Anda di halaman 1dari 8

l~esoul'ces I

conservation
ELSEVIER
a n d ~
Resources, Conservation and Recycling 12 (1994) 177-184

A model recycling process for low density


polyethylene
C.D. Papaspyrides*, J.G. Poulakis, P.C. Varelides
Laboratory of Polymer Technology (Special Chemical Technology), Departmentof ChemicalEngineering,
National Technical University of Athens, Zographou, Athens 157 80, Greece
Received 30 July 1993; revision received 5 October 1993; accepted 14 October 1993

Abstract

A dissolution/reprecipitation process has been developed for recycling low density polyethylene.
In this paper model experiments on virgin material, either in the form of pellets or film for greenhouses,
are presented. It is proposed dissolution of the plastic in an appropriate solvent, reprecipitation by
means of non-solvents, washing of the material obtained and drying. The solvent mixtures involved
are separated by distillation for further reuse. Toluene/acetone proved to be the most satisfactory
solvent/non-solvent system. The recycled material was evaluated in terms of the following properties:
melt flow index (MFI), crystallinity, mechanical performance in tensile mode and grain size analysis.

Keywords: Dissolution/reprecipitation; Polyethylene; Solvent recycling; Selective dissolution

1. Introduction

Society's growing concern for the earth's environment and particularly for overburdened
landfills has made recycling a watchword for the 90's. A large proportion of the annually
produced plastics ends up in municipal disposal sites each year since most of them have an
estimated life cycle of less than 2 years. In the United States plastics account for a 7 - 9 %
range by weight of the municipal solid waste. However, on a volume basis plastics go from
10% to 20% [ 1,2]. The volume data are important in landfilling since the capacity of a
landfill is determined by its volume. It is estimated that 73% of municipal solid waste goes
to landfill, 13% is recycled, and 14% incinerated. Paper is estimated at a 26% recovery rate,
aluminum at 32%, and glass at 12% whereas plastics are just now reaching an approximate
recovery rate of 1% [ 1 ]. This low rate has been a major concern to the plastic industry
since it reinforces the belief that plastics are not recyclable.

* Corresponding author.

0921-3449/94/$07.00 © 1994 Elsevier Science B.V. All rights reserved


SSDI0921-3449(93)EO077-4
178 C.D. Papaspyrides et aL / Resources, Conservation and Recycling 12 (1994) 177-184

Recycling of used plastics is becoming an important solution to the ecological nuisance


and may also serve as a viable approach to recovery of waste material. Approaches to
plastics recycling mainly include: (a) use of the calorific value of the polymer wastes
('energy recycling'); (a) depolymerization and then reuse of monomers or reduction of
polymers to gases and low molecular weight oils ('chemical conversion or chemical recy-
cling'); (c) direct recovery without polymer modification.
According to the first option the recovery of the 'locked-in' energy is aimed by direct
incineration and combustion or conversion to the so called Refuse Derived Fuel [3-6].
This technology has been accused as ecologically unacceptable due to undesired emissions.
Chemical recycling includes pyrolysis, glycolysis, alcoholysis and hydrolysis. In prin-
ciple, cleavage of the polymer chains results in chemical products of lower molecular weight
distribution or even in the original intermediates (monomers) for another complete cycle
of polymerization. In the literature results are referred on the glycolysis of poly(ethylene
terephthalate), alcoholysis of polyurethanes, hydrolysis of nylon 6, and pyrolysis of poly-
propylene [4,7-10]. However, both incineration and chemical recycling are characterized
by the fact that the value added during polymerization is lost. At current polymer prices this
comprises a major disadvantage [ 3-5,11,12].
In terms of direct recovery, reprocessing in the melt phase remains the most popular
recycling technique. It ensures simplicity and low cost, especially when done 'in-plant' and
feeding with clean, uncontaminated, single-type plastic scrap of controlled history. Never-
theless, this route often leads to degraded products, compared to the virgin ones, because
of chemical changes occurred during processing or in-service use [ 13]. As an example,
during melt reprocessing of low density polyethylene various phenomena, such as shear-
modification (disentanglement), chain scission, gel breaking and chain recombination by
free-radical oxidation and crosslinking, have been referred [ 14-17]. Another example is
the thermal oxidation and photo-oxidation ofpolyolefins, resulting in a decrease in molecular
weight, a build-up of hydroxyl and carbonyl compounds and a loss of tensile strength in
solid materials [ 13]. It is very probable that these undesirable chemical species and also all
additives contained will be recycled and remain in the resultant polymer matrix. Moreover,
when dealing with mixtures of plastics, even of the same plastic type, remelting would lead
to inevitable deterioration of the mechanical properties due to thermodynamic incompati-
bility and effects of foreign matter [ 18 ].
Solvent-based processes include stages of treating plastic waste with solvents so that the
polymeric materials are dissolved and then recovered by reprecipitation. Separating and
recycling plastic waste through this route appears technologically feasible and of consid-
erable commercial interest for the following reasons [ 19-23]:
( 1) The dissolution of the plastics will cause a significant increase in the bulk density of
the plastic waste.
(2) The plastic waste is eventually converted into a form acceptable to fabrication
equipment (powder or small grains).
(3) Insoluble contaminants and additives can be removed by filtration, leaving pure
material. These additives may also be reused.
(4) Any defective material, such as gelling lumps, due to the previous degradation history,
are removed during the dissolution stage.
C.D. Papaspyrides et al. / Resources, Conservation and Recycling 12 (1994) 177-184 179

(5) Except heating for dissolving (also related to the solvent and the conditions chosen)
no further degradation, due to the recycling process itself, is anticipated.
(6) The value added during the polymerization stage is maintained intact and the recycled
polymers, free of any contaminants, can be used for any kind of application, since the final
product is of competitive quality compared with the virgin material.
(7) Solvent-based processes have the potential to deal with mixtures of polymers or
polymers alloys, based on the principle of the 'selective dissolution'. According to the latter
one polymer could be dissolved at a time from a plastics mixture with evident impact on
recycling municipal solid waste plastics. On the other hand, solvent recycling of single type
plastic scrap, beyond its technological importance, serves as a model process providing
useful information on the nature of the solvents system employed and the effect of the
solvent process itself on the recycled product. As an example is referred the solvent recycling
process proposed by Drain et al. [ 15,16] concerning polypropylene. The process proposed
comprises dissolution of polypropylene in tetrachloroethylene, subsequent slow cooling,
centrifugation, complete drying and solvent recovery by bed drying in a hot gas stream.
Recycling of polyethylene is of primary interest since it is the most commonly used
plastic. In 1990 low density polyethylene (LDPE) constituted about 22.4% of the total
plastics consumption in Western Europe (5.4 and 24.1 million tonnes, respectively). More
than 80% of LDPE products has a life time of less than 2 years [24].
Solvent-based processes apply to separate LDPE from other plastics, such as high density
polyethylene (HDPE), polypropylene (PP), polystyrene ( PS ), poly ( methyl methacrylate,
PMMA), poly(vinyl chloride, PVC) and poly(ethylene terephthalate, PET). In relevant
studies, toluene [25] or xylene [23,26-29] have been proposed as suitable solvents, but
the information given are very restricted. Such a selective dissolution is accomplished for
each of the polymers of the mixture by heating the waste dispersion at various temperatures.
The dissolved low density polyethylene is recovered by slow cooling at room temperature
[25], drying with ice [26] or by flash devolatilization [23,28].
A thorough investigation of a solvents-based recycling technique is in progress in our
Laboratory and results have been published so far on recycling polyvinyl chloride bottles
or pipes and polystyrene foam [ l 1,20--22]. The dissolution/reprecipitation technique pro-
posed consists of the following stages: (a) cutting the wastes into smaller pieces and washing
with water if necessary; (b) dissolution to the highest possible concentration; (c) filtration
of the solution under pressure to separate any insoluble ingredients, (d) precipitation of the
polymer still in solution by means of non-solvents, and (e) filtration, washing the polymer
obtained and drying. Furthermore, the solvent/non-solvent mixtures involved are separated
by fractional distillation for reuse.
In this paper, preliminary experiments are first presented on establishing a satisfactory
solvent/non-solvent system for LDPE pellets. Moreover, agricultural film for greenhouses
is recycled as an example of a widely used end-product and the collection of which, as a
single type plastic waste, is easy. The research was based on the satisfaction of the following
criteria: a) precipitation of the polymer in an acceptable form (granules), b) total recovery
of the polymer, c) limited, as much as possible, quantities of the solvent and non-solvent
employed. Characterization studies on the recycled grade were focused on melt flow rate,
differential scanning calorimetry, mechanical properties retention as well as grain size
distribution.
180 C D. Papaspyrideset al. / Resources, Conservationand Recycling 12 (1994) 177-184

2. Experimental

Materials. Commercial film of low density polyethylene for greenhouses as a model poly-
ethylene end-product. The term 'recycled from film' describes the product derived upon
applying the recycling procedure on the film.
Virgin low density polyethylene pellets (raw material) under the code name LDPE 149
(DOW Co.) used as the virgin starting material for the production of the commercial film.
The term 'recycled from raw material' describes the product derived upon applying the
recycling procedure on the virgin LDPE pellets.
Mowiol-poly(vinyl alcohol, PVA) 4-88 and 4-98 (Hoechst Co., Greece) as dispersion
agent.
All solvents used were general reagent grade chemicals.

Polymer recovery by the solvent process. Pellets of virgin LDPE or LDPE film for green-
houses cut into pieces were dissolved into toluene up to the level of 0.30 kg L - ~ at 85°C.
The solution obtained was filtered under pressure through a Seitz Merkur EF 6/03 device,
using 5500 Seitz-T-filter sheets of exclusion size in the range of 20-70/~m. Acetone was
then properly added to the filtrate and the polymer contained was precipitated, washed,
filtrated under vacuum and dried overnight in a vacuum oven at 70°C. The solvent/non-
solvent mixture collected (of a volume ratio equal to about 1 : 7) was separated for reuse in
a distillation column (0.85 m height) filled with Raching rings and equipped at the top with
a side condenser.

Meltflow index (MFI). MFI measurements were carried out according to the procedure A
of the ASTM D1238-73. The temperature was fixed at 190°C, and the weight of the ram
was equal to 2160 g. Sample weights varied from 2.5 to 3 g.

Differential scanning calorimetry (DSC). A Perkin-Elmer DSC-4 calorimeter was used to


obtain thermograms of raw material, product recycled from raw material and product
recycled from film. The measurements were carried out between 50°C and 200°C in a
nitrogen atmosphere and using an empty capsule as reference. Sample weights varied from
5.6 to 13 mg and the heating rate was fixed at the level of 10°C/min. Melting points and
heats of fusion were determined.

Tensile breaking tests. Tensile tests were carried out using an Instron tensile machine in
standard laboratory atmosphere. The specimens were tested according to the D638-76
ASTM method with a rate of extension fixed at 20 mm/min. Specimens were prepared by
compression moulding and subsequent cutting. A hydraulic thermopress was employed
under the following conditions: temperature, 230°C; pressure, 7 MPa; time of heating, 6
min. The same exactly cooling rate was always followed to exclude interference with
processing history effects.

Grain size analysis. U.S. sieves were used for evaluating the particle size distribution.
C.D. Papaspyrideset al. / Resources, Conservationand Recycling 12 (1994) 177-184 181

3. Results and discussion

3.1. Selection of the solvent/non-solvent system

In this cycle of experiments virgin LDPE pellets were employed to simulate the LDPE
waste material.
As solvents, xylene and toluene were tested at the temperature of 85°C. Toluene proved
to be the most effective solvent based on the fact that higher concentration levels were
achieved (0.30 kg L - ~ versus 0.20 kg L - ~for xylene). These upper limits of concentration
are determined empirically by the resultant solution viscosity. When increasing further the
concentration, the solutions become so much viscous so that they cannot be processed under
our experimental conditions. Consequently, toluene was selected as a solvent throughout
the rest of this study.
Precipitation of the polymer in the form of grains comprises the basic criterion for
selecting the non-solvent, n-Hexane was tested first, but even for very low toluene/hexane
volume ratios the system still leads to the formation of a polymer emulsion.
A series of experiments were focused on using water as non-solvent for evident cost-
related reasons. This alternative has been successfully employed in previous research on
recycling polystyrene foam [22]. Accordingly, water was slowly added to the polymer
solution in toluene but an emulsion was formed. Then it was attempted the distillation of
this two-phase azeotrope mixture but the polymer was precipitated in the form of gelling
lumps which were stuck on the walls of the reactor and on the stirrer. Finally, the PVA-
based dispersion agents were included in the aqueous phase, at three different concentration
levels (0.1%, 0.5%, 1.0% w/w), but none of these trials had the anticipated result since
either emulsion or gel was again formed.
Experiments with acetone as non-solvent were very successful as the polymer was easily
precipitated in the form of powder without the formation of any gelling lumps. This quench-
ing/precipitating role of the acetone to yield a flaky brittle product was attributed to three
different factors [ 19] :
( 1) Acetone is a non-solvent for polyethylene and causes its precipitation from solution.
(2) Acetone and toluene are miscible and hence the acetone may remove some solvent
from the polymer.
(3) Acetone is a highly volatile liquid and absorbs its heat of evaporation from the
solution.
Acetone presents other advantages as well: it is non-toxic and inexpensive and it is easily
separated by distillation from toluene.
This selection of the most satisfactory solvent/non-solvent system was followed by
investigation of the process in terms of polymer recovery and solvents recovery. Under our
experimental conditions, the yield in polymer nearly attains the theoretical value while
separation and recovery of solvent (toluene) and non-solvent (acetone), succeeded by
fractional distillation, reaches the levels of 95 % and 80%, respectively. Obviously, the effect
of scaling up will lead to much better values, not deviating from the theoretical limits.

3.2. Properties o f the recycled polymer

Table 1 suggests that the melt flow index is almost the same in all three types of the
samples tested (raw material, polymer recycled from raw material and polymer recycled
182 C.D. Papaspyrides et al. / Resources, Conservation and Recycling 12 (1994) 177-184

Table 1
Melt flowrates

Raw material (g per 10 min) 0.203


Recycledfromraw material (g per 10 min) 0.197
Recycledfrom film (g per 10 min) 0.202

from greenhouses film). Since this index is directly related to molecular weight, these
results indicate that no degradation occurs during the recovery process.
DSC runs were performed to study the fusion behavior and crystallinity of the polyeth-
ylene samples. It is well known that the heat of fusion is the amount of energy necessary in
transforming a polymer from a crystalline or a partially crystalline state to a completely
disordered amorphous state. Valid heat effects of a physicochemical process can be esti-
mated by measuring the area under a well-defined thermogram peak. If the heat of fusion
AHf of a perfectly crystalline polyethylene is known, the percentage crystallinity x can be
derived as follows:

X= (AHexp/l~'/f) X 100

where AHexp is the actual heat of fusion of the sample tested; AHexp is calculated by
measuring the area under the thermogram peak, while AHf is taken here equal to 64.5 cal
g - 1, corresponding to the heat of fusion of the crystalline dotriacontane (C32H66) [ 30,31 ].
According to this approach, resulting crystallinity values are listed on the last column of
Table 2. Virgin PE (raw material) possesses a crystallinity content of 34% whereas the
product recycled from PE pellets and the product recycled from film possess a crystallinity
of 37% and 38%, respectively. On the other hand, the melting point remains practically
unchanged. Nevertheless, the melting range of the virgin PE is much broader than that of
the recycled grades since the lower the degree of crystallinity, the broader the melting range
[31].
This small variation of the crystalline content might be attributed to the fact that during
the recycling process the polymer is precipitated from the solution under very mild condi-
tions in terms of cooling. In other words, it could be said that the recycling process itself
serves at the same time as a kind of an annealing treatment.
These DSC tests were also applied on the three PE grades considered after a compression
molding cycle with the same always cooling rate. All samples revealed exactly the same
fusion behavior and the same degree of crystallinity. Therefore, from the results quoted so

Table 2
DSC results

Melting Melting Actual heat Crystalline


range point of fusion content
(°C) (°C) AHexp (%)
(cal/g)

Raw material 63 113 22.0 34


Recycledfrom raw material 35 112 24.1 37
Recycledfrom film 40 112 24.7 38
C.D. Papaspyrides et al. / Resources, Conservation and Recycling 12 (1994) 177-184 183

Table 3
Mechanical properties retention

Raw Recycled Recycled


material from raw from film
material

Tensile modulus ( N mm- 2) 130 155.0 170.0


Yield tensile strength ( N mm- 2) 10.9 10.9 10.8
Ultimate tensile strength ( N mm- 2) 16.0 15.0 15.0
Ultimate elongation (%) 710.0 675.0 640.0

Table 4
Grain size distribution

Grain si~ distribution Retention ~rcenmge


(mm) (%)

d>l 16.2
l>d>0.8 31.5
0.8>d>0.63 38.1
0.63>d>0.5 6.3
0.5>d 7.9

far, it can be concluded that the polymer structure remains unchanged during the recycling
process studied.
Turning to mechanical properties retention, results from tensile breaking tests are pre-
sented in Table 3. The data suggest that the recycled grades (from pellets or film) exhibit
strength levels competent to those of the virgin polymer. Even more, there is a clear
indication that after recycling the tensile modulus increases with the elongation decreasing,
possibly due to the role of the additives initially contained in the raw material or in the
commercial film. Currently, research is in progress to investigate quantitatively additives
removal during the recycling process.
Finally, according to the grain size analysis (Table 4), nearly 84% of the recycled polymer
mass has a grain size smaller than 1 mm, suitable for feeding polyethylene processing units.

4. Conclusions

A dissolution/reprecipitation process has been investigated to recycle low density poly-


ethylene film for greenhouses. Concentrated solutions in toluene were employed (0.30 kg
L - ~) and the polymer was reprecipitated, in the form of small grains, through the addition
of acetone. Excellent recoveries in polymer and solvents are achieved. The process did not
appear to affect the rheological and mechanical performance of the final product, i.e. the
polymer structure remained intact. The recycled grade, free of any soluble or insoluble
additives, can be used in many different applications, competing the virgin material. Larger-
scale experiments are expected to result in even higher concentration levels and better
184 C.D. Papaspyrides et al. /Resources, Conservation and Recycling 12 (1994) 177-184

recovery values for the solvents used. In accordance with previous studies the information
established provide fundamental input for the development of a selective dissolution process
dealing with mixtures of waste plastics.

References

[ 1] Ehrig, J.R., 1992. Plastics Recycling: Products and Processes. Carl Hanser, New York.
[2] Rathje, W.L., 1991. National Geographic 179(5), 116.
[3] Kline, C.H., 1989. Chemistry and Industry, 483.
[4] Matthews, V., 1990. Kunststoffe Europe, 139.
[5] Menges, G., Eysmondt, B., Feldhaus, A. and Offergeld, H., 1988. Kunststoffe 78(7), 573.
[6] Steiner, K.W., 1984. Kunststoffe 74(4), 186.
[7] Bauer, G., 1991. Kunststoffe 81(4), 301.
[8] Fakirof, S., 1984. Kunststoffe 74(4), 218.
[9] New, R., 1986. Plastics waste recycling in the United Kingdom. Department of Trade and Industry, Warren
Spring Laboratory.
[ 10] Vaidya, U.R. and Nadkarni, V.M., 1988. J. Appl. Polym. Sci. 35, 775.
[ 11 ] Kampouris, E.M., Diakoulaki, D.C. and Papaspyrides, C.D., 1986. J. Vinyl. Technol. 8(2), 79.
[ 12] Selke, S.E., 1988. Packaging Technol. Sci. 1,93.
[ 13] Drain, K.F., Murphy, W.R. and Otterburn, M.S., 1981. Conservation & Recycling 4(4), 201.
[14] Ram, A. and Getz, S., 1984. J. Appl. Polym. Sci. 29, 2501.
[ 15] Drain, K.F., Murphy, W.R. and Otterburn, M.S., 1983. Conservation & Recycling 6(3), 107.
[ 16] Drain, K.F., Murphy, W.R. and Otterburn, M,S., 1983. Conservation & Recycling 6(3), 123.
[ 17] Sadrmohaghegh, C. and Scott, G., 1980. Eur. Polymer J. 16, 1037.
[ 18] Ram, A., Narkis, M. and Kost, J., 1977. Polymer Eng. Sci. 17 (4), 274.
[ 19] Murphy, W.R., Otterburn, M.S. and Ward, J.A., 1979. Polymer 20, 333.
[20] Kampouris, E.M., Diakoulaki, D.C. and Papaspyrides, C.D., 1986. J. Vinyl. Technol. 8(2), 83.
[21 ] Kampouris, E.M., Papaspyrides, C.D. and Lekakou, C.N., 1987. Conservation & Recycling 10(4), 315.
[22] Kampouris, E.M., Papaspyrides, C.D. and Lekakou, C.N., 1988. Polymer Eng. Sci. 28(8), 534.
[23 ] Battle, K.E., Moore, A.P., Nauman, E.B. and Lynch, J.C., 1992. Plastics recycling by selective dissolution.
DeWitt Conference, March 25-27.
[24] Anonymous, 1990. Summary document of APME (Association of Plastics Manufacturers in Europe),
Plastics Recovery in Perspective.
[25] Seymour, R.B. and Stahl, G.A., 1976. J. Chem. Educ. 53(10), 653.
[ 261 Kajimoto, H., Shimada, T., Tokuda, M. and Tamura, T., 1976. Separation of plastic from waste by dissolution.
Jpn. Kokai, 16,378.
[27] Kajimoto, H., Shimada, T., Tokuda, M. and Tamura, T., 1976. Recovering and purifying polyolefins from
municipal refuse and industrial wastes. Jpn. Kokai, 28,175.
[28] Kajimoto, H., Shirnada, T., Tokuda, M. and Tamura, T., 1976. Recovering polyolefins from solutions by
flash cooling with concentration and temperature control in municipal waste disposal. Jpn. Kokai, 18,781.
[29] Nishimoto, Y., Mizumoto, Y., Hasegawa, S. and Mitsuoka, S., 1975. Separation of waste plastics. Jpn.
Kokai, 70,480.
[30] Bacon, K. and Charles, F., 1966. In: Encyclopedia of Polymer Science and Technology, edited by H.F.
Mark, N. Gaylord and N. Bikales, Interscience Publishers, Vol. 5, pp. 37-65.
[31 ] Miller, R.L., 1966. In: Encyclopedia of Polymer Science and Technology, edited by H.F. Mark, N. Gaylord
and N. Bikales. Interscience Publishers, Vol. 4, pp. 449-528.