Recycling of waste poly(ethylene terephthalate) with castor oil using microwave heating

The chemical recycling of waste poly(ethylene terephthalate) (PET) using castor oil (CO) as a reagent is reported. CO presents a renewable alternative to petrochemical based reagents, e.g. glycols, and enables also substantial modification of final physico-chemical properties of a received product. Advantageously, microwave irradiation was used to accelerate the depolymerization of PET. A composition of obtained product was strongly influenced by the reaction temperature. When the decomposition of PET was performed at temperature higher than 240 °C, then a significant extent of side products based on PET oligomers and transesterified CO was observed due to dehydration and hydrolysis of CO. Contrary to that, PET decomposition took place at slow rate below 230 °C and the optimal reaction temperature lies in the relatively narrow interval from 230 °C to 240 °C. The product prepared in the optimal temperature range did not contain any high molecular weight PET oligomers. MALDI-TOF mass spectrometry enabled to identify the structures included in the obtained polyol product. The maximum number of six repeating monomeric unit of PET was found in the product, which confirmed practically the complete depolymerization of PET chain and good reactivity of the acylester hydroxyl groups of CO.     

Recycling of poly(ethylene terephthalate) (PET)

After a survey of the mostly utilized recycling methods for fibres and bottles, the possibilities of recovering films are discussed in more detail. This presentation describes primarily the melt-recovery method, which is used by us and by other manufacturers. During this process the greatest difficulties arise from the presence of impurities and contaminations. The influence of these determining parameters on the recycling process and on the re-usability of the recovered PET are elucidated, with special emphasis on the role of the oligomers.     

Recycling technology of poly(ethylene terephthalate) materials

Poly(ethylene terephthalate) (PET) has become one of major post consumer plastics wastes, in addition to polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride) (PVC). The challenge to large-volume plastics companies is to learn how to collect, separate, reprocess and market their low-cost products and make a profit, too. The effort of PET recycling, however, is the most successful story in the plastic recycling technology, including both reclaim and upgrade of PET waste. Beverage bottles made of PET are recycled more than 20% of the total production. The technology of today can reclaim the post-consumer PET bottles to produce high-quality granulated PET with better than 99% purity. A practical reclaim process for recycling PET bottles (including bottle, HDPE base cup, aluminum cap, liner, label and adhesive) is available by the Center for Plastics Recycling Research in USA. PET recycling process, like for other plastics, can be divided into three categories: incineration, physical recycling, and chemical recycling. To make the plastic recycling business pay requires more than simple recovery and marketing. Greatest profit potential is in upgraded and value-added reclaim products. Upgrading involves compounding with additives to make material more processable, adding reinforcement, or producing extrusions or finished parts from reclaim resins. For instance, a modified injection-moldable resin made from PET bottle scrap is claimed to provide high impact and processability at less cost than competitive materials. It is foreseen that chemical recycling of waste PET bottle becomes feasible if the price of raw material goes up. Three economical processes are involved in this technology: pyrolysis, hydrocracking, and hydrolysis. The hydrolysis process is presently employed to recover the raw material for unsaturated polyester resin manufacture or polyols for the production of polyurethane resin. It is reported in this presentation that polymer concrete could be a huge potential market for chemical reclaim of PET materials, especially for green or mixed-color PET, which are priced lower than colorless PET reclaim materials.     

Alkyd resins derived from glycolized waste poly(ethylene terephthalate)

In this investigation the production of secondary value-added products, such as alkyd resins, derived from the glycolysis of poly(ethylene terephthalate) (PET) is examined as an effective way for its recycling. PET was taken from common soft-drink bottles and diethylene glycol (DEG) was used for the depolymerization at several initial molar ratios. The oligomers obtained were analyzed according to their average molecular weights. Furthermore, the glycolyzed PET products (oligomers) were reacted with maleic anhydride, phthalic anhydride and propylene glycol to form unsaturated polyester resins. These were subsequently mixed with styrene and cured using the benzoyl peroxide/amine initiator system to carry out the reaction in ambient temperature. The curing characteristics of the resins produced were investigated with respect to the initial molar ratio of DEG/PET as well as the initial initiator concentration. Finally, the mechanical properties (tensile strength and elongation at the break point) of the resins were compared with the conventional general purpose resin and were found to be comparable.     

Microwave assisted ecofriendly recycling of poly (ethylene terephthalate) bottle waste

Glycolysis of poly (ethylene terephthalate) bottle waste was carried out using microwave energy. A domestic microwave oven of 800 W was used with suitable modification for carrying out the reaction under reflux. The catalysts used for the depolymerization in ethylene glycol (EG) were zinc acetate and some simple laboratory chemicals such as sodium carbonate, sodium bicarbonate and barium hydroxide. Comparison of results was made from the point of view of the yield of bis (2-hydroxyethylene) terephthalate (BHET) and the time taken for depolymerization. It was observed that under identical conditions of catalyst concentration and PET:EG ratio, the yield of BHET was nearly same as that obtained earlier by conventional electric heating. However, the time taken for completion of reaction was reduced drastically from 8 h to 35 min. This has led to substantial saving in energy.     

A chemical procedure for reprocessing of poly(ethylene terephthalate) waste

A procedure was developed for degradation of poly(ethylene terephthalate) waste with water to the starting monomers. The possibility of preparing diethyl terephthalate without a catalyst in a rocking cylindrical pressure vessel with the rocking axis passing through the geometric center was examined.     

The transport of oxygen through oriented poly(ethylene terephthalate)

The transport of oxygen through oriented PET at 25 and 60°C has been studied using the dynamic diffusion method. It did not prove possible to determine the diffusion and solubility coefficients with reasonable accuracy, and only the permeability coefficients are discussed in terms of the structure of the samples. The results suggest that the lowering of the oxygen permeability on drawing is related to the production of additional material with the trans conformation of the glycol residue, either in crystallites or in amorphous regions, rather than solely to the overall development of orientation or crystallinity.     

Study on the pyrolysis of Moroccan oil shale with poly (ethylene terephthalate)

Investigations into the pyrolytic behaviours of oil shale, poly (ethylene terephthalate) (PET) and their mixture have been conducted using a thermogravimetric analyzer. Experiments were carried out dynamically by increasing the temperature from 298 to 1,273 K with heating rates of 2–100 K/min under a nitrogen atmosphere. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperature of each component in the mixture was higher than those the individual components; thus an increase in thermal stability was expected. The kinetic processing of thermogravimetric data was carried out using Flynn–Wall–Ozawa (FWO) method.     

Study on the pyrolysis of Moroccan oil shale with poly (ethylene terephthalate)

Investigations into the pyrolytic behaviours of oil shale, poly (ethylene terephthalate) (PET) and their mixture have been conducted using a thermogravimetric analyzer. Experiments were carried out dynamically by increasing the temperature from 298 to 1273 K with heating rates of 2 to 100 K/min under a nitrogen atmosphere. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperature of each component in the mixture was higher than those the individual components; thus an increase in thermal stability was expected. The kinetic processing of thermogravimetric data was carried out using Flynn-Wall-Ozawa (FWO) method.     

Photolysis of poly(ethylene terephthalate)

The photolysis of poly(ethylene terephthalate) films was studied in vacuo with light of wavelengths 2537 and 3130 A. A very stable filter system which cuts out the 3025 A. line was developed to isolate 3130 A. from a mercury spectrum. Despite the fact that the penetration of 2537 A. light was limited to a depth of a ca. 10³ A. whereas 3130 A. light was more uniformly absorbed it was possible to demonstrate that the quantum yields for CO and CO₂ formation were in agreement for the two wavelengths. Quantum yields for fractures and crosslinks were estimated by sol-gel analysis. An absorption maximum which develops near 13 μ after exposure of poly(ethylene terephthalate) to light or γ-rays was attributed to the formation of groups formed by elimination of CO and CO₂. ESR spectra for trapped radicals were tentatively assigned to the components p-C₆H₃· and ·O? CH₂? CH₂? . It is suggested that the former radicals combine to form crosslinks. Quantum yields (× 10⁴) with 3130 A. light are: CO, 6; CO₂, 2; crosslinks, 5.5; trapped radicals, 1.5; With 2537 A. light, quantum yields are: CO, 6–9; CO₂, 2–3; the network formed was not characterized as to crosslinks and fractures; trapped radicals were observed to exist but not determined.     

Chemical healing in poly(ethylene terephthalate)

A new molecular mechanism for the healing phenomenon in semicrystalline linear polycondensates (healing resulting from chemical reactions between macromolecules located in the interfacial surface) is demonstrated. Strips of commercial poly(ethylene terephthalate) are annealed at 258°C in order to avoid melt sticking. Two such strips are partially overlapped, pressed, and heated in a vacuum at 240°C for 10, 20, 30, and 100 h. By measuring the stress at break outside the contact area and the debonding shear stress the critical overlapping length is computed. It is concluded that transreaction contributes more than solid-state post-condensation to chemical healing.     

Mesophase structures in poly(ethylene terephthalate), poly(ethylene naphthalate) and poly(ethylene naphthalate bibenzoate)

Films of poly(ethylene naphthalate) (PEN) and poly(ethylene naphthalate bibenzoate) (PENBB) have been drawn under a variety of conditions of temperature and strain rate to determine the conditions under which a nematic-like mesophase structure can be produced. In PEN the combination of low temperature and high-strain rate encourages mesophase formation, while in PENBB the mesophase was formed under all conditions where it proved possible to draw the material at all. A molecular modelling study of the mesophase in PEN and in poly(ethylene terephthalate) (PET) offers possible structures for the mesophase and showed that the mesophase structure could be stable once formed © 1997 John Wiley & Sons, Ltd.     

Oxygen and water-vapor diffusion through biaxially oriented poly(ethylene terephthalate)

The gas barrier properties of a wide range of biaxially oriented polyethylene terephthalate films have been investigated. The permeability and diffusion coefficients for oxygen and water vapor transmissions were determined for films prepared by both simultaneous and sequential biaxial stretching. The effect of annealing was also studied and a comparison made with previous results for uniaxially oriented films. It was found that the permeability correlated well with the density of the sample, but that the dependence on the gauche/trans conformer ratio shown for uniaxial material was not so clear. A good empirical correlation was also obtained between permeability and a proposed measure of molecular orientation obtained from refractive index measurements. A more detailed interpretation, based on infrared measurements of orientation, showed that there is a systematic reduction in permeability as the planes of the terephthalate residues become parallel to the film surface.     

Segmented block copolymers of poly(ethylene glycol) and poly(ethylene terephthalate)

A new series of segmented copolymers were synthesized from poly(ethylene terephthalate) (PET) oligomers and poly(ethylene glycol) (PEG) by a two‐step solution polymerization reaction. PET oligomers were obtained by glycolysis depolymerization. Structural features were defined by infrared and nuclear magnetic resonance (NMR) spectroscopy. The copolymer composition was calculated via ¹H NMR spectroscopy. The content of soft PEG segments was higher than that of hard PET segments. A single glass‐transition temperature was detected for all the synthesized segmented copolymers. This observation was found to be independent of the initial PET‐to‐PEG molar ratio. The molar masses of the copolymers were determined by gel permeation chromatography (GPC). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4448–4457, 2004     

Viscoelasticity of oriented poly(ethylene terephthalate)

Time–temperature superposition can be successfully applied to both the stress relaxation and dynamic mechanical properties of oriented PET fibers. Two curves result; one is the time dependence of the modulus at constant temperature, while the other is the shift, log aT, of this curve along the time scale as a function of temperature. This temperature dependence is less than that for both unoriented PET and typical amorphous polymers above T_g. It is about the same as that for oriented nylon 66 and unoriented glassy poly(methyl methacrylate). The isothermal modulus has the same time dependence as that of the unoriented PET; however, it is a factor of 3.3 larger. The modulus curve is almost identical in both shape and magnitude with that of oriented nylon 66. However, a temperature of 82°C. is required to place the viscoelastic dispersion region of PET at the same time scale as nylon 66 at 25°C. This temperature increase is the major difference in viscoelasticity between these two oriented polymers.     

Fast crystallization of poly(ethylene terephthalate)

The crystallization of poly(ethylene terephthalate) (PET) was studied in the presence of nucleating agents and promoters. The effect of both by themselves and in concert was investigated using differential scanning calorimetry. The aim of this work is to find conditions of fast crystallization of PET. Sodium benzoate(SB) and Surlyn® (S) substantially increase the crystallization rate of PET at higher temperature owing to a reduction in the energy barrier towards primary nucleation, but they accelerate crystallization even more at lower temperature with an additional improvement of the molecular mobility of PET chains. Chain scission of PET caused by the reaction with the nucleating agents was proven by determination of molecular weight. The addition of S alone led to a lower reduction in molecular weight. A series of N-alkyl-p-toluenesulfonamides (ATSAs) were shown to effectively promote molecular motion of the PET chains, leading to an increase in crsytallization rate at lower temperature. A remarkable acceleration of crystallization of PET was attained at lower temperature when S and ATSA were added together. When the content of ATSA is low, S has the dominant influence due to its dual effect of decreasing energy barrier towards nucleation and promoting molecular motion of PET chains. A further increase of crystallization rate of PET was found only after an addition of ATSA of above 5 wt.%.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThis work was supported by State Science and Technology Commission, and partially by National Science Foundation.     

Light-scattering characterization of poly(ethylene terephthalate)

By using a closed-circuit filtration system, we have succeeded in clarifying poly(ethylene terephthalate) (PET) dissolved in hexafluoroisopropanol (HFIP). Such static properties as the radius of gyration R_g, the weight-average molecular weight M_w, and the second virial coefficient A₂ and such dynamic properties as the translational diffusion coefficient D, or its equivalent hydrodynamic radius R_h, and the second (diffusion) virial coefficient k_d were determined for several PET samples of different molecular weights by using light-scattering intensity and linewidth measurements. An empirical relation between D_o (or R_h) and M_w was established: R_h = (1.77±0.15)X10^?2 M with R_h and M_w expressed in units of nanometers and grams per mole, respectively. The empirical exponent α_D(ca. 0.58±0.01) is in good agreement with the less precisely determined intrinsic viscosity/molecular weight exponent α_η (ca. 0.71±0.02). Several intensity correlation functions were measured very precisely using long accumulation times. A Laplace inversion was performed using the singular-value decomposition technique. The approximate molecular weight distribution (MWD) determined by light-scattering spectroscopy was in reasonable agreement with a completely independent determination of MWD using gel permeation chromatography (GPC). It was interesting to note, though not surprising, that GPC showed emphasis on lower-molecular-weight fractions, while light-scattering emphasized higher-molecular-weight fractions. The agreement further strengthens some complementary aspects of the two techniques.     

Organocatalytic depolymerization of poly(ethylene terephthalate)

We describe the organocatalytic depolymerization of poly(ethylene terephthalate) (PET), using a commercially available guanidine catalyst, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). Postconsumer PET beverage bottles were used and processed with 1.0 mol % (0.7 wt %) of TBD and excess amount of ethylene glycol (EG) at 190 °C for 3.5 hours under atmospheric pressure to give bis(2‐hydroxyethyl) terephthalate (BHET) in 78% isolated yield. The catalyst efficiency was comparable to other metal acetate/alkoxide catalysts that are commonly used for depolymerization of PET. The BHET content in the glycolysis product was subject to the reagent loading. This catalyst influenced the rate of the depolymerization as well as the effective process temperature. We also demonstrated the recycling of the catalyst and the excess EG for more than 5 cycles. Computational and experimental studies showed that both TBD and EG activate PET through hydrogen bond formation/activation to facilitate this reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Heterogeneous nucleation of poly(ethylene terephthalate)

The effect of various metal salts as nucleating additives for poly(ethylene terephthalate) (PET) has been investigated. In the case of sodium benzoate and probably for all other effective nucleating additives, the nucleation process can be divided into a “heterogeneous particle nucleation” performed by the unreacted salt and a “homogeneous nucleation” due to the polymer–sodium (metal) salt formed during the extrusion. This polymer–sodium (metal) salt is the major nucleating agent in these systems. We have also shown the fundamental difference between the concept of a nucleating additive and that of a nucleating agent.     

Intrinsic birefringence of poly(ethylene terephthalate)

In the existing literature various values are given for the intrinsic birefringence of the crystalline and the amorphous phases in poly(ethylene terephthalate) (PET). These values have either been calculated theoretically or obtained from experimental data on the basis of certain models. In this investigation, using the Samuels two-phase model which correlates sonic modulus with structural parameters, intrinsic birefringence values for the crystalline (Δn_c) and amorphous (Δn_a) phases have been determined by studying 30 PET samples prepared by heat setting to have a wide range of structures; the results are Δn_c = 0.29 and Δn_a = 0.20. These values are discussed along with others in the literature and it is concluded that in the light of the present work, the values used by many authors need reexamination.