Aldehyde-telechelic chains

Quantitative epoxidation of olefin-telechelic polyisobutylenes yielded interesting new epoxy-telechelic products. Isomerization of the linear epoxy-telechelic polyisobutylene quantitatively yielded aldehyde-telechelic chains ... 

The first part concludes with a discussion of the similarity between the mechanisms of initiation and chain transfer, the appreciation of which led to the inifer concept, which in turn yielded new telechelics, networks, sequential copolymers, etc. The second part of this presentation focuses on practical consequences of understanding details of the mechanism of initiation. The synthesis of a new family of telechelic linear and tri-arm star polyisobutylenes will be described. Among the new prepolymers are telechelic olefins, epoxides, aldehydes, alcohols, and amines. The preparation of new ionomers and polyisobutylene-based polyurethanes will be outlined and some fundamental properties of these new materials will be discussed. 

The exo-olefin is a precursor to a variety of chain-end-functionalized polymers via postpolymerization reaaions as shown in Scheme 37. Hydroxy-functionalized PIB has been utilized as a precursor for the preparation of RAFT macromo-lecular CTAs and carboxylic acid end-fimctionalized polymers. Telechelic PIB diols have been prepared using p-dicumyl chloride/BCU initiator system followed by dehydro-chlorination, hydroboration, and alkaline peroxide oxidation. Aldehyde end-fiinctionalized PIBs have been used to prepare carboxyl- and hydroxyl-terminated poly-mers. Carboxylic acid-functionalized PIBs have also been prepared from the oxidation of the methyl ketone-functionalized PIBs." The hydroxyl-functionalized PIBs have also been used to prepare methacrylate macromonomers by their reaction with methacryloyl chloride in the presence of triethylamine. The homopolymerization and copolymerization of these maaomonomers with methyl methacrylate were also reported. Cyanoacrylate-funaionalized PIBs prepared via the hydroxyl-functionalized PIB were also reported by Kennedy et al. ... 

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