New insights into polyurethane biodegradation and realistic prospects for the development of a sustainable waste recycling process

Polyurethanes are polymeric plastics that were first used as substitutes for traditional polymers suspected to release volatile organic hazardous substances. The limitless conformations and formulations of polyurethanes enabled their use in a wide variety of applications. Because approximately 10 Mt of polyurethanes is produced each year, environmental concern over their considerable contribution to landfill waste accumulation appeared in the 1990s. To date, no recycling processes allow for the efficient reuse of polyurethane waste due to their high resistance to (a)biotic disturbances. To find alternatives to systematic accumulation or incineration of polyurethanes, a bibliographic analysis was performed on major scientific advances in the polyurethane (bio)degradation field to identify opportunities for the development of new technologies to recondition this material. Until polymers exhibiting oxo- or hydro-biodegradative traits are generated, conventional polyurethanes that are known to be only slightly biodegradable are of great concern. The research focused on polyurethane biodegradation highlights recent attempts to reprocess conventional industrial polyurethanes via microbial or enzymatic degradation. This review describes several wonderful opportunities for the establishment of new processes for polyurethane recycling. Meeting these new challenges could lead to the development of sustainable management processes involving polymer recycling or reuse as environmentally safe options for industries. The ability to upgrade polyurethane wastes to chemical compounds with a higher added value would be especially attractive.     

Perspectives for synthesis and production of polyurethanes and related polymers by enzymes directed toward green and sustainable chemistry

Enzyme-catalyzed polymerization and degradation will play an important role in both the synthesis and chemical recycling of green and sustainable polyurethane. This minireview covers the new synthetic routes to polyurethane without using diisocyanate, the biodegradation of polyurethane, and the enzymatic synthesis and the chemical recycling of poly(ester-urethane) (PEU) and poly(carbonate-urethane) (PCU). The lipase-catalyzed polymerization of low molecular weight and biodegradable urethanediols with short-chain dialkyl carbonate and alkanedioates produced PCU and PEU, respectively. They were readily degraded in an organic solvent into the repolymerizable cyclic oligomers by lipase as a novel chemical recycling. These results will be applicable for the production strategies of green and sustainable polyurethanes.     

微生物降解塑料的研究进展

塑料广泛应用于人类的生活中,其中约80％的塑料垃圾被填埋,最终成为陆地和海洋垃圾.由于管理与处置不善,这些废弃物造成了巨大的环境污染,目前回收再利用是较好的处置方式,但对某些塑料废弃物并没有妥善的处置方式.生物降解作为环境友好的处置方式,具有巨大的应用潜力.本文对聚对苯二甲酸乙二醇酯、聚乙烯、聚氯乙烯、聚丙烯、聚苯乙烯...     

塑料添加剂向生态环境中的释放与迁移研究进展

塑料废弃物,尤其是粒径小于5 mm的微塑料造成的环境污染问题已引起全球的普遍关注。塑料制品在生产过程中常使用多种添加剂,以提高聚合物的性能并延长其使用寿命。然而,在废弃塑料制品的回收及自然老化过程中,这些添加剂会不断释放出来,对生态环境的安全与人类的健康产生威胁。综述了近年来国内外塑料添加剂的使用情况及其向生态环境释放与迁移等方面的研究进展,具体包括常用塑料添加剂的种类、废弃物塑料回收和塑料老化过程中添加剂向生态环境中的释放与迁移及机制等。未来需要更加关注绿色塑料添加剂的研发、废弃塑料回收工艺的改进以及关于塑料添加剂的释放、在各类环境介质中的迁移转化以及在生态系统各个圈层间的相互作用方面的系统性的研究,并构建相应的迁移模型评估塑料添加剂产生的生态风险。     

Isolation and characterization of a bacterium which utilizes polyester polyurethane as a sole carbon and nitrogen source

Abstract Various soil samples were screened for the presence of microorganisms which have the ability to degrade polyurethane compounds. Two strains with good polyurethane degrading activity were isolated. The more active strain was tentatively identified as Comamonas acidovorans . This strain could utilize polyester-type polyurethanes but not the polyether-type polyurethanes as sole carbon and nitrogen sources. Adipic acid and diethylene glycol were probably the main degradation products when polyurethane was supplied as a sole carbon and nitrogen source. When ammonium nitrate was used as nitrogen source, only diethylene glycol was detected after growth on polyurethane.     

Biological degradation of plastics: a comprehensive review

Lack of degradability and the closing of landfill sites as well as growing water and land pollution problems have led to concern about plastics. With the excessive use of plastics and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. Awareness of the waste problem and its impact on the environment has awakened new interest in the area of degradable polymers. The interest in environmental issues is growing and there are increasing demands to develop material which do not burden the environment significantly. Biodegradation is necessary for water-soluble or water-immiscible polymers because they eventually enter streams which can neither be recycled nor incinerated. It is important to consider the microbial degradation of natural and synthetic polymers in order to understand what is necessary for biodegradation and the mechanisms involved. This requires understanding of the interactions between materials and microorganisms and the biochemical changes involved. Widespread studies on the biodegradation of plastics have been carried out in order to overcome the environmental problems associated with synthetic plastic waste. This paper reviews the current research on the biodegradation of biodegradable and also the conventional synthetic plastics and also use of various techniques for the analysis of degradation in vitro.     

Bioencapsulation within synthetic polymers (Part 2): non-sol-gel protein-polymer biocomposites

Since the introduction of sol-gel bioencapsulation and the demonstration that biological function can be incorporated into, and preserved within, polymer matrices, a number of alternative polymers have been used to immobilize proteins. Various enzymes have been trapped in such diverse polymers as epoxy-amine resins, polyvinyl plastics, polyurethane foams and silicone elastomers. Together with sol-gel encapsulates, these biocomposites represent a powerful approach for immobilizing biological materials for applications as biosensors and biocatalysts, and hold promise as bioactive, fouling-resistant polymers for environmental, food and medical uses. Although still at the developmental stage, these biocomposites promise to revolutionize the whole arena of high-performance bioimmobilization.     

Plastics recycling: challenges and opportunities

Plastics are inexpensive, lightweight and durable materials, which can readily be moulded into a variety of products that find use in a wide range of applications. As a consequence, the production of plastics has increased markedly over the last 60 years. However, current levels of their usage and disposal generate several environmental problems. Around 4 per cent of world oil and gas production, a non-renewable resource, is used as feedstock for plastics and a further 3–4% is expended to provide energy for their manufacture. A major portion of plastic produced each year is used to make disposable items of packaging or other short-lived products that are discarded within a year of manufacture. These two observations alone indicate that our current use of plastics is not sustainable. In addition, because of the durability of the polymers involved, substantial quantities of discarded end-of-life plastics are accumulating as debris in landfills and in natural habitats worldwide.Recycling is one of the most important actions currently available to reduce these impacts and represents one of the most dynamic areas in the plastics industry today. Recycling provides opportunities to reduce oil usage, carbon dioxide emissions and the quantities of waste requiring disposal. Here, we briefly set recycling into context against other waste-reduction strategies, namely reduction in material use through downgauging or product reuse, the use of alternative biodegradable materials and energy recovery as fuel.While plastics have been recycled since the 1970s, the quantities that are recycled vary geographically, according to plastic type and application. Recycling of packaging materials has seen rapid expansion over the last decades in a number of countries. Advances in technologies and systems for the collection, sorting and reprocessing of recyclable plastics are creating new opportunities for recycling, and with the combined actions of the public, industry and governments it may be possible to divert the majority of plastic waste from landfills to recycling over the next decades.     

A review of plastic waste biodegradation

With more and more plastics being employed in human lives and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. This review looks at the technological advancement made in the development of more easily biodegradable plastics and the biodegradation of conventional plastics by microorganisms. Additives, such as pro-oxidants and starch, are applied in synthetic materials to modify and make plastics biodegradable. Recent research has shown that thermoplastics derived from polyolefins, traditionally considered resistant to biodegradation in ambient environment, are biodegraded following photo-degradation and chemical degradation. Thermoset plastics, such as aliphatic polyester and polyester polyurethane, are easily attacked by microorganisms directly because of the potential hydrolytic cleavage of ester or urethane bonds in their structures. Some microorganisms have been isolated to utilize polyurethane as a sole source of carbon and nitrogen source. Aliphatic-aromatic copolyesters have active commercial applications because of their good mechanical properties and biodegradability. Reviewing published and ongoing studies on plastic biodegradation, this paper attempts to make conclusions on potentially viable methods to reduce impacts of plastic waste on the environment.     

Polymers of 3-hydroxyacids in plants

Polyhydroxyalkanoates (PHA) are polyesters of bacterial origin that have properties of biodegradable plastics and elastomers. Synthesis of PHA in crop plants would allow the large-scale production and use of these biodegradable and renewable polymers as substitutes for petroleum-derived plastics. Synthesis of a diversity of PHAs in plants, such as Arabidopsis thaliana, rapeseed, corn and cotton, has been demonstrated through the genetic engineering of metabolic pathways in the cytoplasm, plastid and peroxisome. PHA can also be used as a novel tool to study various aspects of plant metabolism, such as the regulation of carbon flux to the fatty acid biosynthetic and degradation pathways.     

Biodegradation of polyesters containing aromatic constituents

Polymers, which undergo a controlled biological degradation by micro-organisms came to remarkable interest during the last years. Composting for instance could so be established as an alternative waste management system for parts of the plastic waste. Within this group of innovative polymer, polyesters play a predominant role, due to their potentially hydrolyzable ester bonds. While aromatic polyesters such as poly(ethylene terephthalate) exhibit excellent material properties but proved to be almost resistant to microbial attack, many aliphatic polyesters turned out to be biodegradable but lack in properties, which are important for application. To combine good material properties with biodegradability, aliphatic-aromatic copolyesters have been developed as biodegradable polymers for many years. This article reviews the attempts to combine aromatic and aliphatic structures in biodegradable plastics and work, which has been done to evaluate the degradation behaviour and environmental safety of biodegradable polyesters, containing aromatic constituents.     

Innovations in applications and prospects of non-isocyanate polyurethane bioplastics

Currently, conventional plastics are necessary for a variety of aspects of modern daily life, including applications in the fields of healthcare, technology, and construction. However, they could also contain potentially hazardous compounds like isocyanates, whose degradation has a negative impact on both the environment and human health. Therefore, researchers are exploring alternatives to plastic which is sustainable and environmentally friendly without compromising its mechanical and physical features. This review study highlights the production of highly eco-friendly bioplastic as an efficient alternative to non-biodegradable conventional plastic. Bioplastics are produced from various renewable biomass sources such as plant debris, fatty acids, and oils. Poly-addition of di-isocyanates and polyols is a technique employed over decades to produce polyurethanes (PUs) bioplastics from renewable biomass feedstock. The toxicity of isocyanates is a major concern with the above-mentioned approach. Novel green synthetic approaches for polyurethanes without using isocyanates have been attracting greater interest in recent years to overcome the toxicity of isocyanate-containing raw materials. The polyaddition of cyclic carbonates (CCs) and polyfunctional amines appears to be the most promising method to obtain non-isocyanate polyurethanes (NIPUs). This method results in the creation of polymeric materials with distinctive and adaptable features with the elimination of harmful compounds. Consequently, non-isocyanate polyurethanes represent a new class of green polymeric materials. In this review study, we have discussed the possibility of creating novel NIPUs from renewable feedstocks in the context of the growing demand for efficient and ecologically friendly plastic products.     

A Review of Plastic Waste Biodegradation

ABSTRACT

With more and more plastics being employed in human lives and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. This review looks at the technological advancement made in the development of more easily biodegradable plastics and the biodegradation of conventional plastics by microorganisms. Additives, such as pro-oxidants and starch, are applied in synthetic materials to modify and make plastics biodegradable. Recent research has shown that thermoplastics derived from polyolefins, traditionally considered resistant to biodegradation in ambient environment, are biodegraded following photo-degradation and chemical degradation. Thermoset plastics, such as aliphatic polyester and polyester polyurethane, are easily attacked by microorganisms directly because of the potential hydrolytic cleavage of ester or urethane bonds in their structures. Some microorganisms have been isolated to utilize polyurethane as a sole source of carbon and nitrogen source. Aliphatic-aromatic copolyesters have active commercial applications because of their good mechanical properties and biodegradability. Reviewing published and ongoing studies on plastic biodegradation, this paper attempts to make conclusions on potentially viable methods to reduce impacts of plastic waste on the environment.     

Synthesis of new poly(ether–urethane–urea)s based on amino acid cyclopeptide and PEG: study of their environmental degradation

Conventional polyurethanes (PUs) are among biomaterials not intended to degrade but are susceptible to hydrolytic, oxidative and enzymatic degradation in vivo. Biodegradable PUs are typically prepared from polyester polyols, aliphatic diisocyanates and chain extenders. In this work we have developed a degradable monomer based on α-amino acid to accelerate hard segment degradation. Thus a new class of degradable poly(ether–urethane–urea)s (PEUUs) was synthesized via direct reaction of 4,4′-methylene-bis(4-phenylisocyanate) (MDI), l-leucine anhydride (LA) and polyethylene glycol with molecular weight of 1,000 (PEG-1000) as polyether soft segment. The resulting polymers are environmentally biodegradable and thermally stable. Decomposition temperatures for 5 % weight loss occurred above 300 °C by TGA in nitrogen atmospheres. Some structural characterization and physical properties of these polymers before and after degradation in soil, river water and sludge are reported. The environmental degradation of the polymer films was investigated by SEM, FTIR, TGA, DSC, GPC and XRD techniques. A significant rate of degradation occurred in PEUU samples under river water and sludge condition. The polymeric films were not toxic to E. coli (Gram negative), Staphylococcus aureus and Micrococcus (Gram positive) bacteria and showed good biofilm formation on polymer surface. Our results show that hard segment degraded selectively as much as soft segment and these polymers are susceptible to degradation in soil and water. Thus our study shows that new environment-friendly polyurethane, which can degrade in soil, river water and sludge, is synthesized.     

Effect of Biostimulation and Bioaugmentation on Degradation of Polyurethane Buried in Soil

This work investigated biostimulation and bioaugmentation as strategies for removing polyurethane (PU) waste in soil. Soil microcosms were biostimulated with the PU dispersion agent “Impranil” and/or yeast extract or were bioaugmented with PU-degrading fungi, and the degradation of subsequently buried PU was determined. Fungal communities in the soil and colonizing buried PU were enumerated on solid media and were analyzed using denaturing gradient gel electrophoresis (DGGE). Biostimulation with yeast extract alone or in conjunction with Impranil increased PU degradation 62% compared to the degradation in untreated control soil and was associated with a 45% increase in putative PU degraders colonizing PU. Specific fungi were enriched in soil following biostimulation; however, few of these fungi colonized the surface of buried PU. Fungi used for soil bioaugmentation were cultivated on the surface of sterile wheat to form a mycelium-rich inoculum. Wheat, when added alone to soil, increased PU degradation by 28%, suggesting that wheat biomass had a biostimulating effect. Addition of wheat colonized with Nectria haematococca, Penicillium viridicatum, Penicillium ochrochloron, or an unidentified Mucormycotina sp. increased PU degradation a further 30 to 70%, suggesting that biostimulation and bioaugmentation were operating in concert to enhance PU degradation. Interestingly, few of the inoculated fungi could be detected by DGGE in the soil or on the surface of the PU 4 weeks after inoculation. Bioaugmentation did, however, increase the numbers of indigenous PU-degrading fungi and caused an inoculum-dependent change in the composition of the native fungal populations, which may explain the increased degradation observed. These results demonstrate that both biostimulation and bioaugmentation may be viable tools for the remediation of environments contaminated with polyurethane waste.The polyester polyurethanes (PU) are a diverse group of synthetic polymers with many industrial and commercial applications, including insulating and packaging foams, fibers, fabrics, and synthetic leather goods (20). These polymers contain intramolecular bonds analogous to those found in biological macromolecules (such as ester and urethane linkages), making them susceptible to enzymatic degradation and assimilation by environmental microbial communities (17, 42). The susceptibility of plastics to biodegradation is of increasing importance as the generation of plastic waste material continues to increase and plastics now comprise more than 30% of household waste in the United States (32). By exploiting the biodegradability of plastics such as PU, bioremediation by microorganisms in the environment shows great potential for reducing the burden of plastic waste.Although the diversity of natural microbial populations often means that the potential for waste remediation exists at polluted sites, factors such as absence of electron acceptors or donors, low nitrogen or phosphorus availability, or a lack of induction of the metabolic pathways responsible for degradation can inhibit waste remediation. In these cases, addition of exogenous nutrients can enhance the degradation of waste, a process known as biostimulation. Biostimulation of in situ microbial communities has been used to enhance the degradation of crude oil (22, 29), tetrachloroethene (19), diesel fuel (24, 28), and polyaromatic hydrocarbons (41).If communities native to polluted sites lack significant populations of waste degraders, microbes with the desired phenotypes can be added exogenously in a process known as bioaugmentation. This approach has been successfully used to remediate a wide range of waste products, from hydrocarbons (8, 34) to heavy metals (15, 16). Numerous PU-degrading organisms have been isolated from a range of environments (6, 9, 26, 30), and this has provided a large reservoir of organisms for potential bioaugmentation of PU waste.This study was the first study to assess the potential of biostimulation and bioaugmentation as methods for accelerating the degradation of PU waste in the environment. The response of fungal communities in soil microcosms to (i) addition of nutrients or (ii) a large influx of PU-degrading fungi was investigated using culture-based and molecular techniques, and the effect of these treatments on the degradation of PU coupons buried in these microcosms was determined.     

Syntheses and characterization of polymers containing nucleic acid bases

Two different types of polymers containing nucleic acid bases in the backbone or in the pendant groups were prepared. The polymers of the first type were polyureas obtained by the polyaddition reaction of uracil and adenine with hexamethylene diisocyanate (HMD1). The second type that is cationic polyurethanes containing nucleic acid bases in pendant groups, were obtained by the Menschutkin reaction of halogenated derivatives of uracil and adenine with a linear polyurethane containing tertiary nitrogen atoms which was based on HMD1 and N-methyldiethanolamine. Base base interactions were studied for the polymers by ultraviolet (u.r.), optical rotary dispersion (o.r.d.), and nuclear magnetic resonance (n.m.r.) spectra. A relatively high value of hypochromicity, ≈17% was observed for the mixture of the ionic polyurethane with uracil pendant and herring-sperm DNA. Complementary hydrogen bonding interactions were detected for the mixture of the ionic polyurethane with adenine pendant and with uracil pendant. The non-thrombogenic character of the polymers was examined according to the modified Lee White method. The ionic polyurethanes with adenine and uracil pendant exhibited a fairly good anti-clotting properly.     

Degradation of Oxo-Biodegradable Plastic by Pleurotus ostreatus

Growing concerns regarding the impact of the accumulation of plastic waste over several decades on the environmental have led to the development of biodegradable plastic. These plastics can be degraded by microorganisms and absorbed by the environment and are therefore gaining public support as a possible alternative to petroleum-derived plastics. Among the developed biodegradable plastics, oxo-biodegradable polymers have been used to produce plastic bags. Exposure of this waste plastic to ultraviolet light (UV) or heat can lead to breakage of the polymer chains in the plastic, and the resulting compounds are easily degraded by microorganisms. However, few studies have characterized the microbial degradation of oxo-biodegradable plastics. In this study, we tested the capability of Pleurotus ostreatus to degrade oxo-biodegradable (D₂W) plastic without prior physical treatment, such as exposure to UV or thermal heating. After 45 d of incubation in substrate-containing plastic bags, the oxo-biodegradable plastic, which is commonly used in supermarkets, developed cracks and small holes in the plastic surface as a result of the formation of hydroxyl groups and carbon-oxygen bonds. These alterations may be due to laccase activity. Furthermore, we observed the degradation of the dye found in these bags as well as mushroom formation. Thus, P. ostreatus degrades oxo-biodegradable plastics and produces mushrooms using this plastic as substrate.     

Design of recycling system for poly(methyl methacrylate) (PMMA). Part 1: recycling scenario analysis

Introduction

In this series of papers, we present a poly(methyl methacrylate) (PMMA) recycling system design based on environmental impacts, chemical hazards, and resource availability. We evaluated the recycling system by life cycle assessment, environment, health, and safety method, and material flow analysis.

Purpose

Previous recycling systems have not focused on highly functional plastics such as PMMA, partly because of lower available volumes of waste PMMA compared with other commodity plastics such as polyethylene or polypropylene. However, with the popularization of PMMA-containing products such as liquid crystal displays, the use of PMMA is increasing and this will result in an increase in waste PMMA in the future. The design and testing of recycling systems and technologies for treating waste PMMA is therefore a high research priority. In this study, we analyze recycling of PMMA monomers under a range of scenarios.

Methods

Based on the differences between PMMA grades and their life cycles, we developed a life cycle model and designed a range of scenarios for PMMA recycling. We obtained monomer recycling process inventory data based on the operational results of a pilot plant. Using this process inventory data, we quantified life cycle greenhouse gas (LC-GHG) emissions and fossil resource consumption, and we calculated the LIME single index.

Results and discussion

PMMA produces more than twice the amount of GHG emissions than other commodity resins. Through scenario and sensitivity analyses, we demonstrated that monomer recycling is more effective than mechanical recycling. Operational modifications in the monomer recycling process can potentially decrease LC-GHG emissions.

Conclusions

Highly functional plastics should be recycled while maintaining their key functions, such as the high transparency of PMMA. Monomer recycling has the potential to achieve a closed-loop recycling of PMMA.     

Microbiological testing of plastics: Ongoing activities of IBRG plastics project group to improve standard test procedures

The early development of standard test procedures for plastics was based primarily upon results of plasticised PVC. Ring tests carried out in the sixties used this material and provided the basis for national and international test specifications. In the meantime a large variety of plastics formulations has been developed which are chemically and structurally different from the formerly used PVC. This has prompted a re-examination of existing test specifications. For this reason the IBRG established a Plastics Working Group in 1984 to study the mechanism of the deterioration of plastics in relation to current standard test protocols.Fifteen laboratories from several European countries participated in a first international ring test (see Appendix). Two polyurethanes — a polyester and a polyether type — were chosen as test materials. A plasticized PVC was included for comparison with earlier interlaboratory experiments. Petri dish tests were carried out for four weeks and biodeterioration was assessed by visual examination and by weight loss. It was concluded that visual assessment as the sole criterion for the biodeterioration of polyurethanes was insufficient and that a test period of four weeks was too short for weight loss determination.In a second ring test with 12 participants, soil burial tests with the same test materials have been started. They will be conducted over a two-year period. Weight loss determinations and tensile tests will be carried out at six-month intervals. Provisional results are presented and are supplemented by joint experiments of some participants to examine the effects of special test parameters on the biodeterioration of plastics.     

Microbial enzymes will offer limited solutions to the global plastic pollution crisis

Global economies depend on the use of fossil-fuel-based polymers with 360–400 million metric tons of synthetic polymers being produced per year. Unfortunately, an estimated 60% of the global production is disposed into the environment. Within this framework, microbiologists have tried to identify plastic-active enzymes over the past decade. Until now, this research has largely failed to deliver functional biocatalysts acting on the commodity polymers such as polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), ether-based polyurethane (PUR), polyamide (PA), polystyrene (PS) and synthetic rubber (SR). However, few enzymes are known to act on low-density and low-crystalline (amorphous) polyethylene terephthalate (PET) and ester-based PUR. These above-mentioned polymers represent >95% of all synthetic plastics produced. Therefore, the main challenge microbiologists are currently facing is in finding polymer-active enzymes targeting the majority of fossil-fuel-based plastics. However, identifying plastic-active enzymes either to implement them in biotechnological processes or to understand their potential role in nature is an emerging research field. The application of these enzymes is still in its infancy. Here, we summarize the current knowledge on microbial plastic-active enzymes, their global distribution and potential impact on plastic degradation in industrial processes and nature. We further outline major challenges in finding novel plastic-active enzymes, optimizing known ones by synthetic approaches and problems arising through falsely annotated and unfiltered use of database entries. Finally, we highlight potential biotechnological applications and possible re- and upcycling concepts using microorganisms.