The effect of polycaprolactone polyol molecular weight and chain extender type on the physico-mechanical properties and gas permeability of polyurethane thermoplastic elastomer membranes

In this study, polyurethane thermoplastic elastomers (TPU) were synthesized using isophorone diisocyanate (IPDI), 1,4-butanediol (BDO), and 1,6-hexanediol (HDO) as the chain extenders, and polycaprolactone diol (PCL-diol) with three different molecular weights (2000, 4000, and 10,000 g/mol) as polyols. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) patterns, and differential scanning calorimetry (DSC) were conducted to analyze the chemical microstructure and phase morphology of the prepared samples. The results showed that the change in the chain extender's type (BDO and HDO) leads to a decrease in the hydrogen bonding index (HBI). Increasing the molecular weight of PCL-diol in BDO-based TPUs has led to an increase in their crystallinity, Young's modulus, melting temperature, tensile strength, and a decrease in glass transition temperature and elongation at break. Moreover, the increase in the molecular weight of PCL-diol in HDO-based TPUs demonstrated an increase in the crystallinity and elongation at break and tensile strength up to the molecular weight 4000 in PCL-diol, after that, there was a decrease in those properties due to the increase of the soft segments content and change in the chain extender type. Permeability on TPU membranes was performed for N2 and CO2 at three different pressures 3, 6, and 9 atm at room temperature. An increase in pressure led to an increase in membrane permeability due to the increase in gas solubility in TPU based on Henry's law. The permeability of CO2 is higher than N2 due to the proper interactions of CO2 gas with the polar carbonyl groups of polyurethane. It is observed that the permeability increases in BDO-based samples with an increase in the molecular weight of PCL-diol, while the increase in permeability of HDO-based TPU is up to PCL-diol molecular weight 4000 and after that is decreased. The selectivity of CO2 has decreased with increasing pressure due to the higher rate of dissolution of N2 at higher pressures.