Polyolefins, additives Stabilisers

Polyolefins such as polyethylene and polypropylene contain only C—C and C—H bonds and may be considered as high molecular weight paraffins. Like the simpler paraffins they are somewhat inert and their major chemical reaction is substitution, e.g. halogenation. In addition the branched polyethylenes and the higher polyolefins contain tertiary carbon atoms which are reactive sites for oxidation. Because of this it is necessary to add antioxidants to stabilise the polymers against oxidation Some polyolefins may be cross-linked by peroxides. 

Oligomeric hindered amine light stabilisers, such as Tinuvin 622 and Chimassorb 944, resist satisfactory analysis by conventional HPLC and have required direct UV spectroscopic analysis of a polyolefin extract [596], PyGC of an extract [618,648], or SEC of an extract [649]. Freitag et al. [616] determined Tinuvin 622 in LDPE, HDPE and PP by saponification of the polymer dissolution in hot toluene via addition of an... 

Oligomeric additives with broad MWD tend to be a problem in conventional HPLC conditions. In cases where no interest exists in the oligomer distribution it is common practice to solve the problem by creating a uniform structural unit useful for analysis. For example, isocratic (or gradient) LC-UV was used for the determination of the polymeric light stabiliser Tinuvin 622 in polyolefins using dissolution (toluene)/derivatisation (TBAH)-precipitation (alcohol) the diol formed was quantitatively determined by NPLC [653]. 

Intermaterial competition affects the additive business. For example, if metallocene polyolefins displace PVC markets, then the demand for heat stabilisers and plasticisers might decrease, while the need for products such as fluoropolymer processing aids, antiblocks and slip additives might increase. At present, PVC as the main user of additives is under threat as never before. However, green PVC, containing more environmentally friendly FRs and plasticisers as well as non-heavy-metal stabilisers, is now environmentally acceptable. 

Ultraviolet and fluorescent microscopy has been applied to a variety of polymer systems to investigate changes of morphology and composition on the scale of 0.25 ym upwards. Studies are briefly described on the behaviour of stabilisers in polypropylene, diffusion of additives in polymers, spherulite morphology, polyolefin oxidation, inhomogeneities in epoxy resins and polymer blends. 

The useful lifetime of a polyolefin corresponds essentially to the end of the oxidation induction time. In stabilised materials this may be determined either by the time at which the stabiliser has been chemically consumed or that at which it has been lost from the sample by evaporation or extraction. We have developed a model to describe these additive loss processes but it requires a knowledge of the diffusion rates and solubilities of additives in polymer (11, 12). 

PE has a very low compatibility with plasticisers and in fact it does not need plasticisers, however, they may contain other additives (i.e., UV and heat stabilisers). Chloroparaffins or brominated flame-retardants are common used in polyolefins. 

---