Accelerated Crystallization of Poly(lactic acid): Synergistic Effect of Poly(ethylene glycol), Dibenzylidene Sorbitol, and Long-Chain Branching

The crystallization of poly(lactic acid) (PLA) is usually slow and related to the content of D-lactide. A new approach is suggested in this work to accelerate the crystallization of PLA via the synergistic effect of nanofibril nucleating agent (dibenzylidene sorbitol, DBS), plasticizer (poly(ethylene glycol), PEG) and long-chain branching in PLA. It is found that premade DBS/PEG gel can act as an active nucleating agent of PLA, which makes the crystallization peak appear during cooling. The preparation of DBS/PEG gel before mixing with PLA is important because self-assembly of DBS directly in PLA melt is difficult even in the presence of PEG. The mixing temperature is also found to be critical, which determines the amount of residual nanofibrils after melt mixing. Tuning the chain structure into long-chain branching via multifunctional monomer pentaerythritol triacrylate (PETA) will further speed up the crystallization of PLA because of the additional interaction between DBS nanofibrils and the grafted monomers. It is proven that the acceleration of crystallization is not ascribed to the change of crystal form but is due to the dominating increase in the nucleation density as well as the faster growth rate of spherulites in the presence of the plasticizer. Therefore, the problems of low melt strength and slow crystallization of PLA can be solved simultaneously via the present approach.