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We report on the block copolymerization of two structurally different norbornene monomers (±)- endo , exo -bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid dimethylester ( 7 ), and (±)- endo , exo -bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) ester ( 9 ) using ruthenium based Grubbs’ type initiators [(PCy 3 ) 2 Cl 2 Ru(benzylidene)]  G1  (PCy 3  = tricyclohexylphosphine), [(H 2 IMes)(PCy 3 )Cl 2 Ru(benzylidene)]  G2  (H 2 IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H 2 IMes)(py) 2 Cl 2 Ru(benzylidene)]  G3  (py = pyridine or 3-bromopyridine) and Umicore type initiators [(PCy 3 ) 2 Cl 2 Ru(3-phenylinden-1-ylidene)]  U1  (PCy 3  = tricyclohexylphosphine), [(H 2 IMes)(PCy 3 )Cl 2 Ru(3-phenylinden-1-ylidene)]  U2  (H 2 IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H 2 IMes)(py)Cl 2 Ru(3-phenylinden-1-ylidene)]  U3  (py = pyridine or 3-bromopyridine) via ring opening polymerization (ROMP). The crossover reaction and the polymerization kinetics were investigated using matrix assisted laser desorption ionization mass spectroscopy (MALDI-TOF) and nuclear magnetic resonance (NMR), respectively. MALDI showed that there was a complete crossover reaction after the addition of 25 equivalents of the second monomer. NMR investigation showed that  U3  gave a faster rate of polymerization in comparison to  U1 . The synthesis of block copolymers with molecular weights up to  M  n  = 31 000 g/mol with low polydispersities ( M  w / M  n  = 1.2) is reported.

Synthesis and crossover reaction of TEMPO containing block copolymer via ROMP