg(II), Ca(II), Zn(II) and Al(III). The colorless polymers, featuring <1 wt% metal, show tunable thermal (Tg), and mechanical (elongation at break, elasticity, creep‐resistance) properties. The best elastomers show >50‐fold higher Young's modulus and 21‐times greater tensile strength, without compromise to elastic recovery, compared with the starting block polymers. They have wide operating temperatures (−20 to 200 °C), high creep‐resistance and yet remain recyclable. In the future, these materials may substitute high‐volume petrochemical elastomers and be utilized in high‐growth fields like medicine, robotics, and electronics.

Alternatives to fluorinated binders: recyclable copolyester/carbonate electrolytes for high-capacity solid composite cathodes

“…1a). 53–57 From a monomer mixture, this process applies a single catalyst (Scheme S1†) to direct polymerisations between lactone (CL)/cyclic carbonate (TMC) ring-opening polymerisation (ROP) and epoxide ( v CHO)/CO 2 ring-opening copolymerisation (ROCOP) by the presence/absence of CO 2 (Scheme S2†). 53,55,58 These switchable polymerisations are well-controlled, so the catalysis can be manipulated to systematically vary the polymer composition (A : B ratio), molar mass ( M n ) and architecture.…”

Post-polymerization functionalization of aliphatic polycarbonates using click chemistry

“…This was followed by UV-initiated attachment of 3-mercaptopropionic acid via thiol–ene click chemistry and coordination with metal centres to afford thermoplastic elastomers. 91 Another type of elastomer was synthesized by incorporating copper–thioether coordination within a polycarbonate framework. This was achieved through the copolymerization of cyclohexene oxide, vinyl cyclohexene oxide, and CO 2 , followed by the functionalization of unsaturated pendant groups using hexanethiol and dodecylthiol via thiol–ene click chemistry.…”

Where is chemistry's moon? Highlights from the 1st conference for the Center of the Transformation of Chemistry (CTC) at Ringberg Castle 2023

“…Katharina Eisenhardt presented her efforts on “Using Carbon Dioxide to Make Plastics”, highlighting catalysis’ role in developing the next generation of sustainable materials. 57 Her work in the Williams group on ring-opening copolymerization (ROCOP) of propylene oxide (PO) and CO 2 represents an eco-friendly approach to utilize CO 2 waste gas (Fig. 8).…”