George P. Karayannidis

This paper covers the recent research carried out by the authors on the chemical recycling of poly(ethylene terephthalate) (PET) taken from post‐consumer soft‐drink bottles. The chemical recycling techniques used are critically reviewed and the authors' contribution is highlighted. Hydrolysis in either an alkaline or acid environment was employed in order to recover pure terephthalic acid monomer that could be repolymerized to form the polymer again. Alkaline hydrolysis was carried out in either an aqueous NaOH solution or in a non‐aqueous solution of KOH in methyl cellosolve. A phase‐transfer catalyst was introduced in alkaline hydrolysis, in order that the reaction takes place at atmospheric pressure and in mild experimental conditions. The reaction kinetics were thoroughly investigated, both experimentally and theoretically, using a simple, yet precise, kinetic model. Moreover, glycolysis was examined as an effective way for the production of secondary value‐added materials. The glycolysated PET products (oligomers) can be used as raw materials for the production of either unsaturated polyester resins (UPR) or methacrylated oligoesters (MO). UPR can subsequently be cured with styrene in ambient temperature to produce alkyd resins used as enamel paints or coatings. MO are potential monomers that can be cured either by UV irradiation or temperature to produce formulations used as coatings for wood surfaces, paints, or other applications. Thus, recycling of PET does not only serve as a partial solution to the solid‐waste problem, but also contributes to the conservation of raw petrochemical products and energy. magnified image

Summary: In the framework of chemical recycling of polymers, leading to the generation of secondary value‐added products, PET flakes taken from post‐consumer soft drink bottles, were glycolyzed with DEG. The oligomers obtained were analyzed for their molecular weight and characterized by FT‐IR and POM. Subsequently, dimethacrylated oligoesters of PET glycolysate (PET‐GLY‐DMA) were synthesized by methacrylation of the glycolyzed PET product. The resulted monomer PET‐GLY‐DMA was studied by FT‐IR, POM and DSC. Thermal polymerization of this monomer was carried out at 80 °C in the presence of benzoyl peroxide as initiator. A UV‐curable formulation was also prepared on the basis of neat PET‐GLY‐DMA, as well as by mixing PET‐GLY‐DMA with styrene, using DMPA as photoinitiator. Nanoparticles of SiO₂ were dispersed into PET‐GLY‐DMA/styrene copolymers as reinforcing agents and the mechanical properties of resins formed were studied. Preparation of methacrylated PET glycolysate. magnified image Preparation of methacrylated PET glycolysate.

The objective of this work was the study using thermomechanical analysis (TMA) of a peculiar behaviour, which was observed some years ago, around the glass–rubber transition region in some thermoplastic alipharomatic polyesters. For this purpose a series of nine alipharomatic polyesters was prepared by the two‐stage melt polycondensation method in a glass batch reactor and subjected to TMA in both penetration and expansion mode. Differential scanning calorimetry (DSC) was additionally used and the results are discussed focusing mainly on the first derivative curve of TMA thermograms in the penetration mode. From this curve, which shows two distinct peaks, the first peak could be attributed to the glass transition temperature (T_g) of the mobile amorphous fraction, since the value coincides with that obtained from DSC and is due to the abrupt shrinkage of the amorphous part of the sample. The second peak (up to 40 °C higher than T_g) is due most probably to the softening of the rigid amorphous fraction and the passage of the polymeric sample from the glass region to the cold crystallization region. When the sample is more crystalline than amorphous then the first peak is smaller or is completely absent. Copyright © 2006 Society of Chemical Industry

Summary: In the present study, it has been unexpectedly found that solid‐state polycondensation (SSP) can act as a facile method to prepare poly(ethylene terephthalate)/silica (PET/SiO₂) nanocomposites with high molecular weight and an adjustable degree of branching or crosslinking. Fumed silica, with its surface silanol groups, seems to participate in some kind of reaction, probably esterification with the hydroxy end‐groups of PET, during SSP, to act as a multifunctional chain extender. Differential scanning calorimetry and FT‐IR spectroscopy reveal this ability of the silanol groups. The molecular weight increase depends on the used temperatures of SSP as well as on the amount of SiO₂ added. As the amount of silica increases the rate of increase of the intrinsic viscosity slows because of the higher extent of branching. At 5 wt.‐% SiO₂ the extensive branching produces a crosslinked polymeric material. Such polyesters with increased molecular weight and low silica content could be suitable for blown bottle production, while the high SiO₂ content and adjustable branching or crosslinking could make them ideal high‐melt‐strength resins suitable for the preparation of low‐density closed‐shell foams. Schematic representation of PET/SiO₂ crosslinked macromolecules. magnified image Schematic representation of PET/SiO₂ crosslinked macromolecules.

In the present study two series of isotactic polypropylene (iPP)/SiO₂ nanocomposites containing 1, 2.5, 5, 7.5, and 10 wt % SiO₂ nanoparticles were prepared by melt‐mixing on a twin‐screw corotating extruder. In the first series untreated fumed silica nanoparticles were used, whereas in the second nanoparticles were surface‐treated with dimethyldichlorosilane. In both cases, the average size of the primary nanoparticles was 12 nm. Tensile and impact strength were found to increase and to be affected mainly by the type and content of silica nanoparticles. A maximum was observed, corresponding to samples containing 2.5 wt % SiO₂. These findings are discussed in light of the SEM and TEM observations. By increasing the amount of nanoparticles, large aggregates of fumed silica could be formed, which may explain the reduction of mechanical properties with higher concentrations of SiO₂. However, it was found that surface‐treated nanoparticles produced larger aggregates than did those derived from untreated nanoparticles, despite the increased adhesion of the iPP matrix, as was postulated from yield strength. This behavior negatively affected mechanical properties. In addition, an effort was made to determine if toughening theories, mainly the critical interparticle distance for rubber toughening or composites, also might be applicable in nanocomposites. From DSC measurements it was demonstrated that silica nanoparticles acted as effective nucleating agents, increasing the crystallization rate and the degree of crystallinity of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2684–2696, 2006

In this work, three alipharomatic polyesters—poly(propylene terephthalate) (PPT), poly(propylene isophthalate) (PPI), and poly(propylene naphthalate) (PPN)—were prepared and studied with the aliphatic diol 1,3‐propanediol and the corresponding aromatic diacids. Their synthesis was performed by the two‐stage melt polycondensation method in a glass batch reactor. The thermal characterization of these polyesters was carried out with different thermal techniques such as simultaneous thermogravimetry/differential thermal analysis, thermomechanical analysis (TMA), and dynamic thermomechanical analysis. From the recorded values for the glass‐transition temperature (T_g) and melting temperature with all the aforementioned techniques, it could be said that they were in good agreement. According to the thermogravimetric results, PPT and PPI showed about the same thermal stability, whereas PPN seemed to be somewhere more thermostable. Remarkably, a transition existed immediately after T_g that was realized by the first derivative of TMA, and it was characterized as a midrange transition. For all polyesters, the average coefficient of linear thermal expansion was calculated with TMA. The secondary relaxations T_β and T_γ, recorded with dynamic mechanical thermal analysis, were mainly affected by the kinds of monomers. Concerning the mechanical properties, PPN had the highest tensile strength at break, whereas PPT had the highest elongation at break. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3998–4011, 2005

In the present study i-PP/SiO₂ nanocomposites, containing 1, 2.5, 5, 7.5, 10 and 15 wt % SiO₂ nanoparticles, were prepared by melt mixing on a twin-screw co-rotating extruder. Tensile and impact strength were found to increase and to be mainly affected by the content of silica nanoparticles. A maximum was observed, corresponding to the samples containing 2.5 wt% SiO₂. The addition of PP-g-MA resulted in a further enhancement of mechanical properties due to the particle size reduction of silica agglomerates.

The kinetics of crystallization of poly(propylene terephthalate) (PPT) samples of different molecular weights were studied under both isothermal and nonisothermal conditions. The Avrami and Lauritzen–Hoffmann treatments were applied to evaluate kinetic parameters of PPT isothermal crystallization. It was found that crystallization is faster for low‐molecular‐weight samples. The modified Avrami equation, and the combined Avrami–Ozawa method were found to successfully describe the nonisothermal crystallization process. Also, the analysis of Lauritzen–Hoffmmann was tested and it resulted in values close to those obtained with isothermal crystallization data. The nonisothermal kinetic data were corrected for the effect of the temperature lag and shifted alone with the isothermal kinetic data to obtain a single master curve, according to the method of Chan and Isayev, testifying to the consistency between the isothermal and corrected nonisothermal data. A new method for ranking of polymers, referring to the crystallization rates, was also introduced. This involved a new index that combines the maximum crystallization rate observed during cooling with the average crystallization rates over the temperature range of the crystallization peak. Furthermore, the effective energy barrier of the dynamic process was evaluated with the isoconversional methods of Flynn and Friedmann. It was found that the energy barrier is lower for the low‐molecular‐weight PPT. The effect of the catalyst remnants on the crystallization kinetics was also investigated and it was found that this is significant only for low‐molecular‐weight samples. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3775–3796, 2004

The melting point depression and cocrystallization behavior of a series of random poly(ethylene‐co‐butylene 2,6‐naphthalate) P(EN‐co‐BN) copolymers were investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). These copolymers crystallize over the entire range of composition and they exhibit eutectic behavior. WAXD patterns showed that copolymers form exclusively poly(ethylene 2,6‐naphthalate) (PEN) type crystals or poly(butylene 2,6‐naphthalate) (PBN) type crystals. A transition from the PEN‐ to PBN‐type crystal was observed in the middle of the copolymer composition. This confirms that the P(EN‐co‐BN) copolymers show isodimorphic cocrystallization. The cocrystallization was thermodynamically analyzed using the Wendling–Suter model. The defect free energy was found to be about 12.17 kJ mol⁻¹ in the case of incorporation of BN units in the PEN‐type crystals, and about 5.66 kJ mol⁻¹ in the case of incorporation of EN units in the PBN‐type crystal. This means that the incorporation of bulkier BN units in the PEN crystals is more difficult. For low comonomer concentrations it was found that comonomer exclusion is probable. Copyright © 2004 Society of Chemical Industry