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Volumn 333, Issue 2-3, 2007, Pages 246-253

Photopolymerization quantum yields in two reactive diacetylenes, 3BCMU and 4BCMU, and relation to γ-ray induced polymerization

Author keywords

Diacetylene crystals; Initiation yields; Photopolymerization

Indexed keywords


EID: 33947208897     PISSN: 03010104     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.chemphys.2007.02.006     Document Type: Article
Times cited : (13)

References (54)
  • 10
    • 33947213681 scopus 로고    scopus 로고
    • S. Spagnoli, M. Schott, M. Johnson, L. Toupet, Chem. Phys., doi:10.1016/j.chemphys.2007.02.007.
  • 11
    • 33947279188 scopus 로고    scopus 로고
    • T. Barisien, L. Legrand, M. Schott, in preparation.
  • 13
    • 0000745439 scopus 로고    scopus 로고
    • One possible exception is the PDA poly-4U3 for which a distance of 4.81 ± 0.06 Å is quoted in S. Koshihara, Y. Tokura, K. Takeda, T. Koda, A. Kobayashi, J. Chem. Phys. 92 (1990) 7581.
  • 35
    • 33947196620 scopus 로고    scopus 로고
    • note
    • Charge transfer from polymer to monomer is unlikely. From gas phase experimental values mentioned in the text and with a polarization correction of 1.5 eV, the highest valence level in the monomer corresponds to diacetylene and is about 7.5 eV below vacuum level, and the lowest conduction level corresponding to diacetylene is close to the vacum level. On the other hand, the poly-4BCMU valence band top is near -5.3 eV [W.R. Salaneck, M. Fahlman, C. Lapersonne-Meyer, J.-L. Fave, M. Schott, M. Lögdlund, J.L. Brédas, Synth. Met. 67 (1994) 309], and since the gap is ≈2.5 eV [8] the conduction band lowest level is at -2.8 eV. There is therefore an energy difference larger than 2 eV between monomer and polymer levels, both for electrons and for holes.
  • 49
    • 33947249978 scopus 로고    scopus 로고
    • note
    • The energetics of chain propagation in 4BCMU photopolymerization has been studied [21]: the energy released by addition of one monomer to the growing chain was found equal to 0.95 eV, significantly less than the 1.6 eV found in pTS thermal polymerization [23,24]. It was conjectured that the 0.65 eV energy difference was the price paid for breaking H-bonds. It is however very likely that H-bonds are also present in poly-4BCMU, so in one propagation step two "monomer type" H-bonds are broken and two "polymer-type" ones are formed. The energy not appearing as heat would then be twice the difference for one H-bond, so a "monomer-type" bond is 0.32 eV weaker.
  • 53
    • 33947275999 scopus 로고    scopus 로고
    • V.E. Bondybey, T.A. Miller, in: V.E. Bondybey, T.A. Miller (Eds.), Molecular ions: spectroscopy, structure and chemistry, North Holland, Amsterdam, 1983, p. 159.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.