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Title: Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation

Polydivinylbenzene (PDVB) is a thermally stable, optically transparent, crosslinked polymer that until recently has been difficult to synthesize as a thin film. With the recent demonstration of initiated chemical vapor deposition (iCVD) of thin PDVB films, a renewed interest in the material properties of PDVB has developed. In particular, attention is now focused on its oxidation pathways and long-term stability under the desired application use conditions. In this paper, we report on the thermal and environmental stability of PDVB films and show that unreacted pendant vinyl groups drive polymer oxidation upon exposure to either air or light. We demonstrate that such vinyls can be effectively passivated by a simple ex-situ thermal annealing at ca. 300 °C in inert atmosphere that induces an 87% reduction of the PDVB oxidation rate in air and slows light (λ=405 nm) induced oxidation by 56%. While the thermal annealing is less effective at preventing oxidation under higher energy (λ = 365 nm) UV light, we demonstrate that this aging pathway is based on the presence of reactive oxygen species rather than traditional photo-oxidation. Finally, vinyl removal through ex-situ thermal annealing improves the chemical stability of iCVD PDVB to continuous air (over 500 days) or lightmore » (70 hours) exposure and offers a simple option to improve its environmental aging resistance which is important for long-term protective applications.« less
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-740403
Journal ID: ISSN 2365-6549
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Chemistry Select
Additional Journal Information:
Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2365-6549
Publisher:
Wiley
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; aging; PDVB; photo-oxidation; photostability; thermal stability
OSTI Identifier:
1438637

Lepro, Xavier, Ehrmann, Paul, Rodriguez, Jennifer, and Baxamusa, Salmaan. Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation. United States: N. p., Web. doi:10.1002/slct.201702685.
Lepro, Xavier, Ehrmann, Paul, Rodriguez, Jennifer, & Baxamusa, Salmaan. Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation. United States. doi:10.1002/slct.201702685.
Lepro, Xavier, Ehrmann, Paul, Rodriguez, Jennifer, and Baxamusa, Salmaan. 2018. "Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation". United States. doi:10.1002/slct.201702685.
@article{osti_1438637,
title = {Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation},
author = {Lepro, Xavier and Ehrmann, Paul and Rodriguez, Jennifer and Baxamusa, Salmaan},
abstractNote = {Polydivinylbenzene (PDVB) is a thermally stable, optically transparent, crosslinked polymer that until recently has been difficult to synthesize as a thin film. With the recent demonstration of initiated chemical vapor deposition (iCVD) of thin PDVB films, a renewed interest in the material properties of PDVB has developed. In particular, attention is now focused on its oxidation pathways and long-term stability under the desired application use conditions. In this paper, we report on the thermal and environmental stability of PDVB films and show that unreacted pendant vinyl groups drive polymer oxidation upon exposure to either air or light. We demonstrate that such vinyls can be effectively passivated by a simple ex-situ thermal annealing at ca. 300 °C in inert atmosphere that induces an 87% reduction of the PDVB oxidation rate in air and slows light (λ=405 nm) induced oxidation by 56%. While the thermal annealing is less effective at preventing oxidation under higher energy (λ = 365 nm) UV light, we demonstrate that this aging pathway is based on the presence of reactive oxygen species rather than traditional photo-oxidation. Finally, vinyl removal through ex-situ thermal annealing improves the chemical stability of iCVD PDVB to continuous air (over 500 days) or light (70 hours) exposure and offers a simple option to improve its environmental aging resistance which is important for long-term protective applications.},
doi = {10.1002/slct.201702685},
journal = {Chemistry Select},
number = 2,
volume = 3,
place = {United States},
year = {2018},
month = {1}
}