Copolyester toughened poly(lactic acid) biodegradable material prepared by in situ formation of polyethylene glycol and citric acid.

Polylactic acid (PLA) is a high-modulus, high-strength bio-based thermoplastic polyester with good biodegradability, which is currently a promising environmentally friendly material. However, its inherent brittleness has hindered its widespread use. In this study, we reported a simple and non-toxic strategy for toughening PLA, using biodegradable materials such as polyethylene glycol (PEG) and citric acid (CA) as precursors. Through reactive melt blending with PLA, PEG and CA form PEGCA copolyesters in situ during blending. At the same time, CA can react with PLA and PEG, forming a copolyester structure at the interface of the two phases, improving the interfacial compatibility between PEG and PEGCA with PLA. Fourier transform infrared spectroscopy confirms this. Experimental results show that when the content of PEG/CA reaches 15% (PLA/PEG/CA-15%) in the blends, the impact strength of the blend was 4.47 kJ m-2, and the maximum elongation at break was as high as 360.1%, which were about 2 and 44 times higher than those of pure PLA, respectively. Moreover, the tensile strength was still maintained at the level of 70%. This work can expand the application of PLA in food packaging and medical supplies.

Strong synergistic toughening and compatibilization enhancement of carbon nanotubes and multi-functional epoxy compatibilizer in high toughened polylactic acid (PLA)/poly (butylene adipate-co-terephthalate) (PBAT) blends.

Different carbon nanotubes (CNTs) contents on high-toughness polylactic acid (PLA)/poly (butylene adipate-co-terephthalate) (PBAT) blends were prepared by one-step melt blending using multifunctional epoxy oligomers (ADR) as reactive compatibilizer. During reactive blending, the PLA or PBAT chains were grafted onto the CNTs by allowing the carboxyl or hydroxyl groups to react with epoxy groups and form a branched CNTs-based copolymer. The branched copolymer at the interface between PLA and PBAT was dispersed through emulsion to improve the polymer-polymer or polymer-nanoparticle entanglement between the molecular chains. Interfacial adhesion, interface layer stability, and system viscoelasticity and compatibility were improved as indicated by rheological curves and dynamic mechanical analysis. The strength and toughness of the sample were simultaneously improved by the addition of CNTs and ADR. The impact strength reached 35.3 kJ/m2, which was approximately 7 times that of the PLA/PBAT blend, and the tensile strength was also increased from 33.6 MPa to 42.8 MPa. The properties of PLA/PBAT blend synergistically modified by ADR and CNTs were obviously better than those of PLA/PBAT blend modified by ADR or CNTs. The toughening synergistic effect of ADR and CNTs on PLA/PBAT was observed with efficiency reaching 3.05. With the further understanding of the toughening mechanism, the branched CNTs-based copolymers and CNTs clusters induce a synergistic effect, which increased the interfacial adhesion and ability of energy dissipation and stress transmission.

Crystallization behaviors regulations and mechanical performances enhancement approaches of polylactic acid (PLA) biodegradable materials modified by organic nucleating agents.

Polylactic acid (PLA) has attracted much attention because of its good biocompatibility, biodegradability, and mechanical properties. However, the slow crystallization rate of PLA during molding leads to its poor heat resistance, which limit its diffusion for many industrial applications. In this review, the relationship between PLA crystallization and its molecular structure and processing conditions is summarized. From the perspective of the regulation of PLA crystallization by organic nucleating agents, the research progress of organic micromolecule (e.g., esters, amides, and hydrazides), organic salt, supramolecular, and macromolecule nucleating agents on the crystallization behavior of PLA is mainly introduced. The nucleation mechanism of PLA is expounded by organic nucleating agents, and the effect of the interaction force between organic nucleating agents and PLA molecular chains on the crystallization behavior of PLA is analyzed. The effects of the crystallization behavior of PLA on its mechanical properties and heat resistance are discussed. It will provide a theoretical reference for the development and application of high-efficiency nucleating agents.

Effect of maleic anhydride grafted poly(lactic acid) on rheological behaviors and mechanical performance of poly(lactic acid)/poly(ethylene glycol) (PLA/PEG) blends.

A series of polylactic acid (PLA)/polyethylene glycol (PEG) blends was prepared by melt blending using PEG as a plasticizer to address the disadvantages of PLA brittleness. PEG can weaken the intermolecular chain interactions of PLA and improve its processing properties. PLA-grafted maleic anhydride (GPLA) was reactively blended with PLA/PEG to obtain a high tenacity PLA/PEG/GPLA blend. GPLA was prepared by melt grafting using diisopropyl peroxide as the initiator and maleic anhydride as the graft. The effects of different PEG molecular weights (1000-10 000 g mol-1) on the properties of PLA/PEG/GPLA blends were investigated. GPLA reacted with PEG1000 (M w = 1000 g mol-1) to form short PLA branched chains and reacted with PEG10000 (M w = 10 000 g mol-1) to form a small number of PLA branched chains, which was unconducive to increasing the intermolecular chain entanglement. The branched PLA formed by the reaction between PEG6000 (M w = 6000 g mol-1) and GPLA had a remarkable effect on increasing intermolecular chain entanglement. The complex viscosity, modulus, and melt strength values of PLA/PEG6000/GPLA blends were relatively large. The elongation at break of the blends reached 526.9%, and the tensile strength was 30.91 MPa. It provides an effective way to prepare PLA materials with excellent comprehensive properties.

Strategies and techniques for improving heat resistance and mechanical performances of poly(lactic acid) (PLA) biodegradable materials.

Poly(lactic acid) (PLA) has attracted much attention as a substitute for petroleum-based plastics, but its low heat resistance limits its application range in packaging fields and disposable products. This paper summarizes the structural factors affecting the heat resistance of PLA and systematically summarizes methods to improve its heat resistance. PLA is a semi-crystalline polymer, and crystallinity, crystal size, and other factors are important factors affecting heat resistance. This paper systematically analyzes the means to control the crystallization behavior of PLA, and summarizes the effects of nucleating agents, cross-linking, grafting, and annealing processes on the crystallization behavior and heat resistance of PLA. The effects of PLA molecular chain cross-linking and grafting on the motility of PLA molecular chains and the heat resistance of PLA materials are further discussed from the perspective of PLA molecular chain segment movement. The research work on combining PLA with reinforcements such as high heat-resistant polymer materials, fiber, and nanoparticles to improve the mechanical properties and heat resistance of PLA by introducing rigid groups or structures is described in detail. Improving the heat resistance of PLA material is an important strategy to promote the application of biodegradable materials, and has broad research value and application prospects.

Recent progress of preparation of branched poly(lactic acid) and its application in the modification of polylactic acid materials.

Poly (lactic acid) (PLA) with branched structure has abundant terminal groups, high melt strength, good rheological properties, and excellent processability; it is a new research and application direction of PLA materials. This study mainly summarizes the molecular structure design, preparation methods, basic properties of branched PLA, and its application in modified PLA materials. The structure and properties of branched PLA prepared by ring-opening polymerization of monomer, functional group polycondensation, and chain extender in the processing process were introduced. The research progress of in situ formation of branched PLA by initiators, multifunctional monomers/additives through dynamic vulcanization, and irradiation induction was described. The effect of branched PLA on the structure and properties of linear PLA materials was analyzed. The role of branched PLA in improving the crystallization behavior, phase morphology, foaming properties, and mechanical properties of linear PLA materials was discussed. At the same time, its research progress in biomedicine and tissue engineering was analyzed. Branched PLA has excellent compatibility with PLA, which has important research value in regulating the structure and properties of PLA materials.

High-Toughness Poly(Lactic Acid)/Starch Blends Prepared through Reactive Blending Plasticization and Compatibilization.

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-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.

Super tough poly(lactic acid) blends: a comprehensive review.

Poly(lactic acid) or poly(lactide) (PLA) is a renewable, bio-based, and biodegradable aliphatic thermoplastic polyester that is considered a promising alternative to petrochemical-derived polymers in a wide range of commodity and engineering applications. However, PLA is inherently brittle, with less than 10% elongation at break and a relatively poor impact strength, which limit its use in some specific areas. Therefore, enhancing the toughness of PLA has been widely explored in academic and industrial fields over the last two decades. This work aims to summarize and organize the current development in super tough PLA fabricated via polymer blending. The miscibility and compatibility of PLA-based blends, and the methods and approaches for compatibilized PLA blends are briefly discussed. Recent advances in PLA modified with various polymers for improving the toughness of PLA are also summarized and elucidated systematically in this review. Various polymers used in toughening PLA are discussed and organized: elastomers, such as petroleum-based traditional polyurethanes (PUs), bio-based elastomers, and biodegradable polyester elastomers; glycidyl ester compatibilizers and their copolymers/elastomers, such as poly(ethylene-co-glycidyl methacrylate) (EGMA), poly(ethylene-n-butylene-acrylate-co-glycidyl methacrylate) (EBA-GMA); rubber; petroleum-based traditional plastics, such as PE and PP; and various biodegradable polymers, such as poly(butylene adipate-co-terephthalate) (PBAT), polycaprolactone (PCL), poly(butylene succinate) (PBS), and natural macromolecules, especially starch. The high tensile toughness and high impact strength of PLA-based blends are briefly outlined, while the super tough PLA-based blends with impact strength exceeding 50 kJ m-2 are elucidated in detail. The toughening strategies and approaches of PLA based super tough blends are summarized and analyzed. The relationship of the properties of PLA-based blends and their morphological parameters, including particle size, interparticle distance, and phase morphologies, are presented.