Isomerization‐hydroboration‐oxidation strategy: Access to long chain AB‐ and AA‐type oleyl based monomers and polymers thereof

Abstract

A strategy to convert by isomerization‐hydroboration‐oxidation reaction the internal double bond of oleic acid to a terminal alcohol function, leading to linear long‐chain α,ω‐difunctional substrates has been investigated. Using this strategy, oleic acid‐based AB‐ and AA‐monomers were prepared and characterized by FTIR‐ATR and NMR spectroscopy. Thermoplastic aliphatic linear polyesters, polycarbonates, and polyurethanes were then synthesized by reacting the so‐formed bio‐based monomers via polycondensation in bulk, using 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as an organocatalyst. Thus, starting from easily available bio‐based starting compound, the synthesis of linear long methylene chain aliphatic polyesters, polycarbonates, and polyurethanes (by isocyanate free route) is reported. The structural and thermal characterizations of the synthesized polymers were performed by means of NMR, SEC, DSC, and TGA experiments. Practical applications: The objective of the work is to obtain long methylene sequence alpha, omega difunctional fatty acid‐based substrates that can be used as original monomers. A strategy to convert by isomerization‐hydroboration‐oxidation reaction the internal double bond of oleic acid to a terminal alcohol function, leading to linear long‐chain α,ω‐difunctional substrates is described.

Plant‐Oil‐Based Polyamides and Polyurethanes: Toward Sustainable Nitrogen‐Containing Thermoplastic Materials

“…DMC was also used in an isomerization–hydroboration–oxidation strategy to access to long chain AB‐ and AA‐type monomers based on 2 . Oleylamine was thus reacted to the respective methyl carbamate with DMC and the subsequently performed very regioselective isomerization–hydroboration–oxidation procedure yielded an AB monomer for transcarbamoylation polymerization (Scheme ).…”