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

Journal Article · · Chemistry Select
ORCiD logo [1];  [1];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
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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.

Research Organization:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1438637
Report Number(s):
LLNL-JRNL-740403
Journal Information:
Chemistry Select, Vol. 3, Issue 2; ISSN 2365-6549
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

References (1)

Stabilizing the Wettability of Initiated Chemical Vapor Deposited (iCVD) Polydivinylbenzene Thin Films by Thermal Annealing journal May 2017

Figures / Tables (11)

Figure 1(p. 6)figure Figure 1
Table 1(p. 6)table Table 1
Table 2(p. 7)table Table 2
Figure 2(p. 8)figure Figure 2
Figure 3(p. 9)figure Figure 3
Figure 4(p. 10)figure Figure 4
Figure 5(p. 12)figure Figure 5
Figure 6(p. 15)figure Figure 6
Figure 7(p. 15)figure Figure 7
Figure 8(p. 16)figure Figure 8
Table 3(p. 16)table Table 3

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
aging
PDVB
photo-oxidation
photostability
thermal stability