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Stereocomplex Crystallization of Star-Shaped Four-Armed Stereo Diblock Poly(lactide) from the Melt: Effects of Incorporated Linear One-Armed Poly(l-lactide) or Poly(d-lactide)

Tsuji, Hideto, Ozawa, Ryota, Arakawa, Yuki
The Journal of physical chemistry 2017 v.121 no.42 pp. 9936-9946
crystal structure, crystallites, crystallization, geometry, melting, models, molecular weight, temperature
Star-shaped four-armed stereo diblock poly(lactide) (4-LD) and linear one-armed PLLA or PDLA (1-L or 1-D) having a molecular weight similar to that of 4-LD [higher molecular weight 1-L(H) or 1-D(H)] and that of one block of 4-LD [lower molecular weight 1-L(L) or 1-D(L)] were synthesized, and the effects of incorporated 1-L or 1-D on the isothermal and nonisothermal crystallization of 4-LD blends from the melt were investigated. Solely stereocomplex crystallites were formed in unblended 4-LD and 4-LD blends incorporated with 1-L or 1-D during isothermal and nonisothermal crystallization. Incorporated 1-L or 1-D increased normalized stereocomplex crystallinity and accelerated cold nonisothermal crystallization and isothermal crystallization. The accelerating effect became higher with decreasing the molecular weight of 1-L or 1-D. The crystalline growth mechanism was not altered by the incorporation of 1-L and 1-D, whereas the crystalline growth geometry changed from line to sphere or circle, depending on the type of sample and Tc. The difference in crystallization half time and cold crystallization temperature between 4-LD/1-L(H) and 4-LD/1-D(H) blends or 4-LD/1-L(L) and 4-LD/1-D(L) blends was explained by the difference in radial growth rate and spherulite density, which was further discussed considering the non-interpenetrating and interpenetrating models.