Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C0–C22) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C0), 1-hexanol (C6), 1-dodecanol (C12), and 1-docosanol (C22) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having Mn of 6–7 × 103 of 2 × 104 g mol−1, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having Mn of 6–7 × 103 g mol−1, but was not altered by the length of terminal n-alkyl group for PLLA having Mn of 2 × 104 g mol−1.