Green Synthesis of Degradable Polyperoxides

Pal, Sunirmal (2013) Green Synthesis of Degradable Polyperoxides. PhD thesis, Indian Institute of Science Education And Research Kolkata.

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Abstract

The radical polymerization of vinyl monomers in the presence of high oxygen pressure yields polyperoxides, which are alternating copolymers of vinyl monomers and molecular oxygen. Since the first report on vinyl polyperoxide by Staudinger in 1922, only a small number of polymers belonging to this category have been synthesized and characterized. Vinyl polyperoxides are an important class of polymers due to their interesting physico-chemical properties such as highly exothermic degradation, in contrast to common polymers which usually degrade endothermically. In the present study we have synthesized and characterized new water soluble polyperoxide, and parasubstituted polystyrene peroxides. For industrial and commercial applications, it is desirable that polyperoxides should be made easily and in large quantities, which cannot be achieved unless and until we know the reaction kinetics of the chemical process. So, we have decided to develop a reactivity scale for the various vinyl monomers such as para-substituted styrenes towards oxidative polymerization. During the kinetic study, several new polyperoxides were synthesized and characterized for the first time. The benefit of this reactivity scale in synthesis design is obvious. Also, we have synthesized polyperoxides or copolyperoxides with side-chain ligand groups for postpolymerization modifications to obtain degradable polyperoxide-metal complexes. Biodegradable and biocompatible synthetic polymers have recently attracted much attention because of their favourable medical and pharmaceutical applications. Generally, polymers based on a carbon-carbon backbone tend to resist degradation, whereas main chain heteroatom containing polymer backbones give biodegradability. Therefore, biodegradability can be engineered into polymers by the thoughtful addition of chemical linkages such as anhydride, ester, amide, etc. bonds. The labile heteroatom bonds in the polymer main chain undergo scission by hydrolysis or enzymatic cleavage. The presence of peroxy (-O-O-) linkage in the polyperoxide polymers is expected to show biodegradation. Therefore, for the first time we have investigated biodegradability and biocompatibility of various vinyl polyperoxide polymers.

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