Polydispersity control in ring opening metathesis polymerization of amphiphilic norbornene diblock copolymers

Ring opening metathesis polymerization (ROMP) with Grubbs's catalyst was used to synthesize narrow polydispersity (PDI)diblock copolymers of norbornene (NOR) and norbornenedicarboxylic acid (NORCOOH). Norbornene (NOR) and 5-norbornene-2,3,-dicarboxylic acid bis trimethylsilyl ester (NORCOOTMS) were used as precursor monomers for the polymerization. [NORCOOTMS]_m/[NOR]_n was converted to [NORCOOH]_m/[NOR]_n by precipitating the polymer solution in a mixture of methanol, acetic acid, and water. The conversion to 5-norbornene-2,3-dicarboxylic acid was evidenced by ¹H NMR. By polymerizing the bulkier NORCOOTMS precursor monomer first, lower PDIs were observed for the completed [NORCOOH]_m/[NOR]_n block copolymers in comparison to copolymers where the NOR block was polymerized first. The PDI of the diblock copolymers of [NORCOOH]_m/[NOR]_n decreased with increase in block length of the precursor NORCOOTMS monomer. This study shows that the PDI can be controlled by selecting a monomer with appropriate functionality as the starting block of the block copolymer to control the rate of propagation, R_p, as an alternative of using additives to change the reactivity of the catalyst.