Kinetics of Hydrolytic Degradation of PLA

The chemical recycling of poly(lactic acid) (PLA) to its monomer is crucial to reduce both the consumption of renewable resources for the monomer synthesis and the environmental impact related to its production and disposal. In particular, the production of lactic acid from PLA wastes, rather than from virgin raw materials, it is also possible to achieve considerable primary energy savings. The focus of this work is to analyse deeply the PLA hydrolytic decomposition by means of a kinetic model based on two reactions mechanism. To this end, new experimental data have been gathered in order to investigate a wider temperature range (from 140 to 180 °C) and to extend the water/PLA ratio up to 50 % of PLA by weight. The reported results clearly highlight that more than 95 % of PLA is hydrolyzed to water-soluble lactic acid within 120 min, when it is hydrolyzed within 160–180 °C. Furthermore, the kinetic constant is highly influenced by reaction temperature. The proposed “two reactions” kinetic mechanism complies satisfactorily with the experimental data under analysis.     

Degradation of Post-consumer PLA: Hydrolysis of Polymeric Matrix and Oligomers Stabilization in Aqueous Phase

Degradation of post-consumer PLA to lactic acid was analysed in order to assess the economic feasibility of the PLA chemical recycling process. Hydrolysis of PLA, in batch reactor, was analysed in the temperature range of 443–473 K, under autogenous pressure and a constant PLA to water ratio (equal to approximately 0.11 by weight), without the use of a catalyst. The experimental results suggest that the complete degradation of PLA can be obtained using relatively low reaction-times with the production of a mixture containing the monomer and traces of the dimer of lactic acid. The overall process was modelled using a two-step process: bulk degradation of PLA (in the solid or molten phase) with the solubilisation of low molecular weight oligomers, and their subsequent hydrolysis in water (stabilization). The model describes the trend of oligomer concentrations in the aqueous phase and PLA conversion as a function of time with both high accuracy and agreement with experimental results.     

Lactic Acid Production by Hydrolysis of Poly(Lactic Acid) in Aqueous Solutions: An Experimental and Kinetic Study

Poly(lactic acid) (PLA) is increasingly utilized as an alternative to petroleum-based polymers in order to reduce their impact on the environment. The monomer of PLA is mainly produced from corn, which, in addition to its food utilization, can be also used for the production of bioethanol or biofuels. In this work the depolymerization (chemical recycling) of PLA pellets in a batch reactor at temperatures near the melting temperature of solid PLA has been investigated to produce lactic acid. New experimental data are presented and a kinetic model is provided for a first analysis. With a residence time less than 120 min, a yield of lactic acid greater than 95 % has been obtained at temperatures of 160 and 180 °C for pressure equal to water vapour pressure and a water/PLA ratio by weight equal ~10.     

Life Cycle Assessment of Poly(Lactic Acid) (PLA): Comparison Between Chemical Recycling,Mechanical Recycling and Composting

This paper presents a life cycle assessment (LCA) comparing three forms of poly(lactic acid) (PLA) disposal: mechanical recycling, chemical recycling and composting. The LCA data was taken from lab scale experiments for composting and hydrolysis steps. Polymerization data in chemical recycling was obtained from computer simulation. Mechanical recycling data from lab scale were combined with the data from a plastics commercial mechanical recycling plant. The analysis considered two different product systems based on the input of the recycled PLA in the product system. Considering the categories: climate change, human toxicity and fossil depletion, the LCA showed that mechanical recycling presented the lowest environmental impact, followed by chemical recycling and composting. Among the forms of recycling, the most important input was the electricity consumption.     

Removal of inorganic colour pigments from acrylonitrile butadiene styrene by dissolution-based recycling

Reinserting thermoplastic industrial scrap materials back into the production process must be feasible and cost-effective. Unfortunately, many thermoplastic materials contain colour pigments that cause undesired colour effects and, therefore, have to be removed before recycling. The purpose of this study was to reduce the inorganic colour pigments titanium dioxide, chromium(III) oxide and iron(III) oxide from acrylonitrile butadiene styrene. Based on experiences with dissolution-based polymer recycling, the two methods for removing these colour pigments studied in this project were filtration and centrifugation. Multiple laboratory-scale experiments were performed with two solvent formulations, acetone and CreaSolv^? SB. Using the filtration method, both solvent formulations achieved reduction rates of 80% for titanium and iron and 90% for chromium. While similar reduction rates were obtained with high-speed laboratory-type centrifuges for acetone solutions, the results for CreaSolv^? SB solutions were considerably lower under the same experimental conditions. Increasing the temperature or centrifugation speed, however, will also increase the reduction rates. Thereby, CreaSolv^? SB solutions become suitable for industrial-scale processes. This is important because industrial processes based on CreaSolv^? SB solutions are significantly safer than acetone-based processes.     

Chemical Recycling of PLA: A Great Opportunity Towards the Sustainable Development?

This work aims at analyzing the energy efficiency of the chemical recycling process of polylactic acid (PLA) and its sustainability from an environmental point of view. The results show that the production of lactic acid from chemical depolymerization of PLA is preferable, from an energy point of view, to the production of lactic acid by glucose fermentation. The study also shows that the environmental footprint of the analyzed process is larger than that of the PLA mechanical recycling.     

Dispersing Bacterial Cellulose Nanowhiskers in Polylactides via Electrohydrodynamic Processing

In the present study, hybrid electrospun polylactide (PLA) fibers reinforced with highly dispersed crystalline bacterial cellulose nanowhiskers (BCNW) in solution concentrations up to 15 wt% were developed and characterized. The overall aim was to encapsulate dispersed BCNW in fibers to be later re-dispersed in virgin PLA by melt compounding. Initially, the suitability of three different solvents [1,1,1,3,3,3-hexafluoro-2-propanol (HFP), acetone–chloroform and chloroform/polyethylene glycol (PEG)] for fiber production was evaluated and solutions containing 5 wt% BCNW were used to generate electrospun hybrid PLA fibers. These fibers presented a homogeneous morphology, as assessed by scanning electron microscopy, and transmission electron microscopy images demonstrated that BCNW were well distributed along the fibers. Differential scanning calorimetry analyses showed that the incorporation of PEG into the fibers resulted in a T_g drop due to a plasticization effect and decreased thermal stability as a result of low interactions between the matrix and the BCNW. Subsequently, fibers were produced from the selected solutions (HFP and acetone–chloroform) containing up to 15 wt% BCNW. As a result of the great increase in the viscosity of the solutions, lower solids contents were required, leading to a better dispersion and incorporation degree of BCNW within the fibers. HFP was found to be a more suitable solvent, since higher incorporation levels were estimated by X-ray diffraction and improved matrix–filler interactions were suggested by a slight increase in the T_g of the fibers.     

Recycling extruded polystyrene by dissolution with suitable solvents

The amount of extruded polystyrene (XPS) waste has increased in recent years due to the increase of its use in the thermal insulation of buildings, transport vehicles, and refrigerators, among others. Dissolution with suitable solvents to achieve a volume reduction of more than 100 times without degradation of polymer chains is one of the cheapest and most efficient methods of recycling XPS. Several environmentally friendly solvents have been tested as dissolution agents for XPS volume reduction; the action of these solvents does not produce any degradation of polymer chains. The solubility of the polymer in such solvents at different temperatures was investigated. The solvent can be easily recycled by distillation, obtaining a high-quality recycled polymer. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

A Comparison of Modified and Unmodified Cellulose Nanofiber Reinforced Polylactic Acid (PLA) Prepared by Twin Screw Extrusion

The goal of this work was to evaluate the effect of chemical modification of cellulose nanofibers (CNF) on the properties of polylactic acid (PLA) nanocomposites. Acetylated nanofibers (ACNF), with degree of substitution 1.07, were isolated from acetylated kenaf fibers by mechanical treatments. Acetylated nanofibers showed more hydrophobic properties compared to non-acetylated ones. The results showed that both crystallinity and thermal stability of acetylated nanofibers were lower than non-acetylated ones. The nanocomposites were prepared by premixing two PLA master batches, one with a high concentration of ACNF and the second with CNF. These were diluted to final concentrations (5?wt%) during the extrusion. The morphology studies of PLA and its nanocomposites showed nanofiber aggregates in both materials. The results showed that the tensile and dynamic mechanical properties were enhanced for both acetylated and non-acetylated nanocomposites compared to the neat PLA matrix while no significant improvement was observed for the acetylated nanocomposites compared to non-acetylated ones. However, the storage modulus increased slightly for acetylated nanocomposites compared to non-acetylated ones.     

Environmental Impact Assessment of Polylactide(PLA)/Chicken Feathers Biocomposite Materials

The aim of this study is to analyse the environmental impacts (EIs) of the process of preparation of new biocomposite materials obtained from polylactide (PLA) and chicken feathers (CFs). Two CFs stabilization methods and different percentages of CFs have been studied. The EIs of these new composites were compared to the impact of virgin PLA. Cradle-to-gate life cycle inventories were assessed for 0–35% v/v of CFs in a CFs/PLA biocomposite. Two CFs stabilization processes, autoclave and surfactant, were tested and compared with the aim to prioritize one of them from the environmental point of view. A composite plate of 184?×?184?×?2.2 mm³ was defined as the functional unit. Autoclave stabilization process exhibited lower environmental impact compared with surfactant stabilization process mainly due to both the lower requirements of electricity and water and the reduced pollution loads of the generated wastewater. Thus, the autoclave process was selected as the standard method when comparing the EIs of the proposed CFs/PLA biocomposites. In this sense, the addition of CFs to PLA matrix proportionally reduces all the EIs compared to pure PLA due to the replacement of PLA with CFs. This behaviour can be explained because the PLA production accounts for the 99% of the impact of the biocomposite. Consequently, CFs conveniently stabilized might be an alternative raw material to prepare CFs/PLA biocomposites with less environmental impact compared to pure PLA.     

Chemical depolymerisation of PET complex waste: hydrolysis vs. glycolysis

The huge increase in the generation of post-consumer plastic waste has produced a growing interest in eco-efficient strategies and technologies for their appropriate management and recycling. In response to this, PROQUIPOL Project is focused on developing, optimizing and adapting feedstock recycling technologies as an alternative for management for the treatment of complex plastic waste. Among the different plastic wastes studied, PROQUIPOL Project is working on providing a suitable treatment to the highly colored and complex multilayered post-consumer waste fractions of polyethylene terephthalate (PET) by chemical depolymerisation methods. Glycolysis and alkali hydrolysis processes have been studied with the aim of promoting the transformation of PET into the bis(2-hydroxyethyl) terephthalate monomer and terephthalic acid, respectively. In both cases operational conditions such as temperature, reaction time, catalyst to PET rate and solvent to PET rate have been considered to optimize product yield, achieving values near to 90 % and monomer purities over 95 % in both processes. This paper presents results obtained for each treatment as well as a simplified comparison of technical, economic and environmental issues.     

Polylactic Acid (PLA) Biocomposites Filled with Waste Leather Buff (WLB)

A large amount of leather waste is generated from tanning industries and most of which are disposed of landfill or discharged into the natural water bodies without any treatment, causing environmental problems. The aim of this study is to develop eco-biocomposites using waste leather buff (WLB) as filler in Polylactic acid (PLA) matrix to reduce the environmental issues and provide sustainable solution. WLB/PLA composites were prepared by twins-screw micro extruder varying the WLB content from 2% to 30 wt%. These composite were extensively characterise by several techniques. Tensile properties of the composites showed addition of WLB resulted in improvement of tensile property of composite and reduction in percentage crystallinity of PLA matrix observed with increase in WLB content. The effect of WLB on properties of interfacial adhesion and dispersion in WLB/PLA composites were studied by SEM. Wettability of composites was tested by contact angle and water absorption studies. WLB/PLA composite showed increase in water absorption with WLB loading. These WLB/PLA composite could be used to develop low cost eco-friendly product material.     

PLA and Montmorilonite Nanocomposites: Properties, Biodegradation and Potential Toxicity

The concern related to solid waste increases efforts to develop products based on biodegradable materials. At present, PLA has one of the highest potentials among biopolyesters, particularly for packaging. However, its application is limited in some fields. In order to optimize PLA properties, organo-modified montmorilonites have been extensively used to obtain nanocomposites. Although PLA nanocomposites studies are widely reported in the literature, there is still few information about the influence of organoclays on de biodegradation process, which is a relevant information, since one of the main purposals related to the final disposal of biopolymers as PLA is composting. Besides, in the last years some research has been conducted in order to evaluate the potential toxicity of montmorilonite, unmodified or organo-modified. Since the use of montmorilonite is expanding in different applications, human exposure and risk assessment are important issues to be investigated. In this context, this review intends to compile available information related to common organoclays used for PLA nanocomposites, its properties, biodegradation analysis and potential toxicity evaluation of nanocomposites, focused on montmorilonite as filler. Two issues of relevance were pointed out. The first is food safety and quality, and the second consideration is the environmental effect.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Amino-Modified Halloysite Nanotubes to Reduce Polymer Degradation and Improve the Performance of Mechanically Recycled Poly(lactic acid)

From an environmental point of view, mechanical recycling is, in general, a good end-of-life option for poly(lactic acid) (PLA), one of the most important biobased polymers. However, the degradation of PLA during the service life and, especially, during the mechanical recycling process, leads to a decrease in the properties of PLA, thus reducing the applications of the recycled plastic. The main aim of this work was to study the addition of small amounts of halloysite nanotubes, during the recycling step, as the basis of a cost-effective method for improving the properties of the recycled PLA. Raw halloysite was modified with an aminosilane, and 2% by weight of both raw and modified halloysite were melt compounded with PLA previously subjected to accelerated ageing. The addition of the nanotubes led to recycled materials with improved properties because halloysite reduces the degradation of PLA by blocking the carboxyl groups, generated during the ageing and washing steps, which catalyze the degradation during the recycling process. This effect was more intense in the silanized nanotubes, because the carboxyl groups were effectively blocked by acid–base interactions with the amino groups of the chemical modification. The properties of the recycled plastic with only 2 wt% of silanized halloysite were very close to those of the virgin plastic.     

Processing scheme based on selective dissolution to recycle food packaging and other polymeric wastes and its economic analysis

This investigation proposes the development of the selective dissolution process for recycling food packaging and other polymeric wastes. This process takes into account that the specific solvent of a particular polymer which is to be separated, must be a non-solvent for the remaining polymers. Likewise, taking into account the solubility of each polymer into various solvents as well as its production costs, the order of the polymers produced can be polyvinylchloride (PVC), polypropylene (PP), polyethylene (PE), polystyrene (PS), polybutadiene (PB), polyacrylnitrile (PAN), polyesters (PES), nylon and polyurethanes (PU). However, cost analysis of the process revealed that the recycling of food packaging polymers in the order of PE, PVC, PP, and PS is more cost-effective.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Recycling of extruded polystyrene wastes by dissolution and supercritical CO2 technology

Polystyrene (PS) is currently used as packaging, insulating and storing material in various industrial or domestic fields. As a result, a large quantity of PS wastes is produced. Plastic wastes are not usually biodegradable, so it is necessary to suggest a technology to recycle them. Landfills and incineration are reasonably cheap methods but are not environmentally acceptable, therefore, alternative methods for polymer recycling are required. The general purpose of PS foam recycling is to recover a more compact polymeric material without degradation. Dissolution with terpenic solvents is presented here as an efficient and cheap alternative that is developed at room temperature; among the oils studied, limonene was selected because of its intermediate solubility and its abundance. The solvent removal is possible thanks to supercritical technology that provides a high solubility in limonene and almost a complete PS insolubility at moderated pressures (77?bar) and low temperatures (30?°C). Thus, based on the results of thermogravimetric and chromatographic analysis, we propose that.supercritical antisolvent precipitation is an ideal technique for carrying out the separation of PS and limonene, providing a recycled polymer with a reduced volume, almost completely free of solvent and without degradation of the polymeric chains.     

Life Cycle Analysis of Extruded Films Based on Poly(lactic acid)/Cellulose Nanocrystal/Limonene: A Comparative Study with ATBC Plasticized PLA/OMMT Systems

Life cycle analysis (LCA) of limonene plasticized poly(lactic acid) (PLA) films containing cellulose nanocrystals (CNC) extracted, by acid hydrolysis, from Phormium tenax leaf fibres, was assessed and compared with the results of acetyl tributyl citrate (ATBC) plasticized PLA films, having equivalent mechanical properties, containing organo-modified montmorillonite (OMMT). Eco-Indicator 99 tool has been adopted as the main method for life cycle assessment. Results indicated that, despite CNC are biobased fillers obtained by natural sources, the related chemical extraction leads to a large environmental footprint and a relatively relevant energy expense. LCA characterization of these films demonstrated that the environmental impact of PLA/limonene film reinforced with 1% in weight of CNC (PLA/CNC/limonene) is comparable to the environmental impact of polylactic acid films reinforced with OMMT and plasticized with a petroleum based plasticizer (ATBC) (PLA/OMTT/ATBC). A “cradle to gate” approach has been considered for both the film typologies.     

Bioplastic Wastes: The Best Final Disposition for Energy Saving

The pressing need to reduce the consumption of non-renewable resources and the emission of greenhouse gases into the environment, in recent decades has led to the wide development of bio-based plastics that are produced from renewable sources, such as corn, wheat, oil seeds etc. Actually, the most important bio-based plastics on the market are the poly(lactic acid) (PLA) produced from Nature Works (USA) and the Mater-Bi, a starch based bioplastics, made from Novamont (Italy). The aim of this work is not only to assess the actual energy and greenhouse gases (GHGs) savings resulting from the production of bioplastics, compared with the production of conventional plastics, but also to analyze what might be the best final disposition of bioplastic wastes in order to maximize the energy saving. Therefore, by using the Life Cycle Assessment (LCA) methodology, LCAs cradle to gate and cradle to grave were carried out both for PLA and Mater-Bi, taking into consideration as final scenarios composting, incineration, anaerobic digestion and mechanical recycling processes. The work demonstrates how incineration, composting and anaerobic digestion processes are clearly under-performing, from an environmental point of view, with respect to the mechanical recycling process.