Alkyd resins derived from glycolized waste poly(ethylene terephthalate)

In this investigation the production of secondary value-added products, such as alkyd resins, derived from the glycolysis of poly(ethylene terephthalate) (PET) is examined as an effective way for its recycling. PET was taken from common soft-drink bottles and diethylene glycol (DEG) was used for the depolymerization at several initial molar ratios. The oligomers obtained were analyzed according to their average molecular weights. Furthermore, the glycolyzed PET products (oligomers) were reacted with maleic anhydride, phthalic anhydride and propylene glycol to form unsaturated polyester resins. These were subsequently mixed with styrene and cured using the benzoyl peroxide/amine initiator system to carry out the reaction in ambient temperature. The curing characteristics of the resins produced were investigated with respect to the initial molar ratio of DEG/PET as well as the initial initiator concentration. Finally, the mechanical properties (tensile strength and elongation at the break point) of the resins were compared with the conventional general purpose resin and were found to be comparable.     

Poly(ethylene terephthalate) waste derived chemicals as an antistripping additive for bitumen – An environment friendly approach for disposal of environmentally hazardous material

The increasing accumulation of poly(ethylene terephthalate) polymer and poor recycle/disposal practices have made them omnipresent and a major culprit for environmental pollution. Currently global research efforts are focused on primary and secondary recycling of PET waste or through landfills. Chemical recycling of PET through hydrolytic or aminolytic route has been attempted by many researchers however with limited end applications. In our investigations we have used PET waste as a synthon and chemically converted it through a new non-catalytic route into several benzamide derivatives. We have successfully tested them for antistripping performance in bitumen. Our results as elaborated in the paper indicate a comparable performance of the new chemistry products based on PET, to commercially used antistripping chemicals. Our research work thus opens a new route for the recycling of used PET in bituminous concrete roads which may help in alleviating a major environmental problem and disposal of waste PET polymer in large scale.     

Recycling technology of poly(ethylene terephthalate) materials

Poly(ethylene terephthalate) (PET) has become one of major post consumer plastics wastes, in addition to polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride) (PVC). The challenge to large-volume plastics companies is to learn how to collect, separate, reprocess and market their low-cost products and make a profit, too. The effort of PET recycling, however, is the most successful story in the plastic recycling technology, including both reclaim and upgrade of PET waste. Beverage bottles made of PET are recycled more than 20% of the total production. The technology of today can reclaim the post-consumer PET bottles to produce high-quality granulated PET with better than 99% purity. A practical reclaim process for recycling PET bottles (including bottle, HDPE base cup, aluminum cap, liner, label and adhesive) is available by the Center for Plastics Recycling Research in USA. PET recycling process, like for other plastics, can be divided into three categories: incineration, physical recycling, and chemical recycling. To make the plastic recycling business pay requires more than simple recovery and marketing. Greatest profit potential is in upgraded and value-added reclaim products. Upgrading involves compounding with additives to make material more processable, adding reinforcement, or producing extrusions or finished parts from reclaim resins. For instance, a modified injection-moldable resin made from PET bottle scrap is claimed to provide high impact and processability at less cost than competitive materials. It is foreseen that chemical recycling of waste PET bottle becomes feasible if the price of raw material goes up. Three economical processes are involved in this technology: pyrolysis, hydrocracking, and hydrolysis. The hydrolysis process is presently employed to recover the raw material for unsaturated polyester resin manufacture or polyols for the production of polyurethane resin. It is reported in this presentation that polymer concrete could be a huge potential market for chemical reclaim of PET materials, especially for green or mixed-color PET, which are priced lower than colorless PET reclaim materials.     

Anthropogenic chemical carbon cycle for a sustainable future

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time, millions of years, can new fossil fuels be formed naturally. The burning of our diminishing fossil fuel reserves is accompanied by large anthropogenic CO(2) release, which is outpacing nature's CO(2) recycling capability, causing significant environmental harm. To supplement the natural carbon cycle, we have proposed and developed a feasible anthropogenic chemical recycling of carbon dioxide. Carbon dioxide is captured by absorption technologies from any natural or industrial source, from human activities, or even from the air itself. It can then be converted by feasible chemical transformations into fuels such as methanol, dimethyl ether, and varied products including synthetic hydrocarbons and even proteins for animal feed, thus supplementing our food chain. This concept of broad scope and framework is the basis of what we call the Methanol Economy. The needed renewable starting materials, water and CO(2), are available anywhere on Earth. The required energy for the synthetic carbon cycle can come from any alternative energy source such as solar, wind, geothermal, and even hopefully safe nuclear energy. The anthropogenic carbon dioxide cycle offers a way of assuring a sustainable future for humankind when fossil fuels become scarce. While biosources can play a limited role in supplementing future energy needs, they increasingly interfere with the essentials of the food chain. We have previously reviewed aspects of the chemical recycling of carbon dioxide to methanol and dimethyl ether. In the present Perspective, we extend the discussion of the innovative and feasible anthropogenic carbon cycle, which can be the basis of progressively liberating humankind from its dependence on diminishing fossil fuel reserves while also controlling harmful CO(2) emissions to the atmosphere. We also discuss in more detail the essential stages and the significant aspects of carbon capture and subsequent recycling. Our ability to develop a feasible anthropogenic chemical carbon cycle supplementing nature's photosynthesis also offers a new solution to one of the major challenges facing humankind.     

Effect of small amounts of poly(lactic acid) on the recycling of poly(ethylene terephthalate) bottles

Poly(ethylene terephthalate) (PET) is one of the most used commodity polymers, especially for food and beverage applications, and its recycling is of great importance because of the possible use in the textile and construction industries. On the other hand, the interest in biodegradable polymers has led, in recent years, to the use of materials such as poly(lactic acid) (PLA) also in the food and beverage industry. The presence of small amounts of PLA in the PET waste can significantly affect the post-consumer recycling process. In this work, the effect of the presence of small amounts of PLA on the recycling of PET bottles is investigated by rheological, mechanical, morphological and thermogravimetric analysis. The results indicate that this presence can significantly affect the rheological properties under non-isothermal elongational flow, while the mechanical properties were considerably affected only in some circumstances and the thermal stability was not significantly modified.     

Evaluation of the effect of additives on thermo-oxidative and hydrolytic stabilization of recycled post-consumer poly (ethylene terephthalate) using Design of Experiments

The recycling of poly (ethylene terephthalate) (PET), mainly from bottles, has been considered the most promising alternative to reduce municipal solid waste in Brazil. Stabilization processes of this polymer during recycling aim to maintain and improve its physicochemical properties and enhance its applicability. Several classes of additives may be used for PET stabilization, such as antioxidants, metal deactivator or anti-hydrolysis. However, there are no studies in literature about the synergistic or antagonistic effect of the individual or combined use of these additives for the stabilization of PET. The present investigation uses Design of Experiments (DoE) to analyze the effects of the variables that influence the stabilization of post-consumer PET. The variables were humidity and three different classes of additives represented by antioxidants (Irganox 1010® and Irganox B561®), a metal deactivator (Irganox MD1024®) and an anti-hydrolysis (Stabaxol KE7646®), known as polycarbodiimide. Taking intrinsic viscosity into consideration, the post-consumer PET flakes were processed with different additive contents in order to understand both the individual and combined effects that influence stabilization and generate the response surfaces. The results showed that the samples stabilized with polycarbodiimide had an effective increase in intrinsic viscosity. In addition, samples stabilized with antioxidants had lower contribution and the metal deactivator had no effect on the stabilization of recycled PET. Our findings indicate that the hydrolysis overlaps the thermo-oxidative degradation effects and is the main form of PET degradation in the course of recycling. Moreover, besides being marketed as an anti-hydrolysis, results suggest polycarbodiimide is an effective chain extender. Finally, this study sheds some light on the influence of the main additives and variables that influence the degradation and stabilization of PET. The increase in PET intrinsic viscosity promotes its physicochemical properties and allows the recycled polymer to be used in broader market segments.     

Aptamer‐Based Turn‐On Detection of Thrombin in Biological Fluids Based on Efficient Phosphorescence Energy Transfer from Mn‐Doped ZnS Quantum Dots to Carbon Nanodots

This paper presents the first example of a sensitive, selective, and stable phosphorescent sensor based on phosphorescence energy transfer (PET) for thrombin that functions through thrombin–aptamer recognition events. In this work, an efficient PET donor–acceptor pair using Mn‐doped ZnS quantum dots labeled with thrombin‐binding aptamers (TBA QDs) as donors, and carbon nanodots (CNDs) as acceptors has been constructed. Due to the π–π stacking interaction between aptamer and CNDs, the energy donor and acceptor are taken into close proximity, leading to the phosphorescence quenching of donors, TBA QDs. A maximum phosphorescence quenching efficiency as high as 95.9 % is acquired. With the introduction of thrombin to the “off state” of the TBA‐QDs‐CNDs system, the phosphorescence is “turned on” due to the formation of quadruplex‐thrombin complexes, which releases the energy acceptor CNDs from the energy donors. Based on the restored phosphorescence, an aptamer‐based turn‐on thrombin biosensor has been demonstrated by using the phosphorescence as a signal transduction method. The sensor displays a linear range of 0–40 nM for thrombin, with a detection limit as low as 0.013 nM in pure buffers. The proposed aptasensor has also been used to monitor thrombin in complex biological fluids, including serum and plasma, with satisfactory recovery ranging from 96.8 to 104.3 %. This is the first time that Mn‐doped ZnS quantum dots and CNDs have been employed as a donor–acceptor pair to construct PET‐based biosensors, which combines both the photophysical merits of phosphorescence QDs and the superquenching ability of CNDs and thus affords excellent analytical performance. We believe this proposed method could pave the way to a new design of biosensors using PET systems.     

Recycling of poly(ethylene terephthalate) waste through methanolic pyrolysis in a microwave reactor

In this study, the methanolic pyrolysis (methanolysis) of poly(ethylene terephthalate) (PET) taken from waste soft-drink bottles, under microwave irradiation, is proposed as a recycling method with substantial energy saving. The reaction was carried out with methanol with and without the use of zinc acetate as catalyst in a sealed microwave reactor in which the pressure and temperature were controlled and recorded. Experiments under constant temperature or microwave power were carried out at several time intervals. The main product dimethyl-terephthalate was analyzed and identified by FTIR and DSC measurements. It was found that PET depolymerization, is favored by increasing temperature, time and microwave power. High degrees of depolymerization were measured at temperatures near 180 °C and at microwave power higher than 150 W. Most of the degradation was found to occur during the initial 5–10 min. Compared to conventional pyrolysis methods, microwave irradiation during methanolic pyrolysis of PET certainly results in shorter reaction times supporting thus the conclusion that this method is a very beneficial one for the recycling of PET wastes.     

Dual Photo-Responsive Diphenylacetylene Enables PET In-Situ Upcycling with Reverse Enhanced UV-Resistance and Strength

A novel in situ chemical upcycling strategy for plastic waste is proposed by the customized diphenylacetylene monomer with dual photo-response. That is, diphenylacetylene reactive monomers are in situ inserted into the macromolecular chain of polyethylene terephthalate (PET) plastics/fibers through one-pot transesterification of slight-depolymerization and re-polymerization. On the one hand, the diphenylacetylene group absorbs short-wave high-energy UV rays and then releases long-wave low-energy harmless fluorescence. On the other hand, the UV-induced photo-crosslinking reaction among diphenylacetylene groups produces extended π-conjugated structure, resulting in a red-shift (due to decreased HOMO–LUMO separation) in the UV absorption band and locked crosslink points between PET chains. Therefore, with increasing UV exposure time, the upcycled PET plastics exhibit reverse enhanced UV resistance and mechanical strength (superior to original performance), instead of serious UV-photodegradation and damaged performance. This upcycling strategy at oligomer-scale not only provides a new idea for traditional plastic recycling, but also solves the common problem of gradual degradation of polymer performance during use.     

A review on synthesis of value added products from polyethylene terephthalate (PET) waste

Many research papers have been contributed by several authors for making PET waste recycling economically and ecologically more viable. Recycling of PET waste was started in last two decades. Most of the authors are devoting their time in getting economically viable solution for development of methods based on either mechanical or chemical recycling. Some success has been obtained in development of chemical recycling methods which provides value added products from PET waste. However, different products developed by chemical recycling have not provided economically enough and reliable methods of recycling of PET waste.     

Multifunctionality in Epoxy Resins

Abstract

Epoxy resin will continue to be in the forefront of many thermoset applications due to its versatile properties. However, with advancement in manufacturing, changing societal outlook for the chemical industries and emerging technologies that disrupt conventional approaches to thermoset fabrication, there is a need for a multifunctional epoxy resin that is able to adapt to newer and robust requirements. Epoxy resins that behave both like a thermoplastic and a thermoset resin with better properties are now the norm in research and development. In this paper, we viewed multifunctionality in epoxy resins in terms of other desirable properties such as its toughness and flexibility, rapid curing potential, self-healing ability, reprocessability and recyclability, high temperature stability and conductivity, which other authors failed to recognize. These aspects, when considered in the synthesis and formulation of epoxy resins will be a radical advance for thermosetting polymers, with a lot of applications. Therefore, we present an overview of the recent finding as to pave the way for varied approaches towards multifunctional epoxy resins.     

Petroleum Absorbers Based on CNSL,Furfural and Lignin – The Effect of the Chemical Similarity on the Interactions among Petroleum and Bioresins

Summary: The petroleum has become our most important source of energy since the mid-1950s. It is due to its high energy density, easy transportability and relative abundance. However, along extraction, storage or transportation of oil, spill accidents may happen. This kind of accident causes severe impacts on the environment, being directly responsible for the destruction of the marine life, which affects the fishing and even tourism industries. Main goal of this work is related to the use of renewable sources aiming to obtain “absorbent green materials”. These materials were synthesized by a typical phenolic resin polycondensation route using cashew nut shell liquid (CNSL) as main phenolic compound. Focused on keep the green characteristic of the materials, furfuraldehyde from hemicellulose was used as aldehyde and the reaction was catalyzed using a small amount of sulfuric acid. Resins were characterized using Optical Microscopy, Scanning Electron Microscopy, Infrared Spectroscopy with Fourier Transformed (FTIR) and density tests. In addition, contraction of the oil spilled was studied in presence of resins. Obtained results demonstrated that synthesized resins present a good chemical similarity with oil, which produces a good interaction among resins and oil, making easy the contraction of the oil spot on the water and, consequently, the removal process of oil spilled on water.     

Rapid determination of terephthalic acid in the hydrothermal decomposition product of poly(ethylene terephthalate) by thermochemolysis-gas chromatography in the presence of tetramethylammonium acetate

Thermochemolysis-gas chromatography in the presence of tetramethylammonium acetate was applied to the direct determination of terephthalic acid (TPA) contained in solid decomposition products obtained from the hydrothermal recycling process of poly(ethylene terephthalate) (PET). On the chromatograms of the hydrothermal decomposition products of PET, a sharp peak of the TPA component was clearly observed as its corresponding dimethyl ester formed through the thermochemolysis reaction. Based on the peak intensities, the contents of TPA in the decomposition products were determined precisely and rapidly without using any cumbersome sample pretreatments.     

Surface free energies of silica fillers and their relation to the adsorption of poly(ethylene terephthalate)

The surface free energy of modified silica as well as of PET oligomers was evaluated through measurements of specific retention volumes of several probe molecules by use of the adsorption and adhesion principles in inverse gas chromatography. The nondispersive component of surface free energy of most silica fillers was larger than the dispersive component and the acidic component was much larger than the basic one, which indicated that the surfaces of most silica fillers were rather acidic. These methods were also applied to PET oligomer and it was found that the surface free energy of PET oligomer, regardless of preparation method, consisted of an almost dispersive component, suggesting that the surface of PET was neutral. The amount of PET oligomer adsorbed for the heat-treated silica fillers in acidic solvent increased linearly with increased acidic component of the surface free energy, which indicates that the acidic component of the surface free energy may be responsible for the adsorption. However, the adsorption amount on modified silica is much smaller than that for the heat-treated silica fillers because of steric hindrance caused by the attached organic chain, suggesting that the adsorption cannot be determined only by the surface free energy.     

Studies on degradation of PET in mechanical recycling

PET Poly(ethylene terephthalate) was processed repeatedly in a twin extruder. Effect of reprocessing on molecular structure of PET was evaluated in terms of reduction in molecular weight and mechanical properties. This study shows that weight-average molecular weight M_w drops more notably compared with mechanical properties. Mechanical blending of virgin polymer with recycled PET was studied. The results of mechanical testings indicate that there is only slight loss in mechanical properties. The results suggest that mechanical recycling is a suitable method for recycling of PET for economic and environmental purposes.     

In-Situ Formation of BHET/Titanium Compound Nanocomposite and its Catalysis for Polyester

Summary: The tetrabutylorthotitanate (TBOT) was hydrolyzed by H₂O produced during the esterification of pure terephthalic acid (PTA) and ethylene glycol (EG), and the bis(2-hydroxyethyl) terephthalate (BHET)/titanium compound nanocomposite was in-situ formed. The effect of TBOT on the esterification and its product property has been investigated. The results show that the butyl alcohol from the hydrolysis of TBOT is almost distilled out with H₂O and there has no effect on the chemical structure of BHET caused by the introducing of TBOT. A kind of novel titanium compound is manufactured during the esterification under the existence of TBOT, which shows slice-like morphology from SEM micrographs and special XRD pattern with new diffraction peaks between 2-Θ = 6.9° and 10.2°. It is found that the BHET/titanium compound nanocomposite can act as the catalyst of polymerization of poly(ethylene terephthalate) (PET). The PET resins synthesized by in-situ formed catalyst have almost the same physicochemical properties with the commerced resins and have good spinnability.     

Thermal degradation behaviour of resins in aluminium composite under isothermal condition

As a member of the aluminium composite, GLARE (GLAss fibre/epoxy REinforced aluminium laminates) was used in the upper fuselage of Airbus A380 because of its superior mechanical properties over monolithic aluminium alloys. Thermal processing is a potential method for materials recycling and reuse from GLARE scrap with the aim of environmental protection and economic benefits. Thermal delamination is a crucial pre-treatment step for GLARE recycling. Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA) tests have been used to identify the decomposition temperature range of epoxy resins under non-isothermal condition in our previous work [1]. To obtain an appropriate solution for GLARE thermal delamination, the thermal degradation behaviour of epoxy resins in GLARE under isothermal conditions were investigated and isothermal decomposition kinetic models were built up based on DSC and thermogravimetric analysis TGA. The thermal delamination process of GLARE is determined based on thermal analysis results and experimental optimization.     

In situ ATR-FTIR Spectroscopy of Poly(ethylene terephthalate) Subjected to High-Temperature Methanol

Summary: In situ ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopy combined with a high-pressure cell has been applied to measure IR spectra of polymers subjected to superheated or near-critical methanol (100– 200 °C). Spectra of poly(ethylene terephthalate) (PET) have been measured under exposure to high temperature methanol using this ATR-FTIR approach to understand at a molecular level the recycling process of PET. The evolution of the structure and the morphology of the polymer has been studied during the methanolysis. The quantity of trans PET conformer is generally used as a tracer of the crystallinity of PET. During depolymerisation of PET the evolution of crystallinity and of trans conformer appears to be different. The dependence of the rate constant on reaction temperature was correlated by Arrhenius plot, which shows activation energy of 5.8 kJ/mol.     

Mechanochemical Degradation and Recycling of Synthetic Polymers

The accumulation of plastic waste, due to lack of recycling, has led to serious environmental pollution. Although mechanical recycling can alleviate this issue, it inevitably reduces the molecular weight and weakens the mechanical properties of materials and is not suitable for mixed materials. Chemical recycling, on the other hand, breaks the polymer into monomers or small-molecule constituents, allowing for the preparation of materials of quality comparable to that of the virgin polymers and can be applied to mixed materials. Mechanochemical degradation and recycling leverages the advantages of mechanical techniques, such as scalability and efficient energy use, to achieve chemical recycling. We summarize recent progress in mechanochemical degradation and recycling of synthetic polymers, including both commercial polymers and those designed for more efficient mechanochemical degradation. We also point out the limitations of mechanochemical degradation and present our perspectives on how the challenges can be mitigated for a circular polymer economy.