Plastics stabilisers

P. D. Ritchie (ed.). Plasticizers, Stabilisers and Fillers, Butterworth, London, 1971. 

Dicalcium phosphate (anhydrous or sometimes as the dihydrate) has many uses. These include glass manufacture, plastics stabilisation, fertilisers and animal feeds. In addition, it is used as a dough additive, a nutrient and a dietary supplement. In pharmacy, it is used as a tablet diluent and dispersant calcium phosphates have other medical applications [32]. Other uses include paint and pigments and in toothpaste as a secondary abrasive. 

Calcium glycerophosphate (Chapter 5.6) is used as a food additive, a dietary supplement and a plastics stabiliser. 

As indicated in Chapter 1, global lead consumption from secondary sources approached four million tonnes per year in 2005, or 60 per cent of total world consumption. Around 20 per cent of world consumption is for uses where recycling is difficult, such as for plastics stabilisers, for TV tube glass, for shot and ammunition. Of the remainder, ten per cent is used for rolled or extruded alloys and cable sheathing, which have long-term applications, and 70 per cent is used for batteries. Recyclable lead therefore is predominantly from used automotive batteries, with some from reclaimed sheet, cable sheathing and other metallic scrap. In addition there are various residues, drosses and flue dusts containing lead. 

To slow down the degradation of plastics, stabilisation additives are employed. Other additives such as fillers or modifiers can be incorporated to improve the properties of the recyclates. These modifiers can also be of benefit in mixed plastic fractions. First the issues associated with the degradation of materials will be discussed. 

Lead chemicals for glass, enamel, pigments, dyes and plastic stabilisers. 

RITCHIE, p. D. (Ed,), Plasticisers, Stabilisers, and Fillers, Iliffe (published for The Plastics Institute), London (1972)... 

FRISCH, K. c., and saunders, j. h. (Eds.), Plastic Foams Part I, Dekker, New York (1972) GEUSKENS, G. (Ed.), Degradation and Stabilisation of Polymers, Applied Science, London (1975) HAWKINS, E. L. (Ed.), Polymer Stabilisation, Wiley-Interscience, New York (1972)... 

The first five of these techniques involve deformation and this has to be followed by some setting operation which stabilises the new shape. In the case of polymer melt deformation this can be affected by cooling of thermoplastics and cross-linking of thermosetting plastics and similtir comments can apply to deformation in the rubbery state. Solution-cast film and fibre requires solvent evaporation (with also perhaps some chemical coagulation process). Latex suspensions can simply be dried as with emulsion paints or subjected to some... 

There are a number of occasions where a transparent plastics material which can be used at temperatures of up to 150°C is required and in spite of its relatively high cost, low impact strength and poor aging properties poly-(4-methylpent-1 -ene) is often the answer. Like poly(vinyl chloride) and polypropylene, P4MP1 is useless without stabilisation and as with the other two materials it may be expected that continuous improvement in stabilising antioxidant systems can be expected. 

It is an interesting paradox that one of the least stable of commercially available polymers should also be, in terms of tonnage consumption at least, one of the two most important plastics materials available today. Yet this is the unusual position held by poly(vinyl chloride) (PVC), a material whose commercial success has been to a large extent due to the discovery of suitable stabilisers and other additives which has enabled useful thermoplastic compounds to be produced. 

Moulded plastics will also have crack initiation sites created by moulding defects such as weld lines, gates, etc and by filler particles such as pigments, stabilisers, etc. And, of course, stress concentrations caused by sharp geometrical discontinuities will be a major source of fatigue cracks. Fig. 2.72 shows a typical fatigue fracture in which the crack has propagated from a surface flaw. 

Polyvinyl chloride (p.v.c.) P.V.C. is one of the two most important plastics in terms of tonnage and shows many properties typical of rigid amorphous thermoplastics. More individually, it softens at about 70°C, burns only with difficulty and is thermally unstable. To reduce this instability, stabilisers are invariably compounded into the polymer. 

The chloride ion is the most frequent cause of contact corrosion, since chlorine is present in the many chlorinated plastics, and is also frequently retained in residual amounts from reactive intermediates used in manufacture. Thus epoxides usually contain chloride derived from the epichlor-hydin used as the precursor of the epoxide. In addition to the contaminants referred to in Table 18.18, various metal and ammonium cations, inorganic anions and long-chain fatty acids (present as stabilisers, release agents or derived from plasticisers) may corrode metals on contact. 

The BP Chemicals polymer cracking process is based at Grangemouth in Scotland and uses mixed plastics as the raw material. The reactor uses a fluidised bed which operates at 500 °C in the absence of air, and under these conditions the plastics crack thermally to yield hydrocarbons. These vaporize and are carried away from the bed with the fluidising gas. Solid impurities such as metals from PVC stabilisers accumulate in the bed or are carried away in the hot gas to be captured by a cyclone further along in the plant. PVC decomposes to HCl and this is neutralized on a solid lime absorbent to yield CaCl2 which is disposed of in landfill. The purified gas is cooled to condense most of the hydrocarbon which can be employed as commercially useful distillate feedstock. The light hydrocarbons which are less easy to condense are compressed, reheated and recycled as fluidising gas. 

Before MPW is fed into the process, a basic separation of the non-plastic fraction and size reduction is needed. This prepared feedstock is then introduced in the heated fluidised bed reactor which forms the core of the process. The reactor operates at approximately 500 °C in the absence of air. At this temperature, thermal cracking of the plastics occurs. The resulting hydrocarbons vapourise and leave the bed with the fluidising gas. Solid particles, mainly impurities formed from, e.g., stabilisers in plastics, as well as some coke formed in the process mainly accumulate in the bed. Another fraction is blown out with the hot gas and captured in a cyclone. 

It is a well-known fact that specific plastic materials like flexible PVC, Polyurethane or Silicone may be easily attacked by microorganisms leading to discoloration or mechanical failures.14 This susceptibility to microbial attack is mainly attributed to the plasticiser content of the material as well as other ingredients such as stabiliser or antioxidants.5,6 The predominant organisms on the surface of those plastics are fungi and actinomycetes and it is said that by the action of their extracellular enzymes other organisms such as bacteria may be able to grow on the material.7... 

Apart from routine quality control actions, additive analysis is often called upon in relation to testing additive effectiveness as well as in connection with food packaging and medical plastics, where the identities and levels of potentially toxic substances must be accurately known and controlled. Food contact plastics are regulated by maximum concentrations allowable in the plastic, which applies to residual monomers and processing aids as well as additives [64-66]. Analytical measurements provide not only a method of quality control but also a means of establishing the loss of stabilisers as a function of material processing and product ageing. 

Freitag and John [96] studied rapid separation of stabilisers from plastics. Fairly quantitative extraction (>90% of the expected content) of stabilisers from a powdered polymer was achieved by MAE within 3 to 6 min, as compared to 16 h of Soxhlet extraction for the same recovery. MAE and Soxhlet extraction have also been compared in the analysis of cyclic trimer in PET [113]. On the other hand, Ganzler et al. [128] compared the extraction yields for various types of compounds from nonpolymeric matrices for microwave irradiation with those obtained by the traditional Soxhlet or shake-flask extraction methods. Microwave extraction was more effective than the conventional methods, in particular in the case of polar compounds. As expected, the efficiency of the former is high especially when the extraction solvents contain water. With the high dipole moment of water, microwave heating is more... 

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