Hydrolysis of poly(ethylene terephthalate) waste bottles in the presence of dual functional phase transfer catalysts

The hydrolysis of poly(ethylene terephthalate) (PET) obtained from waste bottles was studied. The dual functional phase transfer catalyst [(CH₃)₃N(C₁₆H₃₃)]₃[PW₁₂O₄₀] exhibited outstanding catalytic activity to the hydrolysis of PET. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy were used to confirm the main product terephthalic acid (TPA) of hydrolysis. The effects of temperature, time, particle size of PET and dosage of catalyst on hydrolysis reaction were examined. Under the optimum conditions of reaction temperature 145°C, time 2 h, particle size of PET at 0.5–1 mm and dosage of catalyst at 7 wt %, the conversion of PET and the yield of TPA were almost 100% and 93%, respectively. After easily separated from the product, the catalyst could be reused more than three times without obvious decrease in the conversion of PET and yield of TPA. An economical and convenient process was developed for hydrolysis of PET. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2790–2795, 2013     

Degradation of poly(ethylene terephthalate) waste with dimethyl tin distanoxane as a catalyst

In this article, we report the degradation of poly(ethylene terephthalate) (PET), which occurs through glycolysis in the presence of dimethyl tin distanoxane [(CH₃)₂Sn(OCOCH₃)₂] as a catalyst, triethylene glycol (TEG) as a nucleophilic agent, and decaline like a solvent. A number of experiments were executed, which were derived from a factorial experimental design, in which the reaction time was between 40 and 60 min, the amount of TEG was between 3.4 and 5.6 g, and the amount of catalyst was between 0.04 and 0.06% in ratio to PET. The reaction temperature was constant at 175°C in all of the experiments. Once the glycolytic depolymerization occurred, oligomers with a molecular weight around 6000 g/mol were obtained. These oligomers were analyzed through gel permeation chromatography, differential scanning calorimetry, Fourier transform infrared spectroscopy, and ¹H‐NMR. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3482–3488, 2013     

Using ionic liquid catalyst for conversion of waste polyethylene terephthalate and soybean oil to polyester polyol

An imidazolium ionic liquid was synthesized, characterized and used as a catalyst for conversion of polyethylene terephthalate (PET) and soybean oil to polyester polyol (PE polyol). The degradation of PET waste was carried out using glycerol and low cost soybean oil that resulted in the formation of PE polyols. Formed PE polyols were characterized using Fourier transform infrared (FT‐IR) and mass spectra method, thermo gravimetric and differential thermal analysis and gel permeation chromatoghraphy. The first step in the overall process is proposed to be the transesterification of soybean oil with glycerol to form monoglyceride or/and diglyceride of soybean oil fatty acids. In the second step, the obtained glycerides can react with PET to form PE polyol. Both steps could be combined in one process and acidic catalyzed by an ionic liquid. Ionic liquid can be used as active catalyst and show a high reusability. The influence of some factors such as amount of glycerol used in transesterification of soybean oil with glycerol, PET degradation time, and temperature on PET conversion were investigated to find the suitable conditions for the process. Under suggested optimum parameters (mass ratio of soybean oil to glycerol of 2:1, a time of 8 h and a temperature of 180 °C for PET degradation), a PET conversion of 87.3% was reached. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43920.     

Depolymerization of poly(ethylene terephthalate) waste

Poly(ethylene terephthalate) waste was depolymerized with ethylene glycol in the presence of different catalysts, two conventional metal catalysts (zinc acetate and lead acetate) and two alkalies (sodium carbonate and sodium bicarbonate). The resulting monomer bis(2‐hydroxy ethylene terephthalate) was characterized by thin layer chromatography, melting point, IR spectroscopy, differential scanning calorimetry, and elemental analysis. The results show that the qualitative and quantitative yields of the monomer obtained with alkalies as catalysts were most comparable with the conventional heavy metal catalysts, thus providing a further advantage for the recycling of polyester waste for the cause of environmental pollution abatement. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1765–1770, 2002     

Zinc‐based catalyst for the ring‐opening polymerization of cyclic esters

A zinc‐based catalyst zinc bis[bis(trimethylsilyl)amide] was used for the polymerization of cyclic esters including L ‐lactide (L ‐LA) and 2‐methyl‐2‐carboxyl‐propylene carbonate (MBC). The polymerization of L ‐lactide in THF could be carried out successfully under mild conditions in very short time by using the zinc catalyst and alcohols as the initiators. Kinetic study in solution polymerization prooved the polymerization has high monomer conversion degree close to 100% and the molecular weight of the resulting polyester has linear increase with the increase of [M]₀ /[I] (molar ratio of monomer to initiator). Sequential polymerization of L ‐LA and MBC in THF also showed high MBC conversion of 94% with a narrow molecualr weight maintained, indicating a living nature of this polymerization. The zinc catalyst system has also been used for the L ‐LA bulk polymerization with a high monomer conversion. ¹³C NMR indicated the polymer possesses high regioregularity and the minor regioirregular component was owing to the D ‐LA in the monomer inserted into the polymer mainchain during the transesterifcation. Interaction between monomer and zinc catalyst has been found to be a key factor to sustain a homogenous solution during the initiating procedure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of ethylene terephthalate and ethylene naphthalate (PET‐PEN) block‐co‐polyesters with defined surface qualities by tailoring segment composition

Ethylene terephthalate and ethylene naphthalate oligomers of defined degree of polymerization were synthesized via chemical recycling of the parent polymers. The oligomers were used as defined building blocks for the preparation of novel block‐co‐polyesters having tailored sequence compositions. The sequence lengths were systematically varied using Design of Experiments. The dispersive surface energy and the specific desorption energy of the co‐polymers were determined by inverse gas chromatography. The study shows that polyethylene terephthalate‐polyethylene naphthalate (PET‐PEN) block‐co‐polyesters of defined sequence lengths can be prepared. Furthermore, the specific and dispersive surface energies of the obtained block‐co‐polyesters showed a linear dependence on the oligomer molecular weight and it was possible to regulate and control their interfacial properties. In contrast, with the corresponding random‐block‐co‐polyesters no such dependence was found. The synthesized block‐co‐polyesters could be used as polymeric modifying agents for stabilizing PET‐PEN polymer blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40731.     

Zinc(II)‐triflate as catalyst precursor for ring‐closing depolymerization of end‐of‐life polytetrahydrofuran to produce tetrahydrofuran

The recycling of polymers continues to be an important subject for a greener and sustainable society. Especially, the deconstruction of end‐of‐life polymers to monomers creates a feedstock for new high‐quality polymeric materials and contributes to conserve resources and allow an efficient waste‐managing system. In this study, zinc(II)‐triflate as catalyst precursor has been examined in detail In the ring‐closing depolymerization of end‐of‐life polytetrahydrofuran (PolyTHF) to generate tetrahydrofuran (THF). Noteworthy, the produced THF can be a suitable starting material for new polymeric materials. With the cheap and abundant Zn(OTf)₂ (1.0 mol %) as precatalyst excellent yields (up to 95%) were feasible for the depolymerization of PolyTHF at 180°C within 30 min. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39791.     

Attapulgite‐supported aluminum oxide hydroxide catalyst for synthesis of poly(ethylene terephthalate)

A novel nanocomposite catalyst was prepared from immobilization of aluminum oxide hydroxide onto the attapulgite. Characterizations with scanning electron microscopy (SEM) and wide angle X‐ray diffraction (XRD) of the as‐prepared catalyst revealed that AlO(OH) nanoparticles were distributed on the attapulgite. Thermogravimetric analysis‐infrared spectrometry (TGA‐IR) of the mixture prepared by mixing of bishydroxy ethylene terephthalate (BHET) and the catalyst indicated that attapulgite‐supported aluminum oxide hydroxide catalyst can catalyze BHET polycondensation under the applied conditions. A kinetic model for determining the activation energy has been applied to evaluate the catalyst activity. The catalyst activity was examined through comparative experiments, and the results showed that the new catalyst exhibited higher activity for BHET polycondensation under identical reaction conditions, and the viscosity‐average molecular weight of poly(ethylene terephthalate) (PET) product obtained was increased about 2000 g/mol. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Heterogeneous catalytic synthesis of poly(butylene succinate) by attapulgite‐supported Sn catalyst

An attapulgite‐supported Sn catalyst (Sn‐palgorskite) was successfully prepared by ion‐exchange co‐impregnation method. The catalytic effect of Sn‐attapulgite on the melt polycondensation reaction of poly(butylene succinate) (PBS) was examined by comparing with that of anhydrous SnCl₂ and a blank experiment. The structures and properties of the PBS products synthesized with the three catalytic systems were characterized by means of Fourier transform‐infrared spectra (FT‐IR), viscosity measurements, wide angle X‐ray diffraction (WARD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Meanwhile, the acidolysis degradation behaviors of the PBS samples were also studied. It was found that the intrinsic viscosities and the number‐average molecular weights of the PBS were remarkably increased under the catalysis of Sn‐attapulgite, further leading to an increase in the decomposition temperature, the crystallization temperature, and the viscous flow activation energy, while a decrease in the melting temperature, the relative degree of crystallinity, and the rate of degradation. Additionally, no significant differences were observed in the crystal structures of all the samples, regardless of the reaction system with or without catalyst. The experiment results confirmed that Sn‐attapulgite was an effective heterogeneous catalyst for the synthesis of PBS, and the recycled Sn‐attapulgite still exhibited higher activity than anhydrous SnCl₂ under identical reaction conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41729.     

Butanol alcoholysis reaction of polyethylene terephthalate using acidic ionic liquid as catalyst

The alcoholysis reaction of polyethylene terephthalate (PET) and n‐butanol to produce dibutyl terephthalate (DBTP) and ethylene glycol (EG) was investigated in the presence of a Brönsted–Lewis acidic ionic liquid (IL). It was found that a synergetic effect of Brönsted and Lewis acid sites enhanced the IL catalytic performance, and (3‐sulfonic acid) propyltriethylammonium chlorozincinate [HO₃S‐(CH₂)₃‐NEt₃]Cl‐ZnCl₂ (molar fraction of ZnCl₂ (x) was 0.67) was a good catalyst for the reaction. The conversion of PET was 100%, and the yields of DBTP and EG were 95.3% and 95.7% at 205°C for 8 h, respectively. The reusability of IL was good and after it was used seven times, PET conversion and the yields of DBTP and EG did not significantly decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1840–1844, 2013     

Spinning fibers from poly(ethylene terephthalate) bottle‐grade waste

Poly(ethylene terephthalate) bottle‐grade (BG) waste was converted into spinnable chips and spun on a laboratory‐scale melt‐spinning apparatus into filaments. Virgin fiber‐grade (FG) polyester chips were blended with BG waste during melt spinning so that the influence of blending on the fiber properties could be studied. Subsequently, the scaling‐up of the process was carried out in a polyester recycling plant so that staple fibers could be obtained. In this part of the study, the spinning of blends of BG waste and FG waste was carried out. The BG waste was found to be superior feed stock for melt processing. Fibers with unique properties were obtained from the BG waste. Staple fibers obtained by the blending of FG and BG waste showed properties different from those of fibers spun from BG waste alone. This study also showed that using blends of BG and FG waste could improve the melt processing and staple‐fiber properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3536–3545, 2003     

Synthesis of metal‐free poly(p‐dioxanone) by phosphazene base catalyzed ring‐opening polymerization

Poly(p‐dioxanone) (PPDO) has received significant attention due to its good biocompatibility and fast biodegradation profiles. In addition, PPDO is a polymer with high potential in biomedical applications. However, the conventional syntheses of PPDO via the ring‐opening polymerization (ROP) of p‐dioxanone (PDO) often use a metallic catalyst, which significantly limits its biorelated applications. This investigation was focused on the synthesis of metal‐free PPDO by using phosphazene base t‐BuP₄ as the catalyst. The effects of the reaction conditions including temperature, reaction time, initiators, and feed molar ratios were studied in detail by nuclear magnetic resonance spectroscopy, viscosimetry, differential scanning calorimetry, and thermogravimetric analysis. The results showed that t‐BuP₄ exhibited especially high activity in catalyzing alcohol or aniline to initiate the ROP of PDO, consequently resulting in metal‐free PPDOs. The polymerization was optimum at a reaction temperature of approximately 100°C and 88.7% of PDO was consumed. The viscosity–average molecular weights of the resulting polymer reached as high as 2.09 × 10⁴ g/mol. The molar ratios of [PDO]/[t‐BuP₄] also had an obvious effect on both the polymerization and the resulting polymer. Increasing [PDO]/[t‐BuP₄] ratios facilitated the molecular weight growth, whereas the conversions of PDO significantly decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43030.     

Recycling PET beverage bottles and improving properties

Recycling PET from bottles has been carried out by three different extrusion methods. Under optimized processing conditions, a virgin poly(ethylene terephthalate (PET), recycled PET and a mixture of virgin and recycled PET, with and without the modifier polypropylene functionalized with maleic anhydride [PP‐graft‐MA]), were processed. Different methods were used to characterize the processed products. The results showed that the intrinsic viscosity and molecular weight decreased as the blend ratio of recycled PET was increased. This was due to thermal exposure as well as shear degradation of recycled PET. Thermal cycles of the processes used for recycling PET and its blending specimens with virgin PET show the importance of the thermal treatment in the improvement of mechanical strength and increased crystallinity. Nevertheless, the properties of the functionalized blends were improved. This behaviour is attributed to a series of chemical and physico‐chemical interactions taking place between the two components. Copyright © 2004 Society of Chemical Industry     

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Solvent‐free cyanoethylation of selected alcohols with acrylonitrile (AN) using a weakly basic polymer resin, Amberlyst A‐21 (AA‐21) was studied at 75°C. The conversion of primary alcohols, 1‐octadecanol, hexane‐1,6‐diol, pentaerythritol, but‐2‐yne‐1,4‐diol, N‐methyldiethanolamine, triethanolamine and diethanolamine is higher than secondary alcohols, isopropanol and glycerol in the presence of polymer resin. Of various alcohols, but‐2‐yne‐1,4‐diol gave the product in high conversion (87%) in cyanoethylation with a polymer resin/AN weight ratio of 0.04. The polymer resin showed recycling ability only in two cycles to produce cyanoethylated product from diethanolamine. In case of 1‐octadecanol, hexane‐1,6‐diol, and N‐methyldiethanolamine with AN under similar conditions, no recycling ability was observed. Thermally treated polymer resin at 75°C afforded the product in lower conversion (55%) whereas the same product was obtained in 69% when fresh polymer resin was used in cyanoethylation of 1‐octadecanol. No catalytic effect was observed for polymer resin treated at 100°C. Fourier transform infrared (FTIR) spectra showed CN stretching at 2248 cm^?1 for the polymer resin collected after the reaction which was caused by the AN binding on polymer resin during the reaction. As per thermogravimetric curves, 5% weight loss was observed at 201°C for recovered resin and at 161°C for polymer resin treated at 100°C. Scanning electron microscope images confirmed the AN binding on polymer beads after catalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Recycling of chrome‐tanned leather waste in acrylonitrile butadiene rubber

Chrome‐tanned leather waste generated in huge amount from leather industry causing environmental problem; this leather waste was used as filler in acrylonitrile butadiene rubber before treatment and after treatment with ammonia solution and sodium formate. Different formulations of acrylonitrile butadiene rubber/leather waste (untreated–treated with ammonia solution—treated with sodium formate) composites are prepared. The formed composites exhibit a considerable improvement in some of their properties such as rheometric characteristics especially with composites loaded with treated leather waste. Tensile strength, modulus at 100% elongation, hardness, and Young's modulus were improved for composite loaded with treated leather. Crosslinking density in toluene was increased by the incorporation of leather wastes treated or untreated resulting in decreases in swelling equilibrium. Distinct increase in the ageing coefficient and the thermal stability for composites loaded with both treated and untreated leather. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

废旧塑料的回收与利用

综述了利用区块链技术进行废旧塑料的回收.使用区块链技术建立的塑料银行可以激励人们自发地回收废旧塑料.废旧塑料的回收流程大多是线下的,监管困难,使用区块链技术可以使用户在区块链上查询全流程的回收数据,便于监管.在废旧塑料的分选和利用方面,介绍了聚乙烯和聚丙烯的分选,聚对苯二甲酸乙二酯与聚氯乙烯混合固体塑料的分选.废旧塑料...     

Recycling of waste poly(ethylene terephthalate) into flame‐retardant rigid polyurethane foams

Waste poly(ethylene terephthalate) (PET) textiles were effectively chemical recycling into flame‐retardant rigid polyurethane foams (PUFs). The PET textile wastes were glycolytically depolymerized to bis(2‐hydroxyethyl) terephthalate (BHET) by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst. The PUFs were produced from BHET and polymeric methane diphenyl diisocyanate. The structures of BHET and PUFs were identified by FTIR spectra. The limiting oxygen index (LOI) of the PUFs (≥23.27%) was higher than that of common PUFs (16–18%), because the aromatic substituent in the depolymerized products improved the flame retardance. To improve the LOI of the PUFs, dimethyl methylphosphonate doped PUFs (DMMP‐PUFs) were produced. The LOI of DMMP‐PUFs was approached to 27.69% with the increasing of the doped DMMP. The influences of the flame retardant on the foams density, porosity, and compression properties were studied. Furthermore, the influences of foaming agent, catalyst, and flame retardant on the flame retardation were also investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40857.     

Poly(styrene–divinyl benzene)‐immobilized Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene: Efficient catalyst for the photocatalytic degradation of xylenol orange

A polymer‐supported Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene [PS–Fe(III)BBZNH] was used in the photodegradation of xylenol orange (XO) dye with H₂O₂ under UV irradiation. The catalyst was synthesized and characterized by elemental analysis, and Fourier transform infrared, far‐infrared, and UV–visible–diffuse reflectance spectroscopy, Scanning electron microscopy, Brunauer–Emmett–Teller surface area measurements, thermogravimetric analysis, and magnetic measurements. An octahedral coordination around Fe(III) was confirmed by electronic spectral data, and a decrease in the intensity of the ν_CH2Cl peak in PS–Fe(III)BBZNH was observed compared to the polymer support; this indicated the binding of the ligand to the support. An array of experiments were carried out to assess the influence of various reaction parameters on its photocatalytic performance to ensure maximum dye degradation. The maximum photocatalytic activity was observed at pH 8 with 125 mg of catalyst, 300 ppm of XO, and 200 ppm of H₂O₂ with complete mineralization after 90 min, as confirmed by chemical oxygen demand measurements. Furthermore, the reactions were repeated under sunlight and under dark conditions to check the photocatalytic efficiency of PS–Fe(III)BBZNH. It displayed better catalytic performance compared than the unsupported complex, PS–Cu(II)BBZNH [Cu(II) complex of 1,3‐bis(benzimidazolyl)benzene], and PS–VO(IV)BBZNH [VO(IV) complex of 1,3‐bis(benzimidazolyl)benzene]. PS–Fe(III)BBZNH could be recycled for up to seven runs. A tentative mechanism involving ·OH radical was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46480.     

Depolymerization of poly(ethylene terephthalate) with catalyst under microwave radiation

Grain poly(ethylene terephthalate) (PET) was depolymerized in pure water in the presence of different catalysts. The product quantity of bis(2-hydroxy ethylene) terephthalate (BHET) and glycol obtained was different from the one without catalysts; especially, using zinc acetate as catalyst, the product obtained was in its pure form with sufficiently high yields. Meanwhile, the depolymerization rate nearly reached to 100%. The purified product was characterized by IR spectroscopy. The depolymerization process of PET reported here was economically viable for the high yields of BHET and glycol. Among all the catalysts used in the reaction, zinc acetate was testified as the most effective one, and the optimal dosage of zinc acetate was 0.4% of the feedstock PET. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water‐blown polyurethane/polyisocyanurate foams made from recycled polyethylene terephthalate and liquefied wood‐based polyester polyol

Depolymerized polyethylene terephthalate and liquefied wood polyesters can be used as a polyol for the production of polyurethane/polyisocyanurate foams. In this research, liquefied wood was synthesized by using a combination of diethylene glycol and glycerol and due to the possibility of using glycerol that is a by‐product in biodiesel production, our goal was to use as much glycerol in the liquefaction reagent as possible. We determined the properties of the polyols, properties of produced foams, and explained their correlation. Greater amount of glycerol in the liquefaction reagent resulted in higher OH number, molecular weight, functionality, and viscosity of the polyol, as well as in longer cream time and tack free time in foam preparation. Glass transition temperature, density, and water absorption of the foam increased with increasing amount of glycerol in liquefied wood. Compressive stress increased up to 30% of the glycerol in the reagent and then reduced, while thermal conductivity was not affected. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41522.