中国化学会第21届全国高中学生化学竞赛(决赛)实验试题 利用废聚酯饮料瓶回收对苯二甲酸

一、实验目的 目前市场上大量碳酸饮料、矿泉水、食用油等产品包装瓶几乎都是用PET（聚对苯二甲酸乙二醇酯,简称聚酯）制做的。据统计,我国年生产和消耗聚酯瓶在12亿只以上,折合聚酯废料为6．3万吨。世界范围内每年消耗的聚酯量为1300万吨,其中用于包装饮料瓶的聚酯量达15万吨。废旧聚酯瓶进入环境,不能自发降解,将造成严重的环境污染和资源浪费。因此如何有效地循环利用废旧聚酯瓶是一项非常重要、非常有意义的工作。     

功能化离子液体在聚酯PET降解与合成中的应用

离子液体作为一类新兴的绿色环保型溶剂和催化剂,具有性质可调、溶解性好、催化活性高、热力学稳定性好和易于回收等优点而备受人们关注。聚酯具有多种优良性能,产能巨大,适用范围广,但造成的白色污染和资源浪费问题带来了严重的负面社会效应。通过化学回收方法,聚酯可降解为单体或低聚物从而被循环利用。本文概述了国内外废聚酯常用化学降解方法,包括水解法、甲醇降解法、乙醇降解法、乙二醇降解法等,并对主要化学降解方法的优缺点进行了比较。重点介绍了近年来功能化离子液体催化剂在聚对苯二甲酸乙二醇酯(PET)降解过程中的应用以及Lewis酸性离子液体催化乙二醇醇解PET机理,同时也描述了离子液体在聚酯合成环节中的应用。最后,总结了近年来国内外PET产能及消费量,探讨了离子液体催化剂在催化聚酯降解与合成中面临的诸多挑战。     

微波辐射下从废聚酯饮料瓶中回收对苯二甲酸——推荐一个绿色有机化学实验

推荐一个绿色有机化学实验——微波辐射下从废聚酯饮料瓶中回收对苯二甲酸.以废聚酯饮料瓶为原料,乙二醇和碳酸氢钠为复合解聚剂,在催化剂氧化锌的存在下,利用微波辐射技术使废聚酯在常压下快速、彻底解聚,残留物水溶、过滤除杂,酸析回收对苯二甲酸,减压蒸馏回收乙二醇.并通过IR验证了产物的结构.     

基于高温化学转化的废旧锂离子电池资源化技术

鉴于废旧锂离子电池的环境危害性和资源化价值的双重属性,对其进行无害化处理并对其中的有价资源进行回收再利用具有十分重要的意义。目前电池资源化技术主要通过高温或常温条件下的化学转化实现。高温条件下,废旧锂离子电池中有价元素化学转化速率快、回收流程短、物料适应性强,易于实现工业应用,相关技术成为废旧锂离子电池资源化研究热点之一。本文基于物相化学转化方式的差异,系统分析了高温化学还原、熔盐化学焙烧以及短程材料再生等方法的物理化学机理、技术特征及研究现状,并对比了不同技术的优势和存在的问题。在此基础上,提出今后高温化学转化方法实现废旧锂离子电池资源化研究中需要考虑材料的短程清洁循环再生、深入研究其化学转化机理。基于绿色化学原理的工艺设计开发出低能耗、环境友好的资源化工艺路线,真正实现废旧锂离子电池的绿色处理和循环利用。     

反相高效液相色谱测定对苯二甲酸二乙二醇酯及二聚体

随着我国化纤工业的飞速发展,聚酯(聚对苯二甲酸乙二酯,商品名称涤纶)废旧料分布极为广泛,包括轻纺、电气、包装、磁带,以及人们的日用生活。从六十年代初至今,国外许多科学工作者从事聚酯废料回收利用的研究。我们对所采用特殊化学方法回收废料,重新制成新聚酯切片的中间体—对苯二甲酸二乙二醇酯及二聚体进行了反相高效液相色谱分离及定量测定。采用内标法和外标法对照实验,其结果令人满意。     

涤纶化学降解单体产物的高效结晶提纯研究

为了解决废旧涤纶(PET)纺织品乙二醇醇解法循环利用中存在的醇解产物对苯二甲酸二乙二醇酯(BHET)纯化困难的问题，通过研究BHET晶体的独特的相变性质，发展了BHET纯化新技术.实验结果表明，对结晶的、醇解反应产物BHET使用减压升华操作，在1.33 kPa,130℃的条件下，可获得纯度达99.7%，收率达86.4%，白度(L^*值)达99.8的纯化BHET.回收所得的BHET可再缩聚制备再生PET.该再生PET在相同条件下与由石油基BHET缩聚所制得的PET具有类似的性质，包括白度、分子量及分子量分布等.本文还验证了该种醇解法回收废旧涤纶纺织品的技术的普适性：考察各种含有不同成分及颜色的涤纶纺织品样品的醇解行为及产物分离纯化效果.所研究的BHET纯化方法步骤短、产物纯度高、不额外使用有毒化学试剂，并有效地克服了粉末状BHET在加热纯化时容易发生缩聚的关键难题，为高品质回收废旧涤纶纺织品提供了一种新的路径.     

有机溶剂-聚对苯二甲酸乙二酯（PET）体系热力学性质的研究

聚酯是合成纤维中最重要的一类高分子材料。深入、定量地研究有机溶剂-聚酯体系的热力学性质及其作用规律,对发展以溶剂为介质的染整加工工艺以及聚酯的改性、新品种的开发,有着重要的现实意义。例如,用二甲基甲酰胺处理PET纤维,可使PET纤维具有真丝的光泽和风格,并能显著改善其可染性。     

改性PHB/PET液晶共聚酯的合成

精选八种具有不同结构特征的第三单体,以熔融缩聚法合成了八种改性PHB/PET共聚酯。发现含香草酸第三单体的PHB/PET/VA三元共聚酯具有较快共聚反应速率、较低熔融温度、典型热致液晶行为和良好成纤性。香草酸是最适合于PHB/PET体系共聚改性的第三单体。     

新型侧基含磷共聚酯的阻燃和热降解动力学

利用动态热重分析法(TG)研究了聚酯(PET )及侧基含磷共聚酯(FR-PET)在不同升温速率下的热稳定性及热降解动力学, 并通过极限氧指数法(LOI)考察了FR-PET的阻燃性能; 采用Flynn-Wall-Ozawa方法分析了PET和FR-PET的热降解表观活化能; 利用Coast-Redfern方法通过对不同机理模型的选取, 确定了PET和FR-PET热降解动力学机理及其模型, 得出了主降解阶段的非等温动力学方程及热降解速率曲线图. 研究结果表明, 侧基含磷单元的引入提高了聚酯的阻燃性能, 侧基上的P—C和P—O键易断裂, 从而降低了聚酯的热稳定性. PET和FR-PET的热降解表观活化能(0.1≤α≤0.85)分别为194-227和184-209 kJ/mol; PET和FR-PET热降解反应均属于受减速形α-t曲线控制的反应级数机理, 其机理函数为f(α)=3(1-α)2/3(0.1≤α≤0.85). 侧基含磷单元的引入对PET的主降解阶段的热降解速率并无实质上的影响. 侧基含磷共聚酯的凝聚相阻燃作用有限, 可能以气相阻燃机理为主发挥阻燃作用.     

基于单体设计的可回收高分子研究进展

现代社会的发展越来越依赖高分子材料, 但其大量使用后不当处置不仅造成资源浪费, 更造成严重的生态环境问题. 将废弃高分子材料解聚回单体, 然后通过聚合反应重新生成与解聚之前等值的高分子材料, 实现高分子材料循环利用被认为是解决上述问题的重要手段之一. 近年来, 通过单体设计发展“理想单体”从而调节“聚合—解聚”平衡, 实现温和条件下高分子材料闭环回收的策略取得了长足进展. 本文将从闭环回收聚酯、聚碳酸酯、含硫聚合物、聚环状烯烃等方面进行综述, 并对该领域的挑战和未来发展方向进行简要讨论.     

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.     

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.     

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.     

Sustainability performance of polyethylene terephthalate,clarifying challenges and opportunities

Publications on polyethylene terephthalate (PET) continue to increase including the number of publications on recycling. PET is a versatile material with the ability to be remade from its polymer state through mechanical recycling and even back to its original monomer through advanced recycling. The scale of PET's use affords continued research and applications in improved recycling. Publications on new uses of discarded PET and the ability to clean and convert it into many forms including alternative materials are expanding with an attempt to complete circular use or improve the end of life. As indicated in life cycle assessment studies, increases in recycling lower the energy required to manufacture products. The future for PET will reduce energy demands further with the largest breakthroughs in recycling technologies and bio-sourced resins trending toward zero energy and carbon negative solutions. Opportunities remain for improvement in the use of PET with light weighting. The testing of new resins, development of bio-feedstocks, improvements in engineering, processing, recycling, and design continue to provide benefits. This review provides context for these developments.     

Chemical recycling of post-consumer PET wastes by glycolysis in the presence of metal salts

Chemical recycling of poly(ethylene terephthalate) (PET) has been the subject of increased interest as a valuable feedstock for different chemical processes. In this work, glycolysis of PET waste granules was carried out using excess ethylene glycol in the presence of different simple chemicals acting as catalysts, namely zinc acetate, sodium carbonate, sodium bicarbonate, sodium sulphate and potassium sulphate. Comparable high yields (≈70%) of the monomer bis(2-hydroxyethyl terephthalate) were obtained with zinc acetate and sodium carbonate as depolymerisation catalysts at 196 °C with a PET:catalyst molar ratio of 100:1 in the presence of a large excess of glycol. The purified monomer was characterised by elemental analysis, differential scanning calorimetry, infrared spectroscopy, and nuclear magnetic resonance. These results revealed that, although the intrinsic activity of zinc acetate was significantly higher than that of sodium carbonate, this latter salt could indeed act as an effective, eco-friendly catalyst for glycolysis. Also an exploratory study on the application of this catalytic recycling technology for complex PET wastes, namely highly coloured and multi-layered PET, was performed.     

A New PETase from the Human Saliva Metagenome and Its Functional Modification via Genetic Code Expansion in Bacteria

The discovery and engineering of new plastic degrading enzymes is an important challenge in chemical biotechnology to enable transition to a more sustainable and circular plastics economy. This field has so far yielded a range of enzymes and microbial pathways for the recycling and valorization of plastic waste. New research from Uttamapinant et al. reports the discovery of a novel polyethylene terephthalate (PET) hydrolase from the human saliva metagenome that displays improved properties and catalytic performance over previously characterized PET hydrolases (PETases). The authors also demonstrate the site-specific incorporation of a photocaged unnatural amino acid, 2,3-diaminopropionic acid (DAP), which upon photodecaging enables covalent binding of DAP to the PET surface. Thus, this work highlights metagenomic datasets as an untapped source of new PET degrading enzymes and the chemical modification of PETases via genetic code expansion, enabling new biotechnologies for the circular plastics economy.     

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.     

The selective recycling of mixed plastic waste of polylactic acid and polyethylene terephthalate by control of process conditions

The glycolysis of postconsumer polyethylene terephthalate (PET) waste was evaluated with catalysts of zinc acetate, zinc stearate and zinc sulfate, showing that zinc acetate was the most soluble and effective. The chemical recycling by solvolysis of polylactic acid (PLA) and PET waste in either methanol or ethanol was investigated. Zinc acetate as a catalyst was found to be necessary to yield an effective depolymerization of waste PLA giving lactate esters, while with the same reaction conditions PET remains as an unconverted solid. This provides a strategy to selectively recycle mixed plastic waste by converting one plastic to a liquid and recovering the unreacted solid plastic by filtration.     

X-ray diffraction of the crystallinity of glycolysates derived from PET

Glycolysates coming from the chemical recycling of PET scraps are most often very crystalline compounds making them difficult to perform in further reactions like step growth polyaddition with diisocyanates to obtain polyurethanes. The glycolysis of PET was investigated using unusual reagents: polyesters based oligomers, bisphenol A, cycloaliphatic alcohol and aliphatic diols. The thermal properties of the glycolysates obtained were compared in terms of crystallinity with that of coming from the glycolysis with DEG. The crystallinity extents were calculated using X-ray diffraction. Surprisingly, the crystalline or non-crystalline nature of the reactants do not predict the morphology of the final glycolysates.     

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.