From Aminolysis Product of PET Waste to Novel Biodegradable Polyurethanes

Chemical recycling of PET has been developed by various methods. Aminolysis is one of chemical recycling methods of PET has been developed recently. The obtained product using aminolysis, Bis (2-hydroxy ethylene) terephthalamide (BHETA), has the potential for further reactions to obtain useful products. There are few reports on usage of recycled BHETA from PET waste to synthesis of polyurethanes. On the other hand, various biodegradable polyurethanes have been synthesized using polycaprolactone diol. Therefore, caprolactone is a new potential in synthesis of biodegradable polyurethanes from PET waste. In this work, novel biodegradable polyurethanes have been synthesized using BHETA. In this order, at first polyols with different molecular weights have been synthesized through ring opening polymerization of caprolactone by BHETA, then urethane linkages were formed using HDI (Hexamethylene Diisocyanate) without chain extender. Chemical, thermal, mechanical and dynamic mechanical properties, biodegradability, morphology and UV resistance of synthesized polyurethanes have been investigated.     

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.     

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.     

The Synthesis and FTIR, Kinetics and TG/DTG/DTA Study of Inter Penetrating Polymer Networks (IPNs) Derived from Polyurethanes of Glycerol Modified Castor Oil and Cardanol Based Dyes

Interpenetrating polymer networks from agricultural products such as glycerol modified castor oil polyurethanes and cardanol based dyes have not been extensively studied so far. Such polymers were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate as cross-linker. Characterizations of these polymers were performed by Fourier Transform infra red spectra and thermal analysis techniques such as thermogravimetric analysis, derivative thermogravimetry and differential thermal analysis. The kinetic parameters such as activation energies and orders of reaction were estimated by using Freeman?CAnderson??s method. The effects of changes in polyurethane to dye monomer weight ratio and NCO/OH molar ratio of polyurethanes on the properties of such polymers were studied.     

Effects of Saturated Acids on Physical Properties of UPE Resins Prepared from Recycled PET Products

In this study, effects of saturated acids on physical properties, including hardness, impact strength, flexural properties and thermal properties, of unsaturated polyester or UPE resins prepared from recycled PET bottles and fabrics were investigated. PET was depolymerized by glycolysis reaction with the excess propylene glycol in the presence of zinc acetate as a catalyst. UPE resins were then synthesized by polyesterification of these glycolyzed products with maleic anhydride as an unsaturated diacid as well as succinic acid and adipic acid as a saturated diacid. With the addition of styrene monomer, UPEs were subsequently casted into specimens by crosslinking reaction using methyl ethyl ketone peroxide and cobalt octoate as an initiator and a catalyst, respectively. Physical properties of the cured specimens were then studied. The results showed that, when a saturated acid was incorporated, the hardness of the cured UPE resins decreased due to the decreasing amount of crosslinks. The extended distance between crosslinking sites on molecular chains facilitated load distribution, resulting in the significant improvement of impact strength. The flexural strength was also improved when the small amount of saturated acid was used. The onset thermal degradation temperatures and the glass transition temperatures of the prepared UPE resins were almost unchanged.     

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.     

Detection of a Toxic Product Released by a Polyurethane-Containing Film Using a Composting Test Method Based on a Mineral Bed

The degradation of a film containing a 4,4diphenyl methane diisocyanate (MDI) poly(€-caprolactone)-based polyurethane was followed in a test system based on a mineral solid bed designed to facilitate analysis of break-down products released under composting conditions. The use of a mineral solid bed can help extraction and analytical procedures which could be hindered by the heterogeneous nature of compost. The fermentation conditions are typical of the composting environment and generate a powerfully degradative environment. The film fully disintegrated within 30 days of treatment. Analysis on the mineral bed extracts showed that: (i) about 40% of the initial polyurethane was still present in the bed extracts; (ii) this residue was strongly degraded in the poly(€-caprolactone) part, while the urethane part was almost completely recovered (from 80 to 95%, according to the measurement method); (iii) 4,4 diamino diphenyl methane (MDA), a very dangerous product of MDI, was released during biodegradation. The results indicate that a mineral bed can be employed to study degradation and metabolites formation in solid phase fermentation and that the MDI-based polyurethanes are not susceptible of a full degradation during composting and maintain the potential of a slow release of MDA into the environment after soil application.     

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.     

Synthesis of Segmented Polyurethane Based on Polymeric Soybean Oil Polyol and Poly (Ethylene Glycol)

Polyurethane (PUR) plastic sheets were prepared by reacting hydroxylated polymeric soybean oil (PSbOH) synthesized from autoxidized soybean oil with polyethylene glycol (PEG) in the presence of isophorone diisocyanate (IPDI). FTIR technique was used to identify of chemical reactions. These polyurethanes have different valuable properties, determined by their chemical composition. The effect of stoichiometric balance (i.e., PSbOH/PEG-2000/IPDI weight ratio) on the final properties was evaluated. The polyurethane plastic sheets with the PSbOH/PEG-2000/IPDI weight ratio 1.0/1.0/0.67 and 1.0/0.3/0.3 had excellent mechanical properties indicating elongation at break more than 200%. Increase in IPDI and decrease in PEG weight ratio cause the higher stress–strain value. The properties of the materials were measured by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), stress–strain measurements and FTIR technique.     

Processing Stability and Biodegradation of Polylactic Acid (PLA) Composites Reinforced with Cotton Linters or Maple Hardwood Fibres

Polylactic acid (PLA) composites comprising up to 25 wt% cotton linter (CL) or up to 50 % maple wood fibre (WF) were prepared by compounding and injection moulding. A reduction of crystallinity in the PLA matrix was observed as a result of the thermal processing method. These PLACL and PLAWF composites provided excellent improvements in both stiffness (with increases in tensile and flexural modulus) and toughness (increases in notched impact strength) properties over the neat PLA resin, while the tensile and flexural strengths of the composites were generally unchanged, while the strain at break values were reduced in comparison to the neat PLA. DMA results indicated incorporating these fibres caused the mechanical loss factor (tan δ) to decrease, suggesting better damping capabilities were achieved with the composites. SEM analysis of the impact fractured surfaces of the PLACL composites showed debonding-cavitation at the matrix-fibre interface while the PLAWF composites showed good wetting along its matrix-fibre interface. The composting of these composites up to 90 days showed that the degradation onset time was increased when increasing the fibre loadings, but the maximum degree of degradation and the maximum daily rates of degradation were decreased compared to neat PLA. On a weight basis of fibre loading, the PLACL composites had a quicker onset of biodegradation, a higher maximum daily rate of biodegradation and, overall, a higher degree of biodegradation at 90 days than the PLAWF composites, possibly due to the quicker thermal hydrolysis observed in the PLA matrix of the PLACL composites during processing and composting.     

Natural Oil-Based Alkyd-Acrylic Copolymers: New Candidates for Barrier Materials

The feasibility of using alkyd-acrylic copolymers as a barrier material was studied. Copolymers of tall oil fatty acid or rapeseed oil-based alkyd resin and polyacrylates were synthesized and films of these copolymers were prepared. Nuclear magnetic resonance spectroscopy revealed that after copolymerization the proportion of double bonds in alkyd resin was diminished due to grafting reactions. The mechanical properties, such as strength and flexibility, of the copolymer films were tested, and the performance of the films as water, oil, and oxygen barrier was evaluated. An increased amount of alkyd resin made the films more brittle and increased their oxygen permeability, however, at the same time their hydrophobicity was increased.     

Thermal Degradation and Kinetics of Alginate Polyurethane Hybrid Material Prepared from Alginic Acid as a Polyol

Alginate polyurethane hybrid materials are prepared by varying mole ratio of 2, 4-TDI as a di-isocyanate and alginic acid as a polyol in presence of dimethyl sulfoxide (DMSO) as a solvent. FT-IR and ¹³C one-dimensional (1D) solid state NMR (SSNMR) spectroscopy indicates that alginic acid is converted into alginate-polyurethane hybrid material via urethane linkage. Surface morphology of alginate-polyurethane hybrids changes by varying alginic acid: TDI ratio. The peak at near 221 °C in DSC thermogram of alginic acid (Alg) is shifted to higher temperature in alginate-polyurethane hybrid (Algpu1 and Algpu2). TGA study shows that alginate-polyurethane hybrid prepared using alginic acid: TDI = 1:1 (Algpu2) is more stable than alginic acid: TDI = 1:0.5 (Algpu1) at 300 °C. Kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive 1st order reactions. This study shows that thermal stability of alginate-polyurethane hybrid material was increased by adjusting mole ratio of 2, 4-TDI and alginic acid.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Effects of Diisocyanate and Polymeric Epoxidized Chain Extenders on the Properties of Recycled Poly(Lactic Acid)

Increasing demand in the use of poly(lactic acid) (PLA) leads to a debate about using potential foodstuffs for plastic production and a moral issue when starvation problem is taken into account. One of the solutions is recycling of PLA; however, recycling results in property losses during melt processing due to low thermal stability of PLA. This study focuses on using chain extenders to offset thermal degradation of recycled PLA. The effects of a diisocyanate and a polymeric epoxidized chain extender on the properties of the recycled poly(lactic acid) were investigated. In order to mimic the recycling process, PLA was subjected to thermo-mechanical degradation using a laboratory scale compounder. Chain extender type, loading and mixing time were investigated. On-line rheology and intrinsic viscosity measurements of PLA before and after chain extension confirmed that the molecular weight increased. Dynamic mechanical analysis, rheology and tensile tests revealed that the chain extenders led to a significant increase in modulus, strength and melt-viscosity. It was found that diisocyanate had slightly higher and faster chain extension reactivity than polymeric extender. Differential scanning calorimetry results showed an increase in the crystallization temperature due to the branched and extended chain structure.     

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.     

Synthesis of Soy-Polyol by Two Step Continuous Route and Development of Soy-Based Polyurethane Foam

Soy-polyol has been synthesized via a low energy two-step continuous route thus avoiding intermediate steps and chemicals. The functional groups of soy-polyol thus produced were identified by Fourier transform infrared (FTIR) spectroscopy which confirmed the cleavage of the double bonds, the formation of new epoxy linkages and the presence of hydroxyl groups. The change in chemical structure and physical properties of the soy polyol was further characterized and the results indicated a successful conversion with reduced unsaturation, increased hydroxyl number and increased viscosity. Polyurethane foam was prepared from soy-polyol using isocyanate and thermogravimetric analysis was used to study its thermal decomposition behaviour. Multiple transitions were identified in relation to depolymerization and bond dissociation. Density and compressive strength of the soy-foam were found to be satisfactory. An investigation of microstructure of soy foam by scanning electron microscope and X-ray computed tomography revealed the internal cell morphology and cell structure.     

Biodegradation of Epoxy and MF Modified Polyurethane Films Derived from a Sustainable Resource

Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm⁻¹ and ca. 1050 cm⁻¹ for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.     

Biodegradability of PMMA Blends with Some Cellulose Derivatives

High polymer blends of Polymethyl methacrylate (PMMA) with cellulose acetate (CA) and Cellulose acetate phthalate (CAP) of varying blend compositions have been prepared to study their biodegradation behavior and blend miscibility. Films of PMMA–CA, and PMMA–CAP blends have been prepared by solution casting using Acetone and Dimethyl formamide(DMF) as solvents respectively. Biodegradability of these blends has been studied by four different methods namely, soil burial test, enzymatic degradation, and degradation in phosphate buffer and activated sludge degradation followed by water absorption tests to support the degradation studies. Degradation analysis was done by weight loss method. The results of all the tests showed sufficient biodegradability of these blends. Degradability increased with the increase in CA and CAP content in the blend compositions. The miscibility of PMMA–CA and PMMA–CAP blends have been studied by solution viscometric and ultrasonic methods. The results obtained reveal that PMMA forms miscible blends with either CA or CAP in the entire composition range. Miscibility of the blends may be due to the formation of hydrogen bond between the carbonyl group of PMMA and the free hydroxyl group of CA and CAP.     

Biodegradation of Natural Rubber and Natural Rubber Products by <Emphasis Type="Italic">Streptomyces</Emphasis> sp. Strain CFMR 7

The rubber degrading activity of Streptomyces sp. CFMR 7 whose whole genome sequence was recently determined was tested with non-vulcanized fresh latex and common vulcanized rubber products such as latex glove, latex condom and latex car tyre. The degradation activity was unequivocally demonstrated by scanning electron microscopy with respect to microbial colonization efficiency, disintegration of rubber material and biofilm formation after 3, 6 and 9 months of inoculation. Fourier transform infrared spectroscopy comprising the attenuated total reflectance analysis on these inoculated products revealed insights into the biodegradation mechanism of this strain whereby, a decrease in the number of cis -1,4 double bonds in the polyisoprene chain, the appearance of ketone and aldehyde groups formation indicating an oxidative attack at the double bond of rubber hydrocarbon. In the presence of strain Streptomyces sp. CFMR 7, gel permeation chromatography analysis revealed a significant shift of the molecular weight distribution to lower values. Clear decrease in the molecular weight was observed over 3, 6 and 9 months of cultivation on fresh latex samples compared to other vulcanized products. No shift in the molecular weight distribution was observed for non-inoculated control. These results clearly showed that Streptomyces sp. CFMR 7 was able to cleave the carbon backbone of poly (cis -1,4-isoprene). Although this strain was able to degrade both non-vulcanized and vulcanized rubber products, faster degradation was obtained with natural rubber and rubber products with low complexity.     

The Effect of CTBN Concentrations on the Kinetic Parameters of Decomposition of Blends of Epoxy Resins Modified with Carboxyl-Terminated Liquid Copolymer

Diglycidyl ether of bisphenol—A (DGEBA)—based epoxy resin was blended in the ratio of 3:1 (weight basis) with cycloaliphatic epoxy (CAE) resin. The prepared blend sample was further blended with different weight percentages of carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) ranging between 0 and 25 wt% with an interval of 5 wt% and cured with stiochiometric amounts of 4, 4’- diamino diphenyl sulphone (DDS) cure agent. Structural changes during blending were studied by Fourier-transform infra-red (FTIR) spectroscopic analysis. The kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre-exponential factor (Z) and rate decomposition constant (k), for the decomposition of the samples were calculated by applying Coats-Redfern equation over thermogravimetric (TG) data. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. Further, the blend sample had higher initial degradation temperature and activation energy than its respective pure epoxy resin indicating that the CTBN acted as thermal stabilizer for epoxy resin which improved the thermal stability.