Mikael Gröning

Headspace solid-phase microextraction — a tool for new insights into the long-term thermo-oxidation mechanism of polyamide 6.6

Low-molecular-mass products formed during thermo-oxidation of polyamide 6.6 at 100 degrees C were extracted by headspace solid-phase microextraction and identified by GC-MS. A total of 18 degradation products of polyamide 6.6 were identified. In addition some low-molecular-mass products originating from the lubricants were detected. The identified degradation products were categorized into four groups where compounds within each group contain the same structural feature. In groups A, B and C several new thermo-oxidation products of polyamide 6.6 were identified including cyclic imides, pyridines and structural fragments from the original polyamide chain. 1-Pentyl-2,5-pyrrolidinedione (pentylsuccinimide) showed the largest increase in abundance during oxidation. The cyclopentanones in group D were already present in the un-aged material. Their amounts decreased during ageing and they are thus not formed during thermo-oxidation of polyamide 6.6 at 100 degrees C. The identified thermo-oxidation products can be formed as a result of extensive oxidation of the hexamethylenediamine unit in the polyamide backbone. The degradation products pattern shows that the long-term thermo-oxidative degradation, just like thermal degradation and photo-oxidation of polyamide 6.6, starts at the N-vicinal methylene groups.

Quantitative Determination of Volatiles in Polymers and Quality Control of Recycled Materials by Static Headspace Techniques

A presentation is given of headspace (HS) extraction and headspace solid-phase microextraction (HS-SPME) techniques and their combination with multiple headspace (MHS) extraction to enable quantitative determination of volatiles in solid polymer matrixes. As an example, the development of HS, HS-SPME, and MHS-SPME methods for extraction of volatiles from thermo-oxidized and/or recycled polyamide 6.6 is reviewed with special focus on the problems encountered when extracting analytes from solid-sample matrixes including excessively long equilibrium times and adsorption of analytes to the sample matrix. Examples are also given of the application of HS-SPME in quality control of recycled materials, in durability assessment of polymeric materials and in degradation studies.

Recycling of glass fibre reinforced phenolic prepreg waste. part 1. Recovery and reuse of glass fibres in PP and PA6

The present paper describes a feasible process to reuse glass fibres separated from phenolic prepreg waste as reinforcing filler in polypropylene (PP) and polyamide 6 (PA6). Prior to compounding, the recovered glass fibres were cut into 50 mm long fibre bundles and surface treated with gamma-aminopropyltriethoxysilane (APS) for increased composite interfacial strength. Electron Spectroscopy for Chemical Analysis (ESCA) and Atomic Force Microscopy (AFM) showed that the silane coupling agent was attached to the surface of the glass fibres but the silane layer was somewhat uneven, probably due to the presence of small amounts of organic contaminants. In addition it was found necessary to clean the glass fibres from organic contaminants by thermal treatment in order to attach silane coupling agent to the surfaces. The tensile strengths obtained for PP and PA6 composites with 30 wt% filler level of surface treated recovered glass fibres were 49 MPa and 101 MPa, respectively. This should be compared to 30 MPa and 75 MPa for composites containing untreated glass fibres and 19 MPa and 52 MPa for pure PP and PA6. Addition of 5 wt% PP-g-MA compatibiliser to the PP composite increased the tensile strength by another 14%, i.e. to 56 MPa. The good interfacial compatibility achieved by APS surface treatment and compatibilisation was verified by Scanning Electron Microscopy (SEM).

Recycling of glass-fibre reinforced phenolic prepreg waste. Part 2: Milled prepreg as functional filler in PP and PA6

Phenolic resin impregnated glass-fibre prepreg waste was milled and used as reinforcing filler in polypropylene (PP) and polyamide 6 (PA6). Prepreg was particularly suitable to be used as filler in PA6. The fibres were homogeneously distributed during compounding and the addition of 20 wt% prepreg increased the tensile strength of PA6 by 63%, from 52 MPa to 85 MPa. Milled prepreg alone did not significantly increase the tensile strength of PP. However, if compounded together with maleic anhydride grafted polypropylene (PP-g-MA, Epolene G3003) compatibiliser, prepreg can be used as reinforcing filler in PP as well. Addition of 20 wt% prepreg together with 5 wt% Epolene G3003 increased the tensile strength of PP from 26 MPa to 43 MPa. In order to mill the prepreg for compounding with thermoplastics it has to be cured. A 2 kg batch of prepreg had to be cured for at least 2 hours at 200 °C to prevent the phenolic resin from falling off the glass-fibres. Milling should be performed using screens with holes larger than 3 mm in diameter to reduce the amount of prepreg fibres shorter than 2 mm, as they jam the hopper when feeding the recyclate to the extruder. The initial prepreg fibre length is of little importance to the composite mechanical properties, as the fibres are shortened to approximately the same length during compounding.

Polymer Recycling and Degradation

Polymers are used in numerous applications because of their low weight, high adaptability, and ease …