PolyDODT: a macrocyclic elastomer with unusual properties

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), H 2 O 2 and air was investigated. 800 MHz (1 and 2D) NMR was used to investigate the polymer structures. Sensiti...

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Bibliographic Details
Published in:Polymer chemistry 2022-02, Vol.13 (5), p.668-676
Main Authors: Molnar, Kristof, Kim, Hojin, Chen, Dongjie, Helfer, Carin A, Kaszas, Gabor, McKenna, Gregory B, Kornfield, Julia A, Yuan, Chunhua, Puskas, Judit E
Format: Article
Language:English
Subjects:
Biodegradability
Diffusion coefficient
Elastomers
Experimentation
Hydrogen peroxide
Molecular weight
NMR
Nuclear magnetic resonance
Polymer chemistry
Polymers
Sensitivity analysis
Size exclusion chromatography
Triethylamine
Viscosity
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Summary: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), H 2 O 2 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. Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H 2 O 2 and air is a scalable and green method for the synthesis of biodegradable polysulfides.
ISSN:1759-9954
1759-9962
DOI:10.1039/d1py01426a