## Abstract

The propagation rate coefficient (k_{P}) for vinyl neo-decanoate has been measured by pulsed laser polymerization (PLP) over the range -21 to +21°C. The Mark-Houwink-Sakaruda constants required for GPC analysis were obtained using size-exclusion chromatography with an on-line viscosity detector, whose analysis required careful quantification of the uncertainties. The data, which satisfy various consistency tests for PLP (invariance of k_{P} to laser pulse frequency, etc.), fit the relation k_{P} (dm^{3} mol^{-1} s^{-1}) = 10^{7.31} exp(-22.2 kJ mol^{-1}/RT); the joint confidence region for these Arrhenius parameters is also given. These Arrhenius parameters are close to those for vinyl acetate [10^{7.16} exp(-20.7 kJ mol^{-1}/ RT)]; the small differences between these Arrhenius parameters are, however, statistically significant at the 95% confidence limit. The vinyl neo-decanoate used is actually a mixture of isomers: CH_{2}=CHOCOCR_{1}R_{2}CH_{3}, where the total number of carbons in R_{1} and R_{2} is 7; however, theory suggests that the k_{P} values for all these isomers should be very similar and polymerization of the mixture can be treated as a homopolymerization with a k_{P} equal to the average k_{P}.

Original language | English |
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Pages (from-to) | 3775-3780 |

Number of pages | 6 |

Journal | Macromolecules |

Volume | 30 |

Issue number | 13 |

Publication status | Published - 30 Jun 1997 |

Externally published | Yes |