W.

De Winter

Poly(ethylene terephthalate) Film Recycling

W. De Winter
Agfa-Gevaert N.V., Research & Development, Septestraat, B-2640 Mortsel, Belgium

INTRODUCTION
The impact of man-made polymers on the environment is a problem of high priority in most industrialised countries. Mainly due to a build-up of disposed waste in landfills, and due to campaigns in the press about mistakes made in the management of waste treatment, public opinion is focusing on this problem. The fact that the corresponding percentage by volume is higher, due to the low packing density of wastes, makes the problem more visible. Although plastics constitute not even 10 wt% of the total amount of wastes, both residential and industrial, found in landfills (see Figure 1), public attention to them is increas1 ing. A possible explanation of such a reaction suggests that there is a lack of compatibility of plastics with the environment, despite the fact that the majority of products used in present daily life are made of materials which have also been manufactured by a chemical process. The plastic waste in landfills consists of about two-thirds polyolefines, and only ca. 15 % of styrene polymers, ca.10 % of polyvinyl chloride, and less than 10 % of all other polymers, including poly(ethylene terephthalate) (PET). The largest use of PET is in the fiber sector. PET film and PET bottles repre2 sents only about 10 % each of the total PET volume produced annually. It is also generally known that the total ECO-balance, considering energy consumption, atmospheric and water pollution, as well as solid waste content, is by a factor 2 to 5 more favorable for PET film than for its greatest competitors in the packag3 ing sector, namely glass and aluminium. 4 In addition, PET is one of the largest recycled polymers by volume, because it is suitable for practically all recycling methods.1 PET recycling by the following technological processes is discussed below:

PET Film Recycling

direct re-use re-use after modification monomer recovery incineration and re-use in a modified way. In addition, attention will be given to some other attempts for recycling which have not been thoroughly evaluated so far, like biodegradability and photodegradation. This paper is limited to the discussion of PET-film recycling. A global review of 2 PET-recycling in the sectors of fibres, films, and bottles was published earlier.

Figure 1. Composition of landfill-waste (domestic and industrial).

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DIRECT RE-USE
Over 50 % of the PET film produced in the world is used as a photographic filmbase. The manufacturers of these materials, mainly Agfa-Gevaert, Eastman Kodak, du Pont de Nemours, Fuji, Minnesota Mining & Manufacturing, and Konishiroku have long been interested in PET film recovery. An important motivation for the efforts made by these companies is the fact that photographic films are usually coated with one or more layers containing some amount of rather expensive silver derivatives, which have been recovered since the early 20th century, when cellulosics were used as a film base. Silver recovery makes 5,6 PET-base recovery more economical. In a typical way of operation, PET film recycling is coupled with the simultaneous recovery of silver, as represented in Figure 2.

Figure 2. Combined recovery of silver and PET.

PET Film Recycling

In the first step of the process, photographic emulsion layers containing silver are washed with, for example, NaOH, and after separation, silver is recovered 2 on one side, and cleaned PET-waste on the other side. Important in this process is that the washed PET-film scrap is clean enough to be recovered by direct re-extrusion, although careful analysis remains necessary. Direct recycling of PET-waste in the molten state, before re-extrusion to PET-film, is of course the most economical process thinkable, as recovered PET-scrap can be substituted for virgin PET-granulate without requiring any additional steps. It is well-known that PET in the molten state gives rise simultaneously to polymer build-up and to polymer degradation, so that reaction conditions for this process have to be controlled very carefully in order to obtain an end-product with desired physical, chemical and mechanical properties, like color, molecular weight, and molecular weight distribution.

A large number of reaction parameters have to be kept under permanent control (temperature, environmental atmosphere, holding time in a melt state, amount of impurities, type of used catalysts and stabilizers, etc.). The order of addition of the PET flakes is very important. A typical flowsheet of a 7 batch-PET-process is represented in Figure 3. In such a process, the PET-flakes can be added after polymerization, before the melt enters the film extruder screw (Figure 3, indication 1). Such a procedure, however, has two main drawbacks: a highly viscous melt is difficult to filter (to eliminate possible gels or microgels) resulting low-boiling or volatile side-products cannot be discarded anymore. In order to eliminate these disadvantages, several alternative operation modes have been worked out in the past. A method to add recycled PET during

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Figure 3. Batch process flow sheet.

the esterification step (Figure 3, indication 2) has been described by du Pont. In such a way filtration can take place in the low-viscosity phase, and volatiles can still be eliminated during the prepolymerisation phase. Although PET-recycling by direct re-use is by far the most economical process, it is only useful in practice for well characterized PET-wastes, having exactly known chemical composition (catalysts, stabilizers, impurities). Therefore, this process is the most suited for the recovery of in-production wastes, but it may not be ideal for customer-recollected PET-film. An industrial process for X-ray 9 film-recycling was worked out by the IPR-company and introduced to the market under the name REPET on the basis of a triple motivation: availability of the waste chips on a repetitive basis suitable purity very competitive price.

PET Film Recycling

RE-USE AFTER MODIFICATION

Similar to the method described under direct re-use, in which PET-flakes are added during the esterification process, PET-polymer is broken down into low-molecular, low-viscous fractions. Such method could already be viewed as a method of re-use after modification. Because the intermediate products are not separated at any moment of the process, the degree of purity of PET-scrap must be high. For PET-wastes having a higher degree of contamination, other technological processes are applied, including further degradation by either glycolysis, 10 methanolysis, or hydrolysis, yielding products which can be isolated. The principles of chemical processes on which these methods are based are schematically represented in Figure 4.

Figure 4. PET degradation by glycolysis, methanolysis, and hydrolysis.

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Glycolysis can be considered as a method for direct re-use, whereas methanolysis and hydrolysis are mainly taken into consideration for monomer recovery, as discussed below. 11 The du Pont Company published many details concerning the glycolytic recycling of PET. Less costly ingredients than those required for hydrolysis or methanolysis, and more versatility than direct remelt recycling are quoted as the reasons for glycolysis choice. Goodyear has also developed the PET recycling 12 process based on glycolysis which is called REPETE. Glycolytic recycling of PET, which can be done in a continuous or in a batch process, is preferentially performed by addition of a PET waste to a boiling ethylene glycol, which leads to the formation of low-molecular weight intermediates and eventually to crystallizable diglycol terephthalate (DGT). The rate of the degradation reactions is primarily controlled by varying the holding time and temperature, which depends on a choice of suitable catalysts (e.g., titanium 12,13 derivatives), and by adjusting the PET/glycol ratio. It is also necessary to avoid side reactions which might occur, e.g., by adding buffers or by keeping down reaction time and temperature. The low-molecular weight depolymerizates can be introduced directly into a 14 polymerization system, preferentially after filtration. In this method, particular care has to be taken in order to avoid glycol ether formation, which may lead to PET of inferior properties. The glycolytic degradation can also be pushed to further completion, leading to DGT-recovery, rather than to direct re-use. In addition to the glycolytic recovery of PET for production of a new PET-film, granulate, or monomer (EG and DGT), alternative methods have been described for the preparation of so-called PETGs (i.e., glycol-modified PET), which can be 15,10 used for different purposes. Depending on the type of glycol (or polyol) used for depolymerization, and on the nature of dicarboxylic acid used for subsequent polycondensation, the obtained polyester may be used as a saturated polyester resin (e.g. for films, fibres or engineering plastics), unsaturated polyester resin, mixed with vinyl-type monomers, or alkyd resin, where polycondensation is performed in the presence of tri- or poly-functional organic acids. Although this method for producing unsaturated resin, e.g., for use in regular castings or in fiber-reinforced laminates, has been thoroughly studied by PET-film manufacturers, it is believed that the method is not currently used in 16 production.

PET Film Recycling

MONOMER RECOVERY
Although monomer recovery is the oldest recycling method and can be used to recover PET-waste having a high degree of impurity, it is regrettable that it is not the most economical method. The earliest methods of PET synthesizing were based preferentially on the use of dimethyl terephthalate (DMT), which could be better purified than terephthalic acid (TPA), therefore methanolysis is discussed before hydrolysis. The chemical principles of both processes are already given in Figure 4.

Methanolysis of PET-waste
The waste is treated with methanol (in a ratio 1/2 to 1/10), usually under preso sure at high temperatures (160-310 C) in the presence of transesterification and 17 (or) depolymerization catalysts. Once the reaction is completed, DMT is recrystallised from the EG-methanol mother liquor, and distilled to obtain polymerization-grade DMT. Also EG and methanol are purified by distillation. Eastman Kodak has been using such a process for recycling of X-ray films for 25 18 years, and it is still improving the process, e.g., by using superheated methanol vapor, to allow the use of ever more impure PET-waste. Important factors which have to be dealt with in this process are avoiding coloration and keeping down the formation of ether-glycols.

Hydrolysis of PET-waste19
Although aromatic polyesters are rather resistant to water under atmospheric conditions, compared with other polymers, they can be completely hydrolyzed by water at higher temperatures (and) under pressure. For practical purposes, however, particularly to speed up the process, use has to be made of catalysts. Acidic as well as alkaline catalysts have been studied and worked out in practice. Figure 5 gives a flow chart of both processes. While both systems are completely realistic, their usefulness under practical production conditions remains controversial. As far as acid hydrolysis is concerned, the large acid consumption and the rigorous requirements of corrosion resistance of the equipment make profitability questionable. In addition, the simultaneous (with TPA) regeneration of ethylene glycol is difficult, ecologically undesirable (requiring the use of organic halogenated solvents), and not economical. Concerning alkaline hydrolysis, the profitability is strongly determined by the necessity of expensive filtra-

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Figure 5. Flow chart of acid- and base-catalyzed PET degradation.

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PET Film Recycling

tion and precipitation steps. To our knowledge, recycling of PET-waste by hydrolysis is not practiced on a production scale at present. This situation even persists in spite of the fact that the majority of newer industrial PET-synthesis 20 plants are based on the TPA-process rather than on the DMT-process.

INCINERATION
Another approach which can be used to recycle plastics, particularly when they contain a large amount of impurities and other combustible solids (if such is a case, it is important to keep them away from landfills), is more recently called quaternary recycling, and consists of the energy recovery from the wastes by 21 burning. Research along this line has been performed, particularly in Europe and Japan, since the early 1960s. Strong emphasis has been laid on an optimization of incinerators with regard to higher temperature of their operation and reduction of the level of air pollution. PET has a calorific value of ca. 30.2 MJ/kg, which is about equivalent to that of coal. It is thus ideally suited for the incineration process. The combustion of plastics, however, requires 3 to 5 times more oxygen than for conventional incineration, produces more soot, develops more excessive heat, and incineration equipment had to be adapted in order to cope with these problems. Several processes have been worked out to overcome these technological draw22-27 backs. Examples include Leidners continuous rotary-kiln process, Balikos process for glass-reinforced PET, Crown Zellerbach Corporations combined system for wood fibre and PET to provide steam to power equipment, and ETH-Zurichs fluidized bed system for pyrolysis, especially of photographic film, i.e., in combination with silver recovery. The latter system raises the additional problem of the formation of toxic halogenated compounds, stemming from the presence of silver halides. o Typical operation conditions take place at temperatures around 700 C. At lower temperatures, waxy side-products are formed, leading to clogging. At higher temperatures, in turn, the amount of the desirable fraction of mononuclear aromatics decreases. A representative sample, pyrolysed under optimized conditions, yields, in addition to water and carbon, aromatics like benzene and toluene, and a variety of carbon-hydrogen and carbon-oxygen 1 gases. Studies have been performed to avoid formation of dioxines and disposal of residual ashes containing heavy metals and other stabilizers.

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At present it seems that most problems arising during incineration of PET can 25 be resolved; however, quite a few residual hurdles will have to be taken before an economically feasible and ecologically accepted industrial technical process will be available.

BIO- AND PHOTO-DEGRADATION

Although there certainly has never been a great incentive for making unstable polymers, the idea of making photo- or bio-degradable polymers has long ex28,29 isted, and quite a bit of effort has gone into research along these lines. For such a process, of course, limitations with regard to the percentage of allowable impurities do not exist.

Photodegradation
Special photodegradable polymers were synthesized for the purpose of having them destroyed after use (e.g., in a landfill). Another approach was the incorporation of suitable groups (e.g., carbonyl) in the polymer backbone in order to make polymer photodegradable by sunlight or UV (see Figure 6). A problem arises due to the fact that light exposure conditions on a landfill cannot be regulated. The main difficulty, however, seems to be practically insurmountable: it is
30

Figure 6. Photodegradable monomers and polymers.31

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PET Film Recycling

hardly possible to combine rapid degradation upon exposure to light in a landfill after use with a good light-stability of the film during service. This contradictio 29 in terminis is probably the reason why this method never really caught on. Another problem is a combination of desired properties with favorable economics.

Biodegradation
The main difference between biodegradation and photodegradation lies in the possibility to create in a landfill an environment completely different from that encountered under normal storage conditions; e.g., microorganisms which can destroy plastic films may be added to a landfill. In spite of the fact that substantial research time was spent on studies in this 32 field, it is claimed that surprisingly little is understood about the molecular-level interaction between polymers and microorganisms. This can be explained by a poorly defined environment (in a landfill), and by a large number of complex parameters involved in the process: methods of evaluation based solely on changes in physical properties are thus unsuitable for forming conclusions, similar to the evaluations based only on biogas production. Specifically for polyesters, however, a number of interesting data are available. Esterases (ester-hydrolyzing enzymes) and also some microorganisms are known to biodegrade 29,33 polyesters at a reaction rate depending upon the polyester structure. While many aliphatic polyesters, specifically poly(hydroxy fatty acids) - e.g., the 34-36 BIOPOL packaging material commercialized by ICI - are suited for biodegradation, the aromatic polyesters (e.g., PET) do not possess this prop32,37-39 erty.

Another approach consists of mixing small amounts of biodegradable polymers, e.g., polysaccharides, with a regular polymer (e.g., a polyolefin), in order to make the end-product destroyable as well. Examples of polysaccharides/poly38 40 ethylene have been commercialized. Mixtures of starch with other polymers,

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including PET, have been studied, but no commercialization of the latter mixture is known so far. The fact, however, that the starch additive is only needed in small amounts, which hardly alters the properties of an original polymer, might show some promise for future applications. One has to realize, however, that the o thermal stability of starch derivatives above 230 C is limited, whereas the o PET-film extrusion temperature is in the range of 280 C. There also remain some controversies about the completeness of the degradation of polymer/starch mixtures. Although the development of biodegradable plastics is still in progress, it is becoming evident that the enormous market potential, forecast some years ago, re41,42 quires a real breakthrough in order to be attained. The main reason for this setback is probably the fact that organic polymers do not biodegrade fast 43,44 enough.

CONCLUSIVE REMARKS
From the data presented in this overview, it seems obvious that there exists a clear hierarchy in PET-film recycling technologies. The most important criteria of classification are, first of all, the degree of purity of PET-scrap to be handled, and secondly, the economics of the process. For the cleanest PET grade, the most economical process, i.e., direct re-use in extrusion, is self-explanatory. For less clean PET samples, it is still possible to re-use them after the modification step (partial degradation, e.g., by glycolysis) at a reasonably low price. More contaminated PET-film waste must be degraded into the starting monomers, which can be separated and re-polymerized afterwards, of course, at a higher cost. At present, only the methanolysis process is exploited industrially, as opposed to hydrolysis processes, which are kept in reserve. Finally, the most heavily contaminated PET-shreds have to be incinerated. Here, however, economics may not be favorable enough for industrial development. As an alternative, those PET-shreds are brought to a landfill. Perhaps in future more attention will be given to modification of PET-films in such a way that they may become biodegradable, if the process can be accelerated or if a real breakthrough becomes available.

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PET Film Recycling

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W. De Winter 36. 37. 38. 39. 40. 41. 42. 43. 44. A. Steinbuchel, Nachr. Chem. Techn. Lab., 39 (10), 1112 (1991). P. Klemchuk, Mod. Plastics Int., 82, (Sep-1989). J. Evans and S. Sikdar, Chemtech, 38, (Jan-1990). K. Joris and E. Vandamme, Technivisie, 179, 5, (1992). R. Narayan, Kunststoffe, 79, 1022 (1989). N. Holy, Chemtech, 26, (Jan-1991). A. Calders, Technivisie, 156, 8 (Nov-1990). Anon., Mod. Plast., 20 (1), 72 (1990). H. Pearce, Scient. European, 14, (Dec-1990).

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