Polyolefins lifetime

Extensive studies of polyolefin thermal oxidation at elevated temperatures (above the melt) have been reported, but extrapolation of these data to lower temperatures (below the melt) have led to over optimistic estimates of the life-time of these polyolefins.In order to obtain more realistic values for polyolefin lifetimes, samples were tested at temperatures from llO C to 40°C at 10 C Intervals. Small, Individual static air ovens were used to Isolate Individual types of samples and prevent cross contamination. 

High-MW hindered amine thermal stabiliser (HATS) formulations are designed for advanced extraction resistant long-term stabilisation, i.e. for use in extractive environments such as polyolefin pipes, fulfilling the stringent requirement of guaranteeing product lifetime of more than 50 years [565], These systems offer much better gas and hot water resistance than the low-MW phenolic antioxidant systems. Ethanox 330... 

Antioxidants are species that accept the reactive byproducts of oxidation reactions. They are typically hindered amines or phenols that accept radicals, inactivating them and preventing further effects of oxidation. The level of antioxidant used in a polymeric item depends on the expected lifetime of the final part, the environment in which the part will be used, and the susceptibility of the polymer to oxidation. Figure 9.7 shows two common antioxidants used in polyolefins. 

Transmaterialisation is a more fundamental approach to the problem, which, with the goal of sustainable development, would ultimately switch consumption to only those resources that are renewable on a short timescale. Clearly petroleum, which takes millions of years to form, is not an example of such a sustainable resource. For the method to be truly effective, the wastes associated with the conversion and consumption of such resources must also be environmentally compatible on a short timescale. The use of polyolefin plastic bags for example, which have lifetimes in the environment of hundreds of years, is not consistent with this (no matter how they compare with alternative packaging materials at other stages in their lifecycle), nor is the use of some hazardous process auxiliaries which are likely to cause rapid environmental damage on release into the environment. 

Two different approaches for lifetime prediction are presented. The underlying lifetime limiting processes have been identified in two cases. Mathematical expressions of chemical/physical relevance were used for the lifetime predictions for PE hot-water pipes and cables insulated with plasticized PVC. Accelerated testing, extrapolation and validation of the extrapolation by assessment of the remaining lifetime of objects aged during service conditions for 25 years were successfully applied to cables insulated with chlorosulfonated polyethylene. Polyolefin pipes exposed to chlorinated water showed a very complex deterioration scenario and it was only possible to find a method suitable for predicting the time for the depletion of the stabilizer system. 

A great proportion of plastics end its lifetime as a part of the overall solid waste stream where they represent roughly 10 wt%. The typical distribution of plastics in household wastes is shown in Figure 3.1 [3]. The main components are polyolefins low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and polypropylene (PP), accounting for about 67% of the total amount of plastic wastes. Other important components in plastic wastes are polystyrene (PS), poly (vinyl chloride) (PVC) and poly (ethylene terephthalate) (PET). 

Polyolefins - An Arrhenius model has been developed for lifetime prediction of the light stability of polypropylene . Photooxidation processes in blends of polypropylene with poly(butylene terephthalate) (PBT) are complicated by the thermal sensitivity of the polypropylene and the screening effect of the terephthalate ester . This effect is shown in Scheme 1. 

Impurities and contaminants can also affect the lifetime of polyolefins, generally In an adverse manner. The adverse effect of copper on the long-term stability of polyolefins Is well known.(9.10) Other active metals have also been shown to accelerate the oxidation process.(11. 12)... 

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). 

The sensitivity to hydrolysis is a key issue in many applications. The ester bond in 4GT-PTMO copolymers is sensitive to hydrolysis however, it is fairly protected since most of the ester is contained in a crystalline structure. The addition of a small amount (1-2%) of a hindered aromatic polycarbodiimide substantially increases the lifetime of this material in the presence of hot water or steam (Brown et al., 1974). Polyurethanes are susceptible to hydrolytic attack, especially those with polyester soft segments. However, polyester soft segment polyurethanes are generally more resistant to oils, organic solvents, and thermal degradation. lonomers will swell when exposed to water in fact, a commercial hydrated perfluorosulfonic ionomer (Nation) is used as a membrane separator in chlor-alkali cells. Styrene-diene copolymers and polyolefin TPEs are insensitive to water. 

Polyolefins require the use of additives for process, thermal and light stability in order to be transformed into useful articles that have desirable end-use properties and lifetime (I). Re-use of the polymer from articles that have reached the end of their useful lifetime would be expected to require restabilization. Requirements for restabilization are expected to be a function of the degree of depletion of the original additives added to the virgin material, and the degree of polymer degradation, if any, from the end-use application. 

This book follows the lifetime of polyolefin compounds and materials from their historical and economical input, synthesis and processing, over applications, to recycling and oxo-degradation. 

Hindered amine stabilizers (HAS) are the most common class of the curative additives and their application is the state-of-the-art in photoprotection of carbon-chain polymers, polyolefins in particular. HAS shape future polymer development, promote their consumption in new areas and expand material performance by increasing its lifetime. Application of HAS is based on a long-term effective development and is connected with commercial benefits for polymers. An optimized technical application of HAS required explanation of their chemistry and activity mechanisms in different phases of the oxidative degradation of polyolefins [14-17]. 

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