Circular Polydiketoenamine Elastomers with Exceptional Creep Resistance via Multivalent Cross-Linker Design
[1];
[3];
[4]
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
- University of California, Berkeley, CA (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division
Elastomers are widely used in textiles, foam, and rubber, yet they are rarely recycled due to the difficulty in deconstructing polymer chains to reusable monomers. Introducing reversible bonds in these materials offers prospects for improving their circularity; however, concomitant bond exchange permits creep, which is undesirable. Here, we show how to architect dynamic covalent polydiketoenamine (PDK) elastomers prepared from polyetheramine and triketone monomers, not only for energy-efficient circularity, but also for outstanding creep resistance at high temperature. By appending polytopic cross-linking functionality at the chain ends of flexible polyetheramines, we reduced creep from >200% to less than 1%, relative to monotopic controls, producing mechanically robust and stable elastomers and carbon-reinforced rubbers that are readily depolymerized to pure monomer in high yield. We also found that the multivalent chain end was essential for ensuring complete PDK deconstruction. Mapping reaction coordinates in energy and space across a range of potential conformations reveals the underpinnings of this behavior, which involves preorganization of the transition state for diketoenamine bond acidolysis when a tertiary amine is also nearby.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC02-05CH11231; DGE 1752814; AC02-05-CH11231
- OSTI ID:
- 2216990
- Alternate ID(s):
- OSTI ID: 2350923
- Journal Information:
- ACS Central Science, Vol. 10, Issue 1; ISSN 2374-7943
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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