Crystallization of poly(L‐proline) in the course of polymerization

The heterogeneous polymerization of L-proline N-carboxy anhydride was carried out in acetonitrile and benzene, using butylamine as the initiator. Polyproline I was formed in acetonitrile and polyproline II in benzene in the course of the polymerization. The conversion attained 99% and 66% after 1 week-polymerization in acetonitrile and benzene, resp. Extended chain crystals were obtained by the polymerization in acetonitrile. On the other hand, poly(L-proline) obtained by the polymerization in benzene gave aggregates into which many growing chain ends were occluded. The differences in the crystallization behaviour during the polymerization between the two different liquids may be due to the conformation of the resultant polymers. Polyproline I exhibits a cross-section per chain of 0.709 nm2, whereas polyproline II shows only one of 0,386 nm2. The wider the cross-section per chain the more the growing, active chain ends can react with the monomer, giving rise to a higher conversion. In contrast with the case of crystallization of such α-helical chains as poly(L-alanine) during polymerization, hexagonal lamellar crystals were formed.