Elastomers, additives Peroxides

Diacyl peroxides are used in a broad spectmm of apphcations, including curing of unsaturated polyester resin compositions, cross-linking of elastomers, production of poly(vinyl chloride), polystyrene, and polyacrjlates, and in many nonpolymeric addition reactions. 

Peroxide curing systems are generally the same for CSM as for other elastomers but large amounts of acid acceptor must be present to complete the cure. A small amount of a polyfunctional alcohol, ie, pentaerythritol (PER) in the compound significantly reduces the amount of base required by acting as a solubiHzer. TriaHyl cyanurate [101-37-17 is an additional cure promoter and leads to higher cross-link density. 

The early 1980s saw considerable interest in a new form of silicone materials, namely the liquid silicone mbbers. These may be considered as a development from the addition-cured RTV silicone rubbers but with a better pot life and improved physical properties, including heat stability similar to that of conventional peroxide-cured elastomers. The ability to process such liquid raw materials leads to a number of economic benefits such as lower production costs, increased ouput and reduced capital investment compared with more conventional rubbers. Liquid silicone rubbers are low-viscosity materials which range from a flow consistency to a paste consistency. They are usually supplied as a two-pack system which requires simple blending before use. The materials cure rapidly above 110°C and when injection moulded at high temperatures (200-250°C) cure times as low as a few seconds are possible for small parts. Because of the rapid mould filling, scorch is rarely a problem and, furthermore, post-curing is usually unnecessary. 

Elastomeric composition for dynamic application of cross-linked E-plastomers has been made with filer-reinforced systems which contain a metal salt (typically zinc) of an alpha, beta unsaturated acid. These additives improve the tensile and tear strength of the elastomer and are cured with a peroxide cure system. These cross-linked articles are suitable for dynamic loading applications such as belting, including power transmission and flat belting. 

Deformulation of vulcanised rubbers and rubber compounds at Dunlop (1988) is given in Scheme 2.3. Schnecko and Angerer [72] have reviewed the effectiveness of NMR, MS, TG and DSC for the analysis of rubber and rubber compounds containing curing agents, fillers, accelerators and other additives. PyGC has been widely used for the analysis of elastomers, e.g. in the determination of the vulcanisation mode (peroxide or sulfur) of natural rubbers. 

Additional curing is often achieved with sulfur, peroxide, or maleimide formulations. Chloro-sulfonated polyethylene has improved resistance to oil, ozone, and heat compared to many other elastomers. Applications include harrier membranes and liners, surface coatings on fabrics, automobile air-conditioner hose, electrical cable insulation, and spark-plug boots [Andrews and Dawson, 1986],... 

However, organic peroxides will still form in stored fuel, and their gradual accumulation can contribute to elastomer degradation throughout the fuel storage and distribution system. Hydroperoxide formation and accumulation can be readily controlled by the addition of low levels of traditional fuel oil stabilizers. 

Raman and IR spectroscopic studies dealing with the qualitative and/or quantitative determination of rubber compounding ingredients, i.e., the elastomer itself [22, 26-31], fillers [32, 33], vulcanisation chemicals and other additives [34-37], are not included here. The same applies to studies dealing with the crosslinking of elastomers by means of chemicals other than sulfur or peroxide [38-41], self-crosslinking of elastomers blends [42-44], crystallisation (strain-induced) [45-48] and oxidation/ageing [49-53]. 

The mechanism of peroxide crosslinking of elastomers is much less intricate than that of sulfur vulcanisation. Crosslinking is initiated by the thermal decomposition of a peroxide, which is the overall cure rate determining step. Next, the active radicals thus formed abstract hydrogen from elastomer chains to form macroradicals. Finally, crosslinking results either from the combination of two macroradicals or from the addition of a macroradical to an unsaturated moiety of another primary elastomer chain. 

Based on the IR data of samples before extraction, it is concluded that the allyl groups react rapidly to completion within about 2 minutes, whereas the ester absorption remains constant. More allyl groups per unit of time react than peroxide radical fragments are initiated, it can be concluded that the allyl groups react predominantly via radical addition reactions, probably accompanied by radical transfer reactions. FT-IR analysis after vulcanisate extraction indicates that the co-agent is covalently bound to the elastomer matrix, as shown by the 100% recovery of the ester absorption after 2 minutes of curing. 

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