*Article* **High-Toughness Poly(lactic Acid)**/**Starch Blends Prepared through Reactive Blending Plasticization and Compatibilization**

#### **Huan Hu, Ang Xu, Dianfeng Zhang, Weiyi Zhou, Shaoxian Peng and Xipo Zhao \***

Hubei Provincial Key Laboratory of Green Materials for Light Industry, Collaborative Innovation Center of Green Light-Weight Materials and Processing, Hubei University of Technology, Wuhan 430068, China; huhuan13579@163.com (H.H.); xuang126912@163.com (A.X.); wodiao1066@163.com (D.Z.);

zhouweiyi@hbut.edu.cn (W.Z.); psxbb@126.com (S.P.)

**\*** Correspondence: xpzhao123@163.com

Academic Editors: Marek Brzezi ´nski and Małgorzata Ba´sko

Received: 11 November 2020; Accepted: 7 December 2020; Published: 16 December 2020

**Abstract:** In this study, poly(lactic acid) (PLA)/starch blends were prepared through reactive melt blending by using PLA and starch as raw materials and vegetable oil polyols, polyethylene glycol (PEG), and citric acid (CA) as additives. The effects of CA and PEG on the toughness of PLA/starch blends were analyzed using a mechanical performance test, scanning electron microscope analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, X-ray diffraction, rheological analysis, and hydrophilicity test. Results showed that the elongation at break and impact strength of the PLA/premixed starch (PSt)/PEG/CA blend were 140.51% and 3.56 kJ·m<sup>−</sup>2, which were 13.4 and 1.8 times higher than those of pure PLA, respectively. The essence of the improvement in the toughness of the PLA/PSt/PEG/CA blend was the esterification reaction among CA, PEG, and starch. During the melt-blending process, the CA with abundant carboxyl groups reacted in the amorphous region of the starch. The shape and crystal form of the starch did not change, but the surface activity of the starch improved and consequently increased the adhesion between starch and PLA. As a plasticizer for PLA and starch, PEG effectively enhanced the mobility of the molecular chains. After PEG was dispersed, it participated in the esterification reaction of CA and starch at the interface and formed a branched/crosslinked copolymer that was embedded in the interface of PLA and starch. This copolymer further improved the compatibility of the PLA/starch blends. PEGs with small molecules and CA were used as compatibilizers to reduce the effect on PLA biodegradability. The esterification reaction on the starch surface improved the compatibilization and toughness of the PLA/starch blend materials and broadens their application prospects in the fields of medicine and high-fill packaging.

**Keywords:** poly(lactic acid); starch; reactive blending; plasticization; compatibilization
