Polyolefin peroxide method

GC is extensively used to determine phenolic and amine antioxidants, UV light absorbers, stabilisers and organic peroxide residues, in particular in polyolefins, polystyrene and rubbers (cf. Table 61 of Crompton [158]). Ostromow [159] has described the quantitative determination of stabilisers and AOs in acetone or methanol extracts of rubbers and elastomers by means of GC. The method is restricted to analytes which volatilise between 160 °C and 300 °C without decomposition. A selection of 47 reports on GC analysis of AOs in elastomers (period 1959-1982) has been published... 

Applications Basic methods for the determination of halogens in polymers are fusion with sodium carbonate (followed by determination of the sodium halide), oxygen flask combustion and XRF. Crompton [21] has reported fusion with sodium bicarbonate for the determination of traces of chlorine in PE (down to 5 ppm), fusion with sodium bisulfate for the analysis of titanium, iron and aluminium in low-pressure polyolefins (at 1 ppm level), and fusion with sodium peroxide for the complexometric determination using EDTA of traces of bromine in PS (down to 100ppm). Determination of halogens in plastics by ICP-MS can be achieved using a carbonate fusion procedure, but this will result in poor recoveries for a number of elements [88]. A sodium peroxide fusion-titration procedure is capable of determining total sulfur in polymers in amounts down to 500 ppm with an accuracy of 5% [89]. 

The dynamic cross-linking process is used to produce thermoplastic elastomers from mixtures of crystallizable polyolefins and various rubbers. Variations of basically the same method are employed to produce novel, stable polymer alloys by performing chemical reactions during extrusion of such mixtures. In that case, the cunent industrial term is reactive extrusion. Such processes are used, for example, to improve processability of LLDPE s into tubular film (by introducing long chain branches during extrusion with low levels of peroxides) or to... 

Cross-linking can also be achieved by compounding a polymer with a peroxide such as dicumyl peroxide or di-/-butyl praoxide, followed by heating. This technique, although economically disadvantageous compared to sulfur vulcanization, is particularly useful for saturated polymers that cannot be easily cross-hnked, particularly polyethylene and other polyolefins. Similar results can be obtained through radiation cross-linking, and this method is employed commercially in the production of electrical wires and cable insulation made of polyolefins and poly(vinyl chloride). 

The vector fluid concept was first suggested for a polyethylene (PE)/polyamide (PA) reactive blending system [12], as mentioned earlier in this chapter. This concept is interesting because it has the potential to provide a compatibilization method for polymers that have no chemical functionalities suitable for copolymer formation during melt blending (e.g. the case of polyolefin and polystyrene). It has been seen that the blends of polyolefin/polystyrene are difficult to compatibilize in situ by simply adding a free radical initiator into the blending process. Usually, flie pre-made block or reactive polymers or copolymers, which can be expensive, are needed for polyolefin/polystyrene compatibilization [15-17]. If a suitable vector fluid can be found for the polyolefin/ polystyrene/peroxide in situ compatibilization, the process could become more controllable and more cost efficient. 

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