Obtaining of a PET-CaF2 hybrid multifilament: Non-isothermal crystallization studies

Poly(ethylene terephthalate) (PET) has been mixed with fluorite (CaF₂) particles to obtain micro- and nano-composites aiming to obtain a hybrid multifilament. In first term, the use of two montanic waxes and an amide wax as dispersing agents towards the compatibilization of the inorganic and organic components of the CaF₂/PET composite were considered. To do this, non-isothermal crystallization studies by differential scanning calorimetry have been carried out. Moreover, the influence of the CaF₂ particle size and concentration on the thermal properties of the system have been also studied by this technique. Finally, the extrapolation of the results has materialised as a novel PET/CaF₂ hybrid multifilament. Thermal and mechanical properties and molecular weight of the multifilament have been as well evaluated.     

Effect of small amounts of poly(lactic acid) on the recycling of poly(ethylene terephthalate) bottles

Poly(ethylene terephthalate) (PET) is one of the most used commodity polymers, especially for food and beverage applications, and its recycling is of great importance because of the possible use in the textile and construction industries. On the other hand, the interest in biodegradable polymers has led, in recent years, to the use of materials such as poly(lactic acid) (PLA) also in the food and beverage industry. The presence of small amounts of PLA in the PET waste can significantly affect the post-consumer recycling process. In this work, the effect of the presence of small amounts of PLA on the recycling of PET bottles is investigated by rheological, mechanical, morphological and thermogravimetric analysis. The results indicate that this presence can significantly affect the rheological properties under non-isothermal elongational flow, while the mechanical properties were considerably affected only in some circumstances and the thermal stability was not significantly modified.     

Properties and morphology of recycled poly(ethylene terephthalate)/bisphenol a polycarbonate/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) blends by low‐temperature solid‐state extrusion

Among the various methods available for recycling plastics waste, blending technology is a straightforward and relatively simple method for recycling. In this paper, a new blending technology, low‐temperature solid‐state extrusion, was discussed. Several recycled poly(terephthalate ethylene)/bisphenol a polycarbonate/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) blends (R‐PET/PC/SEBS blends) have been prepared by this technology. The results show that thermal and hydrolytic degradation of R‐PET is improved when extruding temperature was between the glass transition temperature (T_g) and cold crystallization temperature (T_cc). Elongation at break and notched impact strength were increased evidently, from 15.9% to 103.6, and from 8.6 kJ/m² to 20.4 kJ/m², respectively. The appropriate rotating speed of screws was between 100 and 150 rpm. At the same time, the appropriate rotating speed of the screws brings a suitable shear viscosity ratio of R‐PET and PC, which is of advantage to blending of R‐PET and PC together with SEBS. Dispersion of minor phase, PC and SEBS, became finer and smaller, to about 1 µm. Chain extender, Methylenediphenyl diisocyanate (MDI) can react with the end‐carboxyl group and end‐hydroxyl group of R‐PET. FT‐IR spectra testified that the reactions have been happened in the extruding process. A chain extending reaction not only increased the molecular weight of PET and PC, but also can synthesize PET‐g‐PC copolymer to act as a reactive compatilizer. An SEM micrograph shows that a micro‐fiber structure of PET was formed in the blend sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Studies on the recycling of glycolyzed nylon 66 using novel chain extenders

Nylon 66 (NY66) polymer based products widely used in automotive applications undergo deterioration in their mechanical properties when repeatedly exposed to ethylene glycol (EG) solution. In this study, recycling of glycolyzed NY66 (g-NY66) samples was carried out through melt-compounding with novel isocyanate based chain extenders namely hexamethylene 1,6-dicarbamoyl dicaprolactam (HDC) and tolylene 2,4-dicarbamoyl dicaprolactam (TDC). The recycling efficiency of HDC and TDC on g-NY66 was compared with two commercially available chain extenders 1,1-carbonyl biscaprolactam (CBC) and 1,3-phenylene bis(2-oxazoline) (PBO), and the resultant changes in molecular weight, melt flow, and crystallization behavior in the modified NY66 samples were confirmed from intrinsic viscosity, rheology, and differential scanning calorimetry measurements, respectively. The active ingredients (isocyanate and ?-caprolactam) liberated from HDC and TDC during the melt-compounding process reacted efficiently with the end groups of g-NY66 (-OH and -NH₂) resulting in improved molecular weight compared to g-NY66 and the results are reported in detail.     

Morphology and modulus–temperature behavior of semicrystalline poly(ethylene terephthalate) (PET)

The influence of the thermal history on the morphology and mechanical behavior of PET was studied. The degree of crystallinity (density measurements) and the morphological structure (electron microscopy and small-angle x-ray diffraction) depend on the crystallization temperature. The viscoelastic parameters obtained from the modulus–temperature curves are mainly determined by the morphology of the samples. The glass-transition temperature, T_i, is a function of the crystallinity and the crystallization temperature. It is maximum for a crystallinity between 0.34 and 0.39 for a sample crystallized isothermally between 120 and 150°C. This dependence on crystallization conditions is ascribed to the conformation of the amorphous chain segments between the crystalline lamellae as well as the concentration and the molecular weight of the polymer material rejected during isothermal crystallization. Both factors are supposed to be temperature-dependent. The value of the rubbery modulus is a function of both the volume concentration of the crystalline lamellae and the structure of the interlamellar amorphous regions (chain folds, tie molecules, chain ends, and segregated low molecular weight material). Annealing above the crystallization temperature of isothermally crystallized samples has a marked influence on their morphology and mechanical behavior. The morphological structure and the viscoelastic properties of annealed PET samples are completely different from those obtained with samples isothermally crystallized at the same temperature.     

A biobased aliphatic polyester derived from 10-hydroxydecanoic acid: Molecular weight dependence of physical properties

Poly(10-hydroxydecanoate) (PHDA) is of interest as a new-type aliphatic polyester due to its bioresource and flexible mechanical property. A series of PHDAs with varied molecular weights (M_n from 27 kg/mol to 74 kg/mol) were prepared by optimized melt polycondensation of 10-hydroxydecanoic acid (HDA). Through DSC, WAXD, POM and tensile tests, the effects of molecular weight on the physical properties, including thermal properties, crystallization behavior, crystal morphology, rheological behavior and mechanical properties of PHDA were studied in detail. The results demonstrated that the physical properties of PHDA largely rely on the molecular weight. In particular, the brittle-ductile transition of PHDA occurred when the molecular weight increased up to 55 kg/mol. With the increase of molecular weight, the elongation at break was largely improved and finally exceeded 1400%. The ultimate tensile strength kept about 20 MPa. Hence, PHDA has a PE-like mechanical property. Our work highlights that PHDA is a polymer with excellent performance, which provides an alternative to durable petroleum resourced packaging materials.     

Isothermal crystallization kinetics of poly(ethylene terephthalate)s of different molecular weights

The isothermal crystallization kinetics and morphology of poly(ethylene terephthalate) (PET) polymers of different molecular weights have been studied by means of differential scanning calorimetry and transmission microscopy (TM). The kinetic parameters of Avrami exponent n, the rate constant k, half time t _1/2, rate at 50 % crystallinity, τ _1/2 for crystallization of different PETs were evaluated from double logarithmic plots of log {?ln[1 ? X(t)]} versus log t, where X(t) is extent of crystallinity at a given crystallization temperature. The crystallization rate of polymers with high molecular weight found to be lower than that of polymers with low molecular weight, at the same crystallization temperature. It was found that the nucleation mechanism and growth dimension of polymers with low molecular weight are different from those of polymers with high molecular weight. The results of TM and isothermal crystallization kinetics showed a consistent trend for the crystallization of all PET polymers studied, comprising a primary stage and a secondary stage. The activation energy in the PET polymers of low molecular weight was found to be lower than that of polymers with high molecular weight.     

Investigations on the recycling of hemp and sisal fibre reinforced polypropylene composites

Microscopic, mechanical, rheological and thermal tests were carried out in order to determine the recycling behaviour of PP/vegetal fibre composites. Different composites using hemp and sisal were characterized. All results were compared with PP-g-MA/hemp composites and PP/glass fibre composites.The results prove that mechanical properties are well conserved with the reprocessing of PP/vegetal fibre composites but that there is poor adhesion between the fibres and PP without any treatment. The addition of PP-g-MA shows an improvement of the bonding evidenced by MEB pictures. Vegetal fibres induce an increase in the percentage of crystallinity χ_c and in the crystallization temperature T_c which can be explained by the nucleating ability of the fibres improving crystallization of PP. The Newtonian viscosity η₀ decreases with cycles, indicating a decrease in molecular weight and chain scissions induced by reprocessing. The decrease of fibre length with reprocessing could be another reason for viscosity decrease.     

Controlled degradation of polyhydroxybutyrate via alcoholysis with ethylene glycol or glycerol

It was shown that controlled degradation of poly-[(R)-3-hydroxybutyrate] (PHB) can be achieved by alcoholysis with two types of alcohol in the presence of a catalyst. PHB oligomers terminated with free hydroxyl groups were prepared in this way. Molecular weight of the prepared samples was studied with three methods: SEC analysis with polystyrene calibration, SEC analysis using universal calibration, and viscometry. The data lead to the conclusion that SEC analysis using polystyrene calibration is a suitable method for monitoring degradation. The degradation proceeds by random chain scission and the molecular weight was decreased by almost two orders of magnitude depending on the alcoholysis conditions. The crystallinity and melting temperature, T_m, of PHB after alcoholysis, investigated by differential scanning calorimetry (DSC) show the independence of crystallinity on molecular weight and a decrease in T_m with decreased molecular weight. Time dependence of mechanical properties of selected samples (mechanical ageing) reveals that mechanical properties change with time for degraded samples in a similar way as for the parent polymer.     

Effects of initial morphology and molecular weight on the deformability of poly(ethylene terephthalate)

Solution-grown crystal (SGC) mats and solution-cast (SC) films of poly(ethylene terephthalate) (PET) were drawn by solid-state coextrusion followed by tensile drawing of the coextrudates. Drawabilities and properties of the drawn films, such as mechanical and thermal properties, were investigated as functions of molecular weight, initial morphology, and drawing conditions. The initial morphology and molecular weight have a marked effect on the drawability and tensile properties of the resultant drawn films. The attainable maximum draw ratio increases with increasing molecular weight, and the highest draw ratio of 11.5 can be achieved by two-stage drawing of SC films prepared from pellets with an intrinsic viscosity of 1.43 dl/g. Such highly drawn films exhibit a tensile modulus of 17.5 GPa and strength at break of 400 MPa. These values are comparable to those obtained in conventional spinning of standard grade PET. At a given draw ratio, the tensile strength of the drawn films increases with increasing molecular weight, but the molecular weight dependence is not so marked in the tensile modulus as in the tensile strength. At a given molecular weight, the drawability of SGC mats is lower than that for SC films; however, the efficiency of drawing is higher for the former than for the latter. The difference may arise from the difference in crystallinity and/or crystal perfection of predrawn samples.     

Molecular weight distribution and mechanical behavior of PBI fibers

Two different polybenzimidazole (PBI) samples have been investigated in order to correlate the differences in molecular weight distribution (MWD) with changes in the elastic modulus and strength of undrawn and drawn fibers. It has been found that within the weight-average molecular weight range (7,000 ≤ M_w ≤ 13,000) there was no obvious correlation with M_w and M_n. However, one sample had a narrow unimodal molecular weight distribution and the other a wide bimodal molecular weight distribution. The small percentage of high molecular weight present in the latter sample gave its fibers better mechanical properties. X-ray diffraction studies showed that the orientation in both drawn fiber samples was equal. This isolated the effects of the molecular weight distribution on mechanical properties.     

Ultrafast 99% Polyethylene terephthalate depolymerization into value added monomers using sequential glycolysis-hydrolysis under microwave irradiation

Effective and efficient hybrid depolymerisation technologies are emerging as high potential sustainable routes with considerable benefits over conventional recycling methods for the achievement of circular economies for plastics. Herein, combined green and fast glycolysis-hydrolysis depolymerization of polyethylene terephthalate (PET) was carried out under microwave irradiation (MW) with excellent efficiencies. In MW assisted glycolysis of PET, the catalytic activity of two deep eutectic solvents (DES) based on (choline chloride-urea (DES 1)) and (choline chloride-thiourea (DES 2)) was evaluated and compared. Optimised glycolysis conditions were determined using Box Behnken Design (BBD) to attain maximum weight loss of PET, low crystallinity and increased carbonyl index of residual PET. DES volume of 4 mL, 5.5–6 mL of ethylene glycol, and 0.5 min MW irradiation time resulted in a prominent rise in PET weight loss and carbonyl index of residual PET. DES 2 showed an improved catalytic activity than that of DES 1 which is associated to its stronger interaction with EG and PET polymer chains during the course of the reaction. Residual PET obtained post glycolysis reaction was further depolymerized using MW assisted hydrolysis in the presence of weakly basic Na₂CO₃ and EG. Within 3-minute, the proposed sequential depolymerization technologies facilitated ≈99% conversion of PET to terephthalic acid (TPA), monohydroxyethyl terephthalate (MHET), and bis (2-hydroxyethyl) terephthalate (BHET) monomers produced at a yield of 62.79–80.66%, 17.22–34.79% and 0.54–0.59% respectively. Application on post-consumer PET sample also revealed very satisfactory results with 96.77–98.25% PET conversion and 60.98–78.10% yield of TPA.     

Mechanochemical Degradation and Recycling of Synthetic Polymers

The accumulation of plastic waste, due to lack of recycling, has led to serious environmental pollution. Although mechanical recycling can alleviate this issue, it inevitably reduces the molecular weight and weakens the mechanical properties of materials and is not suitable for mixed materials. Chemical recycling, on the other hand, breaks the polymer into monomers or small-molecule constituents, allowing for the preparation of materials of quality comparable to that of the virgin polymers and can be applied to mixed materials. Mechanochemical degradation and recycling leverages the advantages of mechanical techniques, such as scalability and efficient energy use, to achieve chemical recycling. We summarize recent progress in mechanochemical degradation and recycling of synthetic polymers, including both commercial polymers and those designed for more efficient mechanochemical degradation. We also point out the limitations of mechanochemical degradation and present our perspectives on how the challenges can be mitigated for a circular polymer economy.     

Gel Permeation Chromatography of Polyethylene Terephalate

Abstract

This paper describes the development of the gel permeation chromatography (GPC) technique for the measurements of cyclic trimer content, molecular weights, and molecular weight distribution of polyethylene terephthalate (PET), utilizing a solvent system of o-chlorophenol-chloroform. Mark-Houwink constants for this solvent system are also described.

The GPC technique was applied to the study of the cyclic trimer content, molecular weights and molecular weight distribution of a variety of commercial PET resins. The results indicate that the cyclic trimer content in PET is dependent on molecular weight, polycondensation process and catalyst system. Solidstate polymerized PET contains less cyclic trimer than PET made by the melt-phase process of the same molecular weight. The cyclic trimer content in solid-stated PET appears to be dependent on the conditions of solid-state polymerization.

The polydispersity index determine for a variety of PET samples is higher than the theoretically predicted value of 2.0; however, there is no systematic dependence on molecular weight or polycondensation process.     

Effects of the drawing form and draw ratio on the fiber structure and mechanical properties of CO2-laser-heated-drawn poly(ethylene terephthalate) fibers

The structure, mechanical properties, and thermomechanical properties of poly(ethylene terephthalate) (PET) fibers obtained by laser-heated drawing were investigated in terms of their dependence on the draw ratio and feed speed and the differences between neck-drawn fibers and flow-drawn fibers. The long period at a draw ratio of 6.0 reached 19.0 nm, notably larger than at lower ratios, whereas the tilting angle of the laminar structure was constant at about 60°, regardless of the draw ratio. A maximum value of 15.0 GPa was attained for the initial modulus, and 1.07 GPa was attained for the tensile strength. A higher tensile strength orientation-induced crystallized fiber at the same initial modulus was obtained from higher molecular weight PET. The relationship between the compliance and molecular orientation of the amorphous phase was studied with a series model of crystalline and amorphous phases. The results revealed that, in the high-draw-ratio fibers, the compliance of the amorphous phase decreased with the draw ratio at a higher rate than indicated by extrapolation to intrinsic values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 79–90, 2004     

Injection stretch blow moulding process of reactive extruded recycled PET and virgin PET blends

Reactive extruded recycled PET (RER-PET) was blended with virgin PET in order to find optimum composition for producing bottles using injection stretch blow moulding (ISBM) process. Two variables were investigated namely, RER-PET concentration in the blend with virgin PET and RER-PET intrinsic viscosity, [η]. The variability of [η] was facilitated by changing PMDA chain extender concentration in the production of RER-PET. Different molecular, mechanical, barrier and optical tests such as infrared, burst pressure, top load strength, drop impact, environmental stress cracking, liquid permeation, gas permeation, and clarity were conducted. The aim was to evaluate the properties of the bottles in response to different blends compositions. Bottles made from RER-PET and virgin PET blends showed similar and better mechanical and barrier properties at certain compositions to those made from Virgin PET. The effects of RER-PET molecular properties such as intrinsic viscosity, chain orientation and conformation on bottles mechanical, barrier and optical properties are detailed.     

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.     

Dynamic mechanical behavior of oriented semicrystalline polyethylene terephthalate

The dynamic mechanical behavior of molecularly oriented semicrystalline polyethylene terephthalate (PET) induced via the equal‐channel angular extrusion (ECAE) process was investigated. Dynamic mechanical analyses in both torsional mode and bending mode were utilized. The results indicate that the ECAE‐oriented PET has a higher dynamic storage modulus above the glass‐transition temperature than that of the reference (control sample). The combined effect of molecular orientation and crystallinity is responsible for the changes in the primary and secondary relaxations of PET. Further analyses show that the shifting and broadening of the primary and secondary peak positions in oriented PET are mainly due to the amorphous‐phase orientation because the crystallinity of PET decreases upon the ECAE processing. A good correlation was found between the structural anisotropy and the dynamic mechanical properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1394–1403, 2001     

Synthesis of thermoplastic elastomers based on PET glycolysates: Study of their dielectric properties

Thermoplastic elastomers based on PET glycolysates were synthesized in the molten state according to a multistep process. Their chemical structures were studied (¹H NMR, triple detection, steric exclusion chromatography) as well as their thermal properties (ATG, DSC) and their morphology (AFM). Influence of hard segments composition on the different properties was investigated with the same ratio soft/hard segment. DSC study showed that these compounds had thermal properties similar to those of conventional thermoplastic elastomers (low T_g and high T_m). The association of PET with PBT segments seemed to harm the hard segments crystallization. SEC analyses showed that the compounds obtained had low molecular weights. Two factors seemed to explain the difference in properties between the compounds with and without glycolysate: a lower molecular weight of the TPE containing glycolysate, and a lower organization for materials containing both PET and PBT segments in respect to copolymer without glycolysate and containing solely PBT segments.Dielectric measurements showed properties close to those usually encountered for insulators used in electrical engineering. Glycolysate-free materials exhibited the best properties (high resistivity, low loss factor, slight variation of permittivity) and the materials exhibited interesting insulating properties (breakdown voltage up than 35 kV/mm_RMS, resistivity around 10⁹ Ωm). An improvement of the synthesis methodology with the use of catalyst might result in a significant enhancement of the dielectric properties, already promising for this type of materials.