By E. T. Denisov (auth.), Gerald Scott (eds.)
The objective of this e-book is two-fold. within the first position it's meant to check growth within the improvement of functional stabilising structures for a variety of polymers and purposes. A complemen tary and finally extra vital target is to deal with those functional advancements in the framework of antioxidant idea, in view that there will be no doubt that extra significant advances within the perform of stabilisation expertise will in basic terms be attainable on an organization mechanistic starting place. With the continuous elevate within the variety of advertisement anti oxidants and stabilisers, usually functioning by way of mechanisms now not even thought of ten years in the past, there's a desire for a basic idea in an effort to let the aptitude person to foretell the functionality of a specific antioxidant constitution below particular sensible stipulations. such a predictive device needs to contain a simplified kinetic method of inhibited oxidation and, in bankruptcy 1, Denisov outlines a potential mechanistic strategy with the capability to foretell the main priceless antioxidant to take advantage of and the bounds of its usefulness. In bankruptcy 2, Schwetlick studies the present nation of information at the antioxidant mechanisms of the phosphite esters with specific emphasis on their catalytic peroxidolytic job. Dithiophosphate v vi PREFACE derivatives exhibit the same behaviour yet for rather varied purposes and, in bankruptcy three, AI-Malaika studies info to be had from analytical experiences, really utilizing 31p_NMR spectroscopy, to elucid ate the advanced chemistry that ends up in the formation of the antioxidant -active agents.
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Additional info for Mechanisms of Polymer Degradation and Stabilisation
Therefore, the antioxidant activity of phosphites in the solid polymer is lower than in liquid hydrocarbons. 2 Reactions of Phosphites and Phosphonites with Alkylperoxyl Radicals The structural features determining the chain-breaking antioxidant ability of organophosphorus compounds have been elucidated in detail by studying their reactions with alkylperoxyl radicals and alkoxyl radicals. These investigations confirm and expand the results obtained in the inhibition experiments mentioned so far.
Products of reaction of 2,6-di-tert-butyl-4-methylphenyl 0phenylene phosphite with cumyl hydroperoxide in chlorobenzene at 50°C. 1S capable of reacting with alkyl hydroperoxides catalytically, so that more than a stoichiometric amount of hydroperoxide is decomposed by these phosphites. 1O,13,17,19,23,24 The catalytic decomposition is preceded by a fast reaction stage in which the catalytically active species is formed from the phosphite and hydroperoxide. We have observed by HPLC and 31p_NMR spectroscopy two phosphates during the course of reaction of 2,6-di-tert-butyl4-methylphenyl o-phenylene phosphite (IX) with cumyl hydroperoxide (Fig.
Denisov, E. , Khim. , 4 (1985) 67. 16. Denisov, E. , Makromol. , Suppl. 8 (1984) 63. Chapter 2 Mechanisms of Antioxidant Action of Phosphite and Phosphonite Esters KLAUS SCHWETLICK Dresden University of Technology, Dresden, GDR ABSTRACT Phosphite and phosphonite esters are used on a large scale for the stabilisation of polymers against degradation during processing and long-term applications. They function as antioxidants by various mechanisms depending on their structure, the nature of the substrate to be stabilised and the reaction conditions.