Cascade Ring-Opening/Ring-Closing Metathesis Polymerization of a Monomer Containing a Norbornene and a Cyclohexene Ring

Norbornene is polymerized extremely fast when reacted with Grubbs' first (G1) or third generation catalyst (G3) because of its very high ring strain energy. Cyclohexene, on the other hand, cannot be polymerized using G1 or G3 due to its very low ring strain energy. Subsequently, the sequence-selective polymerization of these two monomers is extremely challenging. A sequence-selective cascade ring-opening/ring-closing metathesis polymerization of the monomer M containing both the norbornene and the cyclohexene ring using G1 or G3 is reported. The polymer structure was analyzed by H-1 NMR, H-1-H-1 COSY, and H-1-H-1 ROESY spectroscopy and MALDI-ToF mass spectrometry. Polymers with moderate molecular weight dispersities and good molecular weight control were achieved by varying the ratio between monomer M and G1.