BLANC - Blanc

Vers une synthèse bio-inspirée de polyterpènes et d'homologues du Caoutchouc Naturel – SYNBIORUB

Submission summary

The very high performances of natural rubber (NR), a 100% cis-1,4-polyisoprene are believed to be dependent not only on the chemical structure, molecular weight and molecular weight distribution (typically Mn = 105-106 g/mol and Mw/Mn = 2-10) but could also be influenced by the presence of 'abnormal' structures, such as short-branching, and functional groups, for instance protein residues or fatty alkyl chains. The presence of cyclized polyisoprene sequences was also detected. In spite of extensive research, the exact structure and the structure/properties relationship of NR have not been completely elucidated. The NR biosynthesis is described as a polymerization process involving a series of enzymatic reactions using isopentenyl pyrophosphate (IPP) as elementary building brick. A close inspection of the NR biosynthesis process from the polymer chemist viewpoint led us to conclude that the structure of the entities involved in the biosynthesis is fully consistent with a transferless, stereospecific carbocationic-type polymerization mechanism. This was recently partially sustained by our results on the 'cationic' polymerization of isoprene (IP) and of IPP models in experimental conditions close to the NR biosynthesis (room temperature, aqueous dispersion as polymerization media). We propose to further investigate and develop this new bio-inspired cationic-like polymerization approach with the aim to produce polyterpenes and then NR homologues of tailored molar mass and microstructure that could exhibit properties close to natural polyterpenes and as an ultimate goal close to BioRubber. The cationic polymerization of model molecules derived from IPP and of isoprene will be performed into a biphasic system constituted of hydrophobic hydrocarbon particles dispersed in an aqueous media that simulate the NR biosynthesis in laticiferous vessels of Hevea Brasiliensis and will be focused on the search of appropriate active end groups and specifically designed functional Lewis acid catalysts. We might expect that using a bio-inspired cationic approach, some defects in the chain due to side reactions (branching, cyclization,…), or original chain-ends could approach the supramolecular structure of NR. Besides, the preparation of oligoterpenes could also be, on the short term, of great interest on an industrial point of view, according to the large panel of aroma, perfumes, drugs that belong to this family. The study will be performed at University of Bordeaux (LCPO), Partner 1, which has an expertise in controlled cationic polymerization and in mechanistic studies, at Montpellier (Institut Charles Gerhardt), Partner 2, in the group "Ingénierie et Architectures Macromoléculaires" which possesses an expertise in ionic polymerization in aqueous dispersed media and in collaboration with the polymer Department of the University of Akron (Pr Judit Puskas) and the western regional Research Centre (USDA-ARS) (Dr Colleen McMahan), Partners 3 and 4, which both have an expertise in the in vitro study of polyterpenes and biorubber synthesis.

Project coordination

Frédéric PERUCH (Organisme de recherche)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partnership

Help of the ANR 475,210 euros
Beginning and duration of the scientific project: - 36 Months

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