Recently, an increasing number of research groups started to concentrate on carbohydrate-, plant oil and terpene-based polymers. Some of them have even been commercialized to some extent. When the chemical structures of these products are evaluated, one realizes that they provide different amounts of double bonds that are available for chemical functionalization. The possibility to use the plant oil directly, without chemical modification or functionalization, most often leads to cross-linked structures. A wide range of polymerization and/or functionalization methods, including, radical and metathesis procedures as well as thiol-ene & yne and azide-alkyne addition reactions have been applied. The scope, limitations, and possibility of utilizing such methods reveal that new robust, non-toxic, atom-efficient, orthogonal and industrially attractive chemical pathways are still needed.In this presentation, we will highlight a new click chemistry platform based on triazoline diones (TAD), recently developed by our group[1], with the aim to functionalize and crosslink plant oils and renewable ADMET polymers directly in an atom-efficient and additive-free manner. Although TAD is known as an identification tool for GC-MS[2] and as functionalization tool for triglycerides[3], we show here for the first time the synthesis of cross-linked polymeric materials based on pure plant oils, as well as the modification and crosslinking of fatty acid-derived polymers to achieve new renewable polymers with complex macromolecular structures that are not yet easily achievable by any currently known chemical pathways. Within this contribution, the very first examples of the application of TAD chemistry to the renewable ADMET polymers as well as triglycerides will be reported and compared to thiol-ene addition reactions. TAD chemistry overcomes the drawbacks of the thiol-ene addition reactions, and thus appears to be a perfect and powerful complementary tool, enabling the access to new polymers and broadening the synthesis and/or functionalization of fatty acids and fatty acids derived (co-)polymers.References: [1] S. Billiet, K. D. Bruycker, F. Driessen, H. Goossens, V. Van Speybroeck, J. Winne, F. E. Du Prez, Submitted 2014 .[2] U. Shah, J. Lay, Jr., A. Proctor, J Am Oil Chem Soc 2013  , 90, 155-158.[3] A. Biswas, H. N. Cheng, S. Kim, Z. Liu, J Am Oil Chem Soc 2014  , 91, 125-131.

Triazolinediones as a versatile click chemistry platform providing functionalization and cross-linking of unsaturated renewable building blocks

248th National Meeting (2014)

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