Solid-Phase Microextraction in Polymer Analysis – Extraction of Volatiles from Virgin and Recycled Polyamide 6.6

The extraction and quantitative analysis of low molar mass compounds in polymers is an analytical challenge. It is also important from a practical point of view because the low molar mass compounds in time will migrate from the polymers into the surrounding environment. It is especially important to gain knowledge about the migrating compounds in applications such as medical implants, packaging materials and car interiors. The main aim of this thesis was to develop headspace solid phase microextraction (HS-SPME) methods to meet this challenge. In addition, the work aimed to show the applicability of the methods developed in quality control of polymers, degradation studies and assessment of polymer durability. Factors influencing the extraction of low molar mass compounds from polyamide 6.6 were studied. Particular attention was paid to the matrix effects and to the establishment of headspace equilibrium of 2-cyclopentyl-cyclopentanone in solid polyamide. Hydrogen bonding and adsorption of analyte to the polar matrix was observed and found to cause exceedingly slow establishment of equilibrium. The adsorption could be eliminated by the addition of water, which replaced 2-cyclopentyl-cyclopentanone at the adsorption sites of the polyamide and made it possible to measure the 2-cyclopentyl-cyclopentanone content in polyamide 6.6 using multiple headspace solid-phase microextraction (MHS-SPME). A correlation between the emitted amount of 2-cyclopentyl-cyclopentanone and the amount 2-cyclopentyl-cyclopentanone in the material was found. The correlation was valid also under non-equilibrium conditions, which allows rapid assessment of the 2cyclopentyl-cyclopentanone content in polyamide 6.6 using headspace sampling. 20 different low molar mass compounds were identified in virgin and recycled polyamide 6.6. The compounds could be classified into four groups: cyclic imides, pyridines, chain fragments and cyclopentanones. The structures of the degradation products imply that the thermo-oxidative degradation starts at the N-vicinal methyl group. Larger amounts of degradation products at lower degree of degradation were formed in recycled than in virgin polyamide 6.6. Thus, processing increases the susceptibility of polyamide 6.6 to thermal oxidation. The total amount of cyclopentanones was reduced upon processing and oxidation. Cyclopentanones are thus not thermo-oxidation products of polyamide 6.6. N-pentyl-succinimide showed the most significant increase due to oxidation and processing. The formation of N-pentyl-succinimide was in correlation with the simultaneous changes in tensile strength. The largest increase in N-pentyl-succinimide coincided with the largest drop in tensile strength.