Biodegradation Behavior of Some Vegetable Oil-Based Polymers

The potential biodegradability of several vegetable oil-based polymers was assessed by respirometry in soil for 60–100 days at temperatures of 30–58°C. Films of soybean oil and linseed oil which were oxidatively polymerized (Co catalyst) on a kraft paper support were 90%–100% mineralized to CO₂ after 70 days at 30°C. Mineralization of polymerized tung oil to CO₂ was much slower than soy or linseed oils. Mineralization of epoxy resins made from epoxidized soybean oil (ESO) and aliphatic dicarboxylic acids was rapid while mineralization of similar resins made with a triacid (citric) was slower. There was no significant degradation of polyamine/ESO resins after 100 days at 58°C. Mineralization of the available carbon in vegetable oil polyurethanes and cationically polymerized ESO was less than 7.5% after 70 days at 30°C and 25 days at 55°C compared to 100% for soybean oil. From these results, it appears that triglycerides highly cross-linked with non-degradable linkages are not biodegradable to a significant extent while triglycerides cross-linked with hydrolysable bonds such as esters remain biodegradable.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Preparation of Soybean Oil Polymers with High Molecular Weight

The cationic polymerization of soybean oils was initiated by boron trifluoride diethyl etherate in supercritical carbon dioxide medium. The resulting polymers had molecular weight ranging from 21,842 to 118,300 g/mol. Nuclear magnetic resonance spectroscopy and gel permeation chromatography analysis confirmed the polymerization had occurred. Parameters affecting the polymerization were studied, which included initiator amount and reaction time. Results show that the longer reaction time, up to 3 h, favored the higher molecular weight of polymers at conditions of 140 °C and initiator BF₃·OEt₂ (2.5 g, 0.018 mol). When reaction time was increased further, the molecular weight of polymers stayed the same or slightly decreased. Increased concentration of initiator gave the higher molecular weight of polymers. The high molecular weight polymers were possibly formed through two path ways: polymerization and intermolecular Diels-Alder reaction.     

Novel Polymeric Materials from Biological Oils

A variety of novel polymeric materials ranging from elastomers to tough, rigid plastics have been prepared by the cationic copolymerization of regular soybean oil, low-saturation soybean oil, or conjugated low-saturation soybean oil with various alkene commonomers. Using appropriate compositions and reaction conditions, 70–100% of the soybean oil is covalently incorporated into the cross-linked polymer networks, contributing significantly to cross-linking during copolymerization. The resulting thermosets exhibit thermophysical and mechanical properties that are competitive with those of their petroleum-based counterparts. In addition, good damping and shape memory properties have been obtained by controlling the degree of cross-linking and the rigidity of the polymer backbone. New materials with similar characteristics have also been produced from other biological oils, including tung, and fish oils using the same technique. The new, more valuable properties of these bioplastics suggest numerous promising applications of these novel polymeric materials.     

Development of Anticorrosive Poly(Ether-Urethane) Amide Coatings from Linseed Oil: A Sustainable Resource

Polyetheramide(PEtA) resin was synthesized by the condensation polymerization of N,N-bis(2-hydroxy ethyl) linseed oil fatty amide diol (HELA) with resorcinol. It was further treated with different percentage of toluylene 2-4-diisocyanate (TDI) to obtain the urethane modified polyetheramide resins (UPEtA). The structural elucidation of PEtA and urethane modified polyetheramide(UPEtA) were carried out by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. These analyses confirm the formation of PEtA and UPEtA. Physico-chemical and physico-mechanical analysis were performed by standard laboratory methods. The resin composition UPEtA-24 showed best physico-mechanical properties with scratch hardness 2.0 kg, impact resistance 150 lb/in. and good bending ability. The thermal stability and curing behavior of polymers were respectively studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis shows that these coatings can be used safely upto 190 °C. The coatings of UPEtA resins were prepared on mild steel strips. The anticorrosive behavior of UPEtA coatings were investigated in acid, alkali, water and xylene. All the coatings exhibit good chemical resistance performance in acid, alkali, saline and organic solvents, while the resin UPEtA-24 shows the best performance.     

Conjugation of Soybean Oil and It’s Free-Radical Copolymerization with Acrylonitrile

The conjugated soybean oil was synthesized through the isomerization reaction of soybean oil to transformed the structure of linoleic acid into conjugated linoleic acid structure, and Rhodium complexes (RhCl(Pph₃)₃) was used as catalyst. The efficiency on the conjugation of catalyst RhCl (Pph₃)₃, tin dichloride dehydrate (SnCl₂·2H₂O) and triphenylphosphine (Pph₃) were evaluated. The results showed when RhCl(Pph₃)₃, SnCl₂·2H₂O and Pph₃ are 9.25, 9.0 and 13.1 mg in 100 g soybean oil respectively, the highest conversion of conjugation achieved 96%. The free radical copolymerization of conjugated soybean oil with acrylonitrile (AN) and dicyclopentadiene (DCP) was studied. AIBN was used as the initiator. FT-IR and ¹H-NMR results indicates that the conjugated soybean oil with AN and DCP did occur free radical copolymerization with the initiator AIBN. The product is light yellow powder. The thermal properties of the soy-based copolymer were investigated by TG and DSC. The initial degradation temperature of polymers is higher then 250 °C.     

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     

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.     

Soybean Oil-Based Photo-Crosslinked Polymer Networks

Novel soybean oil-based crosslinked polymer networks were prepared by UV photopolymerization and their mechanical properties were evaluated. Poly(ethylene glycol) diacrylate (PEGDA) and biodegradable poly(ε-caprolactone) diacrylate (PCLDA) were synthesized and used as crosslinking agent to form crosslinked polymer networks by UV-initiated free-radical polymerization with acrylated epoxidized soybean oil (AESO). The synthesis of acrylate end-capped macromers was confirmed using FT-IR and ¹H NMR spectroscopic techniques. Photopolymerization time, the composition of reaction mixture, and the type and length of crosslinking agent were changed to obtain crosslinked polymer networks with various mechanical properties. Polymers prepared from AESO and PCL degraded 6% of the initial weight in 24 days in phosphate buffer solution (pH 7.2) containing lipase enzyme. These potentially biodegradable and biocompatible polymers can be used as ecofriendly materials for biomedical and other applications to replace the existing petroleum-based polymers currently used.     

Gasification of waste plastics by steam reforming in a fluidized bed

The process of producing synthetic gas from waste plastics by steam reforming was investigated. To evaluate this process, the steam reforming of the oils derived from low-density polyethylene and polystyrene were carried out using a laboratory-scale fluidized bed of Ni-Al₂O₃ catalysts. The performance of gasification in terms of carbon conversion, gas yield, and gas compositions was examined. Although oils derived from plastics contain many kinds of heavy hydrocarbons and aromatics, they were well gasified at temperatures above 1023 K with a steam/carbon ratio of 3.5 and a weight hourly space velocity of 1 h⁻¹. The hydrogen content of the product gas was very high at approximately 72 vol% for polyethylene-derived oil and 68 vol% for polystyrene-derived oil. These compositions agreed well with the values calculated from chemical equilibrium.     

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.     

The weathering properties of four unique crude oils from Australia

This paper reports on the results of weathering studies conducted on four light crude oils from production platforms on the northwest shelf of Australia. The laboratory weathering included both evaporative weathering and emulsification studies. The fresh oils and their topped residues were subjected to a battery of physical and chemical characterization analyses. Detailed analyses were performed for n-alkanes by GC/FID and for mono- and polycyclic aromatic hydrocarbons and phenols by GC/MS. The water-in-oil emulsion formation properties of these oils and their topped residues were investigated at two environmentally significant temperatures (13 and 20°C). The results of the analyses indicate that these oils are very different compositionally and have a wide range of physical and chemical properties. The emulsification properties of these oils and their weathered residues ranged from oils that have very rapid water uptake to oils having no water uptake. Unexpectedly, the very waxy oils had very little water uptake and did not form stable water-in-oil emulsions.     

Styrene/Lignin-Based Polymeric Composites Obtained Through a Sequential Mass-Suspension Polymerization Process

A modified sequential mass-suspension polymerization was employed to ensure adequate dispersion of lignin into the monomeric phase. Due to its complex macromolecular structure and low compatibility with styrene, eucalyptus wood-extracted lignin, via a modified Kraft method, was esterified with methacrylic anhydride to ensure organic phase homogeneity into the reaction medium. Infrared spectroscopy showed a decrease in the hydroxyl band, a characteristic of natural lignin (3200–3400 cm^?1) and an increase in the characteristic ester band (1720–1740 cm^?1) whereas nuclear magnetic resonance measurements exhibited intense peaks in the range from 1.7 to 2.05 ppm (–CH₃) and 5.4 to 6.2 ppm (=CH₂), related to methacrylic anhydride. Comparatively, the esterified lignin also displayed an increase of its glass transition temperature for 98?°C, related to natural lignin, whose T _g was determined to be equal to 91?°C. Styrene/lignin-based polymers exhibited higher average molar masses in comparison to the values observed for polystyrene synthesized with similar amounts of benzoyl peroxide, due to the ability of lignin to act as a free-radical scavenger. Composites obtained with styrene and natural or esterified lignin were successfully synthesized, presenting regular morphology and proper lignin dispersion. Based on a very simple polymerization system, it is possible to enhance the final properties of polystyrene through the incorporation of lignin, which represents an important platform for developing attractive polymeric materials from renewable resources.     

The behaviour of selected rare-earth elements during the conversion of phosphogypsum to calcium sulphide and residue

Phosphogypsum (PG) is a large hazardous waste from fertiliser and phosphoric acid industries from which useful products including rare-earth elements (REEs) can be recovered depending on the treatment process. Its conversion to calcium sulphide (CaS) which was achieved at 95% followed by the formation of S, CaCO₃ and residue is one of the plausible treatment processes leading to economic and environmental benefits. This study aimed at monitoring selected REEs behaviour during the conversion of (PG) to (CaS). The concentrations of REEs in the raw PG, the produced CaS and the obtained residue were determined after digestion (microwave and traditional acid leaching) using ICP-OES. The effect of CO₂ and H₂S used in the process of forming CaCO₃ and S from PG on the concentrations of REEs was also investigated. Microwave digestion proved to be more effective than traditional acid leaching in the recovery of REEs. Microwave digestion using 3 mL HNO₃ + 1 mL HCl was more effective than 1 mL HNO₃ + 3 mL in REEs recovery. CaS contained the highest amount of Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, La and Y with values of 2646, 476, 2255, 320, 60.5, 376, 79.8, 1.24, 476, 1185 and 318 µg/g respectively. Based on these findings, the residue could be further processed to recover REEs despite less than 40% decrease in concentration for the majority of REEs observed due to the use of H₂S and CO₂. CO₂ was found to be more suitable as fewer REEs were leached as compared to H₂S. All things considered, the obtained residue could be a good secondary source of REEs as it is easier to leach, retained good amount of REEs and lesser impurities.

     

Photocrosslinking of an Acrylated Epoxidized Linseed Oil: Kinetics and its Application for Optimized Wood Coatings

Over the past few decades, the industry developed an increasing interest in using renewable, bio-based thermosetting polymers as matrix systems for composites and coating systems. In the present paper an acrylated epoxidized linseed oil (AELO) was synthesized from epoxidized linseed oil (ELO) through ring opening of the oxirane group using acrylic acid as the ring opening agent. The synthesized AELO was mixed with three different photoinitiators and cured under monochromatic conditions (???=?365?nm) at different light intensities and at different temperatures. The concentration of the initiators was aligned that all initiators absorb at 365?nm the same amount of light. The evolution of cure was monitored by using real-time infrared spectroscopy with a heated attenuated total reflection unit. The decrease of absorption in the measured spectra at 1,406?cm^?1 was used to calculate the conversion of acrylic double bonds with increasing time of UV light exposure to get information about the cure kinetics for each AELO mixture at different light intensities and different temperatures. Wood substrates were coated in a preliminary work with the AELO mixtures and after UV-curing some technological coating properties like gloss, scratch resistance, adhesion, and solvent resistance were tested. In combination with the information about the cure kinetics in the present work the coating properties were correlated with the cure evolution and the final degree of double bond conversion. The found correlation can be used in the future to find optimized coating conditions for the AELO mixtures on wood substrates.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

Treatment of waste printed circuit board by green solvent using ionic liquid

Recycling of waste printed circuit boards (WPCBs) is an important subject not only for the protection of environment but also for the recovery of valuable materials. A feasibility study was conducted to dissolve bromine epoxy resins of WPCBs using ionic liquid (IL) of 1-ethyl-3-methylimizadolium tetrafluoroborate [EMIM(+)][BF(4)(-)] (nonaqueous green solvent) for recovering copper foils and glass fibers. Experimental results indicated that the initial delamination had seen from the cross-section of the WPCBs by mean of metallographic microscope and digital camera when WPCBs were heated in [EMIM(+)][BF(4)(-)] at 240°C for a duration of 30min. When temperature was increased to 260°C for a duration of 10min, the bromine epoxy resins of WPCBs were throughout dissolved into [EMIM(+)][BF(4)(-)] and the separations of copper foils and glass fibers from WPCBs were completed. This clean and non-polluting technology offers a new way to recycle valuable materials from WPCBs and prevent the environmental pollution of WPCBs effectively.     

Influences of Magnesium <Emphasis Type="Italic">tri-</Emphasis>Silicate on the Physical,Mechanical, and Degradable Properties of Ultraviolet (UV) Radiation Cured Plain Board Surface

A series of formulations were prepared with different percentages of oligomer, epoxy diacrylate (EA-1020 ), monomer, 1,6 Hexane diol diacrylate,(HDDA) and different percentages of filler (Magnesium tri-silicate, Mg₂Si₃O₈). Irgacure 369 [2-Benzyl-2-dimethyl-amine-1 (4-morpholinophenyl) butanone-1] was used in the formulations as photoinitiator. Ultraviolet (UV) cured thin polymer films were prepared from these formulating solutions on clean glass plates. Pendulum hardness (PH), gel content and macro scratch hardness (MSH) of the UV cured films were studied. One percent Mg₂Si₃O₈ containing formulation showed the premium properties. The substrates (plain board) were coated by these formulating solutions and cured under the same UV lamp at different intensities of radiation. Various properties of the coated surface such as PH, gloss, adhesion, abrasion and MSH were investigated. The base coat containing 1% Mg₂Si₃O₈ and top coat containing 48% HDDA produced the best performance among all the formulations inspected. The degradable properties in different weathering conditions on PH, gloss, adhesion, abrasion and MSH were measured. The surface cured with the optimized formulation (E) again yielded the minimum loss of the properties.