Synthesis of fatty ether-esters and polyesters for EPDM plasticization

International @ CDFA+GSCInternational audienceIntroductionThe 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 discussionWe 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 GraphFig. 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.ConclusionThis 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. References1.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

Synthesis of bio-plasticizer from epoxidized vegetable oils

International @ CDFA+GSC:CPI:LDJInternational audienceIntroductionThe use of renewable resources in the elaboration of various industrial materials and chemical has been recently revitalized because of environmental concerns. Nowadays, vegetable oils constitute one of the most important classes of renewable resources. To substitute the phthalate derivatives that are used at present as plasticizers for PVC, modified vegetables oils were prepared as a new bio plasticizer [1]. Efficient oxirane ring opening of fatty epoxides was performed to synthesis various diesters. Modified oils were characterized. In this paper, we wish to present catalyzed ring opening reaction and effects of esters groups on the PVC plasticisation.Results and discussionWe prepared a range of products via successive ring oxirane 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 symmetric and dissymmetric esters were prepared [2-3].Among the evaluated catalysts, NBu4Cl, TiO2 and Nb2O5 exhibited significant activities for both reactions. Optimisations of the reaction conditions were performed in order to achieve complete conversion. The reaction has been perfomed on G scale. The products were characterized by NMR, GC and TGA and their properties as a bioplasticizer for PVC were evaluated.Fig. 1: Viscoelastic profile of plastisol with modified oils(AcMeSBO : acetylated methyl soyate, BzMeSBO : methyl soyate with benzoate,Ac/CyclohMeSBO : methyl soyate with acetate and cyclohexanoate)Plastisols were prepared by mixing PVC and the fatty ester derivatives (PVC/plasticizers: 2/1 in mass?). The angular frequency used is 6.3 rd/s. The storage modulus G’ was recorded as function of temperature (fig. 1). The temperatures of gelation were almost the same as the standard plasticizer (DINP). Some modified vegetable oils may be good candidates to substitute the phthalate derivative usually added as plasticizer. The influence of the chemical modifications on the properties will be described.ConclusionThis two-step ring opening approach allowed to prepare a range of potential bioplasticizers for PVC starting from vegetable oils. is an interesting method to add new functions on fatty acid esters and it can be applied to the synthesis of PVC bio plasticizers.References[1] R. Stringer, I. Labunska, D. Santillo, J. Siddorn, A. Stephenson, Environ Sci Pollut Res 2000 7,1, 27-36.[2] G. Fogassy, C. Pinel, G. Gelbard, Cat. Commun. 2009 10, 557-560[3]G. Fogassy, P. Ke, F. Figueras, P. Cassagnau, S. Rouzeau, V. Courault, G. Gelbard, C. Pinel, Appl. Catal. A, 2011 393, 1–

Synthesis of bio-plasticizer from epoxidized vegetable oils

International @ CDFA+GSC:CPI:LDJInternational audienceIntroductionThe use of renewable resources in the elaboration of various industrial materials and chemical has been recently revitalized because of environmental concerns. Nowadays, vegetable oils constitute one of the most important classes of renewable resources. To substitute the phthalate derivatives that are used at present as plasticizers for PVC, modified vegetables oils were prepared as a new bio plasticizer [1]. Efficient oxirane ring opening of fatty epoxides was performed to synthesis various diesters. Modified oils were characterized. In this paper, we wish to present catalyzed ring opening reaction and effects of esters groups on the PVC plasticisation.Results and discussionWe prepared a range of products via successive ring oxirane 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 symmetric and dissymmetric esters were prepared [2-3].Among the evaluated catalysts, NBu4Cl, TiO2 and Nb2O5 exhibited significant activities for both reactions. Optimisations of the reaction conditions were performed in order to achieve complete conversion. The reaction has been perfomed on G scale. The products were characterized by NMR, GC and TGA and their properties as a bioplasticizer for PVC were evaluated.Fig. 1: Viscoelastic profile of plastisol with modified oils(AcMeSBO : acetylated methyl soyate, BzMeSBO : methyl soyate with benzoate,Ac/CyclohMeSBO : methyl soyate with acetate and cyclohexanoate)Plastisols were prepared by mixing PVC and the fatty ester derivatives (PVC/plasticizers: 2/1 in mass?). The angular frequency used is 6.3 rd/s. The storage modulus G’ was recorded as function of temperature (fig. 1). The temperatures of gelation were almost the same as the standard plasticizer (DINP). Some modified vegetable oils may be good candidates to substitute the phthalate derivative usually added as plasticizer. The influence of the chemical modifications on the properties will be described.ConclusionThis two-step ring opening approach allowed to prepare a range of potential bioplasticizers for PVC starting from vegetable oils. is an interesting method to add new functions on fatty acid esters and it can be applied to the synthesis of PVC bio plasticizers.References[1] R. Stringer, I. Labunska, D. Santillo, J. Siddorn, A. Stephenson, Environ Sci Pollut Res 2000 7,1, 27-36.[2] G. Fogassy, C. Pinel, G. Gelbard, Cat. Commun. 2009 10, 557-560[3]G. Fogassy, P. Ke, F. Figueras, P. Cassagnau, S. Rouzeau, V. Courault, G. Gelbard, C. Pinel, Appl. Catal. A, 2011 393, 1–