The structures of starch and starch-based materials determine additives migration from material matrix. Propionylated starch derived from waxy, normal, G50 and G80 starch were selected as the matrix, the amylose effect on plasticizer (triacetin) migration as well as structural changes in hydrophobic starch-based films were discussed. The constant (k1) of first-order rate and initial release rate (V0) of triacetin migration were consistent with the increment of amylose content. Meanwhile, diffusion model disclosed that Fick's second law was apposite to characterize the short-term migration of triacetin, and larger diffusion coefficient (D) values of short- and long-term migration were also found in films with higher amylose content, indicating that amylose-formed structures were in favor of triacetin migration. In comparison of propionylated amylopectin, Van der Waals's interactions between propionylated amylose and triacetin were easier to be weakened with the migration of triacetin, which promoted the decrease of wavenumber of C-O-C, and enlarged the inter-planner spacing of crystalline structures, promoting the formation of amorphous structures and wrinkles and embossments in films with higher amylose content. This work confirmed that regulating the structures of starch were effective to control the migration behavior of additives from starch-based films.
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