Polyperoxides: Synthesis, Characterization, High Pressure Kinetics and Physical Properties

Mete, Sourav (2020) Polyperoxides: Synthesis, Characterization, High Pressure Kinetics and Physical Properties. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Sourav Mete (15RS033)) 15RS033.pdf - Submitted Version Restricted to Repository staff only Download (5MB)

Abstract

Since 1922, the fabrication of polyperoxide materials containing several -O-O- linkages has been drawing a great deal of attention in both industry and academia due to their various potential usefulness. Generally, polymers having -O-O- groups in the backbone are of four types; (a) vinyl polyperoxides, obtained by oxidative free radical polymerization of vinyl monomers, (b) acid polyperoxides, synthesized by the condensation of organic dibasic acids with sodium peroxide, (c) 1,3-diene based polyperoxides, prepared from the radical alternating copolymerization of 1,3-diene monomers with oxygen at an atmospheric pressure, and (d) polymeric peroxides achieved by solid-state insertion polymerization of reactive monomers. All these polyperoxides degrade highly exothermically in contrast to common polymers which generally degrade endothermically. Thus, their potential use as an auto-combustible fuel has been studied extensively. Polymeric peroxides are biodegradable and biocompatible, and this unique class of polymers finds usefulness as polymeric macro-initiators, curators in coating and moulding applications, dismantlable adhesive, drug carrier, branched polymer precursor, etc. To date, a wide range of acyclic vinyl monomers was utilized to synthesized polyperoxides with distinctive physical properties. However, the polyperoxides with aqueous solubility as well as the polyperoxides from cyclic monomers are scarcely reported. In addition, bio-renewable fatty acids are also not utilized to synthesized polyperoxides, even though they are very much attractive considering the environmental and economical issues. Herein, we will discuss the synthesis of water soluble polyperoxides from various styrenic monomers containing different oligoethylene glycol (OEG) chain lengths showing tuneable cloud point behaviour. We will also discuss the preparation of solid semi-crystalline polyperoxides from the oxidative polymerization of various styrenic monomers containing fatty acid moieties of different chain lengths at the para-position of the phenyl group. The crystallinity was modulated with incorporation of amorphous methylmethacrylate (MMA) content. Apart from that, we will demonstrate the synthesis of polyperoxides from various cyclic monomers followed by the study of high pressure kinetics associated with the corresponding oxidative polymerization.

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