Reprocessable and Recyclable Chain-Growth Polymer Networks Based on Dynamic Hindered Urea Bonds

Mohammed A. Bin Rusayyis, John M. Torkelson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

25 Scopus citations


Conventional cross-linked polymers cannot be reprocessed because of the presence of permanent covalent cross-links, preventing reuse and recycling. Covalent adaptable networks (CANs) employ dynamic covalent bonds that undergo dynamic reactions under external stimulus, allowing recyclability of these network materials. Hindered urea chemistry is one of the recently discovered dissociative dynamic chemistries. While hindered urea bonds have traditionally been exploited in the synthesis of step-growth type CANs, the use of hindered urea bonds in the synthesis of chain-growth-type dynamic networks has only been narrowly explored. Here, we present a simple, catalyst-free, fast method to synthesize a hindered-urea-based dynamic cross-linker that can undergo a free radical polymerization with vinyl-type monomers or polymers to form reprocessable CANs. Using this cross-linker, we developed dynamic polymethacrylate networks that can be (re)processed at 80 °C. These dynamic covalent networks exhibit full recovery of cross-link density after multiple recycling steps; they are only the second chain-growth network synthesized directly and exclusively from carbon-carbon double bond monomers to demonstrate such recovery. Unlike other dissociative dynamic polymer networks, polymethacrylate networks that contain dissociative dynamic hindered urea bonds do not flow and maintain their network structure even at high temperature (300 °C). Despite its relatively fast reprocessability, the network showed delayed and extremely slow stress relaxation at the processing temperature. This work offers a simple approach to obtain reprocessable addition-type networks based on hindered urea bonds while revealing the limitations of stress relaxation experiments in relationship to the processability of some dynamic polymer networks.

Original languageEnglish (US)
Pages (from-to)568-574
Number of pages7
JournalACS Macro Letters
Issue number4
StatePublished - Apr 19 2022

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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