Design, Synthesis and ROMP of Novel Exo-Norbornene Silyl Ethers for Functional Polymer Applications

With the constant development of new polymer chemistry technologies, it is necessary to find modern synthetic pathways for the synthesis of polymers bearing numerous applicable characteristics, in an easy, efficient and environmentally friendly way. One such possibility is to present the use of metathesis type reactions and more specifically ring-opening metathesis polymerisation (ROMP), which provides the opportunity to produce linear unsaturated functionalised polymeric chains in a ‘living’ yet controlled manner with the use of ruthenium-based carbene (Ru=CHR) Grubbs’ catalysts (initiators: G1, G2, G3). In order to achieve satisfying results and obtain full conversion of the monomers, sterically hindered molecules are preferred, because the process of opening the ring results in simultaneous release of the energy that propagates the whole process. The incorporation of silicon-based substituents (such as silyl ethers) into the norbornene matrix can provide higher thermal stability of polymers, leading to the creation of flame-retardant materials. Other applications include gas separation membranes or biomedicine, upon further modification. This paper focusses on the development and optimisation of the synthetic method of previously not reported exo-norbornene silyl ethers along with their metathesis polymerisation to achieve linear unsaturated polymers with high isolation yields.