Understanding the hydrolysis mechanism on segments and aggregate structures: Corrosion-tailored poly (lactic acid)...

Poly (L-lactic acid) (PLLA) based copolymers modified with δ-valerolactone (DVL) through random copolymerization (PVLA-R) and block copolymerization (PVLA-B) with various DVL content were prepared to investigate their degradation regulation and mechanism. Chemical structure, thermal properties, hydrophilicity, crystallization as well as the crystal defects of the obtained copolymers were respectively confirmed. Degradation regulation of both PVLA-R and PVLA-B, such molecular weight and pH value changes of PLLA based copolymers were investigated via vitro degradation method. In order to further explore the degradation principle of the two copolymers, their degradation residues at different stages were systematically studied. The addition and increasing content of DVL disturbs the regularity of original PLLA molecular structure, resulting in accelerating degradation of copolymers. Compared with amorphous region, the crystalline region of both two copolymers has better corrosion resistance, which could be confirmed by increased melting point and crystallinity of both PVLA-R and PVLA-B degradation residues. PVLA-B copolymers show relatively superior degradation resistance mainly due to their higher molecular weight, crystallinity and hydrophobic index than PVLA-R copolymers.