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- W2044091249 abstract "The bulk polymerisation of pivalolactone (PVL) has been investigated using tertiary and quaternary phosphorus compounds as initiators. The quaternary P-compounds were found to be essentially more active than the tertiary ones. The polymerisation mechanism with the two classes of initiators is as follows: Tertiary phosphines (and amines) form zwitterions and macro-zwitterions with PVL, or: positive and negative charges are fixed on the same macromolecule. By chain transfer agents a separation of the charges onto two molecules takes place; the zwitterion character disappears. Using quaternary phosphonium (ammonium) compounds the anion starts the reaction; it is built into the polymeric chain. The gegenion retains its low molecular weight during the entire propagation reaction. During this stage an anion of high and a cation of low molecular weight are present side by side. The mechanism is not changed by any chain transfer reaction. The different reaction rates during propagation in the presence of these initiators are explained on one hand by a macrocation and on the other hand by a cation of low molecular weight. The degree of dissociation, which is higher in quaternary compounds than in tertiary ones, might also influence the reaction. The initiator molecule influences the start reaction as well as the total propagation reaction." @default.
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- W2044091249 date "1979-03-01" @default.
- W2044091249 modified "2023-10-06" @default.
- W2044091249 title "Contribution to pivalolactone polymerisation" @default.
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- W2044091249 doi "https://doi.org/10.1002/pi.4980110106" @default.
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