Recycling of waste from polymer materials: An overview of the recent works

Polymer recycling is a way to reduce environmental problems caused by polymeric waste accumulation generated from day-to-day applications of polymer materials such packaging and construction. The recycling of polymeric waste helps to conserve natural resource because the most of polymer materials are made from oil and gas. This paper reviews the recent progress on recycling of polymeric waste form some traditional polymers and their systems (blends and composites) such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and introduces the mechanical and chemical recycling concepts. In addition, the effect of mechanical recycling on properties including the mechanical, thermal, rheological and processing properties of the recycled materials is highlighted in the present paper.     

Polymer Waste Management–Biodegradation,Incineration, and Recycling

Abstract

Increasing volumes of synthetic polymers are manufactured for various applications. The disposal of the used materials is becoming a serious problem. Unlike natural polymers, most synthetic macromolecules cannot be assimilated by microorganisms. Although polymers represent slightly over 10% of total municipal waste, the problem of nonbiodegradability is highlighted by overflowing landfills, polluted marine waters, and unsightly litter. Existing government regulations in Europe and anticipated regulations in the United States will greatly limit the use of polymers in large volume applications (packaging, water treatment, paper and textile sizing, etc.) unless acceptable means of waste management are available. Total management of polymer wastes requires complementary combinations of biodegradation, incineration, and recycling. Biodegradation is the most desirable long-term future solution and requires intensive research and development before it becomes practical. On the other hand, incineration and recycling can become operational in a relatively short time for the improvement of the situation at present and in the near future.     

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.     

Influence of additives on recycled polymer blends

Polymer systems based on polymer waste offer promising way to increase recycling in the society. Since fillers play a major role in determining the properties and behavior of polymer composites, recycled polymers can also be combined with fillers to enhance the stiffness and thermal stability. In this study, blends of recycled polyethylene and recycled polypropylene with mica and glass fiber were prepared by melt blending technique. The effect of the particle loading, filler type, and filler–matrix interaction on thermal degradation and thermal transition of processed systems were investigated. Thermogravimetric analysis, differential thermogravimetric analysis, and differential scanning calorimetry were used in this investigation. Comparative analysis shows that both fillers produced different effects on thermal properties of the processed systems. These results were confirmed by calculating the activation energy for thermal degradation and thermal transition using Kissinger and Flynn–Wall expressions.     

Efficient Plastic Waste Recycling Using Polymer

This study explores the possible uses of polymers to facilitate the more efficient recycling of plastic waste. Recycling plastics has been singled out as one way to mitigate the damaging effects of plastic trash on the environment. However, traditional recycling methods can only go so far, therefore innovative approaches are needed. This research investigates how a variety of polymers may be able to improve recycling operations. The study simulates the recycling procedure and employs experimental analysis to compare the performance of various polymers. Results show that by selecting the right polymers, recycling plastic trash can be made much more efficient, cutting down on both waste and energy consumption. The results have important ramifications for the plastic waste recycling sector and point the way towards fruitful future study in this area.     

Nitrous oxide emissions from waste incineration

EU energy and environmental policy in waste management leads to increasing interest in developing methods for waste disposal with minimum emissions of greenhouse gases and minimum environmental impacts. From the point of view of nitrous oxide (N₂O) emissions, waste incineration and waste co-combustion is very acceptable method of waste disposal. Two factors are important for attaining very low N₂O emissions from waste incineration, particularly for waste with higher nitrogen content (e.g. sewage sludge, leather, etc.): temperature of incineration over 900°C and avoiding selective noncatalytic reduction (SNCR) de-NO_x method based on urea. For reduction of N₂O emissions retrofitting such plants to ammonia-based SNCR is recommendable. The modern selective catalytic reduction facilities for de-NO_x at waste incineration plants are only negligible source of N₂O.     

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.     

To compost or not to compost: Carbon and energy footprints of biodegradable materials’ waste treatment

Many life cycle assessments of bio-based and biodegradable materials neglect the post-consumer waste treatment phase because of a lack of consistent data, even though this stage of the life cycle may strongly influence the conclusions. The aim of this paper is to approximate carbon and energy footprints of the waste treatment phase and to find out what the best waste treatment option for biodegradable materials is by modelling home and industrial composting, anaerobic digestion and incineration. We have compiled data-sets for the following biodegradable materials: paper, cellulose, starch, polylactic acid (PLA), starch/polycaprolactone (MaterBi), polybutyrate-adipate-terephthalate (PBAT, Ecoflex) and polyhydroxyalkanoates (PHA) on the basis of an extensive literature search, experiments and analogies with materials for which significant experience has been made. During biological waste treatment, the materials are metabolised so a part of their embodied carbon is emitted into air and the remainder is stored as compost or digestate. The compost or digestate can replace soil conditioners supporting humus formation, which is a benefit that cannot be achieved artificially. Experimental data on biodegradable materials shows a range across the amount of carbon stored of these materials, and more trials will be required in the future to reduce these uncertainties. Experimental data has also shown that home and industrial composting differ in their emissions of nitrous oxide and methane, but it should be noted that data availability on home composting is limited. The results show that anaerobic digestion has the lowest footprint for the current level of technology, but incineration may become better in the future if energy efficiency in waste incineration plants improves significantly. Home composting is roughly equal to incineration with energy recovery in terms of carbon and energy footprint when carbon credits are considered. The same applies to industrial composting if carbon credits are assigned for compost to replace straw. Carbon credits can therefore considerably affect the results, but there are significant uncertainties in how they are calculated. Incineration may become better than home composting in the future if the average energy efficiency in waste incineration plants improves significantly. However, biological waste treatment options should be chosen when soil carbon is a limiting factor.     

Quality assurance of recycled engineering plastics using blend technology

The automotive, electrical and electronic sectors account for over 12% of all plastics consumed. A large fraction of these polymers are engineering plastics representing a value considerably higher than that of commodity thermoplastics; hence, mechanical recycling including upgrading efforts appears economically attractive. This paper shows some methods of upgrading the property profile of ABS from dismantled automobiles using polymer blend technology. The results for blends of ABS with PC or PA are reported. The aim of blending of the waste materials is twofold: to reduce the number of plastic materials to be recycled in car dismantling plants, and to improve properties of the ABS scrap, which is the main engineering plastic in the waste stream from automobiles.     

Compostability of bioplastic packaging materials: an overview

Packaging waste accounted for 78.81 million tons or 31.6% of the total municipal solid waste (MSW) in 2003 in the USA, 56.3 million tons or 25% of the MSW in 2005 in Europe, and 3.3 million tons or 10% of the MSW in 2004 in Australia. Currently, in the USA the dominant method of packaging waste disposal is landfill, followed by recycling, incineration, and composting. Since landfill occupies valuable space and results in the generation of greenhouse gases and contaminants, recovery methods such as reuse, recycling and/or composting are encouraged as a way of reducing packaging waste disposal. Most of the common materials used in packaging (i.e., steel, aluminum, glass, paper, paperboard, plastics, and wood) can be efficiently recovered by recycling; however, if packaging materials are soiled with foods or other biological substances, physical recycling of these materials may be impractical. Therefore, composting some of these packaging materials is a promising way to reduce MSW. As biopolymers are developed and increasingly used in applications such as food, pharmaceutical, and consumer goods packaging, composting could become one of the prevailing methods for disposal of packaging waste provided that industry, governments, and consumers encourage and embrace this alternative. The main objective of this article is to provide an overview of the current situation of packaging compostability, to describe the main mechanisms that make a biopolymer compostable, to delineate the main methods to compost these biomaterials, and to explain the main standards for assessing compostability, and the current status of biopolymer labeling. Biopolymers such as polylactide and poly(hydroxybutyrate) are increasingly becoming available for use in food, medical, and consumer goods packaging applications. The main claims of these new biomaterials are that they are obtained from renewable resources and that they can be biodegraded in biological environments such as soil and compost. Although recycling could be energetically more favorable than composting for these materials, it may not be practical because of excessive sorting and cleaning requirements. Therefore, the main focus is to dispose them by composting. So far, there is no formal agreement between companies, governments and consumers as to how this packaging composting will take place; therefore, the main drivers for their use have been green marketing and pseudo-environmental consciousness related to high fuel prices. Packaging compostability could be an alternative for the disposal of biobased materials as long as society as a whole is willing to formally address the challenge to clearly understand the cradle-to-grave life of a compostable package, and to include these new compostable polymers in food, manure, or yard waste composting facilities.     

21世纪的高分子化学展望

对于２１世纪高分子科学的展望大致如下：２１世纪的特征是能源、材料和环保与健康（或称绿色）。作为材料领域中极其重要的部分,２１世纪对高分子材料在质量方面都有要求,大致可分二个方面同是通过控制聚合而得均匀高分子,其分子量概念不再是各种长短不齐高分子链的平均分子量;二是绿色高分子与绿色反应,前者主要是指生物高分子,对环境稳定高分子则将进行回收与重复使用;所谓绿色反应指所有高分子与相应单体的合成方法都必须     

基于1-(4-己氧)苯和2,4,6-三苯基-1,3,5-三嗪功能化芴单元的聚合物蓝光材料的合成与表征

以聚(9,9-二己烷芴)(1)和聚(9,9-二(1-(4-己氧)苯)芴)(2)作为参照物,通过Suzuki偶联反应合成了侧链9位碳含有4-己氧基苯和2,4,6-三苯基-1,3,5-三嗪单元的芴共聚物3.聚合物1,2和3固体粉末的5%质量热损失温度分别是274,318和401℃,玻璃化转变温度分别是91,120和139℃.聚合物1,2和3在甲苯溶液中的最大吸收峰和荧光发射峰分别在380和435 nm.从聚合物1到聚合物3,薄膜的荧光发射最大半峰宽逐渐降低.大体积刚性吸电子2,4,6-三苯基-1,3,5-三嗪基团的引入,使聚合物1,2和3的热稳定性、蓝光发射的色纯度和光谱稳定性逐渐提高,不同工作电压驱动下聚合物3稳定的电致发光光谱进一步证明了这一点.聚合物1,2和3的最高占有轨道能级分别为-5.72,-5.95和-5.96eV,最低未占有轨道能级分别为-2.70,-2.39和-2.43 eV.聚合物1,2和3的三线态能级分别为2.82,2.81和2.97 eV.聚合物1,2和3的单线态-三线态能级差分别是0.32,0.32和0.15 eV.4-己氧基苯的引入使聚合物的能隙变宽,而吸电子的2,4,6-三苯基-1,3,5-三嗪的引入使聚合物单线态-三线态能级差依次减少.聚合物1,2和3粉末均易于形成非晶薄膜.聚合物3粉末的有序性介于聚合物1和2之间,聚合物2侧链的烷氧基苯有助于提高固体粉末有序形态的多样化.综合结果表明,侧链含有刚性4-己氧基苯和2,4,6-三苯基-1,3,5-三嗪基团的无规共聚物3具有更佳的综合光电性质.     

Modification of Particle Filled Polymers with High Energy Electrons Under In-Stationary Conditions of Melt Mixing

Summary: Polymer modification with high energy electrons is well-established in polymer industry and used for degradation, cross-linking, grafting, curing, and polymerization. These applications use local and temporal precise input of energy in order to generate excited atoms or molecules and ions for subsequent molecule changes via radical induced chemical reactions. In the present study, high energy electrons have been used to modify polyolefine (polyethylene and polypropylene) systems in presence of a grafting agent under stationary and in-stationary conditions. Polymer modification with high energy electrons under stationary conditions characterizes a process where required absorbed dose is applied to polymers in solid state and at room temperature. Polymer modification with high energy electrons under in-stationary conditions is a novel process where required absorbed dose is applied in molten state during melt mixing process. In this novel process, the penetration depth of electrons is limited to a part of mixing volume. The total mixing volume is modified due to the change of polymer mass within the penetration depth of electrons during mixing process. A 1.5 MeV electron accelerator has been directly coupled to a banbury mixing chamber in order to study this novel process. In comparison to the stationary process, the main differences are working at higher temperature, absence of any crystallinity, intensive macromolecular mobility as well as intensive mixing during dose application. The influence of both processes on mechanical properties and flame resistance of polymer composites is discussed.     

The origin and role of structural inhomogeneities and impurities in material recycling of plastics

Characteristics of aged polymers intended for material recycling are emphasized. Specific material properties of aged recyclates, containing new functional groups formed during processing and first-life application (structural polymer inhomogeneities) and metallic compounds, pigments or compounds generated from additives (non-polymeric impurities), are considered from the point of view of their influence on the aging resistance in the second-life applications. Chemical transformations of the polymer matrix together with consumption of stabilizers deteriorate material properties of collected waste plastics in reprocessing and subsequent outdoor applications.     

The formation of toxic products during the combustion of halogen-containing polymers

Studies have been made of the decomposition of decabromobiphenyl and decabromobiphenyl ether both during the burning of polymers and under the less oxygen-rich conditions involved in the incineration of plastic waste material. The nature of the products depends on the type of combustion. During flameless combustion, the two flame-retardants volatilize unchanged. However, when polymer containing the additive burns with a flame, hydrogen bromide is the only significant bromine-containing product. Product distributions in flames above burning polymers show that the concentration of the hydrogen halide increases from zero at the molten polymer surface to a value corresponding to total conversion of the halogen at and beyond the flame front.     

Advances and approaches for chemical recycling of plastic waste

The global production and consumption of plastics has increased at an alarming rate over the last few decades. The accumulation of pervasive and persistent waste plastic has concomitantly increased in landfills and the environment. The societal, ecological, and economic problems of plastic waste/pollution demand immediate and decisive action. In 2015, only 9% of plastic waste was successfully recycled in the United States. The major current recycling processes focus on the mechanical recycling of plastic waste; however, even this process is limited by the sorting/pretreatment of plastic waste and degradation of plastics during the process. An alternative to mechanical processes is chemical recycling of plastic waste. Efficient chemical recycling would allow for the production of feedstocks for various uses including fuels and chemical feedstocks to replace petrochemicals. This review focuses on the most recent advances for the chemical recycling of three major polymers found in plastic waste: PET, PE, and PP. Commercial processes for recycling hydrolysable polymers like polyesters or polyamides, polyolefins, or mixed waste streams are also discussed.     

Functional polymer thin films designed for antifouling materials and biosensors

Polymer thin films offer a versatile and ubiquitous platform for a wide variety of real-world applications in biomedicine, nanotechnology, catalysis, photovoltaic devices, and energy conversion and storage. Depending on the chemical composition of the polymers and the associated microenvironment, the physicochemical properties (biocompatibility, stability, wettability, adhesion, morphology, surface free energy, and others) of polymer films can be tuned for a specific application through precisely controlled surface synthesis and the incorporation of desirable and responsive functional groups. In this short review, we first summarise the methods most commonly used for the fabrication of polymer thin films. Then we discuss how these polymer thin films can be used in a selection of biomedical applications in antifouling materials and biosensors. Some directions for the rational design of polymer thin films to achieve a specific function or application are also provided.     

Mechanisms and kinetics of thermal decomposition of plastics from isothermal and dynamic measurements

The kinetics of decomposition of plastics are of interest from different points of view, i.e. evolution of harmful substances during fires or waste incineration, recovering of chemical raw materials from plastic refuses and designing of recycling procedures. To measure the formal kinetic parameters of the degradation of polymers isothermal and dynamic methods are applied in this work. Dynamic measurements are performed by combined thermogravimetry mass spectrometry (TG-MS), the isothermal measurements are carried out with a new closed loop-type reactor. To evaluate consistent kinetic data from isothermal and dynamic measurements, the energy balance for the sample in dynamic measurements has to be considered to obtain the true sample temperature and heating rate. Subject of this investigation is the exploitation of dynamic and isothermal methods for measuring and interpreting the kinetics of thermal decomposition of plastics. Results for commodity plastics polyethylene and poly(vinyl chloride) (PVC) are presented. The combined application of TG–MS, isothermal experiments in the closed loop-type reactor and DSC leads to new results for the decomposition kinetics of PVC. The dehydrochlorination mechanism at moderate temperature can be distinguished in an endothermal and exothermal part. The benzene formation is identified as a second order reaction. A great advantage of the isothermal method is, that changes in the mechanisms are detectable, i.e. changes in the apparent order of the reaction and the apparent activation energy. From that, new mechanistic aspects of the decomposition kinetics of polyethylene were obtained.     

Recycling of polymers used in aerospace industry. Treatment by plasma process

AEROSPATIALE has, for more than 20 years, developed and perfected a device intended to simulate the atmospheric re-entry conditions: the plasma torch. This technology, developed for the needs of space industry, is also applicable in other industrial fields like metallurgy or waste disposal. For most residues, as, for instance, for polymer residues (in particular for composite materials), incineration is the best solution to be considered. Although the organic molecule may be a real danger for man and his environment, it is possible to split it into elementary molecules easy to eliminate without risks by the simultaneous application of heat and a specific chemical environment. The use of additives in the polymers makes it necessary in most cases to use temperatures as high as possible; these high temperatures have the additional advantage of preventing harmful recombinations in the reaction chamber. Only plasma processes give the possibility to ensure high temperatures in large capacity chambers in a controlled atmosphere.     

A study of dilational rheological properties of polymers at interfaces

Viscoelastic properties of two polymers, partially hydrolyzed polyacrylamide and partially hydrolyzed modified polyacrylamide, widely used in chemical flooding in the petroleum industry, were investigated at three interfaces, water-air, water-dodecane, and water-crude oil, by means of a dilational method provided by I.T. Concept, France, at 85 degrees C. Polymer solutions were prepared in brine with 10,000 mg/l sodium chloride and 2000 mg/l calcium chloride. It has been shown that the viscoelastic modulus increases with the increment of polymer concentration in the range of 0-1500 mg/l at the water-air interface. Each polymer shows different viscoelatic behavior at different interfaces. Generally speaking, values of the viscoelastic modulus (E), the real part (E'), and the imaginary part (E") at the crude oil-water interface for each polymer are lower than at the air-water or water-dodecane interface. The two polymers display different interfacial properties at the same interface. Polymer No. 2 gives more viscous interfaces than polymer No. 1. All the information obtained from this paper will be helpful in understanding the interfacial rheology of ultra-high-molecular-weight polymer solutions.