Shape Memory Polyurethanes from Renewable Polyols Obtained by ATMET Polymerization of Glyceryl Triundec-10-enoate and 10-Undecenol Enrique del Rı ´o, Gerard Lligadas, Juan Carlos Ronda,* Marina Galia `, Virginia Ca ´diz, Michael A. R. Meier* Introduction In recent years, the utilization of renewable raw materials, such as plant oils and natural fatty acids, for replacing petroleum derived raw materials for the production of polymeric materials has attracted great attention. [1] The main components of vegetable oils are triglycerides, which are the product of esterification between a molecule of glycerol and three fatty acids. Many of these fatty acids have double bond functional groups in the aliphatic chain, which, in combination with the development of olefin- metathesis, [2] offers manifold new possibilities for the utilization of these renewable resources for organic and polymer chemists. [3] The polymer field has probably benefited most from this development by applying metathesis chemistry for the synthesis of renewable monomers [4] for step-growth polymerizations and the possibility to polymerize plant oil based a,v-dienes via acyclic diene metathesis (ADMET) polymerization. [5] More- over, ADMET was shown to be an efficient tool for the synthesis of a wide variety of linear polymers and polymer architectures that are not available using other polymer- ization methods. [6] It has been demonstrated that ADMET polymerization can proceed in the presence of heteroatoms as long as the terminal olefins are far enough apart from them. [7] Many examples of ADMET of heteroatom-contain- ing a,v-dienes exist in the literature, since the introduction of functionalities to the backbone of a polymers provides different properties and permits further modifications. [8] The development of ADMET polymerization and the possibility to control the polymer molecular weight using chain stoppers has opened new possibilities to obtain desired polymer architectures. [9] Moreover, chain stopper strategies have recently been exploited with the aim of polymerizing monomers with functionalities higher than two in order to avoid cross-linking. The thus named acyclic Full Paper J. C. Ronda, E. del Rio, G. Lligadas, M. Galia `, V. Ca ´diz Departament de Quı ´mica Analı ´tica i Quı ´mica Orga `nica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lı ´ Domingo s/n, 43007 Tarragona, Spain E-mail: juancarlos.ronda@urv.cat M. A. R. Meier Karlsruhe Institute of Technology, Institute of Organic Chemistry, Fritz-Haber-Weg 6, Karlsruhe, Germany E-mail: m.a.r.meier@kit.edu The synthesis of branched polyols from glyceryl triundec-10-enoate by acyclic triene metath- esis polymerization (ATMET) is reported. 10-Undecenol is used as a monofunctional comonomer to end-cap polymer chains, functionalize the periphery of the resulting branched materials, and to control the molecular weight. The thus obtained castor oil derived polyols are reacted with 4,4 0 -methylenebis(phenylisocyanate) (MDI) to yield a series of semicrystalline polyurethane net- works. The investigation of the thermal stability and the thermomechanical and mechanical properties of these thermosets revealed good shape memory properties. 1392 Macromol. Chem. Phys. 2011, 212, 1392–1399 ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/macp.201100025