期刊
MACROMOLECULAR CHEMISTRY AND PHYSICS
卷 204, 期 14, 页码 1755-1764出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/macp.200350036
关键词
activation energy; bisoxazoline; carboxylic acid; chain; kinetic studies
Kinetic studies of the reactions between a model carboxylic acid and bisoxazoline coupling agents, namely 2,2'-(1,3-phenylene)bis(2-oxazoline) (mbox), 2,2'-(1,4-phenylene)bis(2-oxazoline) (pbox), and 2,2'-(2,6-pyridylene)-bis(2-oxazoline) (pybox), were carried out in bulk at 140-220degreesC. a second-order two-step reaction mechanism was proposed and was verified by the experimental results. The results also indicate that the reactivity of the oxazoline groups is unchanged after the reactivity of the oxazoline groups is unchanged after the reaction of the other oxazoline groups are equireactive. Rate constants and activation enthalpies and entropies were determined, allowing the comparison of bisoxazoline reactivity. The following reactivity order was found: pybox > mbox > pbox. The formation of a stabilized protonated complex is postulated to explain the much higher reaction rate observed with the new coupling agent pybox.
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