Efficient chemical recycling of waste fiber-reinforced plastics: use of reduced amounts of dimethylaminopyridine and activated charcoal for the purification of recovered monomer

We have achieved major improvements in the efficient chemical recycling of waste fiber-reinforced plastics (FRPs). The effects of reduction in the amounts of dimethylaminopyridine (DMAP) used for depolymerization were examined. The treatment of waste FRP in the presence of 1 or 2 wt% DMAP resulted in the successful recovery of monomeric materials that could be employed in the polymerization process to produce recycled plastic. The separation of linker units from glass fiber, however, was unsuccessful. The purity of the recovered monomeric material, when treated with activated charcoal, was improved to about 70%. This resulted in effective decoloration of the recovered monomer. Finally, the purified material, after undergoing repolymerization, provided high-quality recycled plastic comparable to new plastics produced from new monomers.     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Improved preparation of recycled polymers in chemical recycling of fiber-reinforced plastics and molding of test product using recycled polymers

We examined an improved preparation method of recycled unsaturated polyester resin from recovered monomeric materials obtained from the depolymerization of fiber-reinforced plastics (FRPs). The formation of unsaturated polyester progressed smoothly in the presence of catalytic amounts of Ca(OAc)₂ and Ti(OBu)₄. The quality of the resin was estimated by the durometer hardness test. The strength test of FRP board prepared from recycled resin showed sufficient hardness for practical use (about 94% of the tensile strength of new resin). We examined the recycled resin by using it to mold successfully an actual test product.     

Commentary: A paradigm for plastics recycling

Possibilities abound for organizing an effective plastics recycling industry. Whatever is done to waste plastic requires some knowledge of what the materials are and an understanding that any mixing, inadvertent or deliberate, will not destroy the material's usefulness. If all polymers could be changed back to monomers, the net result would be that polymers of a thousand different types could be reduced to less than a dozen types of monomer for well over 95 percent of plastic waste. If the cost of depolymerization is less than the current monomer price, the economics of depolymerization is an obvious advantage. Polymerization and depolymerization are both controlled by thermodynamics and kinetics. The paradigm is to discriminate one plastic formulation from another. If the properties are close and selection assured, then direct reuse may be possible. In all other cases, we must use a chemical process where the choices are few and the selection is easy.     

Construction, Characterization and Biological Activity of Chiral and Thermally Stable Nanostructured Poly(Ester-Imide)s as Tyrosine-Containing Pseudo-Poly(Amino Acid)s

In this paper we studied the synthesis of biodegradable optically active poly(ester-imide)s containing different amino acid residues in the main chain. These pseudo-poly(amino acid)s were synthesized by polycondensation of N,N′-(pyromellitoyl)-bis-l-tyrosine dimethyl ester as a diphenolic monomer and two chiral trimellitic anhydride-derived diacid monomers containing s-valine and l-methionine. The direct polycondensation reaction of these diacids with aromatic diol was carried out in a system of tosyl chloride (TsCl), pyridine (Py) and N,N′-dimethylformamide (DMF) as a condensing agent. The structures and morphology of these polymers were studied by FT-IR, ¹H-NMR, powder X-ray diffraction, field emission scanning electron microscopy (FE-SEM), specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA profiles indicate that the resulting PEIs have a good thermal stability. Morphology probes showed these polymers were noncrystalline and nanostructured polymers. The monomers and prepared polymers were buried under the soil to study the sensitivity of the monomers and the obtained polymers to microbial degradation. The high microbial population and prominent dehydrogenase activity in the soil containing polymers showed that the synthesized polymers are biologically active and microbiologically biodegradable. Wheat seedling growth in the soil buried with synthetic polymers not only confirmed non-toxicity of polymers but also showed possibility of phyto-remediation in polymer-contaminated soils.     

Evaluation of material recycling for plastics: environmental aspects

“Zero emissions” is a concept envisaging the creation of a sustainable society with minimal disposal of resources. In order to realize zero emissions for plastics, it is important to establish a method for quantitatively evaluating candidate recycling processes. In this study, the principle of the substitution factor (SF) is introduced. A quantitative evaluation of the recycling process for plastics was then carried out. The production process for monofilament plastics was examined. The recycling of plastics discarded during the production process could be substituted in small amounts for virgin materials, giving reduced CO₂ emissions. Furthermore, production using recycled material mixed with virgin material was more effective in reducing CO₂ emissions than when recycled materials only were used. Received: November 19, 1999 / Accepted: November 28, 2000     

Identification and thermomechanical characterization of polymers recovered from mobile phone waste

The plastic components from waste mobile phones were sorted and characterized using visual, spectroscopic and thermal methods. The sustainable strength of the recovered plastics was investigated by comparing their mechanical and thermal properties with commercially used reference materials. The results revealed that the recovered polymers have significant potential to be reused. However, some properties, such as impact strength and tensile modulus, are significantly low compared to virgin materials and need further improvement. The samples were also tested for brominated flame retardants (BFRs) using gas chromatography–mass spectrometry technique, and the results indicated the absence of BFR in recovered plastics; hence, these can be processed without any risk of BFR toxicity.     

Biodegradable Polyesters and Polyamides From Difunctionalized Lauric and Coconut Fatty Acids

In this work, a major fatty acid from coconut oil was used as starting material in preparing biodegradable polymers. Thus, polyesters and polyamides from varying proportions of monomers, hydroxy- and amino- derivatives of lauric acid were synthesized. Initially, the derivatives were prepared by regioselective chlorination of lauric acid, in the presence of ferrous ions in strong acid medium. Subsequent hydroxylation and amination procedures yielded the hydroxy- and amino- derivatives of lauric acid. These monomers were polymerized in a reaction tube by simple polycondensation method at 220–230 °C for 6–8 h without catalyst. Molecular weight determination using –COOH by end group titration and gel permeation chromatography (GPC) gave an average molar mass of 3,000–5,000 g mol⁻¹ with n = 15–25 monomer units. Thermal properties such as glass transition (T_g) and decomposition (T_d) temperatures were obtained using differential scanning calorimetry (DSC). The same processes of synthesis and determinations above were applied to coconut fatty acids, derived from saponification of coconut oil, and resulted to very similar conclusions. A quick biodegradation assay against fungus Aspergillus niger UPCC 4219 showed that the polymers prepared are more biodegradable than conventional plastics such as polypropylene, poly(ethyleneterepthalate) and poly(tetrafluoroethylene) but not as biodegradable as cellulosic (newsprint) paper.     

Novel Biobased Polyurethanes Synthesized from Nontoxic Phenolic Diol Containing l-Tyrosine Moiety Under Green Media

Ionic liquids (ILs) have been accepted as ‘green’ alternatives to the organic solvents in a range of synthesis, catalysis and electrochemistry, because of their distinctive chemical and physical properties. In this investigation, N,N′-(pyromellitoyl)-bis-l-tyrosine dimethyl ester as a chiral bioactive diphenolic monomer was prepared in three steps. The polycondensation of this monomer with various aromatic and aliphatic diisocyanates such as 4,4′-methylene-bis-(4-phenylisocyanate) (6a), toluylene-2,4-diisocyanate (6b), isophorone diisocyanate (6c) and hexamethylene diisocyanate (6d) were carried out in the presence of tetrabutylammonium bromide as a molten IL under microwave irradiation conditions and was compared with polymerization in traditional solvent like N-methyl-2-pyrrolidone. The results show that IL efficiently absorbs microwave energy, thus leading to a very high heating rate. Thus IL method is safe and green since toxic and volatile organic solvents were eliminated. All of the novel poly(urethane-imides) (PUIs) showed good solubility in various organic solvents. The obtained new polymers were characterized with FT-IR, ¹H-NMR, elemental and thermogravimetric analysis techniques. Thermogravimetric analysis (TGA) of two representative PUIs demonstrated that they are rather thermally stable. In vitro toxicity studies showed that the synthetic materials are biologically active and they are nontoxic to microbial growth then could be classified as bioactive and biodegradable compounds.     

Graft Copolymerization of Methyl Acrylate onto Cellulosic Biofibers: Synthesis,Characterization and Applications

Graft copolymerization of cellulosic biopolymers with synthetic polymers is of enormous interest because of its application in biofiltration, biosorption, biomedical, biocomposites and various other eco-friendly materials. Synthesis of graft copolymers of methyl acrylate onto mercerized Grewia optiva biofibers using ferrous ammonium sulfate–potassium per sulfate as redox initiator in air was carried out. Different reaction parameters such as amount of solvent, monomer concentration, initiator molar ratio, reaction time and reaction temperature were optimized to get the maximum percentage of grafting. The graft copolymers thus formed were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and differential thermogravimetric techniques. A plausible mechanism for explanation of the graft copolymerization reactions pattern shown is offered. The effect of grafting percentage on the physico–chemical properties of raw as well as grafted Grewia optiva biofibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. Green polymer composites were also successfully prepared through compression molding technique by using grafted Grewia optiva biofibers as reinforcement.     

Kinetics and Thermodynamics of Hydrolytic Depolymerization of Polyamide Waste at Various Temperature and Autogenious Pressure by High-Pressure Autoclave

Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10⁻³ min⁻¹. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol⁻¹ respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10⁻¹⁶.     

Vacuum pyrolysis of polymeric wastes containing hazardous cyano groups

Vacuum pyrolysis of polymeric wastes containing hazardous cyano groups was studied using low temperature pyrolysis mass spectrometry. Specifically, the study analyzed the presence of toxic compounds among the pyrolysis products. The polymers were pyrolyzed directly in the solid probe of a quadruple mass spectrometer within an ion source at a pressure of 10^?6 Torr and then sorted by quadrupole mass analyzer. Polyethyl cyanoacrylate degrades by depolymerization, mostly into the ethyl cyanoacrylate monomer units. The degradation of polyurethane produces nonpolymeric urethane, isocyanates, amines and ethers. Polyacrylonitrile degrades via a depolymerization pathway into oligonitriles, acrylonitrile, ammonia and hydrogen cyanide.     

Cracking styrene derivative polymers in decalin solvent with metal-supported carbon catalysts

The cracking of styrene derivative polymers dissolved in decalin was conducted with metal-supported carbon catalysts under an inert gas atmosphere to recover monosubstituted styrene or monosubstituted ethylbenzene in higher yields than is obtained by pyrolysis, and to elucidate the detailed reaction mechanisms in the solvent. Poly-(4-methylstyrene), poly-(4-t-butylstyrene), poly-(α-methylstyrene), and polystyrene were used. In decalin without a catalyst, each polymer was decomposed into the monomer, dimer, and trimer derived from the corresponding polymer except for poly-(α-methylstyrene), which was decomposed into the monomer and styrene. By using metal-supported carbon, the olefinic compounds derived from the corresponding polymer were thoroughly hydrogenated to the saturated form in a nitrogen atmosphere by a hydrogen transfer reaction from decalin, which was simultaneously dehydrogenated to tetralin and naphthalene with the evolution of hydrogen gas. In comparison with metal species, Pd- and Ru-supported carbon catalysts maintained the hydrogenation activity for a longer time and with a lower evolution of hydrogen than Pt or Rh. The dehydrogenation of decalin was mainly observed not on the metal surfaces, but on the carbon surfaces over Pd-supported carbon. Stabilization of the monomers will be able to suppress the coking which occurs with repolymerization in long running process. Received: July 19, 2000 / Accepted: March 16, 2001     

Synthesis of3H- polyethylene and its use for fate studies on degradable plastics

Determining the fate of xenobiotic materials in the environment can be aided by the use of radioactive isotope technology. Previous research on the degradation of polymers such as polyethylene (PE) was aided by the utilization of radiotracers. In order to study the environmental fate of degradable (PE/starch) plastics, we synthesized³H-labeled PE. Results of soil incubation studies indicate that only minimal degradation of the PE component, as indicated by the production of water-soluble metabolites, occurred during 2 years of incubation in soil. Despite the minimal degradation, the³H label did not allow for detection of the degradation products. In addition, the³H-PE was particularly useful for tracing the fate of degradable plastics after consumption by terrestrial isopods. The detection of aqueous-soluble radioactivity in isopod frass was used to indicate degradation of the plastic film.     

Thermoplastic vulcanizates from post consumer computer plastics/nitrile rubber blends by dynamic vulcanization

Due to depletion of natural resources and increasing greenhouse emissions, new technologies for the transformation of waste polymers into valuable materials represent one of our greatest current needs. Acrylonitrile–butadiene–styrene terpolymer (ABS) is one of the most widely used engineering plastics and is used as outer casing for electronic equipment. Nitrile rubber (NBR) is used in many applications that demand oil resistance. In an attempt to explore whether these materials can be successfully recycled, we prepared blends of scrap computer plastics (SCP) based on ABS with NBR and waste NBR powder (w-NBR), and investigated their mechanical properties and recyclability. Specifically, we assessed the effect of dynamic vulcanization and replacement of virgin NBR with w-NBR on the properties of 60/40, 70/30, and 80/20 NBR/SCP blends. These blends exhibited thermoplastic elastomeric behavior. The thermoplastic elastomeric blends showed excellent swelling resistance to standard lubricant oil (namely, IRM 903 oil).     

Recovery of PET from packaging plastics mixtures by wet shaking table

Recycling requires the separation of materials appearing in a mass of wastes of heterogeneous composition and characteristics, into single, almost pure, component/material flows. The separation of materials (e.g., some types of plastics) with similar physical properties (e.g., specific gravity) is often accomplished by human sorting. This is the case of the separation of packaging plastics in municipal solid wastes (MSW). The low cost of virgin plastics and low value of recycled plastics necessitate the utilization of low cost techniques and processes in the recycling of packaging plastics. An experimental study was conducted to evaluate the feasibility of production of a PET product, cleaned from PVC and PS, using a wet shaking table. The wet shaking table is an environmentally friendly process, widely used to separate minerals, which has low capital and operational costs. Some operational variables of the equipment, as well as different feed characteristics, were considered. The results show that the separation of these plastics is feasible although, similarly to the mineral field, in somewhat complex flow sheets.     

Depolymerization of Waste PET with Phosphoric Acid–Modified Silica Gel Under Microwave Irradiation

Chemical recycling of waste poly(ethylene terephthalate) (PET) using phosphoric acid–modified silica gel as a solid catalyst is reported. Advantageously, microwave irradiation was used to progress the depolymerization of PET. In this study, depolymerization of PET with a small amount of water is suggested as a suitable method. The depolymerized product, terephthalic acid was obtained and assigned by ¹H NMR and FT-IR spectroscopy. Finally, over 90 % conversion to terephthalic acid was achieved when waste plastic bottles were treated with the method. This results confirm the importance of the microwave power technique as a promising recycling method for plastic bottles made from PET, resulting in monomer recovery in addition to substantial energy saving.     

Biodegradation of acrylic acid polymers and oligomers by mixed microbial communities in activated sludge

The biodegradability (mineralization to carbon dioxide) of acrylic acid oligomers and polymers was studied in activated sludge obtained from continuous-flow activated sludge (CAS) systems exposed to mixtures of low molecular weight (Mw < 8000) poly(acrylic acid)s and other watesoluble polymers [poly(ethylene glycol)s] in influent wastewater. Dilute preparations of activated sludge from the CAS units were tested for their ability to mineralize acrylic acid monomer and dimer, as well as a series of model acrylic acid oligomers and polymers (Mw 500, 700, 1000, 2000, and 4500), as sole carbon and energy sources. Complete mineralization of acrylic acid monomer and dimer was observed in low-biomass sludge preparations previously exposed to the polymer mixture, based on carbon dioxide production and residual dissolved organic carbon analyses. Extensive (though incomplete) degradation was also observed for the low molecular weight acrylic acid oligomers (Mw 500 and 700), but degradation dropped off sharply for the 1000, 2000, and 4500 Mw polymers. Radiochemical (¹⁴C) data also confirmed the low degradation potential of the 1000, 2000, and 4500 Mw materials. Degradation of two commercial poly(ethylene glycol)s at 1000 and 3400 Mw was complete and comparable to that of the acrylic acid monomer and dimer. Our results indicate that mixed populations of activated sludge microorganisms can extensively metabolize acrylic acid oligomers of seven units or less. Complete mineralization, however, could be confirmed only for the monomer and dimer material, and carbon mass balance data suggested that the true molecular weight cutoff for complete biodegradation was significantly less than the 500–700 Mw range tested.     

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.

     

Multiple use of waste catalysts with and without regeneration for waste polymer cracking

Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidised bed reactor concentrated on the used highly contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C₂-C₇) remained fairly constant. For the first time, these results indicate that “waste” FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity.