New insights into polylactide biodegradation from molecular ecological techniques

Molecular ecological techniques for direct identification of microbes involved in PLA degradation under aerobic composting conditions are described. Gene sequences from genera Paecilomyces, Thermomonospora, and Thermopolyspora were most abundant in the compost samples. Members of these phylogenetic lineages are therefore likely to play an important role in PLA degradation. The use of molecular ecological techniques to design cultivation strategies may also provide a new tool for identification and investigation of biodegradation mechanisms and for future development of efficient biological treatment or recycling processes for PLA and other biodegradable polymers.     

Biodegradable Polylactide and Its Nanocomposites: Opening a New Dimension for Plastics and Composites

The academic and industrial aspects of the preparation, characterization, mechanical and materials properties, crystallization behavior, melt rheology, and foam processing of pure polylactide (PLA) and PLA/layered silicate nanocomposites are described in this feature article. Recently, these materials have attracted considerable interest in polymer science research. PLA is linear aliphatic thermoplastic polyester and is made from agricultural products. Hectorite and montmorillonite are among the most commonly used smectite‐type layered silicates for the preparation of nanocomposites. Smectites are a valuable mineral class for industrial applications because of their high cation exchange capacities, surface area, surface reactivity, adsorptive properties, and, in the case of hectorite, high viscosity, and transparency in solution. In their pristine form, they are hydrophilic in nature, and this property makes them very difficult to disperse into a polymer matrix. The most common way to overcome this difficulty is to replace interlayer cations with quaternized ammonium or phosphonium cations, preferably with long alkyl chains. In general, polymer/layered silicate nanocomposites are of three different types: (1) intercalated nanocomposites, in which insertion of polymer chains into the layered silicate structure occurs in a crystallographically regular fashion, regardless of polymer to layered silicate ratio, with a repeat distance of few nanometer; (2) flocculated nanocomposites, in which intercalated and stacked silicate layers are sometimes flocculated due to the hydroxylated edge–edge interactions between the silicate layers; (3) exfoliated nanocomposites, in which individual silicate layers are uniformly distributed in the polymer matrix by average distances that totally depend on the layered silicate loading. This new family of composite materials frequently exhibits remarkable improvements in its material properties when compared with those of virgin PLA. Improved properties can include a high storage modulus both in the solid and melt states, increased flexural properties, a decrease in gas permeability, increased heat distortion temperature, an increase in the rate of biodegradability of pure PLA, and so forth.

Illustration of the biodegradability of PLA and various nanocomposites.     

Exfoliated Polylactide/Clay Nanocomposites by In‐Situ Coordination–Insertion Polymerization

Poly(L ‐lactide)/layered aluminosilicate nanocomposites were synthesized in bulk by ring‐opening polymerization in the presence of two organo‐modified montmorillonites. When the organo‐modifier consisted of an ammonium cation bearing primary hydroxyl groups, polymerization was initiated by the alcohol functions after adequate activation. The growing polymer chains were directly “grafted” onto the clay surface through the hydroxyl‐functionalized ammonium cations yielding exfoliated nanocomposites with enhanced thermal stability.

TEM image of a fully exfoliated Cloisite®30B‐based nanocomposite, showing delamination of the silicate layers.     

Formation and Detection of Clay Network Structure in Poly(propylene)/Layered Silicate Nanocomposites

Summary: The study of the structure and the rheological properties of poly(propylene) (PP)/montmorillonite (MMT)/maleinated PP (MAPP) composites strongly suggests that a silicate network may form under certain conditions. Network formation could not be proven unambiguously with the usual techniques, i.e., with TEM and by plotting the frequency dependence of viscoelastic properties. Cole‐Cole plots detect the network very sensitively. A certain number of silicate layers are needed to create a house‐of‐cards structure. A threshold concentration of MAPP exists in the investigated system, which depends on the silicate content.

Cole‐Cole representation of the viscoelastic properties of PP/OMMT/MAPP nanocomposites.     

Organically Modified Layered Titanate: A New Nanofiller to Improve the Performance of Biodegradable Polylactide

Summary: The preparation and characterization of a new type of nanocomposite material that is based on biodegradable polylactide (PLA) and organically modified layered titanate, is reported. Layered titanate, modified with a N‐(cocoalkyl)‐N,N‐[bis(2‐hydroxyethyl)]‐N‐methylammonium cation, was used as a new nanofiller (OHTO) for the nanocomposite preparation. Wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) analyses confirmed that titanate layers were intercalated and nicely distributed in the PLA matrix. The materials properties of neat PLA improved remarkably after nanocomposite preparation.

UV/vis transmission spectra of neat PLA and a nanocomposite.     

Poly Lactic Acid (PLA) Nanocomposites: Effect of Inorganic Nanoparticles Reinforcement on Its Performance and Food Packaging Applications

Poly lactic acid (PLA) is a compostable, as well as recyclable, sustainable, versatile and environmentally friendly alternative, because the monomer of PLA-lactide (LA) is extracted from natural sources. PLA’s techno-functional properties are fairly similar to fossil-based polymers; however, in pristine state, its brittleness and delicacy during processing pose challenges to its potential exploitation in diverse food packaging applications. PLA is, therefore, re-engineered to improve its thermal, rheological, barrier and mechanical properties through nanoparticle (NP) reinforcement. This review summarises the studies on PLA-based nanocomposites (PLA NCs) developed by reinforcing inorganic metal/metallic oxide, graphite and silica-based nanoparticles (NPs) that exhibit remarkable improvement in terms of storage modulus, tensile strength, crystallinity, glass transition temperature (Tg) value, antimicrobial property and a decrease in water vapour and oxygen permeability when compared with the pristine PLA films. This review has also discussed the regulations around the use of metal oxide-based NPs in food packaging, PLA NC biodegradability and their applications in food systems. The industrial acceptance of NCs shows highly promising perspectives for the replacement of traditional petrochemical-based polymers currently being used for food packaging.     

Improving the Thermal Behavior and Flame-Retardant Properties of Poly(o-anisidine)/MMT Nanocomposites Incorporated with Poly(o-anisidine) and Clay Nanofiller

The synthesis of MMT and poly(o-anisidine) (MMT/POA) clay nanocomposites was carried out by using the chemical oxidative polymerization of POA and MMT clay with POA, respectively. By maintaining the constant concentration of POA, different percentage loads of MMT clay were used to determine the effect of MMT clay on the properties of POA. The interaction between POA and MMT clay was investigated by FTIR spectroscopy, and, to reveal the complete compactness and homogeneous distribution of MMT clay in POA, were assessed by using scanning-electron-microscope (SEM) analysis. The UV–visible spectrum was studied for the optical and absorbance properties of MMT/POA ceramic nanocomposites. Furthermore, the horizontal burning test (HBT) demonstrated that clay nanofillers inhibit POA combustion.     

聚乳酸与聚丙撑碳酸酯共混体系的性能

采用熔融共混的方法制备了聚乳酸(PLA)/聚丙撑碳酸酯(PPC)共混物。DSC测试结果表明,纯PLA和PPC的玻璃化转变温度分别为54和37℃,不同组成的PLA/PPC共混物有2个明显的玻璃化转变温度,且与纯PLA和PPC的玻璃化转变温度相对应,说明二者是不相容体系。力学测试结果表明,当PPC质量分数超过20%时,可以看到明显的屈服点。共混物在拉伸过程中也有明显的颈缩、应力发白现象,表明随着PPC含量增加,PLA/PPC共混物由典型的脆性断裂向韧性转变。随着PPC含量的增加,共混物模量降低,断裂伸长率增加,当PPC质量分数为50%时,共混物的断裂伸长率达到最大值62%。共混物的粘度可在很宽的范围内予以调控,以满足不同加工的需要。     

Effect of Organoclays on Silicate Layer Structures and Thermal Stabilities of in-situ Polymerized Poly(D-lactide)/Clay Nanocomposites

Six kinds of organoclays were prepared through three kinds of polyols (PTMG, PEA and PCL) to investigate the effects of molecular weight and the chemical structure of organifiers. PTMG based organoclays showed higher ion-exchanged fraction than other organoclays and long chain organifier showed better efficiency in ion-exchanged fraction in the case of PTMG based organifiers. From WAXD and TEM analysis, it was confirmed that PTMG based organoclays formed partially exfoliated or fully exfoliated silicate layer structures. PDLA/clay nanocomposites were prepared by in-situ ring-opening polymerization of D-lactide with PTMG based organoclays as macro-initiators in the presence of equimolar Sn(Oct)₂/PPh₃ complex catalysts. The molecular weight of PDLA/clay nanocomposite decreased as increasing the feeding amount of organoclay because organoclay had hydroxyl terminal groups which can initiate the ring-opening polymerization of D-lactide. From TGA analysis, thermal stabilities of PDLA/clay nanocomposites improved with increasing organoclay content. From WAXD and TEM analysis, organoclay which was prepared by high molecular weight of PTMG based organifier was effective on the exfoliation of silicate layers in the in-situ polymerized PDLA/clay nanocomposite.     

Barrier and Mechanical Properties of Poly(caprolactone)/organoclay Nanocomposites

In this study, biodegradable poly(caprolactone) (PCL) hybrids with two types of organoclays: Cloisite 30B (30B) and Cloisite 93A (93A) have been prepared by melt mixing and their barrier performance to air permeation and mechanical properties were investigated. The hybrids of PCL/30B were found to be nanocomposites resulted from the strong interaction between organic modifier of 30B and PCL and those of PCL/93A were microcomposites. The barrier performance of PCL/30B nanocomposite film to air permeation was much more improved than pure PCL and PCL/93A microcomposites at low organoclay concentration. With the increase of organoclay content the permeability coefficient was also increased that could attributed to the extra tortuous pathway for gas permeation caused by organoclay exfoliation. The barrier behaviour of PCL/30B nanocomposites could be approximately described by a theoretical model developed for composites. The mechanical properties measurements showed that the reinforcement of organoclay 30B in nanocomposites is more significant than 93A in microcomposites. Both tensile modulus and tensile strength were increased in PCL/30B nanocomposites even at at low amount of organoclay without much loss of strain at break as compared to pure PCL. The significant improvements in both barrier and mechanical properties in PCL nanocomposites could be attributed to the fine dispersion state of organoclay 30B platelets in PCL matrix and the strong interaction between organic modifier of 30B and matrix molecules.     

Thermal and Photooxidative Degradation Behaviors of Poly(propylene)/SiO2 Nanocomposites with Various Polymer Morphologies

Photo‐ and thermal stabilities of poly(propylene) (PP)/SiO₂ nanocomposites were studied by varying the particle size of the SiO₂ nanoparticles. It was found that smaller SiO₂ nanoparticles improved the stabilities of the nanocomposites by depressing the size of spherulites. The phenomenon was successfully explained within the infectious spreading model, where the spatial spreading of oxidation was delayed at the interfacial region between the spherulites.

     

New insight into the crystallization behavior of poly(ethylene terephthalate)/clay nanocomposites

Crystallization behavior of poly(ethylene terephthalate) (PET)/clay nanocomposites has been investigated in terms of differential scanning calorimeter (DSC) analysis, polarizing optical microscopy (POM), and scanning electron microscopy (SEM) observation. The nanocomposites for investigation were prepared via in situ polycondensation. Crystalline morphologies were observed through POM and SEM. The nonisothermal and isothermal crystallization rates of different samples were determined for comparison based on DSC data. Secondary nucleation analysis was also performed based on bulk crystallization data derived from DSC analysis. The results revealed that nucleating abilities of montmorillonites (MMT) depended on the dispersion state of clay in matrix, the surface modification status, and the metallic derivatives released from MMT during in situ synthesis. The quantities of metallic elements released were measured by inductively coupled plasma (ICP) analysis. The results showed that the release of these metallic derivatives was also affected by surfactant molecules anchored on the surface of MMT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2380–2394, 2008     

Revisiting Non-Conventional Crystallinity-Induced Effects on Molecular Mobility in Sustainable Diblock Copolymers of Poly(propylene adipate) and Polylactide

This work deals with molecular mobility in renewable block copolymers based on polylactide (PLA) and poly(propylene adipate) (PPAd). In particular, we assess non-trivial effects on the mobility arising from the implementation of crystallization. Differential scanning calorimetry, polarized light microscopy and broadband dielectric spectroscopy were employed in combination for this study. The materials were subjected to various thermal treatments aiming at the manipulation of crystallization, namely, fast and slow cooling, isothermal melt- and cold-crystallization. Subsequently, we evaluated the changes recorded in the overall thermal behavior, semicrystalline morphology and molecular mobility (segmental and local). The molecular dynamics map for neat PPAd is presented here for the first time. Unexpectedly, the glass transition temperature, T_g, in the amorphous state drops upon crystallization by 8–50 K. The drop becomes stronger with the increase in the PPAd fraction. Compared to the amorphous state, crystallization leads to significantly faster segmental dynamics with severely suppressed cooperativity. For the PLA/PPAd copolymers, the effects are systematically stronger in the cold- as compared to the melt-crystallization, whereas the opposite happens for neat PLA. The local β_PLA relaxation of PLA was, interestingly, recorded to almost vanish upon crystallization. This suggests that the corresponding molecular groups (carbonyl) are strongly involved and immobilized within the semicrystalline regions. The overall results suggest the involvement of either spatial nanoconfinement imposed on the mobile chains within the inter-crystal amorphous areas and/or a crystallization-driven effect of nanophase separation. The latter phase separation seems to be at the origins of the significant discrepancy recorded between the calorimetric and dielectric recordings on T_g in the copolymers. Once again, compared to more conventional techniques such as calorimetry, dielectric spectroscopy was proved a powerful and quite sensitive tool in recording such effects as well as in providing indirect indications for the polymer chains’ topology.     

Thermal Properties of Poly(L-lactide)/Calcium Carbonate Nanocomposites

Summary: Thermal properties of nanocomposites prepared of poly(L-lactide) (PLLA) and CaCO₃ applying differential scanning (DSC) calorimetry and thermogravimetry (TG) were studied. Nanocomposites were prepared by extrusion process at 170 °C. DSC measurements show that CaCO₃ has no influence on glass transition and melting point of PLLA but lowers its cold crystallization temperature. There is no difference in glass transition temperature of PLLA before and after extrusion. High temperature thermal stability of the PLLA in the composites is poorer than neat PLLA. Kinetic parameters also indicate greater reactivity of the system upon CaCO₃ addition.     

High‐Performance Exfoliated Poly(propylene)/Clay Nanocomposites by In Situ Polymerization with a Novel Z–N/Clay Compound Catalyst

Highly exfoliated poly(propylene) (PP)/clay nanocomposites with obvious improvements in both the tensile strength and toughness have been prepared by a novel TiCl₄/MgCl₂/imidazolium‐modified montmorillonite (IOHMMT) compound catalysts. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with a high isotacticity and molecular weight, but also to a highly exfoliated structure even at high clay content levels (as high as 19 wt.‐%).

     

Insight into industrial PLA aging process by complementary use of rheology,HPLC, and MALDI

Nowadays, there is a growing availability of biodegradable industrial materials intended to food contact applications whose service life behavior needs to be further investigated. This article is focused on the degradation of two materials based on polylactic acid. The correlation between the rate of degradation and the amount of trapped degradation products was investigated applying three characterization techniques in parallel, namely rheology, high‐performance liquid chromatography (HPLC), and matrix‐assisted laser desorption/ionization (MALDI). The rate of degradation was studied through the evaluation of their rheological properties and calculation of the number of average molecular weights, and weight‐average molecular weights. Water‐soluble oligomers and lactic acid were quantified by HPLC‐ultraviolet. Changes in cyclic and linear oligomers were monitored by MALDI‐time‐of‐flight mass spectrometry. Specimens of 4‐mm thickness of each biopolymer were subjected to hydrolysis in deionized water up to 6 months at two temperatures, simulating service conditions of food packaging. The diminution in viscosity and consequently in molecular weight distribution (20–60%) showed the degradation of the molecular structure of both polylactic acids. The chain scission was followed through the increasing values of lactic acid and hydrolyzed oligomers (twofold to eightfold), and the predominant signal of the linear oligomers over the cyclic ones with aging. Rheology, HPLC, and MALDI showed to be complementary tools to better understand the changes in the molecular structure. The obtained results showed the necessity of adding suitable stabilizers for each particular food packaging application. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Synthesis and characterization of poly(ethylene oxide)/polylactide/poly(ethylene oxide) triblock copolymer

Poly(ethylene oxide/polylactide/poly(ethylene oxide) (PEO/PL/PEO) triblock copolymers, in which each block is connected by an ester bond, were synthesized by a coupling reaction between PL and PEO. Hydroxyl‐terminated PLs with various molecular weights were synthesized and used as hard segments. Hydroxyl‐terminated PEOs were converted to the corresponding acid halides via their acid group and used as a soft segment. Triblock copolymers were identified by Fourier transform infrared spectroscopy, ¹H NMR, and gel permeation chromatography. Differential scanning calorimetry (DSC) and X‐ray diffractometry of PEO/PL/PEO triblock copolymers suggested that PL and PEO blocks were phase‐separated and that the crystallization behavior of the PL block was markedly affected by the presence of the PEO block. PEO/PL/PEO triblock copolymers with PEO 0.75k had two exothermic peaks (by DSC), and both peaks were related to the crystallization of PL. According to thermogravimetric analysis, PEO/PL/PEO triblock copolymer showed a higher thermal stability than PL or PEO. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2545–2555, 2002     

Thermal Degradation and Kinetics of Poly(3-hydroxybutyrate)/Organoclay Nanocomposites

Poly(3-hydroxybutyrate)/Cloisite30B (PHB/30B) nanocomposites were prepared by solution-intercalation method. The influence of 30B content on the thermal stability of PHB was investigated. With the addition of 3 wt. % of 30B the highest thermal stability of PHB was achieved. The kinetic analysis of the non-isothermal degradation was performed using the isoconversional Friedman method and invariant kinetic parameters method.