Synthesis of fatty ether-esters and polyesters for EPDM plasticization

G. Scalabrino (1) , L. Djakovitch (1) , C. Betron , V. Bounor-Legare , P. Cassagnau , C. Pinel (1)

1 IRCELYON - Institut de recherches sur la catalyse et l'environnement de Lyon

Introduction The use of renewable resources in the elaboration of various industrial materials and chemicals has been recently revitalized because of environmental concerns. Nowadays, vegetable oils constitute one of the most important classes of renewable resources. They can be extracted from the soybean or rapeseed press cakes. They are already a part of some polymeric material formulations but can also be used as polymer plasticizers To substitute paraffinic oil that are used at present as plasticizers for EPDM, modified vegetables oils were prepared as a new bio plasticizer. Efficient oxirane ring opening of fatty epoxides was performed to synthesis various poly ester and ether-ester. Some physico-chemical characterization of the synthetized modified oils were reported [ref]CC. In this paper, we wish to present our contribution in the synthesis of this bioplasticizers together with some characterizations in EPDM formulation. Results and discussion We prepared a range of products via successive ring oxirane opening reaction. The ether-ester modified vegetable oils were prepared in two steps from epoxide derivatives. Initially, the ring opening of the epoxide with an alcohol was carried out to yield the hydroxyl-ether intermediate which was esterified in the presence of an anhydride. The polyester derivatives were prepared from the fatty epoxide via opening reaction with a series of acids then esterification of the resulting alcohol with anhydride. The reaction was performed in solvent free conditions and the influence of the catalysts (homogeneous or heterogeneous) in these reactions was evaluated. With this approach ether-ester and poly esters were prepared. Homogeneous (strong acid, Lewis acid [1, 2]) or heterogeneous catalysts (Amberlyst 15 [3]) were compared in solvent free conditions and with an excess of alcohol. With this approach fatty ether-esters were prepared. Among the evaluated catalysts, Amberlyst 15 and BF3.OEt2 exhibited significant activities for the two steps. Optimisations of the reaction conditions were performed in order to achieve complete conversion. The products were characterized by NMR, GC, GPC and TGA. Thermal stability plays a key role for EPDM plasticization (figure 1). Their properties as EPDM bioplasticizer are compared to non-modified oil and fatty polyester. Cyrille Graph Fig. 2: Rheology analysis of modified and non modified oil. Some vegetable oils derivatives may be good candidates to substitute paraffinic oils usually added as plasticizer . The influence of the chemical modifications on the properties will be described. Conclusion This two-step ring opening approach allowed to prepare a range of potential bioplasticizers for EPDM starting from vegetable oils. This is an interesting method to add new functions on fatty acid esters and to have low polarity with different functions. References 1.Soi, H.S., et al., Monomers of polyhydroxy compounds and manufacturing methods therefor, CN1962601A, 2007. 2.Hwang, H.-S. and Erhan, S.Z., Industrial Crops and Products, 2006. 23, 3: 311-317. 3.Cramail, H., et al., Manufacture of polyols having ester groups from vegetable oils for manufacture of polyurethanes, FR2950051A1, 2011.

Domaines: Catalyse; Environnement et Société

G. Scalabrino, L. Djakovitch, C. Betron, V. Bounor-Legare, P. Cassagnau, et al.. Synthesis of fatty ether-esters and polyesters for EPDM plasticization. 3rd International Symposium on Green Chemistry, May 2015, La Rochelle, France. ⟨hal-01137909⟩