Synthesis of Inorganic Silica Grafted Three-arm PLLA and Their Behaviors for PLA Matrix
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The low melt strength and poor crystallization behavior severely limit the processing and application of poly(lactic acid) (PLA) as biodegradable film materials. In this work, three-arm poly(L-lactic acid) (3A-PLLA) grafted silica nanoparticles with two kinds of topology structures were introduced into PLA matrix to improve the biodegradation performance. Different methods were used to characterize the structure of the grafted 3A-PLLA chains, the grafting density, and the thermal decomposition behavior of the nanoparticles. By varying the mass ratios of raw materials and altering the order of dropping solution in the reaction, high grafting densitytangled 3A-PLLA grafted SiO2 was synthesized as “3A-PLLA grafting to SiO2” (GTS), while low grafting density-stretched 3A-PLLA grafted SiO2 was obtained as “SiO2 grafting to 3A-PLLA” (GTA). Topology of nanoparticles as well as the filler-matrix interaction is critically important to structure bio-nanocomposites with desirable properties. Thus, the GTS and GTA nanoparticles were introduced into PLA matrix to assess the effect. The SEM images showed the uniform dispersion of the modified nanoparticles, while the shear rheology results revealed that GTA nanoparticles made a more significant contribution on the melt-strengthening and relaxation time-extension of PLA. Moreover, it is suggested that GTA nanoparticles were more effective to act as a nucleating agent for PLA, which was proved by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) researches. All of the improvements mentioned above of GTA nanocomposites can be ascribed to stronger entanglements between 3A-PLLA stretched by nano-SiO2 and PLA matrix.
KeywordsPoly(lactic acid) Nanocomposites Surface grafting Topology Crystallization
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The authors sincerely acknowledge the financial support of National Natural Science Foundation of China (Nos. 51721091, 21674069 and 21174092).
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