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Polymer Engineering and Science, Vol.48, No.3, 425-433, 2008
Investigations on the morphology and melt crystallization of poly(L-lactide)-poly(ethylene glycol) diblock copolymers
Ring opening polymerization of L-lactide was realized in the presence of monomethoxy poly(ethylene glycol), using zinc lactate as catalyst. The resulting PLLA-PEG diblock copolymers were characterized by using (HNMR)-H-1, SEC, WAXD, and DSC. All the copolymers were semicrystalline, one or two melting peaks being detected depending on the composition. Equilibrium melting temperature (T-m(o)) of PLLA blocks was determined for three copolymers with different EO/LA molar ratios. Tmo decreased with decreasing PLLA block length. A copolymer with equivalent PLLA and PEG block lengths was selected for melt crystallization studies and the resulting data were analyzed with Avrami equation. The obtained Avrami exponent is equal to 2.6 +/- 0.2 in the crystallization temperature range from 80 to 100 degrees C. In addition, the spherulitle growth rate of PLLA-PEG was analyzed by using Lauritzen-Hoffmann theory in comparison with PLLA homopolymers. The nucleation constant was found to be 2.39 x 10(5) K-2 and the free energy of folding equal to 53.8 erg/cm(2) in the range of 70-94 degrees C, both higher than those of PLLA homopolymers, while the spherulite growth rate of the diblock copolymer was lower.