Contributions of hard and soft blocks in the self-healing of metal-ligand-containing block copolymers

Ranjita K. Bose, Marcel Enke, Antonio M. Grande, Stefan Zechel, Felix H. Schacher, Martin D. Hager, Santiago J. Garcia*, Ulrich S. Schubert, Sybrand van der Zwaag

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

32 Citations (Scopus)
59 Downloads (Pure)


The main aim of this work is to study the respective contribution of the hard and soft blocks of a metal-ligand containing block copolymer to the self-healing behavior. To this aim, different block copolymers containing terpyridine were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These block copolymers consisted of polystyrene as the hard block, n-butyl acrylate (BA) as soft block and terpyridine units as the ligand moiety placed at different locations in the soft block. These block copolymers were complexed with manganese(II) chloride to introduce transient crosslinks and, thus, self-healing behavior. Homopolymers with the hard and soft block only were also synthesized and tested. A quasi-irreversible crosslinking, i.e. by using nickel(II) nitrate, was performed in order to study the dynamics of the permanently (strongly) crosslinked network. Rheological master curves were generated enabling the determination of the terminal flow in these networks and the reversibility of the supramolecular interactions. Additionally, the macroscopic scratch healing behavior and the molecular mobility of the polymer chains in these supramolecular networks were investigated. A kinetic study of the scratch healing was performed to determine the similarities in temperature dependence for rheological relaxations and macroscopic scratch healing. In our previous work, we have explored the effect of strength of the reversible metal-ligand interaction and the effect of changing the ratio of hard to soft block. This work goes further in separating the individual contributions of the hard and soft blocks as well as the reversible interactions and to reveal their relative importance in the complex phenomenon of scratch healing.

Original languageEnglish
Pages (from-to)417-427
Number of pages11
JournalEuropean Polymer Journal
Publication statusPublished - 1 Aug 2017


  • Block-copolymer
  • Metallopolymer
  • Rheology
  • Self-healing polymer
  • Supramolecular network


Dive into the research topics of 'Contributions of hard and soft blocks in the self-healing of metal-ligand-containing block copolymers'. Together they form a unique fingerprint.

Cite this