Poly(n-hexyl isocyanate)s (PHICs) with chiral moieties at both ends of their polymeric chains were synthesized by living anionic polymerizations. Such PHICs were synthesized using a bidirectional initiator (sodium naphthalenide (Na-Naph)) and terminated with a chiral acid chloride, (S)-2-acetoxypropionyl chloride ((S)-Ct). Na-Naph created a covalent linkage in the middle of the chains by radical–radical coupling. PHICs containing a chiral moiety at both ends adopted conformations with an opposite helical sense in comparison with those PHICs that had the same chiral moiety at only one end of their chain. By observing these structural differences, it was hypothesized that such a “helicity inversion” occurred in the PHICs due to the covalent linkage in the middle of the chain. Therefore, to prove this assumption about helicity inversion, a comparison study of the helical behaviors between the PHIC with the chiral moiety at both ends and the PHIC with the chiral moiety at only one end was performed. The synthesized PHICs were characterized using size exclusion chromatography-multiangle laser light scattering (SEC-MALLS), MALDI-TOF mass spectrometry, NMR spectrometry, and circular dichroism (CD).

We report for the first time the conformational and structural details of peptide-mimic poly(n-hexyl isocyanate) (PHIC). PHIC is a representative poly(n-alkyl isocyanate)s, which have received significant attention because of their unique stiff chain characteristics and potential applications in various fields. A well-ordered hexagonal close packing structure of PHIC with 8 3 helical conformation was clearly observed in the nanoscale thin films that were selectively annealed with carbon disulfide (CS 2 ). A well-ordered multi-bilayer structure of the polymer with b-sheet conformation was also clearly formed in the films that were selectively annealed with toluene. In addition, a fully reversible transformation between these two self-assembled structures was demonstrated by consecutive annealings with CS 2 and toluene.

A novel amphiphilic polyisocyanate block copolymer with hydroxyl side groups was synthesized by a combination of living anionic polymerization and thiol−ene click chemistry. First, the living anionic block copolymerization of allyl isocyanate (AIC) and n-hexyl isocyanate (HIC) produced a well-defined block copolymer (PAIC-b-PHIC) as a precursor. The subsequent free-radical-mediated thiol−ene click reaction of this polymer with 2-mercaptoethanol at room temperature quantitatively converted the allyl side groups of the PAIC domain to hydroxyl groups, finally creating PAIC(OH)-b-PHIC. The amphiphilicity of PAIC(OH)-b-PHIC led to lamellar and cylindrical phase separations in the thin films cast from different solvents (THF and toluene). The functionalities and phase separation behaviors of PAIC(OH)-b-PHIC were characterized by NMR, SEC-MALLS, and TEM analysis.

Poly(n-hexyl isocyanate) (PHIC) with varying molecular weights were synthesized using a chiral initiator and chiral terminator by living anionic polymerization. In such PHICs, chirality of the initiator plays a decisive role in determining the helical sense of the entire polymeric chain, whereas chirality of the terminator plays a supportive role.

Poly(n-hexyl isocyanate) was synthesized by anionic polymerization using various oxy-initiators, including sodium phenoxide (Na-PO), sodium benzhydroxide (Na-BH), and sodium methoxyphenylethoxide (Na-MPE). We optimized polymerization conditions. To confirm the living natures of the polymerization, we carried out various polymerizations changing mole ratio between monomers and initiators and a postpolymerization by sequential monomer addition method. Our results indicated that the anionic polymerization of n-hexyl isocyanate was not controlled using Na-PO and Na-MPE. However, Na-BH as an initiator is favorable for the living anionic polymerization of n-hexyl isocyanate because it has a dual function in the initiation and in the efficient prevetion of trimerization by reducing the reactivity at the growth chain ends. Polymers were thus synthesized with predictable molecular weights (MW), narrow molecular weight distributions (MWD), and high yields.