Ionic liquid‐catalyzed aminolysis of poly(ethylene terephthalate) waste

Aminolytic depolymerization of poly(ethylene terephthalate) (PET) bottle waste with ethanolamine and hydrazine hydrate under atmospheric conditions was investigated in the presence of room temperature ionic liquids. 1‐Hexyl‐3‐methylimidazolium trifluoromethanesulfonate (Hmim.TfO) and 1‐butyl‐3‐methylimidazolium hydrogen sulfate (Bmim.HSO₄). (Hmim.TfO) was found to be the most efficient catalyst to obtain high yields of the aminolysis products bis(2‐hydroxy ethylene) terephthalamide and terephthalic dihydrazide using ethanolamine and hydrazine hydrate, respectively. These products were characterized by IR spectroscopy, ¹H NMR, ¹³C NMR, mass spectroscopy, and differential scanning calorimetry. The influence of experimental parameters, such as the amount of catalyst, reaction time, molar ratio of ethanolamine, and hydrazine hydrate with respect to PET was investigated. This protocol proves to be efficient and environmentally benign in terms of high yields (>84%) and low reaction times (up to 30 min). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis, characterization, and properties of poly(ethylene terephthalate)/poly(1,4-butylene succinate) block copolymers

Reactive blending at 290 °C of a series of mixtures of poly(ethylene terephthalate) (PET) and poly(1,4-butylene succinate) (PBS) led to the formation of block PET/PBS copolyesters. The block lengths of the resulting copolymers decreased with the severity of the treatment. Copolyesters with PET/PBS molar compositions of 90/10, 80/20, 70/30, and 50/50 were prepared by this method and their composition and microstructure were characterized by ¹H and ¹³C NMR, respectively. The T_g, T_m, and crystallinity of the copolymers decreased as the content in PBS and the degree of randomness increased. The elastic modulus and tensile strength of the copolymers decreased with the content of PBS, whereas, on the contrary, the elongation at break increased. The PET/PBS copolymers exhibited a pronounced hydrolytic degradability, which increased with the content in 1,4-butylene succinic units. Hydrolysis mainly occurred on the aliphatic ester groups.     

Glycolysis of poly(ethylene terephthalate) wastes in xylene

To reclaim the monomers or prepare intermediates suitable for other polymers zinc acetate catalayzed glycolysis of waste poly(ethylene terephthalate) (PET) was carried out with ethylene or propylene glycol, with PET/glycol molar ratios of1 : 0.5–1 : 3, in xylene at 170–245°C. During the multiphase reaction, depolymerization products transferred to the xylene medium from the dispersed PET/glycol droplets, shifting the equilibrium to glycolysis. Best results were obtained from the ethylene glycol (EG) reaction at 220°C, which yielded 80 mol % bis-2-hydroxyethyl terephthalate monomer and 20 mol % dimer fractions in quite pure crystalline form. Other advantages of employment of xylene in glycolysis of PET were improvement of mixing at high PET/EG ratios and recycling possibility of excess glycol, which separates from the xylene phase at low temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2311–2319, 1998     

Acetaldehyde scavengers and their effects on thermal stability and physical properties of poly(ethylene terephthalate)

The acetaldehyde (AA) scavenging abilities of poly(ethylene terephthalate) (PET) blends containing various concentrations of anthranilamide, meta-xylenediamine (MXDA), or alpha-cyclodextrin have been evaluated. It was found that higher AA scavenger concentrations generally resulted in greater reductions in detectable AA in terms of both the AA generation rates and residual AA contents. As little as 100 ppm, by weight, of anthranilamide and MXDA were respectively shown to reduce residual AA detected in PET preforms by 46% and 36%. Melt-blending 500 ppm of alpha-cyclodextrin, into PET, reduced preform residual AA concentration by 42%. The scavengers acted as PET nucleating agents causing more rapid crystallization while heating the blends from the glassy state and when cooling from the melt; however, they caused no changes in the glass transitions, melting characteristics, or oxygen permeation behaviors of the blends. Addition of optimal scavenger concentrations had minimal effects on preform intrinsic viscosity and color changes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of radiation dose on the thermal degradation of poly(ethylene terephthalate) fabric

The effect of radiation dose (10–30 kGy) on the thermal decomposition of poly(ethylene terephthalate) was studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD) analysis. The TGA and DSC were carried out in a flowing nitrogen atmosphere at heating rates of 5 and 30°C/min for TGA and 10°C/min for DSC. The degradation process was composed of three overlapping stages. The second stage, at which a rapid degradation occurs, was studied in detail. The process was found to follow a second‐order kinetics and was independent of radiation dose or heating rate. The reaction rate constant (k) was found to depend on the heating rate and iradiation dose. The apparent activation energy (Q) and the logarithm of the preexponential rate constant (log A) were found to decrease linearly with the increase in dose at rates of 3.32 kJ mol^?1 kGy^?1 and 0.177 s^?1 kGy^?1 with intercepts of 249 kJ/mol and 12.26 s^?1 for Q and log A of unirradiated fabric, respectively. A direct relationship was found between the percentage decrease in Q and log A and the percentage decrease in the temperature corresponding to 50% conversion (T_50%) for samples irradiated at different doses. It was found that a decrease in T_50% by 1% resulted in a decrease in Q and log A by 1.855 and 2.1%, respectively. Changes in Q and log A resulting from radiation, mechanical and thermal treatments, or their combinations can be predicted from the shift in T_50%. The history of the fibers substantially affected the thermal properties. DSC and XRD studies revealed changes in the fabric crystallinity. DSC measurements indicated a linear increase in heat of fusion with dose increase at a rate of 0.855 kJ kg^?1 kGy^?1. XRD analysis confirmed structural changes, rearrangement by plane rotations, and formation of compact crystalline lattice with patterns characterizing irradiated samples. An attempt to explain the dependency of the apparent activation energy on dose was given. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3710–3720, 2004     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Synthesis of modified poly(ethylene terephthalate) fibers with antibacterial properties and their characterization

Poly(ethylene terephthalate) (PET) fibers were grafted with vinyl monomers by utilizing benzoyl peroxide. Grafted PET fibers were modified in optimized conditions with several functional groups such as amine, chlorine, hydrogen peroxide_, and triclosan to gain antibacterial feature. The second part of this study comprised examination of the antibacterial features of PET fibers via use of Staphylococcus aureus (ATCC 29213) and Escherichia coli (ATCC 25922) bacteria. Kirby-Bauer test is used to study antibacterial properties. The longest zone diameter for Trc-GMA-g-PET fibers was 56?mm for E. Coli whereas the biggest diameter for S. aureus bacteria was 130?mm with Trc-MMA-g-PET fibers.     

Synthesis and characterization of unsaturated polyesters based on the aminolysis of poly(ethylene terephthalate)

The depolymerization of poly(ethylene terephthalate) via an aminolysis process was studied. An excess of ethanol amine in the presence of sodium acetate as a catalyst was used to produce bis(2‐hydroxyl ethylene) terephthalamide (BHETA). Unsaturated polyester (UP) resins were obtained by the reaction of BHETA with different long‐chain dibasic acids such as decanedioic acid, tetradecanoic acid, and octadecanoic acid in conjunction with maleic anhydride as a source of unsaturation. The chemical structure of the UP resins was confirmed by ¹H‐NMR. The vinyl ester resins were used as crosslinking agents for UP. The curing behavior and mechanical properties of the UP resins with vinyl ester were evaluated at different temperatures ranging from 25 to 55°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005     

Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by ¹H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of urethane oils from waste poly(ethylene terephthalate) bottles

Waste poly(ethylene terephthalate) (PET) bottles were glycolyzed by propylene glycol (PG) at a weight ratio of PET to PG of 37.5 : 62.5 using zinc acetate as a catalyst. The glycolyzed product, consisting of oligomeric diols with a number‐average molecular weight range of 458–844, was obtained. It was further reacted with soybean oil and toluene diisocyanate to obtain urethane oils at hydroxyl to isocyanate ratios from 1 : 1 to 1 : 0.7, with and without methanol acting as a blocking agent. All the synthesized urethane oils were yellowish, transparent, low‐viscosity liquids of low molecular weights. A lower diisocyanate content and the presence of a blocking agent resulted in higher viscosity, higher molecular weight, and shorter drying time. The films of all synthesized urethane oils exhibited good hardness and adhesion. They also showed excellent water and acid resistance but only fair alkali resistance. However, these prepared urethane oils had lower flexibility and poorer wear resistance compared to those of the commercial urethane oil. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3040–3045, 2004     

Chain extension of poly(ethylene terephthalate) with bisphenol‐A dicyanate

Chain extension of poly(ethylene terephthalate) (PET) with bisphenol‐A dicyanate (BADCy) was studied using an internal mixer under reactive blending conditions. The reaction between PET and BADCy was confirmed by Fourier transform infrared (FTIR) and chemical titration. With increasing amount of BADCy introduced, the modified PET gave rise to higher torque during stirred in an internal mixer, higher viscosity (η′), and higher storage modulus (G′). Measurement of intrinsic viscosity showed that BADCy indeed extended the molecular weight of PET. DSC analysis represented that T_m and T_c of the modified PET were shifted to low temperatures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Modification of the thermal properties and crystallization behaviour of poly(ethylene terephthalate) by copolymerization

Poly(ethylene terephthalate) (PET) is a widely used polyester, which can be crystallized from the melt over a wide range of supercooling conditions or, alternatively, quenched into the amorphous state and, subsequently, crystallized by thermal treatment above the glass‐transition temperature. It is well known that the crystallization of PET can be hindered by means of copolymerization or reactive blending. The incorporation of comonomeric units into the polymer backbone leads to an irregular chain structure and thereby inhibits regular chain packing for crystallization. The crystallization of PET copolyesters is strongly influenced by the chain microstructure regarding comonomer distribution, randomness and length of the crystallizable ethylene terephthalate sequences. This paper is mainly devoted to the thermally induced crystallization behaviour of PET and to reviewing the efforts that have been made in the last decade to modify the glass‐transition and melting temperatures, the crystallinity and the crystallization rate of this polyester. Furthermore, some illustrative experimental data obtained from isothermal and non‐isothermal crystallization of PET are included in this study. © 2003 Society of Chemical Industry     

Mechanical,thermal, and structural characterization of poly(ethylene terephthalate) and poly(butylene terephthalate) blend systems by the addition of postconsumer poly(ethylene terephthalate)

The focus of this study was mainly on the use of scrap poly(ethylene terephthalate) (PET) in poly(butylene terephthalate)‐rich blend systems. A good combination of tensile and impact properties was observed in the newly formed blend system with scrap PET. The morphology depicted controlled and well‐dispersed phases. The thorough mixing of the constituents was observed in the thermal study. For this innovative blend system, an attempt to correlate the mechanical, thermal, structural, morphological properties and the chemistry of the blend system seemed to be technoeconomical. This study contributed to the recycling of waste material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of new poly(amide‐imide)s based on 2,5‐bis(trimellitimido)chlorobenzene

A series of new aromatic poly(amide‐imide)s were synthesized by the triphenyl phosphite‐activated polycondensation of the diimide‐diacid, 2,5‐bis(trimellitimido)chlorobenzene (I) with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), pyridine, and calcium chloride. The poly(amide‐imide)s had inherent viscosities of 0.76–1.42 dL g⁻¹. The diimide‐diacid monomer (I) was prepared from 2‐chloro‐p‐phenylenediamine with trimellitic anhydride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents, including NMP and N,N‐dimethylacetamide. Transparent, flexible, and tough films of these polymers could be cast from N,N‐dimethylacetamide or NMP solutions. Their cast films had tensile strengths ranging from 74 to 95 MPa, elongations at break from 7 to 11%, and initial moduli from 1.38 to 3.25 GPa. The glass transition temperatures of these polymers were in the range of 233°–260°C, and the 10% weight loss temperatures were above 450°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1691–1701, 1999     

Synthesis of novel poly(phthalazinone ether sulfone ketone)s and improvement of their melt flow properties

A series of novel poly(phthalazinone ether sulfone ketone)s was synthesized from bis(4-fluorophenyl) ketone, bis(4-chlorophenyl)sulfone, and 4-(4-hydroxybenzyl)-2,3-phthalazin-1-one through nucleophilic substitution polycondensation. The synthesized polymers exhibited surprisingly high glass transition temperatures and had excellent thermooxidative properties. The melt viscosities of these synthesized polymers are generally too high to be processed by common processing methods because of their very high glass transition temperatures and amorphous microstructure. An attempt was made to reduce their melt viscosities by solution blending the synthesized polymer with two kinds of oligomers: low molecular weight poly(phthalazinone ether sulfone ketone) and commercial poly(ether sulfone). The results proved that the addition of the oligomers to the polymers led to a marked decrease in melt viscosities. Furthermore, no obvious changes were observed in the thermal and mechanical properties of these blends after oligomer additions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1425–1432, 1997     

Glycolytic aminolysis of poly(ethylene terephthalate) waste for recovery of value‐added comonomer at atmospheric pressure

Reaction of poly(ethylene terephthalate) waste (PETW) powder with ethylene glycol (EG) using 0.003 mol lead acetate as a catalyst was carried out in a batch reactor at 470 K under atmospheric pressure. Reactions were undertaken with various particle sizes ranging from 50 to 512.5 μm and reaction times ranging from 10 to 60 min at 10‐min intervals. A low molecular weight product of PETW was obtained using this reaction. Then hydrazine monohydrate, chlorobenzene, and cyclohexylamine (CHA) were introduced to convert the low molecular weight product of PETW into terephthalohydrazide (TPHD). To increase the PETW conversion rate, an external catalyst (lead acetate) was introduced during the reaction. The reaction product was deposited onto the surface of unreacted PETW that was removed from the surface by introducing dimethyl sulfoxide. To accelerate the reaction rate CHA was introduced during the second stage of reaction, which has industrial significance. Depolymerization of PETW was proportional to the reaction time and inversely proportional to the particle size of PETW. Analyses of value‐added products (TPHD and EG) as well as PETW were undertaken. A kinetic model was developed and experimental data were simulated consistent with the model. A thermodynamic study was undertaken because this is required during the transfer of laboratory data through the pilot plant for commercialization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3437–3444, 2003     

Temperature and atmosphere influences on smoke composition during thermal degradation of poly(ethylene terephthalate)

The less‐volatile compounds forming a smoke emitted during the thermal degradation of poly(ethylene terephthalate) (PET) in different conditions were studied. Thermal degradation of PET was carried out within the temperature range of 200–700°C in both a nitrogen and an air atmosphere. The less‐volatile thermal degradation products were trapped on a glass‐fiber filter and analyzed by capillary gas chromatography with mass selective detector (GC‐MS) and high performance liquid chromatography (HPLC). The results are collected in tables and presented on plots as a function of the degradation temperature. The temperature and atmosphere effects on the emission and composition of the smoke during PET thermal degradation were considered. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3064–3068, 2001     

Sequence analysis of poly(ethylene terephthalate)/poly(butylene terephthalate) copolymer prepared by ester-interchange reactions

The molecular structure of the copolyester formed through the interchange reaction in poly(ethylene terephthalate)/poly(butylene terephthalate) blends was investigated with ¹³C-NMR spectroscopy. The molar fractions of heterolinkage triads in the copolyesters were lower than the values calculated by Bernoullian statistics; this indicates that the sequence of heterolinkages was far from a random distribution at the initial stage of the interchange reaction. However, the randomness increased and the number-average sequence length decreased with reaction time. The solubility of the blend decreased with increasing sequence length, resulting from the formation of block copolymers with long sequence lengths at the initial stage of the interchange reaction. The solubility of the copolyester formed by a dibutyltin dilaurate (DBTDL)-catalyzed reaction was higher than that of the copolyester formed by a titanium tetrabutoxide-catalyzed reaction; this is related to the fact that alcoholysis prevailed in the DBTDL-catalyzed reaction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 159–168, 2001