Coupled heterogeneous and homogeneous catalysis: Synthesis and transformation of bio-butadiene for the preparation of unsaturated ethers – H2CAT

Heterogeneous catalysts are developped for the selective synthesis of biobutadiene from ethanol. This research is accelerated from the use of the REALCAT screening platform. Homogeneous catalysis is in a second step involved for the synthesis of polyol ethers. The heterogeneous and homogeneous processes are ultimately planed to be coupled.
The thus synthsized monomers wil be ultimately used for the elaboration of new 100% agro-based resins.

- The project has allowed the synthesis of glycerol ethers at 200 g scale. For this purpose, 1L and 3L glassware reactors have been used.

- Concerning the synthesis of biobutadiene, the catalysts that have been developped showed very promising catalytic activies and selectivies in respect to the results already reported in the litterature.

The project will now start to tackle two important aspects :

- The coupling of homogeneous and heterogeneous reactors.
- The synthesis of the first new polymers from the industrial partner.

Articles in international journals :

1. A. Mifleur, A. Mortreux, I. Suisse, M. Sauthier “Synthesis of C4 chain glyceryl ethers via nickel-catalyzed butadiene hydroalkoxylation reaction” J. mol. Catal. A : Chem. 2017, 427, 25–30
2. G. Pomalaza, M. Capron, V. Ordomsky and F. Dumeignil, “Recent Breakthroughs in the Conversion of Ethanol to Butadiene” Catalysts – review 2016, 203, 6-41


Articles in a national journal «l'actualité chimique« :
1. P. Zinck « La chimie dans la région Hauts-de-France » L’actualité Chimique, 2017, 420, 40-45
2. A. Mifleur , I. Suisse , A. Mortreux , M. Sauthier « La réaction d’hydroalcoxylation du butadiène : une voie de synthèse d’éthers catalytique et économe en atomes à partir d’alcools » L’actualité Chimique, 2016, 408-409, 126-129

6 orale communications and 1 poster

From an industrial point of view, the synthesis of agro-based and innovative products is a key issue to insure future economic growth and reduce our dependency on fossil carbon. 100 % agro-based compounds with valuable applicative properties are for example needed in the fields of materials, solvents and paint formulations. The chemistry of carbohydrates and more generally polyols is in this context of strong interest as these motifs are available at very high industrial scales. The conversion of polyols in products of industrial interest necessitates the implementation of suitable chemical processes based on catalytic reactions. Among the different possibilities, the etherification reactions of alcohols with butadiene are relevant chemical transformations that allow introducing ether groups with unsaturated aliphatic tails. However, in order to build 100 % agro-based molecules, a critical point is the access to bio-based 1,3-butadiene.

In this context, the H2CAT project aims at synthetizing 100 % agrobased monomers and resins with applicative properties in the field of paint formulation. Catalytic reactions are planned to be used for the synthesis of the monomers from bio-butadiene and polyols according to catalytic processes.
The whole project thus encompasses different aspects: 1) The development of heterogeneous catalysts for the production of bio-butadiene from butanediols and ethanol with improved selectivitiy and efficiencies. 2) The synthesis of polyol ethers from homogeneously catalyzed transformations in biphasic conditions with polar catalysts. 3) The setup of a suitable reactor to combine two catalytic reactions (heterogeneous and homogeneous) thus allowing production and transformation of 1,3-butadiene in a continuous manner. 4) The synthesis of 100 % agrobased resins from the synthesized ethers and the evaluation of their applicative properties in the field of paint formulations. The H2CAT project is thus transdisciplinary and will involve two academic research groups from the University of Lille with strong expertise in both fields of homogeneous and heterogeneous catalysis as well as an industrial partner, IFMAS that combines the expertise of polymerization and paint formulation.