Biocompatible Polyurethane Scaffolds Prepared from Glycerol Monostearate-Derived Polyester Polyol

Biodegradable polyester polyol was synthesized from oleochemical glycerol monostearate (GMS) and glutaric acid under a non-catalyzed and solvent-free polycondensation method. The chemical structure of GMS-derived polyester polyol (GPP) was elucidated by FTIR, ¹H and ¹³C NMR, and molecular weight of GPP was characterized by GPC. The synthesized GPP with acid value of 3.03 mg KOH/g sample, hydroxyl value of 115.72 mg KOH/g sample and M_n of 1345 g/mol was incorporated with polyethylene glycol (PEG) and polycaprolactone diol (PCL diol) to produce a water-blown porous polyurethane system via one-shot foaming method. The polyurethanes were optimized by evaluating glycerol as a crosslinker, silicone surfactant and water blowing agent on tensile properties of polyurethanes. All polyurethanes underwent structural change, and crystalline hard segments of polyurethanes were shifted to higher temperature suggested that hard segments undergone re-ordering process during enzymatic treatment. In terms of biocompatibility, polyurethane scaffold produced by reacting 100% w/w of GPP with isophorone diisocyanate and additives showed the highest cells viability of 3T3 mouse fibroblast (94%, day 1), and MG63 human osteosarcoma (107%, day 1) and better cell adhesion as compared to reference polyurethane produced by only PEG and PCL diol (3T3 cell viability: 8%; MG63 cell viability: 2%). The current work demonstrated GPP synthesized from renewable and environmental friendly resources produced polyurethanes that allows improvement in physico-chemical, mechanical and biocompatibility properties. By blending with increasing content of GPP, the water-blown porous polyurethane scaffold has shown great potential as biomaterial for soft and hard tissue engineering.     

A New Approach to Chemical Recycling of Polyamide 6.6 and Synthesis of Polyurethanes with Recovered Intermediates

A new efficient method for the chemical decomposition of polyamide 6.6 by the glycolysis and amino-glycolysis processes was proposed. The glycolysis was conducted using the mass excess of ethylene glycol (EG) as a decomposing agent in the presence of a catalyst. Also, a mixture of EG and triethylenetetramine was used as another decomposing agent in the amino-glycolysis process. The described process of decomposition did not require the use of elevated pressure. The hydroxyl and amine numbers, rheology behavior and the presence of characteristic chemical groups in the obtained glycolysates and aminoglycolysates were determined in order to characterize the reaction products. The decomposition products were defined as non-Newtonian fluids that could be described by suitable mathematical models. The conducted studies showed that the properties of the obtained intermediates depend on the mass excess of the decomposing agent used. The resulting semi-products are suitable for reusing in the synthesis of polyurethanes, which has been confirmed by the exemplary synthesis. In the reaction, 10 and 15 wt% of commercial polyol were replaced with the recovered intermediates.     

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.     

废旧硬质聚氨酯泡沫塑料的木质素改性及再生

采用含有二乙二醇(DEG)和乙醇胺(ETA)的双组分解交联剂降解废旧硬质聚氨酯泡沫塑料(PU硬泡),并利用降解得到的低聚物多元醇与木质素复合制备出性能增强的再生PU硬泡。通过对制备的再生PU硬泡的红外光谱、密度、吸水率、抗压强度、热稳定性、导热系数、热重曲线等进行分析测试,考察m(DEG)∶m(ETA)对再生PU硬泡性能的影响。实验结果表明:m(DEG)∶m(ETA)=1∶3时废旧PU硬泡的降解效果最好;木质素加入量为2.0%(w)时再生PU硬泡的密度低、抗压强度高、保温性能良好,达到国家标准《建筑绝热用硬质聚氨酯泡沫塑料》(GB/T 21558—2008)的品质要求。     

Scaled-up and economic assessment approach of the split-phase glycolysis process for the recycling of flexible polyurethane foam wastes

The economic viability of the split-phase glycolysis process for the recycling of any kind of flexible polyurethane foam waste employing crude glycerol as cleavage agent has been demonstrated. First, experiments at pilot plant scale were carried out to check that the process can be extrapolated to larger scales. With the goal of scaling-up the process from laboratory scale to pilot plant, geometric similarity criteria were applied together with dynamic similarity for laminar flow in agitated tank reactors. Hence, a pilot plant installation was designed with geometrically similar equipment to those used for lab scale, obtaining analogous results in terms of recovered polyol properties. Then, the basic design of a split-phase glycolysis industrial plant with a capacity for treating 270 Tm per year of flexible PU foams scraps was proposed. Finally, the economic feasibility of such recycling process was confirmed because of the obtention of a Net Present Value (NPV) of 1,464,555€, with an Internal Rate of Return (IRR) of 27.99%, and a payback time between 4 and 5 years.

     

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial,UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance (¹HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.     

Development of Lignin and Nanocellulose Enhanced Bio PU Foams for Automotive Parts

The green rigid polyurethane (PU) foam has been developed with 100 % soy polyol after optimization of formulation ingredients and lignin has been introduced and isocyanate content reduced in the green rigid PU foam. The cellulosic nanofibers have also been successfully incorporated and dispersed in green rigid PU foam to improve the rigidity. The influence of nano cellulose fiber modification (enzymatic treatment, hydrophobic modification with latex) on the foam density, open cell content, foam raise height, water vapor, and mechanical properties of rigid PU foam were studied. The foamed structures were examined using scanning electron microscopy to determine the cell size and shape due to the addition of cellulosic nanofibers. The odor test were performed to evaluate the odor concentration 100 % soyol based PU foam including lignin and nanofiber and compared to 100 % synthetic based polyol PU foam. The experimental results indicated that the compression and impact properties improved due to the modification of nano cellulosic fibers. The odor concentration level of nanofiber reinforced rigid PU foam reduced significantly compared to 100 % PU foam due to the replacing of isocyanate content. It can be said that with an appropriate combination of replacing isocyanate by lignin and addition of nanofiber, rigid PU foam properties could be improved.     

Polyols and Polyurethanes from Hydroformylation of Soybean Oil

This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.     

Gasification applicability study of polyurethane solid refuse fuel fabricated from electric waste by measuring syngas and nitrogenous pollutant gases

To recycle polyurethane foam waste generated from electric appliance recycling centers for use as fuel in a gasification process, polyurethane solid refuse fuel fabricated as pellets was analyzed for the characteristics of elemental composition, proximate analysis, heating value, and thermo-gravimetric testing. It has a high heating value of 29.06 MJ/kg with a high content of combustibles, which could be feasibly used in any thermal process. However, the nitrogen content, of up to 7 %, was comparably higher than for other fuels such as coal, biomass, and refuse-derived fuel, and may result in the emission of nitrogenous pollutant gases of HCN and NH₃. By conducting gasification experiments on polyurethane solid refuse fuel in a fixed-bed reactor, a syngas with a heating value of 9.76 kJ/m³ and high content of both H₂ and CO were produced with good gasification efficiency; carbon conversion 54 %, and cold gas efficiency 60 %. The nitrogenous pollutant gases in syngas were measured at the concentrations of 160 ppm hydrogen cyanide and 40 ppm ammonia, which may have to be reduced using proper cleaning technologies prior to the commercialization of gasification technology for polyurethane waste.     

Biobased Polyurethanes from Rapeseed Oil Polyols: Structure, Mechanical and Thermal Properties

Biobased polyols were synthesized from rapeseed oil (RO) with diethanolamine (DEA), triethanolamine (TEA) and glycerol (GL) at different molar ratios. The structures of the synthesized polyols were analyzed using FTIR-ATR spectroscopy. Polyurethane (PU) networks from RO/DEA polyols and polymeric MDI showed higher tensile strength, modulus and hardness, but their elongation at break decreased, compared to the case of the PU obtained from RO/TEA and RO/GL polyols. The tensile strength and modulus of PU networks increased with increasing PU cohesion energy density (CED) and decreasing molecular weight between crosslinks M _c . From the thermogravimetric analysis and its derivative thermograms, at the first stage of destruction (below 5 % weight loss) in the air and inert atmosphere, the PU obtained from RO polyols were ranked in the following order: PU RO/GL > PU RO/TEA > PU RO/DEA, and their thermostability was higher than that of the PU based on propylene oxide.     

Environmentally Friendly Polyurethane Composites: Preparation, Characterization and Mechanical Properties

The waterborne polyurethane (PU) prepolymer was prepared based on isophorone diisocyanate (IPDI), polyester polyol (N220), dimethylol propionic acid (DMPA) and hydroxyethyl methyl acrylate (HEMA). The modified waterborne polyurethane–acrylate (PUA) emulsions were obtained with different proportions of acrylate (butyl acrylate and methyl methacrylate) and initiating agent by in situ dispersion technique. The structures and thermal properties of prepared PU and PUA were analyzed and characterized with FT-IR, UV–Vis spectroscopy and DSC. The PUA hybrid samples had lower glass transition temperature of hard segment and higher decomposition temperatures than PU sample. Performances of the emulsion and film were studied by means of apparent viscidity, particle size and polydispersity, surface tension and mechanical properties. The results indicated that the particle sizes of the PUA dispersions were larger than those of the pure PU and the solvent resistance, mechanical properties of PUA films was improved compare with the unmodified polyurethane film. The film had the biggest hardness and the least water absorption when the BA/MMA mass ratio 5:5 modified PU. The obtained PUA have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.     

Effects of Wood Fiber and Microclay on the Performance of Soy Based Polyurethane Foams

Various polyurethane (PU) foams were prepared by in situ reaction of isocyanate and soy-based polyol. The effects of wood fiber and microclay on the foam morphologies, mechanical properties and thermal behaviors of PU foams were investigated. NCO index had fundamental impacts on the influences of wood fiber and microclay on the performance of PU foams. The reinforcement behavior of flexible foams was different to that of both semi-rigid and rigid foams. Both fiber and microclay improved the compressive strength at a high NCO index of 140–250, and contributed to relative high decomposition temperatures. Unlike the compressive strength, the tensile strength was decreased due to the amount of hard polyurea formation from secondary reactions at the highest NCO level. In addition, wood fiber had different reinforcement mechanism from microclay. Wood fiber desired to form chemical bonds during foaming while microclay had potential to form physical insertions. This difference was expressed by the change of their thermal degradation temperature.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.     

Effect of alkali catalyst on biodiesel production in South Korea from mixtures of fresh soybean oil and waste cooking oil

Biodiesel from waste cooking oil (WCO) and soybean oil (SO) mixture was produced by changing the alkali catalyst (NaOH) content and the WCO to SO ratio in the feedstock. All the prepared biodiesel samples satisfied the standard requirement in terms of free glycerol, density, and acid value. The minimum catalyst content and the highest WCO composition to get biodiesel from the WCO/SO mixture feedstock without ruining the biodiesel properties were 1.0 and 60 wt %, respectively. This conclusion implies that the waste cooking oil mixture, which contains 40 wt % fresh soybean oil, could be treated like the fresh soybean oil to produce biodiesel, and that this behavior would be helpful to reduce the biodiesel production cost when waste cooking oil used as feedstock. The unsaturated methyl esters such as linoleic, and oleic acid were dominant (almost 80 % w/w) in the fresh soybean oil. However the saturated methyl ester was increased due to the double bond breaking during the frying process. These results may deteriorate the biodiesel quality by changing the methyl ester composition.     

A New and Sound Technology for Biogas from Solid Waste and Biomass

Organic waste, as a main constituent of municipal solid waste, has as well as solid biomass a high potential for biogas generation. Despite the importance of biogas generation from these materials, the availability of large-scale biogas processes lacks behind the demand. A newly developed double-stage solid–liquid biogas process, consisting of an open hydrolysis stage and a fixed-bed methane reactor, allows the biogas production from almost all biodegradable solid waste and renewable resources like maize, grass, sugar cane, etc. Furthermore, residues from industrial processes, like the glycerine waste water from biodiesel production, can also be converted into biogas successfully. Due to the strong separation of hydrolysis and methanation, the process is extremely stable. No malfunction has been detected so far. The open hydrolysis releases CO₂ and allows oxidation of sulfur. Consequently, the biogas has a high methane (>72%) and low H₂S concentration (<100 ppm). Stirrers or other agitation equipment are not necessary; only liquids are pumped. The biogas generation becomes controllable for the first time; thus, the actual generation can be easily adapted to the consumption.     

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.     

Recovery of different waste vegetable oils for biodiesel production: A pilot experience in Bahia State,Brazil

In Brazil, and mainly in the State of Bahia, crude vegetable oils are widely used in the preparation of food. Street stalls, restaurants and canteens make a great use of palm oil and soybean oil. There is also some use of castor oil, which is widely cultivated in the Sertão Region (within the State of Bahia), and widely applied in industry. This massive use in food preparation leads to a huge amount of waste oil of different types, which needs either to be properly disposed of, or recovered. At the Laboratorio Energia e Gas-LEN (Energy & Gas lab.) of the Universidade Federal da Bahia, a cycle of experiments were carried out to evaluate the recovery of waste oils for biodiesel production. The experiences were carried out on a laboratory scale and, in a semi-industrial pilot plant using waste oils of different qualities. In the transesterification process, applied waste vegetable oils were reacted with methanol with the support of a basic catalyst, such as NaOH or KOH. The conversion rate settled at between 81% and 85% (in weight). The most suitable molar ratio of waste oils to alcohol was 1:6, and the amount of catalyst required was 0.5% (of the weight of the incoming oil), in the case of NaOH, and 1%, in case of KOH.The quality of the biodiesel produced was tested to determine the final product quality. The parameters analyzed were the acid value, kinematic viscosity, monoglycerides, diglycerides, triglycerides, free glycerine, total glycerine, clearness; the conversion yield of the process was also evaluated.     

Immobilization of copper ions laden kaolin waste: influence of thermal treatment on its immobilization in cement paste

This work aims to study the influence of thermal treatment of Cu²⁺ laden kaolin wastes on its immobilization efficiency in cement paste. Compressive strength and toxicity characteristic leaching procedure (TCLP) of 5–20 % kaolin waste blended cement pastes were tested. X-ray diffraction (XRD) results illustrate that adsorption of Cu²⁺ ions modify the crystal structure of kaolinite mineral. Fourier transform infrared (FTIR) results indicate that the adsorption sites on the kaolin surface that were occupied with free water molecules have been replaced with Cu²⁺ ions adsorbed from aqueous solutions. The thermal treatment of kaolin waste improves fixation ratio of Cu²⁺ in cement pastes containing up to 20 % of thermally treated waste. This is due to: pozzolanic activity of calcined kaolin, conversion of leachable adsorbed Cu²⁺ ions into encapsulated unleachable phase that does not retard the hydration of cement as well as adsorption of much of leachable Cu²⁺ ions on surfaces of hydration products and occlusion in its lattice structure as illustrated from XRD, FTIR, thermogravimetric, scanning electron microscopy and TCLP results. The fixation ratio of Cu²⁺ in cement paste blended with 20 % of thermally treated kaolin waste, reaches maximum value of about 97 % compared to 82 % for cement paste blended with 20 % of untreated kaolin waste.     

Solid recovery rate of food waste recycling in South Korea

Source-separated collection system of household food waste has been implemented national wide in South Korea. Food waste recycling rate that means conversion rate to recycle is over 90 % in present. However, over the value of 90 %, we need to enhance the efficiency of food waste recycling process. We analyzed material flow of 24 food waste recycling facilities and calculated solid recovery rate to key-process. We found that 3–13 % of the solids from food waste outflows with foreign materials and 27–33 % of the solids outflow with wastewater. As a result, solid recovery rates are 65.3, 60.9, and 56.3 % in wet feed facility, dry feed facility, and composting facility, respectively. Alternative ways to recovery solid from wastewater or collection tools to exclude plastic bags, salt, and moisture content are required to make food waste recycling more efficient.     

Cost–benefit analysis of waste reduction in developing countries: a simulation

Waste reduction activities such as recycling, composting, and pig feeding in Peru and other developing countries are mainly informal but already reduce about 15 % of waste generation. Although much research on informal recycling in Latin America recommends partnership with current waste pickers, there is a lack of methodologies on how to systematize these activities. This paper proposes a mathematical model that calculates yields and costs of separate waste collection, and analyzes and measures the effect of improvements such as source separation by residents and location of recycling and composting centers. The analysis finds that the largest effect comes from source separation. In this case, separate collection yield can be increased from the current 30 kg/waste picker/day to about 200 kg/waste picker/day, and the cost can be reduced from 110 US$/t to 20 US$/t. These changes affect the profitability of the recycling and composting business. The environmental and social effects of these improvements are also discussed.