Crossover experiments applied to network formation reactions: Improved strategies for counting elastically inactive molecular defects in PEG gels and hyperbranched polymers

Huaxing Zhou, Eva Maria Schön, Muzhou Wang, Matthew J. Glassman, Jenny Liu, Mingjiang Zhong, David Díaz Díaz, Bradley D. Olsen, Jeremiah A. Johnson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

57 Scopus citations

Abstract

Molecular defects critically impact the properties of materials. Here we introduce a paradigm called isotopic labeling disassembly spectrometry (ILDaS) that facilitates unprecedented precise experimental correlations between elastically inactive network defects (dangling chains and primary loops) and network formation kinetics and precursor structure. ILDaS is inspired by classical crossover experiments, which are often used to interrogate whether a reaction mechanism proceeds via an inter- or intramolecular pathway. We show that if networks are designed from labeled bifunctional monomers that transfer their labels to multifunctional junctions upon network formation, then the extent of junction labeling correlates directly with the number of dangling chains and cyclic imperfections within the network. We demonstrate two complementary ILDaS approaches that enable defect measurements with short analysis times, low cost, and synthetic versatility applicable to a broad range of network materials including polydisperse polymer precursors. The results will spur new experimental and theoretical investigations into the interplay between polymer network structure and properties.

Original languageEnglish (US)
Pages (from-to)9464-9470
Number of pages7
JournalJournal of the American Chemical Society
Volume136
Issue number26
DOIs
StatePublished - Jul 2 2014

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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