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1、附录A英文翻译（原文）Recycling of PVCAbstractRecycling of used PVC needs a careful characterization of PVC waste. The analysis of the scrap, especially with respect to the thermal stability and the molecular weight, is useful before reprocessing. Additional stabilization of used PVC can be done by up to 10 wt
2、% fillers, e.g. chalk, which does not change the mechanical properties. A literature survey on the proposed concepts and methods for material and chemical recycling of PVC isgiven. q 2002 Published by Elsevier Science Ltd.Keywords: Poly(vinyl chloride); Degradation; Stabilization; Material and chemi
3、cal recyclingContents1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12. Characterization of PVC waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32.1. Thermal stability . . . . . . . . . . . . . . . . . . . . . . .
4、 . . . . . . . . . . . . . . . . . 32.2. Analysis of stabilizers and other additives . . . . . . . . . . . . . . . . . . . . .62.3. Molecular weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .73. Stabilization of used PVC . . . . . . . . . . . . . . . . . . . . .
5、. . . . . . . . . . . . . . . .83.1. Addition of heat stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93.2. Improvement of thermal stability by fillers . . . . . . . . . . . . . . . . . . . . 93.3. Processing of filled PVC . . . . . . . . . . . . . . . . . . . . . . . . .
6、 . . . . . . . . . 103.4. Practical examples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124. Recent investigations on material recycling. . . . . . . . . . . . . . . . . . . . . . . 155. Chemical recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7、 . . . . . . . . . . . . 186. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .201. IntroductionWith a todays worldwide annual p
8、roduction capacity of approximately more than 30 million to poly(vinyl chloride) (PVC) is the second largest volume thermoplastic only to polyethylene as volume leader in the plastics industry 1. Its ability to be compounded with many additives to a wide range of flexible and rigid products constitu
9、tes the major factor responsible for the versatile application of PVC.Because of the low cost and the processability by a wide variety of techniques (e.g. calendering,extrusion, injection moulding, and plastisol techniques) combined with good physical, chemical and weathering properties, PVC has bec
10、ome a universal polymer 2 with many applications, e.g. for pipes,profiles, floor coverings, cable insulation, roofing sheets, packaging foils, bottles, and medical products.At the end of the service-time of these articles, large amounts of scrap arise. Therefore, the question of the disposal of used
11、 PVC has gained increasing importance in the public discussion because of the environmental problems resulting from the rapid growth of the plastic waste during the last years.Landfilling of municipal solid waste is becoming a burden as, for example, in the United States about80% of waste is dumped
12、into landfills. A continuation at the present rate could exhaust the landfill capacity in the near future 3. Also the European countries are faced with a similar dilemma because the availability of suitable sites is limited 4. Thus, landfilling as a disposal process is increasingly seen asthe last o
13、ption.The energy recovery by incineration is another way to dispose the municipal solid wastes 5. But environmental argumentation, such as toxic emissions from inadequate equipment or inappropriate incineration conditions, are building up a public resistance against these techniques 6. Especially, P
14、VC incineration is connected with some technological problems due to the high chlorine content of this polymer which yields large amounts of hydrogen chloride during thermal decomposition, beside the possibility of formation of toxic dioxines and furans. Therefore, plans to expand capacities of such
15、installations meet with growing difficulties.The recycling activities can be distinguished between chemical from material recycling. The chemical recycling is based on the idea of converting polymers back into short-chain chemicals for reuse in polymerization or other chemical processes. Four differ
16、ent process technologies are currently considered for chemical recycling: cracking, gasification, hydrogenation and pyrolysis 7. In the meantime, some commercial-scale plants are working and a number of interesting investigations with these techniques are available 810. At the end, the economic effi
17、ciency will be decisive for the application of each recycling process in the future.The material recycling is already practiced in plastics industry over many years with postmanufacturing waste. These experiences can be used to develop new concepts for material recycling of post-consumer waste. The
18、major problem in the recycling of used plastics is connected to a great inhomogeneity of the polymers present in the waste 11. A statistical study by the Information System on Plastics Recycling in Western Europe shows that about 7.4% of the 9 million to of municipal solid waste in Western Europe ar
19、e plastic materials. Fig. 1 shows the percentage of different polymer types in the total plastics waste.Fig. 1. Percentage of different polymer types in the municipal solid plastic waste.The incompatibility of these components is the most important reason of the difficult processing and inferior mec
20、hanical properties of the resulting products from mixed, chemically different polymers.Therefore, it is necessary to separate various polymers to boost their value. Although there are many practical problems some interesting developments for plastics waste separation were found 12,13. The separation
21、 in a hydrocyclone, which works on the principle of sorting by a centrifugal force field, usingdensity difference of the various polymers is one possible solution 14. Also identification by IR analysis in a continuous process can be used for separation of the most common plastics. Sometimes,prior to
22、 separation, it becomes necessary to clean the polymer waste to remove contaminations like dirt,food, and paper.In the future, a clean PVC-stream of the municipal solid wastes and from the building sector ready for material recycling can be expected. This will be accelerated by new regulations made
23、by the governments in some countries. In Germany, the first item of legislation to be introduced was the act on the avoidance of packaging waste 15. Its aim is to reduce the large amounts of packaging waste through avoidance and material recycling. Another fact is that the manufacturers and traders
24、are made responsible for their used packaging to relieve the local authorities of the burden to dispose the waste. In this respect, material recycling is a necessary way to reduce the municipal solid waste problem.2. Characterization of PVC wasteMany different grades and types of PVC are available a
25、llowing applications as diverse as flexible sheets, pressure pipes, transparent bottles, and medical products to be produced. For these articles, a lot of different additives and stabilizer systems are used to get suitable properties for the respective applications 16. Moreover, during the high temp
26、erature processing and throughout the service live of the products the polymer might be subjected to degradation 17,18. Therefore, characterization of the PVC waste is necessary to obtain information on properties such as the residual stability, molecular weight, and content of additives of the indi
27、vidual PVC species.2.1. Thermal stabilityThe main disadvantage of PVC is the rather limited thermal stability which requires addition of heat stabilizers to prevent dehydrochlorination and discolouration during processing and application. With respect to the great practical importance of the polymer
28、, the thermal and photochemical degradation of PVC has been studied for a long time and there is a large number of published surveys 1921. The elimination of hydrogen chloride at relatively low temperatures (about 100 ) or under the influence of light is one of the fundamental aspects of PVC decompo
29、sition. In the first stage, this reaction leads to the formation of double bonds followed by a so-called rapid zipper-like splitting off of further HCl molecules to give polyene sequences (Fig. 2). These sequences, with an average length of 614 conjugated double bonds, cause the polymer to turn yell
30、ow, brown, and eventually black. Fig. 2. Scheme of dehydrochlorination of PVC.The thermal stability of PVC is considerably lower than that of its low-molecular weight model analogues. Therefore, initial sites, such as allylic chlorines adjacent to internal double bonds, tertiary chlorines at branche
31、d carbons, head-to-head units, and oxygen-containing structures are believed to be responsible for the instability. The mechanisms, which occur during degradation are not yet fully understood. There are radical or ionic mechanisms suggested, and the type of reaction depends also on the conditions (t
32、emperature, presence of oxygen, etc.) during the decomposition.The main function of heat stabilizers is to prevent degradation during processing. They have in common the ability to react with HCl when it is liberated from the polymer. Another task is to replacelabile chlorine atoms, which may initia
33、te the dehydrochlorination of more stable groups, and thus to enhance the heat stability. A number of organometallic compounds and inorganic salts are especially effective and since long time in practical use.A part of the stabilizer will be consumed during processing and sometimes during the applic
34、ation period. Therefore, the efficiency of the stabilizer system is remarkably reduced after compounding PVC with the necessary additives 22 that makes it useful to get information about the residual stability of PVC articles before they can be recycled.For this purpose, the determination of the the
35、rmally induced hydrogen chloride elimination from PVC seems to be the best way. The study of the early stages of the reaction requires a combination of good reproducibility, high accuracy and a low detection limit. Fig. 3 shows an apparatus which is very suitable and often used for such studies sinc
36、e many years 23.Fig. 3. PVC degradation measuring apparatus. (a) Rotameter, (b) degradation vessel with PVC sample, (c) thermostat, (d)conductivity cell, (e) conductivity-meter and (f) computer.The PVC-sample (,0.1 g) is introduced into the degradation vessel and then the measurement iscarried out u
37、nder isothermal conditions (e.g. 180 ). A stream of warmed up carrier gas (nitrogen or air)transports the evolved hydrogen chloride into the conductivity cell filled with distilled water. The HCl determination is performed by continuous conductometric measurements. As a result the conversiontime cur
38、ve is obtained as schematically shown in Fig. 4.Fig. 4. Schematic degradation curve of stabilized PVC.The degradation curve of stabilized PVC shows an induction period where no HCl is evolved. During this period, the heat stabilizer is consumed and afterwards the dehydrochlorination begins. The time
39、 of induction, ti, gives an important information required to estimate the remaining stability of a PVC specimen and to decide whether an additional stabilization is necessary for the material recycling. In some cases, it can be sufficient to use the simple Congo Red Test, e.g. according to DIN 5341
40、8, instead of the more expensive apparatus for quantitative measuring the hydrogen chloride elimination.2.2. Analysis of stabilizers and other additivesAs mentioned above, the limited thermal stability of PVC requires the use of heat stabilizers in almost all fields of application. Besides, also oth
41、er additives (e.g. light stabilizers, fillers, lubricants) are used to modify the properties of PVC or to improve its processability. At present, about 1/3 of all used PVC is plasticized by various types of modifiers 24. Therefore, it is helpful to get some detailed information about the composition
42、 of a special PVC scrap before reuse. As an example, for plasticized PVC, the analysis of PVC roofing sheets is described and show in Fig. 5 25.Fig. 5. Analysis of PVC roofing sheets.The first step is a Soxhlet-extraction of the powdered PVC sample with diethyl ether to isolate plasticizers. After e
43、vaporation of the solvent, the type and amount of plasticizer can be determined.The rest of the material is then dissolved in tetrahydrofuran (THF), and, after filtration, the fibrous materials are obtained. The other components, insoluble in THF, are separated by a centrifuge. The remaining residue
44、 can be divided to fillers and cross-linked PVC by burning to ash. By dropping the THF solution in a surplus of methanol the dissolved PVC is precipitated. The single components are determined gravimetrically and identified by chemical and spectroscopic methods.Usually the quantitative analysis of t
45、he main parts of a PVC sample (plasticizer, filler, PVC itself) will give enough information about the material. For the qualitative analysis the IR-spectroscopy is particularly suited because the main additives, including co-polymers and impact modifiers, show typical IR-bands 26. Also other spectr
46、oscopic methods can be used for identification but the expenditures of sample preparation and equipment are higher. A complete qualitative and quantitative analysis of all ingredients of a PVC compound is described in Ref. 27.Finally, the determination of the heat stabilizers, as an important point
47、in the analysis of PVC waste, is particularly considered. The selection of a stabilizer system for PVC depends on many factors including application, tradition of the market, and local legislation 28. Lead stabilizers still are the most widely used PVC heat stabilizers for some technical application
48、s because they provide cost-effective stabilization systems and easy processing. They maintain volume resistivity in plasticized PVC cable insulation and are the principal stabilizers for many general-purpose applications. Important are several mixed metal carboxylate soaps as PVC stabilizers, e.g.
49、bariumcadmium, bariumzinc, calciumzinc. Since many years, bariumcadmium systems have been used in Europe in white window frames with good weathering properties. But the utilization of cadmium in stabilizers or pigments recently became under increasing scrutiny. At present, all manufacturers use alternative systems such as calciumzinc stabilizers 29,30. They are applied for food packaging,
