Novel Biobased Polyurethanes Synthesized from Nontoxic Phenolic Diol Containing l-Tyrosine Moiety Under Green Media

Ionic liquids (ILs) have been accepted as ‘green’ alternatives to the organic solvents in a range of synthesis, catalysis and electrochemistry, because of their distinctive chemical and physical properties. In this investigation, N,N′-(pyromellitoyl)-bis-l-tyrosine dimethyl ester as a chiral bioactive diphenolic monomer was prepared in three steps. The polycondensation of this monomer with various aromatic and aliphatic diisocyanates such as 4,4′-methylene-bis-(4-phenylisocyanate) (6a), toluylene-2,4-diisocyanate (6b), isophorone diisocyanate (6c) and hexamethylene diisocyanate (6d) were carried out in the presence of tetrabutylammonium bromide as a molten IL under microwave irradiation conditions and was compared with polymerization in traditional solvent like N-methyl-2-pyrrolidone. The results show that IL efficiently absorbs microwave energy, thus leading to a very high heating rate. Thus IL method is safe and green since toxic and volatile organic solvents were eliminated. All of the novel poly(urethane-imides) (PUIs) showed good solubility in various organic solvents. The obtained new polymers were characterized with FT-IR, ¹H-NMR, elemental and thermogravimetric analysis techniques. Thermogravimetric analysis (TGA) of two representative PUIs demonstrated that they are rather thermally stable. In vitro toxicity studies showed that the synthetic materials are biologically active and they are nontoxic to microbial growth then could be classified as bioactive and biodegradable compounds.     

The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Effects of heating rate and temperature on product distribution of poly-lactic acid and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate

In this study, poly-lactic acid (PLA) and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (PHBH) were pyrolyzed at various temperatures (300, 350, 400, 500, 600, and 700 °C) and heating rates (5, 10, 20, 30, and 40 °C min⁻¹) using a pyrolysis–gas chromatograph/mass spectrometer (Py–GC/MS). The results revealed that the main pyrolysis products of PLA were acetaldehyde, lactide (including meso-lactide and d-, l-lactide), and oligomers. Crotonic acid and its oligomers accounted for most of the PHBH pyrolyzates. The pyrolysis temperature significantly correlated with the product distribution, but the heating rate had a small effect on the product distribution. Lactide and crotonic acid were two kinds of high-value chemicals, and their highest yields were obtained at 400 and 600 °C with 29.7 and 72.6 area %, respectively. Secondary reactions could not be neglected at 700 °C, and acetaldehyde and crotonic acid decreased to 65.0 and 69.6 area %, respectively. These results imply that pyrolyzate selectivity can be controlled by temperature management during pyrolysis.

     

Biodegradable Polyesters and Polyamides From Difunctionalized Lauric and Coconut Fatty Acids

In this work, a major fatty acid from coconut oil was used as starting material in preparing biodegradable polymers. Thus, polyesters and polyamides from varying proportions of monomers, hydroxy- and amino- derivatives of lauric acid were synthesized. Initially, the derivatives were prepared by regioselective chlorination of lauric acid, in the presence of ferrous ions in strong acid medium. Subsequent hydroxylation and amination procedures yielded the hydroxy- and amino- derivatives of lauric acid. These monomers were polymerized in a reaction tube by simple polycondensation method at 220–230 °C for 6–8 h without catalyst. Molecular weight determination using –COOH by end group titration and gel permeation chromatography (GPC) gave an average molar mass of 3,000–5,000 g mol⁻¹ with n = 15–25 monomer units. Thermal properties such as glass transition (T_g) and decomposition (T_d) temperatures were obtained using differential scanning calorimetry (DSC). The same processes of synthesis and determinations above were applied to coconut fatty acids, derived from saponification of coconut oil, and resulted to very similar conclusions. A quick biodegradation assay against fungus Aspergillus niger UPCC 4219 showed that the polymers prepared are more biodegradable than conventional plastics such as polypropylene, poly(ethyleneterepthalate) and poly(tetrafluoroethylene) but not as biodegradable as cellulosic (newsprint) paper.     

Biodegradation of Poly(3-Hydroxybutyrate) Produced from Cupriavidus necator with Different Concentrations of Oleic Acid as Nutritional Supplement

The environmental impact caused by the disposal of plastics has motivated the development of biodegradable materials. Recent studies showed that supplementation with oleic acid (OA) in cultures producing poly(3-hydroxybutyrate), P(3HB), increased the polymer productivity. However only few studies have shown the properties and biodegradation profile of the polymer obtained. This research investigated the influence of OA concentration on the biodegradation of the P(3HB) obtained from cultures of Cupriavidus necator. The crystallinity of the casting films determined by differential scanning calorimetry (DSC) was reduced from 70% (0 g L⁻¹ of OA) to 52% (3.0 g L⁻¹ of OA). A reduction of 11 °C in the melting temperature was observed with 3.0 g L⁻¹ of OA. The kinetic of biodegradation was: 3.0 > 1.5 > 0.9 > 0.3 > 0 g L⁻¹ of OA.     

Synthesis and Characterization of Novel Heat Stable and Processable Optically Active Poly(Amide–Imide) Nanostructures Bearing Hydroxyl Pendant Group in an Ionic Green Medium

Ionic liquids (IL)s have been recognized as ‘green’ alternatives to the organic solvents in a range of synthesis, catalysis and electrochemistry due to their unique chemical and physical properties. In this investigation, a series of organosoluble, thermally stable and optically active hydroxyl-containing poly(amide–imide)s (PAI)s were prepared via polycondensation reaction of an aromatic diamine, 3,5-diamino-N-(4-hydroxyphenyl)benzamide (4), and different chiral amino acid-based diacids (3a–3e) in the presence of molten tetrabutylammonium bromide as a molten IL and triphenyl phosphite under classical heating method. This process is safe and green since toxic and volatile organic solvents such as N-methylpyrrolidone (NMP) and N,N′-dimethylacetamide (DMAc) were eliminated. The resulting new polymers were obtained in good yields with inherent viscosities ranging between 0.23 and 0.54 dL g^?1 and were characterized by Fourier transform infrared spectroscopy, specific rotation, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis, elemental analysis, and in some cases by ¹H-NMR techniques. The FE-SEM micrographs and XRD showed that the synthesized PAIs were nanostructured and amorphous polymers. The effect of ultrasonic irradiation on the size of polymer particles was also investigated and the results showed that the size of polymer nanoparticles after ultrasonication became smaller than the size of them, before ultrasonic radiation. All of the polymers were readily soluble in many organic solvents such as N,N′-dimethyl sulfoxide, DMAc and NMP.     

Valorisation of Vegetal Wastes as a Source of Cellulose and Cellulose Derivatives

Different qualities of CMC were prepared from an agricultural residue (date palm rachis) and a marine waste (Posidonia oceanica). These starting lignocellulosic materials were used as such and after chemical pulping and bleaching. The carboxymethylation reaction was carried out in presence of NaOH (40%) and monochloroacetic acid (ClCH₂COOH, MAC), in n-butanol as the reaction solvent. The substitution degrees (DS) of the obtained CMCs varied from 0.67 to 1.62 and between 0.98 and 1.86, for P. oceanica and date palm rachis, respectively. The CP-MAS ¹³C-NMR spectra of the prepared polyelectrolytes displayed the presence of the main peaks associated with cellulose macromolecules (C1–C6) and that corresponding to carboxyl functions at around 175 ppm. Unfortunately, the peak attributed to methylene groups neighbouring carboxyl moieties are overlapped by C2 and C3, which renders them hardly detectable. Nevertheless, it is worth noting that the CP-MAS ¹³C-NMR spectra revealed the presence of different signals originating from residual impurities (ca. 27 ppm), such as traces of lignin macromolecules (110–150 ppm) and methyl groups attributed to hemicelluloses. Work is in progress to establish a more efficient purification procedure, in order to have more accurate values of DS.     

Utilization of Broken Rice for the Production of Poly(3-hydroxybutyrate)

The feasibility of utilizing non edible rice (broken rice) for production of fine materials such as poly(3-hydroxybutyrate) (PHB) was considered as one of the alternative ways of keeping the environment clean for sustainable development. Thus, production of PHB from broken rice by simultaneous saccharification and fermentation (SSF) was investigated. During the SSF process, the rice (15% w/v) material was hydrolyzed to glucose, which was utilized by Cupriavidus necator for growth and production of PHB. The PHB content reached 38% at 58 h fermentation. The PHB had weight average molar mass (Mw) and polydipersity index of 3.82 × 10⁵ (g/mol) and 4.15, respectively. Differential calorimetric scan of the PHB showed a melting temperature (Tm) of 176 °C. Given that the PHB was a homopolymer (which consisted of (R)-3-hydroxybutyric acid monomers), it was thought that broken rice could be a raw material for production of both PHB and (R)-3-hydroxybutyric acid. This SSF process would not only help in the utilization of broken rice or non edible rice, but would also serve as a model for utilization of other raw materials that contain starch for production of PHB.     

Tannic acid as a novel and green leaching reagent for cobalt and lithium recycling from spent lithium-ion batteries

Tannic acid–acetic acid is proposed as novel and green chemicals for cobalt and lithium recycling from spent lithium-ion batteries through a leaching process. The synergism of both acids was documented through batch and continuous studies. Tannic acid promotes cobalt dissolution by reducing insoluble Co³⁺ into soluble Co²⁺, while acetic acid is critical to improve the dissolution and stabilize the metals in the pregnant leach solution. Based on batch studies, the optimum conditions for metal recovery at room temperature are acetic acid 1 M, tannic acid 20 g/L, pulp density 20 g/L, and stirring speed 250 rpm (94% cobalt and 99% lithium recovery). The kinetic study shows that increasing temperature to 80 °C improves cobalt and lithium recovery from 65 to 90% (cobalt) and from 80 to 99% (lithium) within 4 h at sub-optimum condition (tannic acid 10 g/L). Kinetic modeling suggests the leaching process was endothermic, and high activation energy indicates a surface chemical process. For other metals, the pattern of manganese and nickel recovery trend follows the cobalt recovery trend. Copper recovery was negatively affected by tannic acid. Iron recovery was limited due to the weak acidic condition of pregnant leach solution, which is beneficial to improve leaching selectivity.

     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

Purification and Properties of Extracellular Poly(3-hydroxybutyrate) Depolymerase Produced by <Emphasis Type="Italic">Aspergillus fumigatus</Emphasis> 202

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase produced by a thermotolerant fungal soil isolate, Aspergillus fumigatus 202, was purified and characterized. Maximum PHB depolymerase production was obtained at the end of 48 h with initial medium pH 7.0 and 45 °C in Bushnell Haas Minerals medium containing PHB as sole source of carbon. The PHB depolymerase was purified using size exclusion chromatography to a fold purification of 20.62 and 61.62% yield. SDS-PAGE and isoelectric focusing revealed the molecular weight and pI of the purified enzyme as 63,744 Da and 4.2, respectively. N-terminal amino acid sequence of purified enzyme was HAXDAYLVK. This non-glycosylated enzyme was most active at pH 9.0 and 45 °C. Purified enzyme was inactivated by N-bromosuccinimide and dithiothreitol suggesting the involvement of tryptophan residues and disulfide bonds at its active site. Nonionic detergents like Tween 20, Tween 80 and Triton X-100 inhibited the enzyme activity. Ions like Ca⁺² and Mg⁺² (5 mM) increased the enzyme activity 1.5 times. Fe⁺² effectively inhibited the enzyme activity to 88% whereas Hg⁺² completely inhibited the enzyme.     

Evaluating the longevity of a PFAS in situ colloidal activated carbon remedy

The remediation of per‐ and polyfluoroalkyl substances by injection of colloidal activated carbon (CAC) at a contaminated site in Central Canada was evaluated using various visualization and modeling methods. Radial diagrams were used to illustrate spatial and temporal trends in perfluoroalkyl acid (PFAA) concentrations, as well as various redox indicators. To assess the CAC adsorption capacity for perfluorooctane sulfonate (PFOS), laboratory Freundlich isotherms were derived for PFOS mixed with CAC in two solutions: (1) PFOS in a pH 7.5 synthetic water that was buffered by 1 millimolar NaHCO₃ (K_f = 142,800 mg^1‐a L^a/kg and a = 0.59); and (2) a groundwater sample (pH = 7.4) containing PFOS among other PFAS from a former fire‐training area in the United States (K_f = 4,900 mg^1‐a L^a/kg and a = 0.24). A mass balance approach was derived to facilitate the numerical modeling of mass redistribution after CAC injection, when mass transitions from a two‐phase system (aqueous and sorbed to organic matter) to a three‐phase system that also includes mass sorbed to CAC. An equilibrium mixing model of mass accumulation over time was developed using a finite‐difference solution and was verified by intermodel comparison for prediction of CAC longevity in the center of a source area. A three‐dimensional reactive transport model (ISR‐MT3DMS) was used to indicate that the CAC remedy implemented at the site is likely to be effective for PFOS remediation for decades. Model results are used to recommend remedial design and monitoring alternatives that account for the uncertainty in long‐term performance predictions.     

Lactic acid production with undefined mixed culture fermentation of potato peel waste

Potato peel waste (PPW) as zero value byproduct generated from food processing plant contains a large quantity of starch, non-starch polysaccharide, lignin, protein, and lipid. PPW as one promising carbon source can be managed and utilized to value added bioproducts through a simple fermentation process using undefined mixed cultures inoculated from wastewater treatment plant sludge. A series of non-pH controlled batch fermentations under different conditions such as pretreatment process, enzymatic hydrolysis, temperature, and solids loading were studied. Lactic acid (LA) was the major product, followed by acetic acid (AA) and ethanol under fermentation conditions without the presence of added hydrolytic enzymes. The maximum yields of LA, AA, and ethanol were respectively, 0.22 g g^?1, 0.06 g g^?1, and 0.05 g g^?1. The highest LA concentration of 14.7 g L^?1 was obtained from a bioreactor with initial solids loading of 60 g L^?1 at 35 °C.     

Biodegradation of Epoxy and MF Modified Polyurethane Films Derived from a Sustainable Resource

Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm⁻¹ and ca. 1050 cm⁻¹ for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.     

A methodology to determine gaseous emissions in a composting plant

Environmental impacts associated to different waste treatments are of interest in the decision-making process at local, regional and international level. However, all the environmental burdens of an organic waste biological treatment are not always considered. Real data on gaseous emissions released from full-scale composting plants are difficult to obtain. These emissions are related to the composting technology and waste characteristics and therefore, an exhaustive sampling campaign is necessary to obtain representative and reliable data of a single plant. This work proposes a methodology to systematically determine gaseous emissions of a composting plant and presents the results obtained in the application of this methodology to a plant treating source-separated organic fraction of municipal solid waste (OFMSW) for the determination of ammonia and total volatile organic compounds (VOC). Emission factors from the biological treatment process obtained for ammonia and VOC were 3.9 kg Mg OFMSW⁻¹ and 0.206 kg Mg OFMSW⁻¹ respectively. Emissions associated to energy use and production were also quantified (60.5 kg CO₂ Mg OFMSW⁻¹ and 0.66 kg VOC Mg OFMSW⁻¹). Other relevant parameters such as energy and water consumption and amount of rejected waste were also determined. A new functional unit is presented to relate emission factors to the biodegradation efficiency of the composting process and consists in the reduction of the Respiration Index of the treated material. Using this new functional unit, the atmospheric emissions released from a composting plant are directly related to the plant specific efficiency.     

Innovative process routes for a high-quality concrete recycling

This study presents alternative methods for the processing of concrete waste. The mechanical stresses needed for the embrittlement of the mortar matrix and further selective crushing of concrete were generated by either electric impulses or microwaves heating. Tests were carried out on lab-made concrete samples representative of concrete waste from concrete mixer trucks and on concrete waste collected on a French demolition site. The results obtained so far show that both techniques can be used to weaken concrete samples and to enhance aggregate selective liberation (that is the production of cement paste-free aggregates) during crushing and grinding. Electric pulses treatment seems to appear more efficient, more robust and less energy consuming (1–3 kW h t^?1) than microwave treatment (10–40 kW h t^?1) but it can only be applied on samples in water leading to a major drawback for recycling aggregates or cement paste in the cement production process.     

Approaches on the Complex Crystallization in PLA/Babassu Based on Modulated Differential Scanning Calorimetry Analyses

Journal of Polymers and the Environment - Poly(lactic acid) (PLA) and PLA/5% Babassu compounds were molten mixed, afterwards aged at temperatures ranging from 50 to 90&nbsp;°C during 15 to...     

Gene Cloning and Characterization of a Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactic Acid) Depolymerase from <Emphasis Type="Italic">Pseudomonas</Emphasis> sp. Strain DS04-T

A gene encoding a poly(l-lactic acid) (PLA) depolymerase from Pseudomonas sp. strain DS04-T was cloned and overexpressed in Escherichia coli. The recombinant PLA depolymerase with a molecular weight of 19.2 kDa was purified to homogeneity. The optimum pH and temperature of the PLA depolymerase are 8.5 and 60 °C, respectively. K⁺, Ca²⁺ and Ni²⁺ enhance the enzyme activity, while Na⁺, Zn²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Mn²⁺ and Co²⁺ inhibit it. The inhibition of different chemicals on the PLA depolymerase activity were examined, in which EDTA was found to have a significantly inhibitory effect. The main degradation product of the depolymerase is identified as lactic acid monomer by mass spectrometric analysis. Physicochemical properties, substrate specificity and sequence analysis indicated that PME is a new type of PLA depolymerase.     

Polymerization of l-lactide with SnCl2: A Low Toxic and Eco-friendly Catalyst

Polymerizations of l-lactide catalyzed either by neat SnCl₂ or by SnCl₂?+?difunctional cocatalysts were conducted in bulk at 180, 160 and 140 °C with variation of the Lac/Cat ratio and time. With neat SnCl₂ poly(L-lactide) having weight average molecular weights (uncorrected M_w’s) up to 190 000 g mol^?1 were obtained mainly consisting of linear chains. Addition of salicylic acid or 1,1-bisphenol yielded a higher fraction of cyclic polylactides but lower molecular weights. Furthermore, SnCl₂ was compared with Bu₂SnCl₂ and various other metal chlorides and the best results were obtained with SnCl₂. With ethyl L-lactate as initiator SnCl₂-catalyzed ROPs were performed at 120 °C and the lac/initiator ratio was varied. All these experiments were conducted under conditions allowing for comparison with ROPs catalyzed with neat Sn(II)-2-ethyhexanoate. Such a comparison was also performed with ε-caprolactone as monomer.

     

Biodegradable Polymers from 5-Hydroxylevulinic Acid: 1. Synthesis and Characterization of Poly(5-hydroxylevulinic acid)

As an attempt to synthesize new biodegradable polymers from renewable cellulose resources, melt polycondensation of 5-hydroxylevulinic acid (5-HLA) was reported for the first time. The resulting product, poly(5-hydroxylevulinic acid) (PHLA), was synthesized and characterized with GPC, FTIR, ¹H NMR and DSC. The in vitro degradation behaviors in phosphate-buffered saline (PBS) and in deionized water (DW) were also examined. The molecular weight of PHLA is not high (several 1,000s), but it possesses unordinary high glass transition temperature (as high as 120 °C). This is very different from existing aliphatic polyesters that usually have T _gs lower than 60 °C. The high T _g is attributed to the formation of inter- and/or intramolecular hydrogen bonds due to a characteristic keto–enol tautomerism equilibrium in the polymer structure. PHLA readily degraded hydrolytically in aqueous media.