Optical rotation of random copolyisocyanates of chiral and achiral monomers: Sergeant and soldier copolymers

Optical rotation (OR) of random copolymers of chiral 2,6-dimethylheptyl isocyanate (NIC) and achiral hexyl isocyanate (HIC) was measured as a function of mole fraction x of the chiral monomer, temperature, and molecular weight, with hexane, 1-chlorobutane, and dichloromethane as the solvents. The data as a function of molecular weight were analyzed by the statistical mechanical theory of copolymers developed (Gu, H.; et al. Polym. J. 1997, 29, 77-84), in which a polyisocyanate chain is modeled by an alternating sequence of left-handed and right-handed helices occasionally interrupted by helical reversals. The theory involves two parameters, the left-handed-right-handed free energy bias, 2 Delta G(h), and the helical reversal free energy, Delta G(r). With appropriate values for these parameters, the experimental OR values were well described by the theory. When compared with poly((R)-i-deuterio-n-hexyl isocyanate (i = 1, 2), the values of Delta G(r) were nearly the same but those of \2 Delta G(h)\ were much larger: 71 +/- 14 cal/mol for the terpene derived chiral unit vs 1 similar to 2 cal/mol for the deuterated chiral monomer units. These free energy values are reasonable considering the chemical structures of the respective chiral monomer units.