The combination of the Ugi four-component reaction (Ugi-4CR) with acyclic diene metathesis (ADMET) or thiol-ene polymerization led to the formation of poly-1-(alkylcarbamoyl) carboxamides, a new class of substituted polyamides with amide moieties in the polymer backbone, as well as its side chains. 10-Undecenoic acid, obtained by pyrolysis of ricinoleic acid, the main fatty acid of castor oil, was used as the key renewable building block. The use of different primary amines, as well as isonitriles (isocyanides) for the described Ugi reactions provided monomers with high structural diversity. Furthermore, the possibility of versatile post-modification of functional groups in the side chains of the corresponding polymers should be of considerable interest in materials science. The obtained monomers were polymerized by ADMET, as well as thiol-ene, chemistry and all polymers were fully characterized. Finally, ortho-nitrobenzylamide-containing polyamides obtained by this route were shown to be photoresponsive and exhibited a dramatic change of their properties upon irradiation with light.

Thiol‐ene additions of methyl 10‐undecenoate, a castor oil derived renewable platform chemical, were studied with the goal of preparing a set of renewable monomers. Good to excellent yields were obtained for these solvent and initiator free thiol‐ene additions. The resulting monomers were then polymerized using TBD as a catalyst, to linear as well as hyperbranched polyesters that also contain thio‐ether linkages. All thus prepared polymers were fully characterized (NMR, GPC, DSC, and TGA) and the results of these investigations will be discussed within this contribution. The thermal analysis of these polymers revealed melting points in the range from 50 to 71 °C. Moreover, no significant weight loss was observed below 300 °C.magnified image

This review covers the discovery and development of radical thiol‐ene addition reactions as functionalization and polymerization method. First, some general and important developments within the field of polymer chemistry are introduced. However, the utilization of this efficient coupling procedure for the syntheses of materials derived from plant oils are the focus of this manuscript. Applications of this unique reaction will also be discussed in terms of green chemistry requirements as well as reaction conditions and efficiency.

The syntheses of new fatty acid-derived amine functional monomers via the thiol-ene addition reaction as well as the thereof derived renewable polyamides were investigated. The thiol-ene addition of cysteamine hydrochloride to the double bonds of methyl 10-undecenoate, methyl oleate, and methyl erucate yielded heterodifunctional monomers in good yields. The thus obtained monomers were homopolymerized, copolymerized with each other as well as copolymerized with adipic acid and 1,6-hexamethylene diamine to yield copolyamides. 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was used as an efficient amidation catalyst for all these polymerizations. GPC and DSC characterization of the polymers revealed that the renewable monomers can be used to produce polyamides with good properties and copolyamides with adjustable thermal and solubility properties.