Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Polyacetal Polyols for Polyurethanes

The synthesis of telechelic polyacetals with terminal hydroxyl groups (polyacetal polyols), by the reaction of triethylene glycol divinyl ether with dipropylene glycol in the presence of trimethylolpropane or other triols or diols as starters, in acidic catalysis, has been studied. The synthesized liquid polyacetal triols and polyacetal diols were characterized by hydroxyl number, viscosity, acidity, number average molecular weight (M_n), weight average molecular weight (M_w), molecular weight distribution (M_w/M_n), FT-IR spectra. The obtained polyacetals were transformed in cast elastomers by the reaction with the isocyanate Mondur CD (modified diphenyl methane diisocyanate) with properties very close to the elastic polyurethanes obtained by using conventional polyether triols, copolymers propylene oxide–ethylene oxide. The polyacetal polyols are suitable for the synthesis of elastic polyurethanes (polyurethane elastomers, flexible polyurethane foams). Polyacetals are well known biodegradable polymers. Therefore, the polyurethanes based on polyacetal polyols are expected to be biodegradable.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.     

Hydrogen-rich fuel gas production from refuse plastic fuel pyrolysis and steam gasification

In this study, experimental conditions were optimized to maximize the production of hydrogen gas from refuse plastic fuel (RPF) by pyrolysis and steam gasification processes conducted in a laboratory-scale reactor. We carried out gasification using 10-g RPF samples at different temperatures (700°-1000°C) with and without steam. The effect of the amount of steam (0–0.25 g/min) for RPF steam gasification was also studied. The effect of K₂CO₃ as a catalyst on these processes was also investigated. Experimental results showed that the hydrogen gas yield increased with temperature; with respect to the gas composition, the hydrogen content increased mainly at the expense of other gaseous compounds, which highlights the major extension of secondary cracking reactions in the gaseous fraction at higher temperatures.     

Treatment of discarded oil in supercritical carbon dioxide for preparation of carbon microspheres

Carbon microspheres with diameter of 1–10 μm were prepared by treatment of waste oil in a supercritical carbon dioxide (scCO₂) system. The structure and morphology of the products were characterized by X-ray diffraction, field-emission scanning electron microscopy, and Raman spectrometry. It is shown that the products consist of graphite microspheres with relatively low graphitization. The yield of solid products increased from 26.8 wt% to 42.2 wt% as the reaction temperature was raised from 530°C to 600°C. Spheres with multilayer structure could be obtained by means of subsequent vacuum annealing of the carbon microspheres at 1500°C. The formation mechanisms of carbon microspheres in the scCO₂ system and the influence of vacuum annealing on the structure are discussed in detail.     

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.     

Aliphatic–Aromatic Polyols by Thiol–Ene Reactions

Aliphatic–aromatic polyols were synthesized by thiol–ene reactions (photochemical or thermal) using mercaptanized starting materials from bio-based compounds: limonene dimercaptan, thioglycerol, mercaptanized castor oil and isosorbide (3-mercaptopropyl) ether. Aromatic starting materials were phenols containing double bonds; ortho-allyl phenol (OAP, petrochemical-based) and eugenol (EUG, bio-based). The phenolic hydroxyl groups were blocked by alkoxylation with propylene oxide (PO) or glycidol (GLY) prior to use in thiol–ene reaction. The aromatic rings were attached to the mercaptans by reacting thiol groups with the double bonds of alkoxylated OAP (OAP–PO and OAP–GLY) and alkoxylated EUG (EUG–PO and EUG–GLY). These synthesized aliphatic–aromatic polyols were utilized for preparation of rigid polyurethane foams whose physical–mechanical properties were superior to those made only from bio-based aliphatic polyols. These rigid PU foams can be used in a wide range of applications; such as thermal insulation of freezers, buildings, pipes and storage tanks for food and chemical industries, as wood substitute, packaging materials and flotation materials.     

Reduction of tar using cheap catalysts during sewage sludge gasification

Solid-fuel conversion or gasification study of sewage sludge and energy recovery has become increasingly important because energy recovery and climate change are emerging issues. Various types of catalysts, such as dolomite, steel slag and calcium oxide, were tested for tar reduction during the sewage sludge gasification process. For the experiments on sewage sludge gasification reactions and tar reduction using the catalysts, a fixed bed of laboratory-scale experimental apparatus was set up. The reactor was made of quartz glass using an electric muffle furnace. The sewage sludge samples used had moisture contents less than 6%. The experimental conditions were as follows: sample weight was 20 g and reaction time was 10 min, gasification reaction temperature was from 600 to 800°C, and the equivalence ratio was 0.2. The quantity of catalysts was 2–6 g, and temperatures of catalyst layers were 500–700°C. As the reaction temperature increased up to 800°C, the yields of gaseous products and liquid products increased, whereas char and tar products decreased, showing effects on gas product compositions. These results were considered to be due to the increase of the water-gas reaction and Boudouard reaction. In the case of experiments with catalysts, dolomite (4 g), steel slag (6 g) and calcium oxide (6 g) were used. When the temperature of catalysts increased, the weight of the tar produced decreased with different cracking performances by different catalysts. Reforming reactions were considered to occur on the surface of dolomite, steel slag and calcium oxide, causing cracking of the hydrocarbon structure, which eventually showed reduced tar generation.     

Natural Weathering of Kenaf Bast Fibre-Filled Poly(Butylene Succinate) Composites: Effect of Fibre Loading and Compatibiliser Addition

Natural weathering was performed on poly(butylene succinate) (PBS) and its kenaf bast fibre (KBF) filled composites by exposing the specimens to a tropical climate for a period of 6 months (max–min temperature: 31.5–23.9 °C; relative humidity: 78.9%). The aim of this study was to investigate the effects of KBF loading and the addition of maleated PBS compatibiliser (PBSgMA) on the performance of the composites under natural weathering. As expected, the flexural properties of both the uncompatibilised and compatibilised composites dropped with increasing exposure time. The weathered specimens were also assessed by colour change analysis, FTIR spectroscopy analysis and SEM examination. The total colour change, ΔE _ab , of both the uncompatibilised and compatibilised composites increased with weathering time. FTIR spectroscopy analysis confirmed the presence of oxidation products such as hydroxyl, carbonyl and vinyl species in the weathered uncompatibilised and compatibilised composites. SEM examination revealed the presence of surface defects such as cracking, tiny holes and degraded fibre, which explain the poor performance of the composites upon weathering.     

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.     

Dechlorination/detoxification of aromatic chlorides using fly ash under mild conditions

An efficient dechlorination/detroxification method for p-nitrochlorobenzene, p-chloroanisole and 1-chloronaphthalene on municipal waste incinerator fly ash in presence of reducing agents with water/alcohol mixtures was developed. Dechlorination% was higher in water/isopropanol mixture at temperature <100 °C. Metal contents of fly ash played a vital role in enhancing dechlorination at low temperature. Moreover, the fly ash particles provided the surface to accomplish reduction and substitution reactions by adsorbing the chlorinated aromatic compound, hydrogen and hydroxyl ions. The mechanism of dechlorination was envisaged.     

Biohydrogen using leachate from an industrial waste landfill as inoculum

Since hydrogen is a renewable energy source, biohydrogen has been researched in recent years. However, data on hydrogen fermentation by a leachate from a waste landfill as inoculum are scarce. We investigated hydrogen production using a leachate from an industrial waste landfill in Kanagawa Prefecture. The results showed no methane gas production, and the leachate was a suitable inoculum for hydrogen fermentation. The maximum H₂ yield was 2.67 mol of H₂ per mol of carbohydrate added, obtained at 30°C and an initial pH of 7. The acetate and butyrate production was significant when the H₂ yield was higher. Oxidation–reduction potential analysis of the culture suggested that hydrogen-producing bacteria in the leachate were facultative anaerobic. Scanning electron microscope observations revealed that the hydrogen-producing bacteria comprised bacilli about 2 μm in length.     

Novel Biobased Polyurethanes Synthesized from Soybean Phosphate Ester Polyols: Thermomechanical Properties Evaluations

Biobased polyurethanes from soybean oil–derived polyols and polymeric diphenylmethane diisocyanate (pMDI) are prepared and their thermomechanical properties are studied and evaluated. The cross-linked biobased polyurethanes being prepared from soy phosphate ester polyols with hydroxyl contents ranging from 122 to 145 mg KOH/g and pMDI within 5 min of reaction time at 150°C in absence of any catalyst show cross-linking densities ranging from 1.8 × 10³ to 3.0 × 10³ M/m³, whereas glass transition temperatures vary from approximately 69 to 82°C. The loss factor (tan ) curves show single peaks for all these biobased polyurethanes, thus indicating a single-phase system. The storage moduli (G) at 30°C range from 4 × 10⁸ to 1.3 × 10⁹ Pa. Upon postcure at 150°C, the thermomechanical properties can be optimized. Cross-link densities are improved significantly for hydroxyl content of 139 and 145 mg KOH/g at curing time of 24 h. Similarly, glass transition temperature (T_g) and storage moduli around and after T_g are increased. Meanwhile, tan intensities decrease as result of restricted chain mobility. Longer exposure time (24 h) induces thermal degradation, as evidenced by thermogravimetric analysis (TGA). The dynamic mechanical (DMA) analysis shows that postcure at 100°C for times exceeding 24 h also leads to improved properties. However, cross-linking densities are lower compared to postcure carried out at 150°C.     

Preparation of Cellulose Nanocrystals Using an Ionic Liquid

In this paper cellulose nanocrystals were prepared by treating microcrystalline cellulose with 1-butyl-3-methylimidazolium hydrogen sulphate ionic liquid. Cellulose nanocrystals, after separation from ionic liquid, were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Field emission scanning electron microscopy (FESEM) Transmission Electron Microscope (TEM) and Thermogravimetric analysis. XRD results showed no changes in type of cellulose after the treatment with ionic liquid, however, high crystallinity index was observed in the ionic liquid treated sample. Cellulose nanocrystals, having length around 50–300 nm and diameter around 14–22 nm were observed in the ionic liquid treated sample under FESEM and TEM, and similar patterns of peaks as that of microcrystalline cellulose were observed for cellulose nanocrystals in the FTIR spectra. The thermal stability of the cellulose nanocrystals was measured low as compare to microcrystalline cellulose.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Effect of Solvent Composition on Porosity,Surface Morphology and Thermal Behavior of Metal Alginate Prepared from Algae (<Emphasis Type="Italic">Undaria pinnatifida</Emphasis>)

Alginates, extracted from algae are linear unbranched polymers containing β-(1→4)-linked d-mannuronic acid (M) and α-(1→4)-linked l-guluronic acid (G) residues. The conversion of alginic acid into the metal alginate is confirmed using FTIR spectroscopy. Asymmetric and symmetric stretching of free carboxyl group present in metal alginate occurs almost at the same position in various solvent compositions. Total intrusion volume of metal alginate prepared in propanol (0.0742 mL/g) is greater compared to those in ethanol (0.0648 mL/g) and methanol (0.0393 mL/g) as solvent. Surface morphology as well as porosity and pore size distribution of metal alginate are greatly influenced by solvent. It can be seen from thermal analysis results that calcium alginate prepared using different solvent compositions started decomposing at 100 °C, but rapid degradation started around 200 °C. The results showed a stepwise weight loss during thermal sweep, indicating different types of reactions during degradation. First and second step of rapid degradation was situated around 200–300 and 300–550 °C, respectively; whereas the final step is situated around 550–650 °C. The trend of degradation was similar for all the solvents, although the amount of final residue varied from one solvent to another. At the same time, lower thermal stability was also observed with higher heating rates. Additionally, a kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive first order reactions.     

Synthesis and Characterization of Polyols and Polyurethane Foams from PET Waste and Crude Glycerol

In this study, polyethylene terephthalate (PET) waste from post-consumer soft-drink bottles and crude glycerol from the biodiesel industry were used for the preparation of polyols and polyurethane foams. PET waste was firstly depolymerized by the glycolysis of diethylene glycol. The glycolyzed PET oligomers were then reacted with crude glycerol at different weight ratios to produce polyols via a series of reactions, such as esterification, transesterification, condensation, and polycondensation. The polyols were characterized by titration, viscometry, gel permeation chromatography (GPC), and differential scanning calorimetry. Subsequently, polyurethane (PU) foams were made via the reaction between the produced polyols and polymeric methylene-4,4′-diphenyl diisocyanate and were characterized by mechanical testing, scanning electron microscopy, and thermogravimetric analysis. Polyols from crude glycerol and their PU foams were also prepared to compare properties with those of polyols and PU foams from PET and crude glycerol. The influence of aromatic segments existing in glycolyzed PET and glycerol content on the properties of the polyols and PU foams was investigated. It was found that aromatic segments of polyols from glycolyzed PET helped increase their molecular weights and improve thermal stability of PU foams, while high glycerol content in polyols increased the hydroxyl number of polyols and the density and compressive strength of PU foams.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Utilization of Natural Oils for Decomposition of Polyurethanes

The model polyurethane foam and model compact polyurethane material were prepared and then decomposed by means of natural oils. Castor oil and fish oil based polyol were used in this study. Optimal conditions for the polyurethane decomposition were found. Temperature 250 °C was necessary for efficient polyurethane decomposition by castor oil whereas 200 °C is sufficient in the case of fish oil based polyol. Prepared products have hydroxyl number in the range of 95–168 mg KOH g⁻¹. During the polyurethane decomposition no cleavage of double bonds in the fatty acid chains of castor oil and fish oil based polyol was observed.