PACKAGING TECHNOLOGY AND SCIENCE

Packag. Technol. Sci. 11, 19±27 (1998)

A New Recycling System for Expanded

Polystyrene using a Natural Solvent. Part 1. A
New Recycling Technique

Tsutomu Noguchi,* Mayumi Miyashita, Yasuhito Inagaki and

Haruo Watanabe
Sony Corporation Research Center, 174 Fujitsuka-cho, Hodogaya-ku, Yokohama 240,
Japan

A new recycling technique has been developed which uses a natural solvent, d
limonene, to shrink expanded polystyrene (EPS). d-Limonene is a natural
vegetable oil which is extracted from the rinds of citrus fruits and is a good
solvent of EPS. Limonene has almost the same solubility as toluene at room
temperature. This technique reduces the volume of EPS to about 1/20th of the
original. Contracted EPS is recyclable with almost no molecular weight
degradation because d-limonene acts as an antioxidant of polystyrene during
the heating process. O 1998 John Wiley & Sons, Ltd.

Keywords: limonene; expanded polystyrene; shrinking; recycle; antioxidant

INTRODUCTION
Expanded polystyrene (EPS) is widely used for packaging various products because of its
good shock-absorbing properties, low thermal conductivity and cost effectiveness. About
400,000 tons of EPS were produced in Japan in 1994, constituting a difficult problem of
disposal.
In 1995 about 25% of used EPS was recycled in Japan. However, conventional
methods of recycling EPS, such as crushing and shrinking by heated air or frictional
heat,1,2 have the disadvantages of molecular degradation caused by oxidation and
contamination by other materials, resulting in a reduction of the quality of the recycled
polymer.1 Therefore such methods cannot be used to recycle EPS.
To increase the amount of recycled EPS the quality of recycled polystyrene (PS) has to

* Correspondence to: T. Noguchi, Sony Corporation Research Center, 174 Fujitsuka-cho, Hodogaya-ku, Yokohama 240,
Japan.

CCC 0894–3214/98/010019–09 $17.50 Received 23 April 1997

 1998 John Wiley & Sons, Ltd. Accepted 11 June 1997
20 T. NOGUCHI ET AL.

Table 1. The ¯ash points of the solvents

Samples Flash point (°C) Boiling point (°C)

Limonene 47 175
Methyl cyclohexane ÿ3 101
Toluene 4 110
Acetone ÿ18 56

be improved. A method of shrinking using a solvent is promising for improving the

quality of recycled PS because there is no heat degradation in the shrinking process.
In this paper we report on a new method of shrinking EPS3,4 and on the properties of
recycled PS when a natural solvent is used.

PROPERTIES OF d-LIMONENE
An aromatic hydrocarbon, toluene, and a cyclic hydrocarbon, methylcyclohexan, are
well-known EPS solvents. However, these solvents have the disadvantages of toxicity
and a low flash point for use as EPS shrinking agents. The flash point of these solvents is
shown in Table 1.
We researched the application of a natural solvent or a food-additive fragrance as EPS
shrinking agents. Considering their molecular structure and the solubility parameters of
solvents, monoterpene derivatives, such as d-limonene, isoamyl acetate, benzyl
propionate and ethyl butyrate, are good solvents for EPS. Among these solvents d-
limonene, which is a natural vegetable oil extracted from the rinds of citrus fruits, is the
best shrinking agent because of its high solubility, safety, stable supply and fragrance. In

Table 2. The properties of two EPS shrinking agents

Molecular structure Solubility of EPS

d-Limonene bp m175°C 40%

Toluene 45%

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
RECYCLING EXPANDED POLYSTYRENE 1 21

Figure 1. The shrinking process of EPS by limonene spray

addition, d-limonene dissolves only EPS, so contamination by other materials, such as

expanded polyolefins and labels, can easily be removed by filtering the limonene solution.
Table 2 shows the properties of two EPS shrinking agents. d-Limonene was purchased
from Yasuhara Chemical Corp. It purity determined by gas chromatography, was 95%.
The molecular weight and specific gravity of the EPS used were 2.2  105 and 0.02. d-
Limonene has almost the same solubility as toluene at room temperature. Figure 1 shows
shrinking of EPS by limonene spray. A volume of 5 cm3 limonene was sprayed on an EPS
block (volume 125 cm3). After 3 min the EPS block had dissolved. The volume of EPS
can be reduced to 1/20th of the original. For example, 18 l limonene can dissolve about 10

Figure 2. The time required to dissolve EPS completely at room temperature

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
22 T. NOGUCHI ET AL.

Figure 3. The effect of addition of ethanol to limonene on the rate of dissolution of EPS

kg EPS, which equals the amount of packaging for about 40 sets of 21 inch TVs in weight
(total volume about 750 l).
The time required to dissolve EPS completely at room temperature increases
exponentially as the concentration of the limonene solution is increased (Figure 2). The
EPS used had a specific gravity of 0.02. The volume of each the EPS sample block was
1000 cm3.
To increase the rate of dissolution of EPS, the effectiveness of an addition of ethanol to
limonene was investigated. Ethanol is a poor solvent of EPS, but with 3 vol.% added
ethanol the rate of dissolution of EPS about doubled (Figure 3). This is because

Figure 4. The effect of addition of ethanol to limonene on the viscosity of the limonene
solution

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
RECYCLING EXPANDED POLYSTYRENE 1 23

Figure 5. The effect of the molecular weight of recycled PS on heating time in air

penetration of the limonene solution into EPS is raised, as the viscosity of the limonene
solution has a minimum value at 3 vol.% added ethanol (Figure 4).
The flash point and ignitability of pure limonene and a 10 wt% addition of PS–
limonene solution was measured using the standard method. The flash point of the
PS–limonene solution was 49.5°C, which is 2.5°C higher than limonene. A limonene and
PS-limonene solution does not ignite when in contact with a iron bar heated to about
800°C. We also confirmed that a limonene and PS–limonene solution does not ignite
when a cigarette is thrown into the solution.

Figure 6. The effect of the molecular weight of recycled PS on heating time in nitrogen

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
24 T. NOGUCHI ET AL.

Figure 7. The molecular weight and heating time of the sample of limonene and toluene
solution in a nitrogen atmosphere

PROPERTIES OF RECYCLED POLYSTYRENE

Molecular weight (Mw)

The effect of molecular weight of recycled PS on heating time was investigated. The
molecular weight (Mw) was measured by gel permeation chromatography. The 30 wt%
content of limonene solution and EPS was heated to 180, 200 or 225°C for 60 min in an
air and nitrogen atmosphere. The results are shown in Figures 5 and 6. In air the molecular
weight of both samples decreased greatly with heating time because of oxidative
decomposition,5 but the sample containing limonene had less reduction in molecular
weight. In a nitrogen atmosphere (oxygen content 120 p.p.m.) almost no molecular
weight degradation was observed in the sample containing limonene at 200°C. The small
increase in molecular weight is due to evaporation of the low molecular weight fraction of
polystyrene. Under the same heating conditions EPS shows a 20% degradation in
molecular weight after 60 heating for min. Figure 7 shows the molecular weight and
heating time of the sample of limonene and toluene solution in a nitrogen atmosphere.
The sample containing toluene shows a decrease of about 10% in molecular weight.
These results suggest that limonene is an antioxidant of polystyrene.

Analysis of the decomposition products

The heat decomposition products of a limonene solution and PS under heating conditions
of 225°C for 20 min in air were analysed. Gas chromatography, infrared absorption and a
mass spectrum analytical system were used to examine the decomposition products. The
results are shown in Figure 8. Styrene monomers, ethyl benzene and benzaldehyde are

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
RECYCLING EXPANDED POLYSTYRENE 1 25

Figure 8. The heat decomposition products of the limonene solution

observed as the main decomposition products of PS. On the other hand, the amount of
styrene monomers is about 25% compared with PS and ethyl benzene and benzaldehyde
are not observed in the decomposition products of PS/limonene. For this reason we
conclude that limonene depresses the oxidative decomposition of PS, i.e. it acts as an
antioxidant of PS, because limonene epoxide and some oxidative products of limonene
were found in this mixture.

Mechanical properties of recycled PS

The mechanical properties of recycled PS were measured using a viscoelastic analyzer
(frequency 2 Hz, strain ratio 0.2%, temperature rise 2°C/min, apparatus RSA II,
Rheometric Inc.). The sample was about 100 mm thick. The film sample was prepared by
casting from a limonene solution and vacuum dried at 150°C. Virgin PS film with the

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
26 T. NOGUCHI ET AL.

Figure 9. The mechanical properties of recycled PS

same molecular weight was measured as a reference. The results are shown in Figure 9.
The elastic modulus E' is about 10% higher than that of the virgin PS over the whole
temperature range. At round 100°C the peak of the loss modulus E'' which is defined as
the glass transition temperature Tg, is observed. The Tg values of both samples, which
correspond to the heat resistivity of plastics, were 104.8 and 102.6°C. This result shows
that recycled PS has a slightly higher elastic modulus and heat resistivity than the
reference sample. As a result, EPS recycled by the limonene method retains its original
mechanical properties because almost no molecular weight decomposition of PS occurs.

CONCLUSION
We have developed a new recycling technology to shrink expanded polystyrene using d-
limonene. The volume of EPS can be reduced to about 1/20th of the original. We found
that d-limonene depresses the oxidative decomposition of PS. Contracted EPS is
recyclable with almost no molecular weight degradation and retains its original
mechanical properties.

Acknowledgement
We acknowledge Dr Jun’etsu Seto of Sony Corporation for his useful advice.

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)
RECYCLING EXPANDED POLYSTYRENE 1 27

REFERENCES

1. Sasao, S., Harade, T., Sugioka, M. and Fukuda, A. Kagaku Kogyo, 66, 395 (1992) (in Japanese).
2. Kano, T. and Suzuki, E. J. Jpn. Packag. Inst., 31, 33 (1993) (in Japanese).
3. Noguchi, T., Miyashita, M. and Matsate, M. Polymer Reprints Jpn, 43, 734 (1994).
4. Noguchi, T., Miyashita, M. and Matsate, M. Proceedings of the ’96 MRS-J Symposium, p. 329
(1996).
5. Dickens, B. Polymer Degradation Stability, 2, 249 (1980).

O 1998 John Wiley & Sons, Ltd. Packag. Technol. Sci. 11: 19±27 (1998)