In situ crosslinking of surface-initiated ring opening metathesis polymerization of polynorbornene for improved stability

Ishan A. Fursule, Ashkan Abtahi, Charles B. Watkins, Kenneth R. Graham, Brad J. Berron

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


Hypothesis In situ crosslinking is expected to increase the solvent stability of coatings formed by surface-initiated ring opening metathesis polymerization (SI ROMP). Solvent-associated degradation limits the utility of SI ROMP coatings. SI ROMP coatings have a unique capacity for post-functionalization through reaction of the unsaturated site on the polymer backbone. Any post-reaction scheme which requires a liquid solvent has the potential to degrade the coating and lower the thickness of the resulting film. Experiments We designed a macromolecular crosslinking group based on PEG dinorbornene. The PEG length is tailored to the expected mean chain to chain distance during surface-initiated polymerization. This crosslinking macromer is randomly copolymerized with norbornene through SI ROMP on a gold coated substrate. The solvent stability of polynorbornene coatings with and without PEG dinorbornene is quantitatively determined, and the mechanism of degradation is further supported through XPS and AFM analyses. Findings The addition of the 0.25 mol% PEG dinorbornene significantly increases the solvent stability of the SI ROMP coatings. The crosslinker presence in the more stable films is supported with observable PEG absorbances by FTIR and an increase in contact angle hysteresis when compared to non-crosslinked coatings. The oxidation of the SI ROMP coatings is supported by the observation of carbonyl oxygen in the polynorbornene coatings. The rapid loss of the non-crosslinked SI ROMP coating corresponds to nanoscale pitting across the surface and micron-scale regions of widespread film loss. The crosslinked coatings have uniform nanoscale pitting, but the crosslinked films show no evidence of micron-scale film damage. In all, the incorporation of minimal crosslinking content is a simple strategy for improving the solvent stability of SI ROMP coatings.

Original languageEnglish
Pages (from-to)86-94
Number of pages9
JournalJournal of Colloid and Interface Science
StatePublished - Jan 15 2018

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation [Grant No. CMMI-1334403 ]. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund [ 52743-DNI5 and 57619-DNI10 ] for partial support of this research.

Publisher Copyright:
© 2017 Elsevier Inc.


  • Crosslinker
  • Film stability
  • Norbornene
  • Oxidative degradation
  • Polynorbornene
  • ROMP
  • Surface-initiated ring opening metathesis polymerization

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Biomaterials
  • Surfaces, Coatings and Films
  • Colloid and Surface Chemistry


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