A following new interpretation of apparent induction period is proposed considering the experimental results obtained: octamethylcyclotetrasiloxane (D4) is activated by the reaction with acid to generate an activated derivative (A4). A4 reacts with D4 to generate A8, an active species containing eight dimethylsiloxane units. A8 backbites to generate mostly A4 and D4, which causes retardation in polymerization, but occasionally to form A3 and D5. A3 is highly reactive, and when the concentration of A3 exceeds a certain limit, much Ai where i is large enough is formed and promotes fast growth of chain at the interfacial area due to high concentration of D4. The interpretation assumes that A3 accelerates growth of chain faster than other species, and that A8 tends to backbite rather than grow. The interpretation is supported by the experimental results of polymerization conducted with D4 and D3, or D5 and D3 charged.
Unimolecular reactions of diethyl malonate cation (CH3CH2OC(῎O)CH2C(῎O)OCH2CH3ῌῌ ; 1 ῌῌ , Mw : 160) induced by electron ionization, have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectrometry and D-labeling in conjunction with thermochemistry. In the metastable time window, the molecular ions ῌ ) ions decompose into the ions at m/z 115, 106, and 105 by the losses of H2O, C2H3, and C2H4, respectively. A large part of the first fragment ions would be in the keto form and it decomposes into the m/z 71 and 43 ions by the losses of CO2 and C3H4O2 (or C2O3), and a small part would be in the enol form and decomposes into the m/z 87 ions by the loss of C2H4, not CO. The m/z 43 ions are isobaric, C2H3Oῌ and C3H7 ῌ .
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