Multifunctional coupling agents. II. Chain extension and terminal group modification of polyamides

New bifunctional coupling agents possessing one 2-oxazoline group and one 2-oxazinone group were converted in a Haake melt mixer or extruder with PA6 and PA12. It was shown by means of NMR spectroscopic investigations that the 2-oxazoline group reacted mainly with carboxylic groups whereas the oxazinone group reacted preferably with the amino groups. Both reactions proceeded with high selectivity and independent from each other. In the case of carboxy/amino group terminated polyamides, the conversions resulted in increased molecular weights since both reactive terminal groups of the polyamides were addressed simultaneously by the coupling agent. In the case of amino group terminated polyamides, the conversion with the bifunctional coupling agent resulted in oxazoline terminated polymer chains. Unlike PA6, it was possible to convert PA12 in two steps. At lower temperatures (210°C) and short reaction times (2 min), the reaction of the oxazinone group with the amino groups was predominant, whereas the reaction of the oxazoline group with the carboxylic groups proceeded to a sufficient extent only after longer reaction times or at higher temperatures. In the case of PA6, processing temperatures of about 250°C were necessary. Here, a side reaction was observed that resulted in the formation of cyclic quinoxaline structures under evolution of water. This side reaction did not disturb the chain extension significantly. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2170–2177, 2004