Glycolysis of postconsumer polyethylene terephthalate waste

Glycolytic depolymerization of polyethylene terephthalate (PET) bottle waste was attempted using ethylene glycol (EG) in the presence of chlorides of zinc, lithium, didymium, magnesium, and iron as catalysts. Virtual monomer bis (2‐hydroxyethyl terephthalate) (BHET) was obtained in all cases with nearly 74% yield, the highest yield being achieved with zinc chloride catalyst 0.5% w/w, PET : EG ratio 1 : 14 and 8 h under reflux conditions. The results were comparable to other catalysts like common alkalis, acids, and salts of some earth metals and zeolites used earlier although parameters of glycolysis were observed to vary depending on the catalyst. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface hydrolysis of postconsumer polyethylene terephthalate to produce adsorbents for cationic contaminants

In this work, the surface hydrolysis of postconsumer polyethylene terephthalate (PET) was used to produce an ion exchange material to adsorb cationic contaminants from water. The PET surface hydrolyses were carried out in neutral, alkaline, and acid media (NaOH or HNO₃ at 7, 10, and 15 mol L^?1) under reflux producing surface carboxylic acid sites (? COOH) characterized by ATR‐IR, pyridine adsorption, titration, TG, and DSC analyses. Acid hydrolysis produced high concentrations of ? COOH (up to 0.5 mmol g^?1_PET), whereas no significant concentration of carboxylic acid sites was obtained by neutral and alkaline hydrolysis. SEM analyses suggest that the acid sites are likely located at the cracks and defects produced on the PET surface by acid hydrolysis. Neutral or alkaline hydrolysis produced a very regular and smooth PET surface with very low acid site concentrations. The adsorption isotherms of Cd⁺² as a model of heavy metal and the dye methylene blue as a model of large organic cationic molecules showed high adsorption capacities for the HNO₃‐hydrolyzed PET, whereas no adsorption takes place on the neutral‐ or alkaline‐hydrolyzed polymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5284–5291, 2006     

Solid‐state hydrolysis of postconsumer polyethylene terephthalate after plasma treatment

Plasma treatments were applied on the surface of postconsumer polyethylene terephthalate (PET) bottles to increase their wettability and hasten the subsequent hydrolysis process. Sixty‐four treatments were tested by varying plasma composition (oxygen and air), power (25–130 W), pressure (50–200 mTorr), and time (1 and 5 min). The best treatment was the one applied in air plasma at 130 W and 50 mTorr for 5 min, as it provided the lowest contact angle, 9.4°. Samples of PET before and after the optimized plasma condition were subjected to hydrolysis at 205°C. Although the treatment changed only a thin surface layer, its influence was evident up to relatively high conversion rates, as the treated samples presented more than 40% higher conversion rates than the untreated ones after 2 h of reaction. Infrared spectroscopy showed that the terephthalic acid obtained from 99% of depolymerization was similar to the commercial product used in PET synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and film properties of epoxy esters modified with amino resins from glycolysis products of postconsumer PET bottles

Glycolysis of waste polyethylene terephthalate (PET) flakes obtained from grinding postconsumer bottles was carried out at 225–250°C and molar ratios of PET/ethylene glycol were taken as 1/1, 1/1.5, 1/5, and 1/10. Reaction product was extracted by hot water for three times and water‐soluble crystallizable fraction and water‐insoluble fraction were obtained. These fractions were characterized by acid and hydroxyl value determinations, differential scanning calorimeter analysis, and ¹H‐NMR analysis. Glycolysis product was used for synthesis of PET‐based epoxy resin. This epoxy resin was used to prepare epoxy ester resins having 40% and 50% oil content. Epoxy ester resin having 40% oil content was modified with urea‐formaldehyde and melamine‐formaldehyde resins for synthesis of epoxy ester–amino resin. Physical and chemical film properties of epoxy ester and modified epoxy ester resins were investigated. All the epoxy ester and modified epoxy ester films were having excellent adhesion, water, and salt water resistance properties. Modification of PET‐based epoxy ester resins with amino resin has significantly improved hardness, impact resistance, and alkaline and acid resistance of resin films. As a result, PET oligomers obtained from glycolysis of postconsumer PET bottles are suitable for manufacturing of amino‐resin‐modified epoxy ester resins that have improved physical and chemical surface coating properties. POLYM. ENG. SCI., 55:2519–2525, 2015. © 2015 Society of Plastics Engineers     

Catalyzed hydrolysis of polyethylene terephthalate melts

The effect of zinc catalysts on the hydrolytic depolymerization of polyethylene terephthalate (PET) melts in excess water was studied using a 2-L stirred pressure reactor at temperatures of 250, 265, and 280°C. The main products of the reaction were found to be terephthalic acid, ethylene glycol, and diethylene glycol. Rate constants were calculated from initial rate data at each temperature and found to be about 20% greater than the corresponding rate constants for uncatalyzed hydrolysis. The catalytic effect of zinc, as well as sodium, salts is attributed to the electrolytic destabilization of the polymer-water interface during hydrolysis. The depolymerization rate data at 265°C were found to fit a kinetic model proposed earlier for the uncatalysed hydrolysis of PET. The effect of zinc and sodium salts on the activation energy of hydrolysis, or on the formation of ethylene glycol monomer is unclear. © 1994 John Wiley & Sons, Inc.     

Solid-state polycondensation of poly(ethylene terephthalate) recycled from postconsumer soft-drink bottles. II

Poly(ethylene terephthalate) (PET) taken from postconsumer soft-drink bottles was subjected to solid-state polycondensation after cutting into small pieces or after dissolution in trifluoracetic acid, trifluoracetic acid/dichloromethane mixture (50/50%, v/v), or nitrobenzene, and coagulation in methanol. The effect of various reaction parameters such as time and temperature of reaction (180, 200, 220, and 230°C) on intrinsic viscosity [η] and carboxyl and hydroxyl end-group content have been investigated. The highest number average molecular weight, M?_n = 61,400 was obtained from PET (M?_n = 20,300) dissolved in nitrobenzene and solid-state polycondensated by heating under vacuum at 230°C for 8 h. The thermal behavior of solid-state samples was studied by differential scanning calorimetry (DSC); all samples showed a characteristic double endothermal melting peak and no glass-transition temperature. The PET samples taken from the bottles without dissolution were also studied by thermomechanical analysis. The heat distorsion temperatures obtained by this analysis were in very good agreement with the two endothermal melting peaks taken by DSC. This finding indicates that in these samples the crystallites form a coherent matrix and the amorphous phase is dispersed in the voids. © 1995 John Wiley & Sons, Inc.     

Simultaneous glycolysis and hydrolysis of polyethylene terephthalate and characterization of products by differential scanning calorimetry

Simultaneous glycolysis and neutral hydrolysis of waste polyethylene terephthalate (PET) has been carried out at 170 and 190 °C with constant amount of ethylene glycol (EG) and increasing amounts of water, in the presence of xylene. The organic solvent made it possible to employ very low amounts of reactants as well as application of lower temperatures and pressures in contrast with previous methods, yielding intermediates suitable for PET or other polymeric materials. These intermediates were characterized by acid value (AV), hydroxyl value (HV) determinations as well as by differential scanning calorimetry (DSC). A water soluble crystallizable fraction with high purity, consisting of mono 2-hydroxy ethyl ester of terephthalic acid (monohydroxyethyl terephthalate, MHT) monomer has been obtained with significant yield and its polymerization tendency has been compared with that of bis(2-hydroxy ethyl) terephthalate (BHET) by application of multiple heating/cooling cycles in DSC.     

Investigation of alkaline hydrolysis of polyethylene terephthalate by differential scanning calorimetry and thermogravimetric analysis

The hydrolytic depolymerization of polyethylene terephthalate (PET) with alkaline hydroxides was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The reactions of the mixtures were conducted in their solid states under nitrogen atmosphere. The experimental results showed that potassium hydroxide possessed the hydrolytic activity of depolymerizing PET into small molecules such as ethylene glycol; in contrast, sodium hydroxide did not. The production rate of ethylene glycol was enhanced by increasing charge ratio of potassium hydroxide to PET. The presence of water facilitated the alkaline hydrolysis of PET; however, the presence of metal acetates decreased the hydrolysis rate. The activation energy for alkaline hydrolysis of PET determined by the thermograms was in good agreement with the value obtained from the experiments in a batch reactor. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1939–1945, 1998     

醇酸树脂水分散型乳液的研究进展及性能

水分散型醇酸树脂乳液不依赖石油资源,且绿色环保。但由于水分散型树脂延长了涂膜的干燥时间且耐水性下降。寻求具有良好水分散性、适宜干燥时间及力学性能的水性醇酸树脂,是目前亟需解决的问题。综述了水性醇酸树脂的国内外研究状况,展望了其发展方向。     

Chemical,thermal, and mechanical properties and ultraviolet transmittance of novel nano-hydroxyapatite/polyethylene terephthalate milk bottles

Polyethylene terephthalate (PET)/nano-hydroxyapatite (nHAp) composite granules were obtained using twin-screw extruder. Preforms were prepared by injection molding and then PET/nHAp bottles were produced by blow molding. For PET bottles with nHAp, the migration amounts of carboxylic acid (COOH), acetaldehyde (AA), diethylene glycol (DEG), and isophthalic acid (IPA); glass transition temperature (T_g); melting temperature (T_m); and the maximum crystallization temperature (T_cry) were measured. The load-carrying capacity, burst strength, stress cracking, and regional material distribution tests were carried out on the bottles. X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and ultraviolet transmittance analyses were conducted to explain the changes in mechanical, chemical, physical properties, and light transmission of bottles. It was found out that the COOH amount increased and the AA content decreased with increasing nHAp amount. On the other hand, no change was observed in the amounts of DEG and IPA. Although the mechanical properties such as load-carrying capacity and burst strength of the bottles have improved, it has been determined that the standard environmental stress crack resistance test procedure cannot be applied to such a composite. Experimental findings indicate that nHAp disrupts the chemical structure of PET and it isolates harmful chemicals such as AA by forming intermolecular bonds. Moreover, with the addition of up to 0.8% nHAp, PET bottles block the light transmission approximately 80% within 400–700 nm wave length zone. The study demonstrates that the PET/nHAp composite bottles can be used in the food industry, particularly in the packaging of milk and milk products which are vulnerable to light exposure.     

Kinetics of hydrolysis of polyethylene terephthalate pellets in nitric acid

The hydrolysis of polyethylene terephthalate (PET) pellets in nitric acid was investigated to determine the kinetic parameters. Experiments were conducted with cylindrical shaped pellets in 13M nitric acid at 80, 90, and 100°C respectively. Also, an experiment was conducted with a waste PET bottle sheet in 9.5M nitric acid at 100°C. The kinetics of the reaction was explained by the shrinking core model with surface chemical reaction as rate controlling step and accounting for surface area reduction due to the deposition of the product terephathalic acid (TPA) on the reaction surface. The activation energy for the reaction was found to be 135 kJ/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87:1781–1783, 2003     

Melt viscoelasticity of polyethylene terephthalate resins for low density extrusion foaming

The rheological properties of conventional polyethylene terephthalate (PET) resins are not particularly suitable for low density extrusion foaming with physical blowing agents; as a result, chemically modified resins through chain extension/branching reactions are often used. Such resins have overall higher melt viscosity and higher melt strength/melt “elasticity” than unmodified materials. In this work, following a review of the prior art on PET chemical modification, an unmodified and a chemically modified resin were selected and characterized for their melt viscoelastic properties including shear and dynamic complex viscosity over a broad shear rate/frequency range, storage and loss modulus, and die swell. Certain rheological models were found to provide better fits of the entire viscosity curve for the unmodified vs. the modified resin. Foamed extrudates having variable densities (from about 1.2 to 0.2 g/cc), were prepared by carbon dioxide injection in monolayer flat sheet extrusion equipment. Foams with increasingly lower density, below 0.5 g/cc, were obtained by increasing gas pressure only in the case of the chemically modified resin. The effects of variables such as concentration of the physical blowing agent, resin rheology, resin thermal properties and choice of process conditions are related to product characteristics including density, cell size and crystallinity.     

Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins

Hyperbranched alkyd resins (HBRA) were synthesized by modification of hydroxylated hyperbranched polyester (HBP1‐4) with tall oil fatty acids (TOFA). The core is a hydroxylated hyperbranched polyester of fourth generation with OH groups in the periphery (18), which is endcapped with tall oil fatty acids. The occurrence of these reactions, HBP1‐4 and TOFA, was determined by making use of acid value, nuclear magnetic resonance, and hydroxyl values. The effects of TOFA and HBP1‐4 on properties of the HBRA resins were investigated by vapor pressure osmometry, differential scanning calorimetry, thermogravimetric analysis, friction resistance, and hardness. The resins with higher modification percentage (HBRA4) presented the best thermal and hydrolytic stability, but lower friction resistance and hardness. All HBRA resins presented amorphous characteristics, OH groups, and double bonds in the periphery. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Viscoelastic characteristics of chain extended/branched and linear polyethylene terephthalate resins

Two chemically modified chain extended/branched polyethylene terephthalate (PET) resins and one unmodified resin, considered to be linear, were characterized in terms of their melt flow, die swell, and viscoelastic properties. The three resins had reportedly similar nominal intrinsic viscosities but exhibited different viscoelastic behavior. The modified resins had lower melt flow index, higher die swell, higher complex viscosity and higher storage modulus than the unmodified one. The Cole–Cole plots of the resins were independent of temperature, and the data for modified resins formed a group that lay below the data group for the unmodified PET. The distribution of relaxation times was determined. The modified resins had higher relaxation strength, G_i, especially at high relaxation times, λ_i. The mean relaxation times of the chain extended/branched resins were approximately an order of magnitude higher than that of the unmodified resin, implying pronounced elastic character. The modified resins had better foaming characteristics in extrusion foam processing than the unmodified one owing to their elastic nature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1371–1377, 2000     

Study of glycolysis of poly(ethylene terephthalate) recycled from postconsumer soft‐drink bottles. III. Further investigation

A modified glycolysis reaction of recycled poly(ethylene terephthalate) (PET) bottles by ethylene glycol (EG) was investigated. Influences of the glycolysis temperature, the glycolysis time, and the amount of catalysts (per kg of recycled PET) were illustrated in this study. The manganese acetate was used as a glycolysis catalyst in this study. Bis‐2‐hydroxyethyl terephthalate (BHET) and its dimer were predominately glycolysis products. It was found the optimum glycolysis temperature is 190°C. And the best glycolysis condition is 190°C of glycolysis temperature, 1.5 h of glycolysis time, and 0.025 moles of manganese acetate based on per kg of recycled PET. If the best glycolysis condition is conducted, the glycolysis conversion may be as high as 100%. For a given reaction time (1.0 h), the ln(% glycolysis conversion) is linear to 1/T (K^?1) and the activation energy (E) of glycolysis reaction is around 92.175 kJ/(g mole). The glycolysis conversion rate increases significantly with increasing the glycolysis temperature, the glycolysis time, or the amount of manganese acetate (glycolysis catalyst). Thermal analyses of glycolysis products were examined by a differential scanning calorimetry (DSC) and a thermogravimetric analysis (TGA). According to the definition of a 2³ factorial experimental design, the sequence of the main effects on the glycolysis conversion of the recycled PET, in ascending order, is the glycolysis time (0.18) < the amount of catalyst per kg of the recycled PET (0.34) < the glycolysis temperature (0.40). Meanwhile, the prediction equation of glycolysis conversion from the result of a 2³ factorial experimental design is ? = 0.259+0.20X₁+0.09X₂+0.17X₃+0.06X₁ X₂+0.145X₁X₃+0.05X₂X₃+0.035X₁X₂X₃. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2004–2010, 2003     

聚对苯二甲酸乙二醇异山梨醇酯的结构和性能

以异山梨醇、乙二醇、对苯二甲酸(PTA)为原料,采用PTA法制备了异山梨醇质量分数为20%的对苯二甲酸/乙二醇/异山梨醇的无规共聚酯(PESIT)。PESIT的氢核磁共振谱和红外光谱分析表明,异山梨醇参与了对苯二甲酸与乙二醇的聚合反应。差热和热失重分析表明:PESIT具有较好的热稳定性,玻璃化转变温度和热分解温度较聚对苯二甲酸乙二酯(PET)高。纺丝速度3150 m/min的POY纺丝实验表明:PESIT与PET一样具有好的可纺性,制得的POY断裂强度为1.72 cN/dtex,断裂伸长为175%。     

The effect of mixing shear rate on the properties of liquid crystalline polymer/polyethylene terephthalate blends

The effect of mixing speed of a batch mixer on the properties of liquid crystalline polymer/polyethylene terepthalate (LCP/PET) blends is investigated through two techniques: scanning electron micrographs to examine morphological changes, and tensile testing to determine the mechanical property dependence of the degree of mixing. The results of the two methodologies are well correlated, indicating that the increased degree of mixing of the blend, which is a function of the mixing speed, can be related directly to improved mechanical properties. The results are discussed in the light of existing theories on polymer mixing. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1783–1787, 2000     

Effect of titanium dioxide on the rheological properties of polyethylene terephthalate melts

The rheological properties of polyethylene terephthalate melts containing a different amount of TiO₂ were investigated within wide limits of stresses and shear rate gradients at 260–300°C. It was found that the anomaly of the viscosity properties of the melt increases with an increase in the concentration of TiO₂. The apparent activation energy of viscous flow of PETP melts containing different amounts of TiO₂ was estimated. The temperature dependence of the effective viscosity of the melts is intensified with an increase in the concentration of TiO₂ in them.Mogilev Institute of Technology, Belorussiya. Translated from Khimicheskie Volokna, No. 4, pp. 12–16, July–August, 1995.