Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published February 7, 2022 | Supplemental Material
Journal Article Open

PolyDODT: a macrocyclic elastomer with unusual properties

Abstract

The effect of reaction conditions on the structure of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H₂O₂ and air was investigated. 800 MHz (1 and 2D) NMR was used to investigate the polymer structures. Sensitivity analysis provided direct evidence for high purity cyclic polyDODT up to M_n ∼ 100 000 g mol⁻¹. Comparative analysis by High Resolution Multidetector Size Exclusion Chromatography (SEC) using integrated data showed that the cycles had lower viscosity and were more compact (both for R_g and R_h) than linear samples of similar molecular weight. However, differential data revealed unusual behavior. While lower molecular weight cyclic polymers eluted later and had lower intrinsic viscosity than their linear counterparts at the same molecular weight, at higher molecular weights the polymers showed strange behavior: both the diffusion coefficient measured by Quasielastic Light Scattering (QELS) and Mark–Houwink–Sakurada plots of intrinsic viscosity for linear and cyclic polyDODT were found to converge. R3P, an aqueous based "green" method is capable of producing polymers at the 10–100 g scale in the lab, which will allow more detailed studies of this new class of biodegradable elastomers so further experimentation can be performed to elucidate the reasons for the unusual findings.

Additional Information

© The Royal Society of Chemistry 2022. Received 22nd October 2021, Accepted 23rd December 2021, First published 04 Jan 2022. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE–SC0018891 and a start-up fund of The Ohio State University #11232011000-11-PUSKAS. The work at TTU and Caltech was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Awards DE-SC0018657 and DE-SC0018655. There are no conflicts to declare.

Attached Files

Supplemental Material - d1py01426a1.pdf

Files

d1py01426a1.pdf
Files (2.0 MB)
Name Size Download all
md5:47762c310ef8dbb1ca3bc66088c1e35f
2.0 MB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 23, 2023