Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Synthesis of unsaturated polyester resin from glycolysed postconsumer PET wastes

The purpose of this study was to explore ways to extend the chemical recycling of poly(ethylene terephthalate) (PET) as a valuable feedstock for chemical processes. First, PET wastes were depolymerised using a glycolysis method in the presence of sodium carbonate, which is considered to be a less environmentally damaging option for a catalyst. Good yields of the monomer bis(2-hydroxyethyl) terephthalate (BHET) were obtained (80 %). Second, to develop an economically viable recycling programme for the reclaimed BHET, the conversion of purified BHET into unsaturated polyester resins (UPR) was studied. The recovered monomer was thus polyesterified with maleic anhydride and subsequently mixed with styrene monomer to prepare UPRs. The resins were casted by a crosslinking reaction using methyl ethyl ketone peroxide and cobalt 2-ethylhexanoate as the initiator and catalyst, respectively. The polyesterification reaction was followed by gel permeation chromatography. The curing process was studied by differential scanning calorimetry and infrared spectroscopy. The cured resin was subjected to various characterisation methods in order to determine its chemical, physical and mechanical properties. Resins with suitable properties for commercial application were obtained.     

Synthesis and Characterization of Polyols and Polyurethane Foams from PET Waste and Crude Glycerol

In this study, polyethylene terephthalate (PET) waste from post-consumer soft-drink bottles and crude glycerol from the biodiesel industry were used for the preparation of polyols and polyurethane foams. PET waste was firstly depolymerized by the glycolysis of diethylene glycol. The glycolyzed PET oligomers were then reacted with crude glycerol at different weight ratios to produce polyols via a series of reactions, such as esterification, transesterification, condensation, and polycondensation. The polyols were characterized by titration, viscometry, gel permeation chromatography (GPC), and differential scanning calorimetry. Subsequently, polyurethane (PU) foams were made via the reaction between the produced polyols and polymeric methylene-4,4′-diphenyl diisocyanate and were characterized by mechanical testing, scanning electron microscopy, and thermogravimetric analysis. Polyols from crude glycerol and their PU foams were also prepared to compare properties with those of polyols and PU foams from PET and crude glycerol. The influence of aromatic segments existing in glycolyzed PET and glycerol content on the properties of the polyols and PU foams was investigated. It was found that aromatic segments of polyols from glycolyzed PET helped increase their molecular weights and improve thermal stability of PU foams, while high glycerol content in polyols increased the hydroxyl number of polyols and the density and compressive strength of PU foams.     

Recycling of waste PET into useful textile auxiliaries

Polyethylene terephthalate (PET) waste fibers were initially depolymerized using a glycolysis route in the presence of sodium sulfate as a catalyst, which is a commonly used chemical and ecofriendly as compared to heavy metal catalysts. Good yield of the pure monomer bis(2-hydroxyethylene terephthalate) (BHET) was obtained. Further, to attempt its reuse, the purified BHET was converted to different fatty amide derivatives to obtain quaternary ammonium compounds that have a potential for use as softener in the textile finishing process. The products were characterized by infrared spectroscopy. Application of these synthesized compounds was carried out on cotton fabric; they were evaluated for performance and were found to give good results. The chemicals used during depolymerization and reuse of PET are inexpensive and comparatively less harmful to the environment, and thus offer advantages in the chemical recycling of polyester waste fibers.     

Novel polyol initiator from polyurethane recycling residue

Flexible polyurethane foams can be advantageously treated by two-phase glycolysis in order to recover polyols with improved quality. The bottom phase obtained, which contains highly toxic reaction by-products and the excess glycol, presents an environmental and economic problem which should be solved. The main purpose of this work is the development of process for the valorization of these by-products, converting them in non-dangerous and profitable substances. For this process, most of the glycol can be recovered by means of vacuum distillation in order to reuse it in the glycolysis. On the other hand, the vacuum residue, containing the isocyanate part of the glycolysis by-products, was assayed as initiator in the synthesis of new polyols. Propoxylation of the initiator was carried out in different experimental conditions to obtain several polyether-polyols. Rigid polyurethane foams with suitable technical properties were synthesized with those polyols synthesized with the dangerous glycolysis by-products.     

Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(6)kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.     

聚对苯二甲酸乙二醇酯废料的回收方法

介绍了聚对苯二甲酸乙二醇酯传统的化学回收方法：甲醇醇解法、水解法和醣酵解法;简述了聚酯新的回收工艺：伊斯曼乙二醇水解工艺、超临界水水解工艺和Reco-PET工艺,及有关国家聚酯回收的工业化实践,并对聚酯回收的前景及影响聚酯回收的因素进行了分析。     

镁铝水滑石制备复合金属氧化物及其催化处理废弃聚酯材料

采用共沉淀法合成了镁铝水滑石并将其在不同温度下煅烧得到复合金属氧化物。将两者作为催化剂用于醇解聚对苯二甲酸乙二醇酯(PET)反应中。实验结果表明:复合金属氧化物的催化活性明显高于其前体,最佳煅烧温度为500℃;在催化剂与PET质量比为1.0%、醇解反应时间为50 min时,产物对苯二甲酸乙二醇酯(BHET)的产率可达到81%。镁铝水滑石煅烧后得到的复合金属氧化物是一种高效、环境友好型醇解PET催化剂,可以替代目前常用的均相催化剂。     

Effect of Recycling on Material Properties of Glass-filled Polyethylene Terephthalate

Recycled plastics are considered low performance materials because their properties are expected to decrease drastically with recycling. The objective of this study was to characterize a 15 wt.% glass filled polyethylene terephthalate (rPET-15GF) using six recycle generations and four recycle ratios. Mechanical properties such as tensile strength, elastic modulus, and percent elongation to failure of the PET composite were determined for various recycle generations and recycle ratios. Results show that the mechanical properties of rPET-15GF decrease slightly per recycle generation. In contrast, thermal properties of rPET-15GF were not at all affected by the recycling process. This data demonstrates that recycled glass filled PET can be used effectively to fabricate components without significantly affecting their mechanical performance.     

From Aminolysis Product of PET Waste to Novel Biodegradable Polyurethanes

Chemical recycling of PET has been developed by various methods. Aminolysis is one of chemical recycling methods of PET has been developed recently. The obtained product using aminolysis, Bis (2-hydroxy ethylene) terephthalamide (BHETA), has the potential for further reactions to obtain useful products. There are few reports on usage of recycled BHETA from PET waste to synthesis of polyurethanes. On the other hand, various biodegradable polyurethanes have been synthesized using polycaprolactone diol. Therefore, caprolactone is a new potential in synthesis of biodegradable polyurethanes from PET waste. In this work, novel biodegradable polyurethanes have been synthesized using BHETA. In this order, at first polyols with different molecular weights have been synthesized through ring opening polymerization of caprolactone by BHETA, then urethane linkages were formed using HDI (Hexamethylene Diisocyanate) without chain extender. Chemical, thermal, mechanical and dynamic mechanical properties, biodegradability, morphology and UV resistance of synthesized polyurethanes have been investigated.     

Effects of Saturated Acids on Physical Properties of UPE Resins Prepared from Recycled PET Products

In this study, effects of saturated acids on physical properties, including hardness, impact strength, flexural properties and thermal properties, of unsaturated polyester or UPE resins prepared from recycled PET bottles and fabrics were investigated. PET was depolymerized by glycolysis reaction with the excess propylene glycol in the presence of zinc acetate as a catalyst. UPE resins were then synthesized by polyesterification of these glycolyzed products with maleic anhydride as an unsaturated diacid as well as succinic acid and adipic acid as a saturated diacid. With the addition of styrene monomer, UPEs were subsequently casted into specimens by crosslinking reaction using methyl ethyl ketone peroxide and cobalt octoate as an initiator and a catalyst, respectively. Physical properties of the cured specimens were then studied. The results showed that, when a saturated acid was incorporated, the hardness of the cured UPE resins decreased due to the decreasing amount of crosslinks. The extended distance between crosslinking sites on molecular chains facilitated load distribution, resulting in the significant improvement of impact strength. The flexural strength was also improved when the small amount of saturated acid was used. The onset thermal degradation temperatures and the glass transition temperatures of the prepared UPE resins were almost unchanged.     

Application of fluidization to separate packaging waste plastics

The objective of the experimental work described in this paper is the study of the separation of PS (polystyrene) from PET (polyethylene terephthalate) and PVC (polyvinyl chloride) from drop-off points using a fluidized bed separator. This is a low-cost process commonly used in the hydro-classification of mineral ores. Firstly, experimental tests were carried out with artificial granulated samples with different grain sizes, types and sources of plastic ("separability tests"). The particle settling velocities were determined under different operating conditions. Then, based on the results, the laboratory tests continued with real mixtures of waste plastics ("separation tests") and the efficiency of the process was evaluated. From a PET-rich mixture, a concentrate of PS with a 75% grade in PS was produced while the underflow was quite clear from PS (grade less than 0.5% in PS).     

Modification of Thermo-Mechanical Properties of Recycled PET by Vinyl Acetate (VAc) Monomer Grafting Using Gamma Irradiation

Vinyl acetate (VAc) monomer of different percentage was grafted onto the recycled polyethylene terephthalate (r-PET) films using gamma irradiation. The properties of these modified films were characterized by Fourier transform infrared spectroscopy (FTIR), mechanical properties testing (Tensile strength, Elongation at break), dynamic mechanical analysis (DMA) and thermo-gravimetric analysis (TGA). The Tensile Strength (TS) of the modified PET film increased by 132.25?% to the highest value of 50.12 MPa at 15% VAc monomer concentration at 3 kGy gamma dose, while the elongation at break (EB) decreased by 31.83?%. FTIR was used to investigate the molecular interaction of the modified films. TGA revealed that curve of the modified PET film shifted toward higher temperature region by 95?°C, which is very close to that of PET film made from virgin flakes. The results indicate that modified PET films of better mechanical and thermal properties were successfully prepared using VAc monomer grafting by gamma irradiation technique.     

Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst

Flexible polyurethane foam wastes can be advantageously treated by two-phase glycolysis to recover the polyols with an improved quality compared to single-phase processes. This reaction has been traditionally catalyzed by alkanolamines, titanium compounds, or acetates. Recently, the employment of new catalysts based on potassium and calcium octoates has opened up a new way to catalyze the glycolysis of polyurethanes. In this work, the use of stannous octoate, which has never before been applied in the glycolysis reactions of polyurethanes, is proposed. The catalytic activity of stannous octoate in such a process was studied. The decomposition rate and the purity of polyol obtained were greater than those obtained using other catalysts previously employed for this application.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Biopolymers in the Existing Postconsumer Plastics Recycling Stream

The existing plastic bottle reclaiming industry has working technology, satisfied customers, raw material, and investors. Adding new materials to the current mix requires satisfying all four needs for those materials. Rigid plastic container recycling focuses on high-density polyethylene (HDPE) and polyethylene terephthalate (PET) bottles, the overwhelming percentage of bottles sold in North America. Bottles of other resins, including polyvinyl chloride (PVC), polypropylene and biopolymers, lack critical mass necessary for independent reclamation. To be mechanically recycled, biopolymers must be either completely fungible with existing recycled resins or be available in sufficient quantity to achieve the needed critical mass. So far, biopolymer volume projections are not encouraging. Biopolymers, like all minor bottle resins, must pay their own way in sorting and processing without subsidy from PET and HDPE recycling. Based on limited data, some biopolymers may have little effect on recycled HDPE performance, but will represent a yields loss and added economic burden at some level of occurrence. Biopolymers have not been shown to be compatible with PET and likely will represent performance problems and economic burdens at even low levels of occurrence. Applications for biopolymers should be carefully selected so as to not interfere with currently recycled materials unless critical mass can be achieved quickly.

PET from Used Beverage Bottles: A Material for Preparation of Biologically Degradable Copolyesters

Poly(ethylene terephthalate) from used colorless beverage bottles was solvolyzed by ethane-1,2-diol. Hydroxyl end-groups present in the mixture of polyols formed were used to initiate the polymerization of ??-caprolactone (CLO) at 190?°C. Polycondensation (190?°C) of the reaction mixture containing an equilibrium amount of lactone corresponding to the reaction temperature yield an aliphatic?Caromatic copolyester. A variety of copolyesters containing 20?C60?mol. % CLO structural units was prepared. The microstructure of their macromolecules was analyzed using ¹H?NMR spectroscopy. Copolyesters were characterized by thermal analysis and tensile tests and their biodegradation potential was checked by the composting test.     

Alkaline hydrolysis of PVC-coated PET fibers for simultaneous recycling of PET and PVC

Journal of Material Cycles and Waste Management - Polyvinyl chloride (PVC)-coated poly(ethylene terephthalate) (PET) woven fibers are one of the hardest-to-recycle polymeric materials. Herein we...     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Chemical Recycling of PET Waste with Multifunctional Pentaerythrytol in the Melt State

Chemical recycling of poly(ethylene terephthalate) PET waste in the melt state through alcoholysis with multifunctional alcohol—pentaerythrytol (PENTE)—was performed in a internal mixer Haake Rheomix 600, at 250 °C, 60 rpm, for 10 min, in presence of zinc acetate. The following PET:PENTE molar ratios 1:0; 1:0.16; 1:0.48 and 1:3.4 were studied. The chemical structure of the end-products was characterized by FT-IR. Thermal properties and X-ray diffractograms were also assessed. The esterification and alcoholysis reactions took place and were dependent on the molar ratio. The first one is dominant in compositions rich in PET leading to the formation of star-branching copolymer. The second one brings about the PET oligomerization and an oligoester named herein bis(tri-hydroxylneopentyl) terephthalate (BTHNPT) was obtained. The end-products have potential application as asphalt additive or adhesive.