Aggregation behavior of new cyclic saturated copolymers synthesized via ring-opening metathesis polymerization

Cyclic saturated copolymers were prepared from 8-methyl-8-methoxycarbonyltetracyclo4.4.0.1^2,5.1^7,10]dodec-3-ene (MMT) with polar ester group and dicyclopentadiene (DCP) without polar group. This procedure consisted of ring-opening metathesis polymerization (ROMP) followed by hydrogenation. Monomer reactivity of DCP was higher than that of MMT; the monomer reactivity ratio r_DCP/r_MMT varied from 2.135 to 1.159 in a temperature range from 80 to 130 °C. These kinetic results indicated that the copolymer had distribution of DCP composition in a macromolecule chain, which could provide the interesting aggregation behavior. The aggregation behaviors of the hydrogenated copolymer and the homopolymer in various solvents were also examined using dynamic light scattering (DLS) and static light scattering (SLS). DLS analysis indicated that the fast mode in each polymer is attributed to the diffusive motion of each single polymer chain, while the slow mode in the copolymer is caused by aggregated polymer. The aggregation degree of the copolymer decreased with increasing hydrophobicity of solvent, decreasing polymer concentration, decreasing molecular size of solvent and increasing temperature. Based on these findings, the mechanism of aggregation behavior was clarified that the DCP-rich unit in a macromolecule might be acting as core to give the aggregation in poor solvent.