Adding Value in Production of Multifunctional Polylactide (PLA)–ZnO Nanocomposite Films through Alternative Manufacturing Methods

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites.     

Effect of polyethylene glycol on the crystallization and impact properties of polylactide‐based blends

Polylactide (PLA) was plasticized by polyethylene glycols (PEGs) with five different molecular weights (M_w = 200–20,000 g/mol). The effects of content and molecular weight of PEG on the crystallization and impact properties of PLA were studied by wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and V‐notched impact tests, respectively. The results revealed that PEG‐10,000 could significantly improve the crystallization capacity and impact toughness of PLA. When the PEG‐10,000 content ranged from 0 to 20 wt%, the increases in both V‐notched Izod and Charpy impact strengths of PLA/PEG‐10,000 blends were 206.10% and 137.25%, respectively. Meanwhile, the crystallinity of PLA/PEG‐10,000 blends increased from 3.95% to 43.42%. For 10 wt% PEG content, the crystallization and impact properties of PLA/PEG blends mainly depended upon PEG molecular weight. With increasing the M_w of PEG, the crystallinity and impact strength of PLA/PEG blends first decreased and then increased. The introduction of PEG reduced the intermolecular force and enhanced the mobility of PLA chains, thus improving the crystallization capacity and flexibility of PLA. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation of Bottlebrush Polymers via a One‐Pot Ring‐Opening Polymerization (ROP) and Ring‐Opening Metathesis Polymerization (ROMP) Grafting‐Through Strategy

Bottlebrush polymers are synthesized using a tandem ring‐opening polymerization (ROP) and ring‐opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well‐defined bottlebrush polymers with molecular weights in excess of 10⁶ Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d ,l ‐lactide initiated by an alcohol‐functionalized norbornene. ROMP grafting‐through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size‐exclusion chromatographic and ¹H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain‐free transmission electron microscopy on graphene oxide.

     

Chemical modification of poly(lactic acid) induced by thermal decomposition of N‐acetoxy‐phthalimide during extrusion

Chemical modification of poly(lactic acid) (PLA) with N‐acetoxy‐phthalimide (NAPI) was performed in the melt by reactive extrusion, without using any peroxide initiator. The aminyl and nitroxide radicals produced from the NAPI thermal degradation, were, respectively, used (a) to create PLA macroradicals, and (b) to functionalize the PLA samples through nitroxide radical coupling. Depending on the extrusion temperature and the initial NAPI concentration, grafting rates up to 0.24 mol % were measured, modifying the PLA optical properties. This study represents an original new way of modification of PLA without the use of conventional peroxide initiators. Indeed, the undesirable side reactions (PLA branching or crosslinking) usually observed when using peroxides to initiate the radical grafting of PLA were avoided when using NAPI. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 120–129     

Polymerization of lactide and synthesis of block copolymer catalyzed by copper(Ⅱ) Schiff base complex

In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization (ROP) of lactide and block polymerization of poly(lactide) with poly(ethylene glycol)methyl ether.     

Biosynthesis of a lactate (LA)-based polyester with a 96 mol% LA fraction and its application to stereocomplex formation

A poly(lactic acid) (PLA)-like terpolyester consisting of 96 mol% lactate (LA), 1 mol% 3-hydroxybutyrate and 3 mol% 3-hydroxyvalerate was produced in recombinant Escherichia coli LS5218 expressing LA-polymerizing enzyme (LPE). The strain was grown on glucose with a feeding of valerate as the monomer precursor. The glass transition and melting temperatures of the terpolyester were close to those of chemically synthesized poly(L-LA)s (PLLAs) having similar molecular weights. Additionally, a blend of the terpolyester, which was composed entirely of (R)-LA (D-LA) due to the strict enantiospecificity of LPE, with PLLA formed a stereocomplex with higher melting temperature (201.9 °C). These results indicate that the biological PLA-like polyester produced via this one-step microbial process has comparable thermal properties to chemically synthesized PLAs.     

Polyaspartamide–Polylactide Graft Copolymers with Tunable Properties for the Realization of Fluorescent Nanoparticles for Imaging

Here, the synthesis and the characterization of novel amphiphilic graft copolymers with tunable properties, useful in obtaining polymeric fluorescent nanoparticles for application in imaging, are described. These copolymers are obtained by chemical conjugation of rhodamine B (RhB) moieties, polylactic acid (PLA), and O‐(2‐aminoethyl)‐O′‐methyl poly(ethylene glycol) (PEG) on α,β‐poly(N‐2‐hydroxyethyl)‐d,l ‐aspartamide (PHEA). In particular, PHEA is first functionalized with RhB to obtain PHEA–RhB with a derivatization degree in RhB (DD_RhB) equal to 0.55 mol%. By varying the reaction conditions, different amounts of PLA are grafted on PHEA–RhB to obtain PHEA‐RhB‐PLA with DD_PLA equal to 1.9, 4.0, and 6.2 mol%. Then, PEG chains are grafted on PHEA‐RhB‐PLA derivatives to obtain PHEA‐RhB‐PLA‐PEG graft copolymers. The preparation of polymeric fluorescent nanoparticles with tunable properties and spherical shape is described by using PHEA‐RhB‐PLA‐PEG with DD in PLA and PEG equal to 4.0 and 4.9 mol%, by following easily scaling up processes, such as emulsion‐solvent evaporation and high pressure homogenization (HPH)‐solvent evaporation techniques.

     

Dimensional considerations on the mechanical properties of 3D printed polymer parts

Additive manufacturing offers a useful and accessible tool for prototyping and manufacturing small volume functional parts. Polylactic acid (PLA) and thermoplastic polyurethane (TPU) are amongst the most commonly used materials. Characterising 3D printed PLA and TPU is potentially important for both designing and finite element modelling of functional parts. This work explores the mechanical properties of additively manufactured PLA/TPU specimens with consideration to design parameters including size, and infill percentage. PLA/TPU specimens are 3D-printed in selected ISO standard geometries with 20%, 60%, 100% infill percentage. Tensile and compression test results suggest that traditional ISO testing standards might be insufficient in characterising 3D printed materials for finite element modelling or application purposes. Infill percentage in combination to design size, may significantly affect the mechanical performance of 3D printed parts. Dimensional variation may cause inhomogeneity in mechanical properties between large and small cross section areas of the same part. The effect was reduced in small cross section parts where reducing the nominal infill had less effect on the resulting specimens. The results suggest that for 3D printed functional parts with significant dimensional differences between sections, the material properties are not necessarily homogeneous. This consideration may be significant for designers using 3D printing for applications, which include mechanical loading.     

Nanoperlite effect on thermal,rheological, surface and cellular properties of poly lactic acid/nanoperlite nanocomposites for multipurpose applications

In this study, poly lactic acid (PLA) based nanocomposites containing perlite nanoparticles were prepared by melt mixing method. Various characterization techniques were employed to evaluate the performance PLA/nanoperlite nanocomposites. The nanocomposites were characterized via FTIR to investigate the functional groups and chemical structure of the nanocomposites. Thermal properties of the nanocomposites, examined by DSC, showed that the increase of nano-perlite content in the PLA matrix reduces the crystallinity and melting temperature of the nanocomposites. The rheological studies indicated that both of storage and loss modulus are increased when the nanoperlite is added up to 5 wt%. However, the modulus is reduced in samples containing more than 5 wt% nanoparticle due to their agglomeration. The in-vitro degradation studies of the nanocomposites at elevated and normal temperatures showed hydrolytic degradation around 13–15 months. The surface behavior results implied that the water contact angle values exhibit a reducing trend when the nanoperlite content increases up to 3 wt%, which can be related to the decreased crystallinity of PLA and also to the hydrophilic nature of perlite. Moreover, the adhesion of osteoblast cells and their viability on an electrospun scaffold, made of optimized sample, showed the initial implications of potential applications of the nanocomposites in bone regeneration and biomedical applications. These multipurpose nanocomposites can also be used for packaging applications.     

3D printed polylactic acid nanocomposite scaffolds for tissue engineering applications

In this study, biodegradable polylactic acid (PLA) and PLA nanocomposite scaffolds reinforced with magnetic and conductive fillers, were processed via fused filament fabrication additive manufacturing and their bioactivity and biodegradation characteristics were examined. Porous 3D architectures with 50% bulk porosity were 3D printed, and their physicochemical properties were evaluated. Thermal analysis confirmed the presence of ~18 wt% of carbon nanostructures (CNF and GNP; nowonwards CNF) and ~37 wt% of magnetic iron oxide (Fe₂O₃) particles in the filaments. The in vitro degradation tests of scaffolds showed porous and fractured struts after 2 and 4 weeks of immersion in DMEM respectively, although a negligible weight loss is observed. Greater extent of degradation is observed in PLA with magnetic fillers followed by PLA with conductive fillers and neat PLA. In vitro bioactivity study of scaffolds indicate enhancement from ~2.9% (PLA) to ~5.32% (PLA/CNF) and ~ 3.12% (PLA/Fe₂O₃). Stiffness calculated from the compression tests showed decrease from ~680 MPa (PLA) to 533 MPa and 425 MPa for PLA/CNF and PLA/Fe₂O₃ respectively. Enhanced bioactivity and faster biodegradation response of PLA nanocomposites with conductive fillers make them a potential candidate for tissue engineering applications such as scaffold bone replacement and regeneration.