Synthesis and characterization of statistical and block copolymers of n‐hexyl isocyanate and 2‐chloroethyl isocyanate via coordination polymerization

Statistical and block copolymers of n‐hexyl isocyanate (HIC) and 2‐chloroethyl isocyanate (ClEtIC) were synthesized via cοοrdination polymerization employing the half‐titanocene complex [(η5‐C5H5)((S)‐2‐Bu‐O)TiCl2] as initiator. The complex, bearing a chiral substituent, led to optically active products, as confirmed by circular dichroism measurements. The molecular characterization of all products was carried out by NMR and IR spectroscopy and size exclusion chromatography (SEC), while their thermal stability was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The reactivity ratios of the two monomers were determined using various graphical methods, as well as the COPOINT program, according to the terminal copolymerization model. Structural parameters, such as the dyad monomer sequences and the mean sequence lengths were calculated as well. In addition, the kinetics of the thermal degradation of the statistical copolymers was studied, and the activation energies of the thermal degradation were calculated employing the Kissinger, Ozawa–Flynn–Wall (OFW), and Kissinger–Akahira–Sunose (KAS) methods. The block copolymers were synthesized by sequential addition of monomers starting from the polymerization of HIC. Well‐defined products were obtained in a controlled way as revealed by SEC, IR, and NMR measurements.