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Supercritical Fluid Chromatography with Evaporative Light Scattering Detection (SFC-ELSD) for Determination of Oligomer Molecular Weight Distributions

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Abstract

Ultraviolet curable polyureas and polyurethanes enjoy a wide range of applications in the coatings industry. They demand less energy for curing compared to thermal processes that offer relatively low viscosities before photocuring, and provide mechanical property improvements due to hydrogen bonding physical crosslinks. Mechanical properties of the coatings are dependent on a variety of factors, including chemical composition, molecular weight, and molecular weight distribution. Formulations are designed for a wide variety of end use applications, ranging from soft, elastomeric coatings to harder, nonflexible sealants. This report demonstrates that the thermomechanical behavior of photocured coatings is a function of molecular weight distribution. Step-growth polymerization and endcapping afforded a variety of acrylate-terminated, urea-/urethane-containing photocurable oligomers from amine-terminated poly(propylene glycol), dicyclohexylmethane-4,4′-diisocyanate (HMDI), and 2-hydroxyethyl acrylate (HEA) at various stoichiometric ratios. The state-of-the-art supercritical fluid chromatography coupled with evaporative light-scattering detection (SFC-ELSD) enabled the elucidation of oligomeric molecular weight distributions as a function of reaction stoichiometry. SFC-ELSD demonstrated the efficient separation of oligomeric species with single repeat unit resolution (i.e., n = 2 vs. n = 3). Dynamic mechanical analysis probed thermomechanical response of photocured films as a function of molecular weight distribution and demonstrated that the presence of a hydrogen-bonding, small molecule photoactive reaction byproduct, i.e., HEA doubly-endcapped HMDI, had a much more profound effect on thermomechanical response as compared to changes in oligomer molecular weight in the molecular weight range investigated. This combination of chromatographic technique and thermomechanical analysis afforded an in-depth investigation of the structure–property relationships of urea-/urethane-containing photocurable oligomers.

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Acknowledgments

The authors acknowledge Bayer MaterialScience (now Covestro) for providing HMDI. The authors also acknowledge TA Instruments-Waters LLC for loaning the Aquity UPC2 SFC-ELSD system.

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Authors and Affiliations

  1. Department of Chemistry, Macromolecules Innovation Institute, Virginia Tech, Blacksburg, VA, 24061, USA

    Justin M. Sirrine, Mehdi Ashraf-Khorassani, Nicholas G. Moon, Ryan J. Mondschein & Timothy E. Long

Authors
  1. Justin M. Sirrine
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  2. Mehdi Ashraf-Khorassani
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  3. Nicholas G. Moon
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  4. Ryan J. Mondschein
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  5. Timothy E. Long
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Corresponding author

Correspondence to Timothy E. Long.

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The authors declare no conflicts of interest.

Human participant or animals

This article does not contain any studies with human participants or animals performed by any of the authors.

Additional information

Published in the topical collection 2015 International Symposium on GPC/SEC and Related Techniques with guest editor André M. Striegel.

Electronic supplementary material

Below is the link to the electronic supplementary material.

10337_2016_3098_MOESM1_ESM.pdf

The materials and methods section, a table of theoretical and experimental number-average molecular weights (Mn) of SFC-ELSD samples, a table of theoretical number-average molecular weights (Mn) of various expected species in SFC-ELSD chromatograms, and 1H NMR molecular structure confirmation of a dialyzed 1.0 : 3.0 : 5.0 oligomer are provided, as well as additional SFC-ELSD chromatograms for additional samples, including D* and HEA alone. This information is available on the Journal’s website (PDF 758 kb)

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Sirrine, J.M., Ashraf-Khorassani, M., Moon, N.G. et al. Supercritical Fluid Chromatography with Evaporative Light Scattering Detection (SFC-ELSD) for Determination of Oligomer Molecular Weight Distributions. Chromatographia 79, 977–984 (2016). https://doi.org/10.1007/s10337-016-3098-9

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  • DOI: https://doi.org/10.1007/s10337-016-3098-9

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