Stoichiometric analysis of competing intermolecular hydrogen bonds using infrared spectroscopy

We quantitatively analyze multiple hydrogen bonds in mixtures of two monomers: urethane dimethacrylate (UDMA) and triethylene glycol-divinylbenzyl ether (TEG-DVBE). The carbonyl stretching band in infrared (IR) absorption spectra is deconvoluted into free and hydrogen-bonded carbonyl groups. The amounts of the sub-components are determined for 21 mixture compositions and initially analyzed using a simple stoichiometric model (based on one dominant hydrogen acceptor group per monomer species) for the equilibrium state of hydrogen bond formation. However, our in-depth stoichiometric analysis suggests that at least two UDMA acceptor groups (carbonyl and alkoxy oxygens) and one TEG-DVBE acceptor group (ether oxygen) contribute to intermolecular hydrogen bonding interactions. This finding is further supported by a quantitative analysis of the hydrogen bonding effect on the N–H stretching band. Moreover, the equilibrium constants of these hydrogen bond formations confirm that the inter-association between UDMA and TEG-DVBE is non-negligible in comparison to the UDMA self-associations. Such quantitative information on intermolecular interactions provides insight into the effect of hydrogen bonding on the copolymerization kinetics of these monomer mixtures.