Polyols and Rigid Polyurethane Foams from Cashew Nut Shell Liquid

Cashew nut shell liquid (CNSL) is a natural aromatic oil consisting of a mixture of phenolic structures with a carboxyl group in ortho position and substituted in meta position with a hydrocarbon chain of 15 carbon atoms. The major component of CNSL is anacardic acid (90?%), which is easily decarboxylated to cardanol by distillation. The present work describes the synthesis of new biobased Mannich polyols for rigid polyurethane foams in two steps: synthesis of Mannich bases by reacting phenolic ring of cardanol with N-(2-hydroxyethyl)-1,3-oxazolidine followed by alkoxylation reactions. The polyols were characterized by wet methods (hydroxyl numbers, viscosity, acid value, density, water content, iodine value etc.), spectroscopic methods (FT-IR, ¹H NMR and ¹³C NMR) and by Gel Permeation Chromatography. The Mannich polyols from cardanol are excellent replacements for petrochemical derived Mannich polyols based on nonyl phenol. Cardanol-based polyols were used successfully for the preparation of rigid polyurethane foams of good physical?Cmechanical and fireproofing properties.     

Diethanolamides of Castor Oil as Polyols for the Development of Water-Blown Polyurethane Foam

Castor oil was chemically modified into a diethanolamide by a two step process. The first step was the hydroxylation of double bonds in castor oil and second step was the transamidation using diethanolamine to increase the hydroxyl value. Water blown polyurethane foams were developed with this castor oil based polyol using polypropylene glycol of molecular weight 1,000 as the copolyol and polymeric MDI. The density and mechanical properties namely compression and flexural strength depended on the composition of the foam formulation. The hydroxyamide content and molecular weight of commercial polyol had significant effect on the micro structure as observed by optical microscopy.     

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.     

Thermal and Mechanical Properties of Polyurethane Rigid Foam Based on Epoxidized Soybean Oil

A soypolyol based on epoxidized soybean oil (ESO) was prepared in the presence of HBF₄ and diethanolamine (DEA) was used as ring opener. A series of polyurethane rigid foam were prepared by mixing polyol with TDI using an isocyanate index of 1.1. The polyol used in this paper were a mixture of soypolyol and a commercial PL-5601 polyester polyol and the mass fraction of PL-5601 was in the range of 0–60%. The thermal properties of the resins were characterized by DSC and TG. The results showed that these rigid foams possess high thermal stability. There were two glass transition temperature of each foam and Tg₁ was increasing with the increasing of OH value. The compression strength of the foam was also recorded, and the effect of mass ratio of soypolyol and PL-5601 polyester polyol on the compression strength was discussed.     

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.     

Water-Blown Castor Oil-Based Polyurethane Foams with Soy Protein as a Reactive Reinforcing Filler

To decrease the usage of petroleum based materials, a kind of bio-resource based composite foams were developed with soy protein isolate (SPI) as reactive reinforcing filler in castor oil based polyurethane foams (PUF) prepared by self-rising method using water as a blowing agent. The resulting composite foams were evaluated for their morphology, density, mechanical and biodegradation properties, etc. Fourier transform infrared spectroscopy study exhibited characteristic peaks for SPI and PUF and indicated that the amino groups and hydroxyl groups on SPI reacted with polyphenyl polymethylene polyisocyanates (PAPI) to increase the crosslinking degrees of the composite foams. Densities of the resultant composites were found to increase with increasing SPI content. Mechanical properties of the samples were improved with the increase of SPI content. The compost tests further proved that the composite PUF had better biodegradability than neat PUF. Therefore, this research has provided a simple method of preparing the bio-resource based polyurethane foams, while exploring the potential of using SPI in polyurethane foam applications.     

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.     

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.     

Structure,Mechanical, Thermal and Fire Behavior Assessments of Environmentally Friendly Crude Glycerol-Based Rigid Polyisocyanurate Foams

In this work, rigid polyisocyanurate foams were prepared at partial substitution (0–70 wt%) of commercially available petrochemical polyol, with previously synthesized biopolyol based on crude glycerol and castor oil. Influence of the biopolyol content on morphology, chemical structure, static and dynamic mechanical properties, thermal insulation properties, thermal stability and flammability was investigated. Incorporation of 35 wt% of crude glycerol-based polyol had reduced average cell size by more than 30% and slightly increased closed cell content, simultaneously reducing thermal conductivity coefficient of foam by 12% and inhibiting their thermal aging. Applied modifications showed also positive impact on the mechanical performance of rigid foams. Increase of crosslink density resulted in enhancement of compressive strength by more than 100%. Incorporation of prepared biopolyol resulted in enhancement of thermal stability and changes in degradation pathway. Up to 35 wt% share of crude glycerol-based polyol, foams showed similar flammability as reference sample, which can be considered very beneficial from the environmental point of view.     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

Aminolysis and aminoglycolysis of waste poly(ethylene terephthalate)

This paper describes the chemical degradation of waste poly(ethylene terephthalate) (PET) with polyamines or triethanolamine, the characteristics of the products, and a search for ways to use these products. Solvolysis of the polymer ester bonds was caused by diethylenetriamine, triethylenetetramine, and their mixtures, as well as mixtures of triethylenetetramine and p-phenylenediamine or triethanolamine. Products of aminolysis or aminoglycolysis of PET obtained in reactions performed at 200–210°C (with a molar ratio of the recurrent polymer unit to amine of 1 : 2) have been characterized using nuclear magnetic resonance (NMR). Viscosity and hydroxyl number measurements have been done for PET/triethanolamine products. Substances from aminolytical reactions with polyamines were tested as hardeners for liquid epoxy resins, and the product of polymer aminoglycolysis with triethanolamine was tested as an epoxy resin hardener, e.g., for water-borne paints, and a polyol component for rigid polyurethane foams. The compositions of epoxy resin hardeners have been characterized using DSC and rheometry. Comparative analyses of the hardened epoxy materials have been done on the basis of glass temperature and mechanical properties data, as well as some specific properties of the coating materials and rigid polyurethane foams. Received: September 15, 2000 / Accepted: September 21, 2000     

Novel Renewable Polyols Based on Limonene for Rigid Polyurethane Foams

Novel renewable polyols based on limonene were synthesized using thiol-ene “click” chemistry. These limonene based polyols were structurally characterized using wet methods (hydroxyl number, acid value and viscosity), gel permeation chromatography and spectroscopic methods. The results indicated that high yield of polyols from limonene based materials can be obtained using thiol-ene reaction. These limonene based polyols were used successfully for preparation of rigid polyurethane foams. These foams had regular shape cells and uniform cell size distribution. Thermal studies on these foams indicated that foams were thermally stable up to 250 °C. The glass transition temperature of the foams was higher than 200 °C. These rigid polyurethane foams had high compressive strength and the highest compressive strength of 195 kPa was observed. These foams have good physical–mechanical characteristics and could be suitable for all the applications of rigid polyurethane foams such as thermal insulation of freezers, storage tanks for the chemical and food industries, and packing materials for food industries.     

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.     

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.     

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.

     

Soybean-Oil-Based Polyisocyanurate Rigid Foams

Polyisocyanurate foams were prepared from polymeric 4,4-diphenylmethane diisocyanate (MDI), soy polyol and polypropylene oxide polyol by varying isocyanate index from 110 to 350. The higher isocyanate index produced polyisocyanurate foams with higher thermal stability, improved flame resistance, tensile strength, higher modulus, and higher glass transition. Soy-based foams displayed better thermal stability, lower flammability, higher rigidity (modulus) and higher compression strength than those based on the propylene oxide polyols of the same molecular weight and functionality.     

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.     

Novel polyol initiator from polyurethane recycling residue

Flexible polyurethane foams can be advantageously treated by two-phase glycolysis in order to recover polyols with improved quality. The bottom phase obtained, which contains highly toxic reaction by-products and the excess glycol, presents an environmental and economic problem which should be solved. The main purpose of this work is the development of process for the valorization of these by-products, converting them in non-dangerous and profitable substances. For this process, most of the glycol can be recovered by means of vacuum distillation in order to reuse it in the glycolysis. On the other hand, the vacuum residue, containing the isocyanate part of the glycolysis by-products, was assayed as initiator in the synthesis of new polyols. Propoxylation of the initiator was carried out in different experimental conditions to obtain several polyether-polyols. Rigid polyurethane foams with suitable technical properties were synthesized with those polyols synthesized with the dangerous glycolysis by-products.     

Hybridized Biocomposites from Agro-Wastes: Mechanical,Physical and Thermal Characterization

Agricultural wastes, oil palm trunk (OPT) veneer and oil palm empty fruit bunch (EFB) mat were used for the preparation of hybridized plywood using 250 and 450 g/m² of urea formaldehyde (UF) as gluing agent. The mechanical (flexural strength, flexural modulus, screw withdrawal, shear strength), physical (density, water absorption, thickness swelling and delamination) and thermal (TGA) properties of the biocomposites were studied. Images taken with a scanning electron micrograph (SEM) indicated an improvement in the fiber–matrix bonding for the laminated panel glued with 450 g/m² of UF.     

Hybrid Composites Made from Oil Palm Empty Fruit Bunches/Jute Fibres: Water Absorption,Thickness Swelling and Density Behaviours

In this research, hybrid composite materials were prepared from combination of oil palm Empty fruit bunches (EFB) fibre and jute fibre as reinforcement, epoxy as polymer matrix. This study intended to investigate the effect of jute fiber hybridization and different layering pattern on the physical properties of oil palm EFB-Epoxy composites. Water absorption and thickness swelling test reveal that hybrid composite shows a moderate water absorption which is 11.20% for hybrid EFB/Jute/EFB composite and 6.08% for hybrid Jute/EFB/Jute composite. The thickness swelling and water absorption of the hybrid composites slightly increased as the layering pattern of hybrid composites changed. Hybrid composites are more water resistance and dimensional stable compare to the pure EFB composites. This is attributed to the more hydrophilic nature of EFB composites. Hybridization of oil palm EFB composites with jute fibres can improve the dimensional stability and density of pure EFB and Jute fibre reinforced composites has higher density of 1.2 g/cm³ compared to all other composites.