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.     

Cardanol Polymerization Under Acid Conditions By Addition And Condensation Reactions

Cashew nut shell liquid (CNSL) is a byproduct of the cashew nut industry and consists predominantly of phenolic compounds that have an side chain with different degrees of unsaturation. Cardanol, one of these components, is biodegradable and widely available. Studies have revealed several polymerization reactions involving cardanol. However, the mechanisms and detailed structures of polymerization reactions have not been explored, although the final product shows different applications. In this work, we evaluated the mechanism and the products structure of the reaction of cardanol with: (i) boron trifluoride diethyl etherate (BF₃O(CH₂CH₃)₂), and (ii) formaldehyde. The characterizations were performed by FTIR, ¹H NMR, SEC and TGA. The results show that the reaction of cardanol with aldehyde produces the expected like-comb structure with a long hydrocarbon pendent chain. Nevertheless, the reaction of cardanol with BF₃O(CH₂CH₃)₂ can exhibits a more complex structure since it was identified aromatic ring linkages, besides the expected polymerization through C=C.     

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.     

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.     

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.     

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     

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.     

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.     

PET from Used Beverage Bottles: A Material for Preparation of Biologically Degradable Copolyesters

Poly(ethylene terephthalate) from used colorless beverage bottles was solvolyzed by ethane-1,2-diol. Hydroxyl end-groups present in the mixture of polyols formed were used to initiate the polymerization of ??-caprolactone (CLO) at 190?°C. Polycondensation (190?°C) of the reaction mixture containing an equilibrium amount of lactone corresponding to the reaction temperature yield an aliphatic?Caromatic copolyester. A variety of copolyesters containing 20?C60?mol. % CLO structural units was prepared. The microstructure of their macromolecules was analyzed using ¹H?NMR spectroscopy. Copolyesters were characterized by thermal analysis and tensile tests and their biodegradation potential was checked by the composting test.     

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.     

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.     

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.     

Influence of Palm Oil-Based Polyol on the Properties of Flexible Polyurethane Foams

This paper describes the effect of the modification of polyurethane system with palm oil-based polyol on the cell structure and physical?Cmechanical properties of polyurethane foams. Flexible polyurethane foams were prepared by substituting a part of petrochemical polyether-polyol with the palm oil polyol. Selected physical?Cmechanical properties of these foams were examined and compared to the properties of reference foam. The properties such as apparent density, tensile strength, elongation at break, resilience, compressive stress and thermal stability were analyzed. It was found that the modifications of polyurethane formulation with palm oil polyol allow to improve selected properties of final products.     

One-Pot Reaction of Waste PET to Flame Retardant Polyurethane Foam,via Deep Eutectic Solvents-Based Conversion Technology

Depolymerization of polyethylene terephthalate (PET) is a promising technology for producing recycled monomers. Using a deep eutectic solvent (DES)-based catalyst, the PET glycolysis process produces bis-(2-hydroxyethylene terephthalate) (BHET). This recycled monomer reacts with isocyanate and forms polyurethane foam (PUF). The DES-based one-pot reaction is advantageous because it is a low-energy process that requires relatively lower temperatures and reduced reaction times. In this study, choline chloride/urea, zinc chloride/urea, and zinc acetate/urea based DESs were adopted as DES catalysts for glycolysis. Subsequently, the conversion of PET, BHET yield, and OH values were evaluated. Both filtered and unfiltered reaction mixtures were used as polyols for PUF polymerization after characterization of the acid and hydroxyl values of the polyols, as well as the NCO (–N=C=O) value of isocyanate. In the case of unfiltered reaction mixtures, PUF was obtained via a one-pot reaction, which exhibited higher thermal stability than PUF made from the filtered polyols. This outcome indicated that oligomeric BHET containing many aromatic moieties in unfiltered polyols contributes to the thermal stability of PUF. This environmentally friendly and relatively simple process is an economical approach for upcycling waste PET.

     

Eco-Friendly, Vascular Shape and Interpenetrating Poly (Acrylic Acid) Grafted Pectin Hydrogels; Biosorption and Desorption Investigations

The synthesis and characterization of poly (acrylic acid) grafted pectin hydrogel followed by biosorption and desorption characteristics of cadmium, as a model heavy metal, have been studied. The grafted eco-friendly pectin based interpenetrating hydrogel was prepared in the presence of gluteraldehyde crosslinker under N₂ atmosphere and characterized using ¹H-NMR, FTIR, TGA and SEM techniques. Gluteraldehyde was found to form one-arm and two-arm crosslinks in the copolymer. Upon grafting, two-dimensional sheet structures bounded to tubular and vascular cylindrical rods were observed. The biosorption and desorption data, determined experimentally, were fitted to pseudo-second order reaction kinetics. At higher ionic strength values, the maximum metal uptake value (q _max) was lowered and pseudo-second order rate constant (k ₂) was increased. Whereas, at higher pH values the maximum metal uptake value (q _max) was increased and Pseudo-second order rate constant (k ₂) was decreased. 0.1?M HCl solution was a suitable eluent to regenerate the hydrogel surface and recover the adsorbed cadmium metal ions. Pectin based copolymer could be used as an efficient candidature biosorbent for the recovery of cadmium metal ions from aqueous solutions.     

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.     

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.     

Release and fate of fluorocarbons in a shredder residue landfill cell: 2. Field investigations

The shredder residues from automobiles, home appliances and other metal containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to determine the gas composition, attenuation, and emission of fluorocarbons in a monofill shredder residue landfill cell by field investigation. Landfill gas generated within the shredder waste primarily consisted of CH₄ (27%) and N₂ (71%), without CO₂, indicating that the gas composition was governed by chemical reactions in combination with anaerobic microbial reactions. The gas generated also contained different fluorocarbons (up to 27 μg L^?1). The presence of HCFC-21 and HCFC-31 indicated that anaerobic degradation of CFC-11 occurred in the landfill cell, as neither of these compounds has been produced for industrial applications. This study demonstrates that a landfill cell containing shredder waste has a potential for attenuating CFC-11 released from polyurethane (PUR) insulation foam in the cell via aerobic and anaerobic biodegradation processes. In deeper, anaerobic zones of the cell, reductive dechlorination of CFCs to HCFCs was evident, while in the shallow, oxic zones, there was a high potential for biooxidation of both methane and lesser chlorinated fluorocarbons. These findings correlated well with both laboratory results (presented in a companion paper) and surface emission measurements that, with the exception from a few hot spots, indicated that surface emissions were negative or below detection.     

Synthesis and Characterisation of Polyester Based on Isosorbide and Butanedioic Acid

Copolyesters based on isosorbide and butanedioic acid in combination with monomers such as adipic acid and dimethyl terephthalate, poly(isosorbide-co-butanedioic acid) (and -co-adipic acid) and poly(isosorbide-co-butanedioic acid-co-dimethyl terephthalate), were synthesized and characterized. Linear OH-functionalized polyesters were obtained via melt polyesterification of dicarboxylic acids with OH-functional monomers. The type of end-group was controlled by the monomer stoichiometry and hydroxyl functional group is formed in time. Average molecular masses of synthesised polyesters were measured by gel permeation chromatography. The glass transition temperatures and thermal stability of the obtained polyesters were effectively adjusted by varying polymer composition and molar mass. Addition of adipic acid or dimethyl terephthalate increased glass transition temperatures of obtained polyesters. Thermal stability of obtained polyester slightly increases by the increasing of dimethyl terephthalate content. Molecular structures of obtained polyester were assessed by Fourier transform infrared spectra and ¹H NMR spectroscopy.