Direct polymerization of N‐carboxy anhydride of L‐glutamic acid

A new method of polymerization of the N-carboxy anhydride (NCA) of glutamic acid is presented by which poly(glutamic acid) is obtained directly from the NCA without protecting its carboxyl group. The principle underlying is that by adjusting the mole ratio of the initiator butylamine, [I], to the monomer, [A], butylamine can be used as protecting agent for the carboxyl group of the NCA so that the rest of butylamine acts as initiator in the heterogeneous polymerization in acetonitrile. Quantitative conversion was obtained for an [A]/[I] ratio of 1. In analogy to other heterogeneous polymerizations of NCAs in acetonitrile, this is due to the formation of the helix during polymerization, which was confirmed by IR absorption and X-ray diffraction measurements. As the [A]/[I] ratio increases, the conversion, the helix content of the resultant polymer, and the amount of butylamine combined with it decrease drastically. It is suggested that “copolymerization” of the amine-protected and unprotected NCAs occurs, giving rise to a partially helical chain, whose contents of the amine-protected side chains and accordingly of the helix are the higher the smaller the [A]/[I] ratio.