Polymer Degradation and Stability 91 (2006) 3354e3359

www.elsevier.com/locate/polydegstab

Improving chemical recycling rate by reclaiming polyurethane

elastomer from polyurethane foam
Hiroko Watando*, Shioko Saya, Taro Fukaya, Shinetsu Fujieda, Masaaki Yamamoto
Corporate Research & Development Center, Toshiba Corporation, 1, Komukai-Toshiba-cho, Saiwai-ku, Kawasaki, Yokohama 212-8582, Japan
Received 5 April 2006; received in revised form 29 May 2006; accepted 31 May 2006
Available online 20 July 2006

Abstract

Flexible polyurethane foam was decomposed into a polyol mixture by an extruder with diethanolamine (DEA) as a decomposing agent. The
resulting decomposed product could be used as an alternative virgin polyol in reclaiming polyurethane. In the case of reclaiming elastomer by
using the decomposed product without any purification, virgin polyol could be alternated by the decomposed product up to 80%. It is a great
improvement compared with the reclamation to foam, whose percentage was maximum 5%. Furthermore, the percentage could be improved up
to 100% by purifying the decomposed product. We have found that physical properties of reclaimed polyurethane elastomer, such as tensile
strength, hardness, and elongation, can be regulated by the ratio of unrefined/refined polyol. Whereas the tensile strength and the hardness
increased as the content increased, the elongation decreased.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Polyurethane; Chemical recycling; Foam; Elastomer; Reclamation

1. Introduction Our previous study revealed that a continuous urethane de-

composition process using an extruder enables a remarkable
Flexible polyurethane foam is one of the most widely used reduction in the amount of decomposing agent required and
cushion materials in automobiles, furniture, and so on. How- the reaction time. In the present study, we examined, firstly,
ever, a considerable amount of scrapped polyurethane foam the applicability of this method for flexible polyurethane and
is disposed off by landfill or by incineration, because a recycle secondly, the process of reclaiming polyurethane elastomer
process capable of treating all scrapped polyurethane with suf- from the decomposed product. Our reclamation process from
ficient efficiency has not been established yet. In the mechan- foam to elastomer without purification is expected to save
ical recycling process, flexible polyurethane foam is smashed cost and processing energy, because the former reclamation
into fine powder and used as recycled urethane filler [1e3]. process from foam to foam generally requires intensive purifi-
However, the amount of polyurethane foam treated by this cation [10]. In this study, the characteristics of reclaimed elas-
process has not increased significantly up to date. tomer with various decomposed polyurethane content are
On the other hand, several chemical recycling techniques, such evaluated and the issue of whether purification of the decom-
as hydrolysis [4], glycolysis [3,5e7] and aminolysis [8,9], includ- posed product is required is discussed.
ing the decomposition process with alkanolamines have been re-
ported. In these studies, however, it takes considerable time to 2. Experimental
complete the decomposition reaction, because of the low density
and low thermal conductivity of the foam structure, even though 2.1. Preparation of flexible polyurethane foam
an excessive amount of the decomposing agent is used.
Three kinds of flexible polyurethane foam were evaluated.
* Corresponding author. Tel.: þ81 44 549 2327; fax: þ81 44 520 1307. Two of them (samples 1 and 2) were urethane scraps supplied
E-mail address: [email protected] (H. Watando). by Toyo Tire and Rubber Co., Ltd. The other one (sample 3)

0141-3910/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.05.017
 H. Watando et al. / Polymer Degradation and Stability 91 (2006) 3354e3359 3355

was a reference polyurethane foam prepared in order to have Table 2

a polyurethane foam, whose composition was known, for The decomposition conditions
chemical analysis of the decomposed products. Samples 1 Polyurethane PU/DEA Reaction Temperature of Feed
and 2 were used for reclamation to elastomer and sample 3 (w/w) time (s) a cylinder in amount
the extruder ( C) (kg/h)
was used for chemical analysis.
In preparing sample 3, the contents of which are shown in Sample 1 8/1 240 250 13.0
Sample 2 10/1 190 270 6.2
Table 1, three catalysts, water as a blowing agent and a chain Sample 3 10/1 220 270 5.5
extender were added to virgin polyol and premixed with a stir-
rer (T.K. homodisper f-model, Tokushu Kika Kogyo Co.,
Ltd.). And then, isocyanate was added to the mixture and The pressure was kept at 1.0 kPa or less and the temperature
stirred to react. The foam was cured at 25  C for more than was raised from room temperature to 300  C, and these condi-
24 h before use in order to react and be stiffened securely. tions were kept until the condensed drop was not observed. In
this paper, the residue of the process is called ‘‘refined
2.2. Decomposition of flexible polyurethane foam polyol’’.

Polyurethanes (samples 1e3) were decomposed by the fol- 2.4. Reclamation to polyurethane elastomer
lowing process. Smashed flexible polyurethane (3e20 mm) was
premixed with equivalent mol of diethanolamine (DEA, Mitsui The surfactant (TSA720; GE Toshiba Silicones) and unre-
Chemicals, Inc.). The mixing ratio (w/w) is shown in Table 2. fined or refined polyol obtained by the decomposition were
Then the mixture was fed into an extruder (one screw, di- added to the virgin polyol (Mn3050; Mitsui Takeda Chemi-
ameter of screw: 65 mm, length of screw: 1830 mm, reaction cals, Inc.) and premixed with a stirrer. Then, the isocyanate
volume: 4  103 m3, Toshiba Machine Co., Ltd.) (Fig. 1). pre-polymer (Mn3050 with toluene diisocyanate at both
The working conditions of the extruder are also shown in Ta- ends) was added and the mixture was stirred for 3 min. The
ble 2. In this process, all foam samples were fully decomposed mixture was molded to No. 3 dumbbell shape and plates
in a few minutes. The reaction scheme is shown in Fig. 2. whose thickness is more than 12 mm, according to Japanese
The decomposed polyurethane discharged from the extruder Industrial Standard (JISK-7312: physical testing methods for
separated into two layers spontaneously. The upper layer was molded products of thermosetting polyurethane elastomers).
composed mainly of polyol and the lower layer was composed The composition of the reclaimed elastomer and the reaction
mainly of amines and other low molecular weight compounds. scheme are shown in Table 3 and Figs. 2 and 3, respectively.
(Composition of the layers is discussed in detail in the next sec- The content of unrefined or refined polyol was defined as
tion.) However, the upper layer included a few amines and other follows:
low molecular weight compounds except for polyol. Hereafter,
the upper layer is called ‘‘unrefined polyol’’ in this paper. The content of unrefined=refined polyol
2.3. Purification of unrefined polyol ¼ unrefined=refined polyol ðgÞ=ðunrefined=refined polyol
þ virgin polyolÞ ðgÞ  100:
The amines and the other low molecular weight compounds
in unrefined polyol were distilled out under reduced pressure.
In this process, bubbles generated in the mixture were elim-
Table 1
inated by setting the mold in vacuum for about 5 min.
The components and the composition of the foam After curing at room temperature for more than 24 h,
Item Chemicals Manufacturer Content
test samples for measurement of characteristics were
formed according to the Japanese Industrial Standard (JISK-
Virgin Polyethertriol Mitsui Takeda 100
polyol (Mn3050) Chemicals
Isocyanate Toluene Mitsui Takeda NCO/OH Polyurethane
diisocyanate Chemicals (mol/mol) ¼ 1.0b resin
(T-80a)
Blowing Water 8.0 Decomposing
agent agent
Catalyst Tetramethylene- Wako Pure 2.0
diamine Chemical
Industries Extruder
Catalyst Dibutyltin dilaurate Wako Pure 0.2
Chemical Industries
Catalyst Surfactant (SZ-1923) Dow Corning Toray 2.0
Chain Glycerol Kanto Chemical 2.0
extender Decomposed product
a
T-80: 2,4-/2,6-toluene diisocyanate ¼ 8/2.
b
NCO index: actual amount of isocyanate per calculated amount of Fig. 1. A model of the extruder used for the decomposition of polyurethane
isocyanate. foam.
3356 H. Watando et al. / Polymer Degradation and Stability 91 (2006) 3354e3359

O O
* R R' + OH
N N O O n * HN 2
H H
Polyurethane
Decomposing Agent
(Urethane Bond)

O O
R OH R'
N N N 2 + HO O
H H
Decomposed Product 1 Decomposed Product 2

O
H
N NH2 + OH
R O N

By-product 1
By-Product 2
(Amine)

Fig. 2. The reaction scheme of polyurethane and decomposing agent.

7312: physical testing methods for molded products of ther- layer, respectively, indicating the low mutual solubility be-
mosetting polyurethane elastomers). tween polyols and amines.
In this study, only the upper layer, whose main component
2.5. Chemical analysis was polyol, was investigated for use in the reclamation pro-
cess. The GPC patterns of the unrefined polyol (sample 3)
The molecular weight was measured by gel permeation that decomposed with three polyurethane/DEA ratios are
chromatography (GPC; GPCA1100 YHP) at 40  C using TO- shown in Fig. 5. These results showed that the reclamation
SOH TSKgel G3000HXL column and a tetrahydrofuran eluent without the distillation process, as mentioned in the next sec-
(1.0 ml/min). Low polydispersity polystyrene standards were tion, was easy in the case of unrefined polyol with a high poly-
used for calibration. Then, the composition was measured by urethane/DEA ratio, because the amine content decreased
gas chromatography (GC/MS; HP5890/HP5972) after the according to the increase of the polyurethane/DEA ratio.
sample was dissolved into methanol. The temperature of the
column (DB-5MS, 30 m  0.25 mm) was raised from 50  C 3.2. Purification of unrefined polyols
to 300  C at a rate of 8  C/min.
In general, the reaction rate of polymerization between iso-
3. Results and discussion cyanate and polyol is accelerated by the existence of amines
[11]. Thus, in the reclamation process for foam, the elimina-
3.1. Decomposition process tion of amines was necessary because the reclamation rate
was too fast [10]. In this study, amines were eliminated easily
All samples of foam were decomposed easily into a mixture by distillation under reduced pressure. As shown in Figs. 5 and 6,
of polyols, amines, and so on, by the extruder in a few minutes almost all amines and the low molecular weight compounds
and separated into two layers. were eliminated by this process. In addition, the viscosity of
The molecular weight of the decomposed product of sam- refined polyol was lower than that of unrefined polyol and
ple 3, regarding its two layers, was measured by gel perme- closer to that of virgin polyol (Table 4); equivalent weight
ation chromatography (GPC) and the patterns are shown in means the molecular weight per hydroxyl group.
Fig. 4. The peaks were assigned to polyol, the low molecular
compounds and TDA (toluene diamine). This result in Fig. 4 3.3. Reclamation for elastomer with unrefined and
revealed that the main contents of the decomposed products refined polyols
were polyols in the upper layer and amine, TDA in the lower
In the reclaimed elastomer with unrefined polyol, homoge-
neous reclaimed elastomer equivalent to 80% of the total pol-
Table 3 yol content could be obtained. It was a great improvement
The components and the composition of the reclaimed elastomer compared with the reclamation to foam, whose content of un-
Ingredients Content refined polyol was 5%. The difference between the reclama-
Virgin polyol 100e0 tion to foam and elastomer was caused by the reaction
Unrefined or refined polyol 0e100 speed. The reaction speed of foam was so fast that the influ-
Surfactant (TSA720) 0.05 ence of amine was very serious, so the recycling rate was max-
Isocyanate pre-polymer NCO/OH (mol/mol) ¼ 1.0
imum 5%. On the other hand, the reaction speed of elastomer
 H. Watando et al. / Polymer Degradation and Stability 91 (2006) 3354e3359 3357

O O O
R' + R" NCO R" R'
HO O N O O
H
Decomposed Product 2 Isocyanate Reclaimed Polyurethane

Fig. 3. Reclamation scheme.

was slower than foam, so the influence was smaller and more elastomer with refined polyol was higher than that of virgin
amount of unrefined polyol could be used for the reclamation. polyol as the chain length of refined polyol among hydroxyl
But more than 80% of virgin polyol could not be alternated by groups was shorter than in the case of virgin polyol, although
unrefined polyol, because the influence of the acceleration by almost all amines were eliminated by distilling out.
amine contained in unrefined polyol could not be ignored at The elongation of the reclaimed elastomer decreased with
high content of unrefined polyol. On the other hand, virgin raising the content of unrefined polyol as shown in Figs. 7
polyol could be alternated by refined polyol up to 100%, and 8. In general, it is known that the elongation decreases
when refined polyol was used for the reclamation, because when the equivalent weight is smaller [11], that is, the
amines were almost eliminated. cross-linking density is higher. It was supposed that the de-
crease was caused by the differences in the cross-linking den-
3.4. Characteristics of reclaimed polyurethane sity: the reclaimed elastomer with unrefined polyol had higher
elastomers cross-linking density because of the amines and the low mo-
lecular compounds in unrefined polyol, which behaved as
The hardness of the reclaimed elastomer with unrefined cross-linkers.
polyol increased with raising its content (Fig. 7), where re- On the other hand, in reclaimed elastomer with refined pol-
fined/unrefined polyols 1 and 2 are the polyols given by the de- yol, the decrease of the elongation was smaller than that with
composition of samples 1 and 2, respectively. unrefined polyol, as the amines were eliminated by distillation.
The increase of hardness of the reclaimed elastomer with In every reclaimed elastomer, the elongation decreases signif-
unrefined polyol might be attributable to the influence of icantly at 20% of the content. The significant decrease at 20%
urea bond formation between the isocyanate and the amines, of the content might be attributable to the influence of the in-
which are known to form urea bonds as hard segments and crease of the cross-linking density caused by the remaining
cross-link preferably. On the other hand, the hardness of the low molecular weight compounds, which behaved as cross-
reclaimed elastomer with refined polyol increased monoto- linkers.
nously but the degree was smaller than that of unrefined polyol.
That was because the cross-linking density of the reclaimed

polyurethane/DEA=1/3.3(mol/mol)
polyurethane/DEA=1/1(mol/mol)
upper layer (Sample3) polyurethane/DEA=1/0.67(mol/mol)
(unrefined polyol)
lower layer (Sample3)

(a)
Intensity
Intensity

(b)
The low
molecular The low
compounds Polyol Toluene diamine molecular Polyol
weight
compounds

Toluene diamine (c)

100 1000 10000

Molar Mass
100 1000 10000
Molar Mass Fig. 5. GPC patterns of unrefined polyols yielded from the decomposition of
sample 3 with various polyurethane/DEA molar ratios from 1/3.3 to 1/0.67.
Fig. 4. GPC patterns of upper and lower layers yielded from the decomposition (a) Polyurethane/DEA ¼ 1/3.3, (b) polyurethane/DEA ¼ 1/1, (c) polyure-
of sample 3 (calibration: polystyrene standard). thane/DEA ¼ 1/0.67 (calibration: polystyrene standard).
3358 H. Watando et al. / Polymer Degradation and Stability 91 (2006) 3354e3359

60
refined polyol
unrefined polyol
50

40

Hardness (A)
Intensity

30

20
refined polyol 1
refined polyol 2
10 unrefined polyol 1
unrefined polyol 2

100 1000 10000 0

0 20 40 60 80 100
Molar mass
Content of unrefined / refined polyol (wt%)
Fig. 6. GPC pattern of unrefined and refined polyols (calibration: polystyrene
Fig. 7. The hardness of the reclaimed elastomer with unrefined or refined
standard).
polyol.

The tensile strength of reclaimed elastomer increased in the decomposed product by distilling out of amines was effec-
proportion to the content of both unrefined and refined polyols tive for improving the recycling rate to 100% based on the pol-
as shown in Fig. 9. yol. This result highlights the advantage of reclamation of
This seems to be attributable to the same reason as the in- elastomer from polyurethane foam, compared with the
crease in hardness. In the case of the elastomer containing the reclamation of the same foam, whose content of unrefined
unrefined polyol, the tensile strength increased. It was caused polyol was a maximum of 5%. The reclaimed elastomer can
by the increase of the cross-linking density and the amount of be applied to sealing compounds, molded elastomers and
hard segment depends on the urea bond between amines and printer rolls, although further development for each use is
isocyanate. On the other hand, the tensile strength of re- required.
claimed elastomer with refined polyol depended on the content We have found that the characteristics of the reclaimed
much less than that with unrefined polyol. That was because elastomer, such as the tensile strength, the elongation and
the tensile strength was related to the elongation, and the de- the hardness, can be controlled by changing the content of un-
gree of the increase of the tensile strength was smaller than the refined/refined polyol. The tensile strength and the hardness
hardness because of the influence of the decrease of the
elongation.
2000
4. Conclusion refined polyol 1
refined polyol 2
We have confirmed that used polyurethane foam was de- 1600 unrefined polyol 1
composed into a mixture of polyol and amines by an extruder unrefined polyol 2
with diethanolamine (DEA) as a decomposing agent and ho-
mogeneous reclaimed elastomer can be obtained equivalent
Elongation (%)

1200
to up to 80% of the content of the decomposed product in
the case without purification. In addition, the purification of
800

Table 4
Viscosity of various polyols: unrefined polyol, refined polyol (sample 3) and
virgin polyol 400
Sample Viscosity (mPa s) Molecular weight
per hydroxyl group
Unrefined polyol 1100 342 0
0 20 40 60 80 100
(sample 3)
Refined polyol 440 921 Content of unrefined / refined polyol (wt%)
(sample 3)
Fig. 8. The elongation of the reclaimed elastomer with unrefined or refined
Virgin polyol 340 1000
polyol.
 H. Watando et al. / Polymer Degradation and Stability 91 (2006) 3354e3359 3359

2.5 Our result is promising in regard to the practical possibility

of urethane recycling.

2.0
Tensile Strength (MPa)

Acknowledgement
1.5
We wish to thank Toyo Tire and Rubber Co., Ltd. for pro-
viding the flexible polyurethane foam.
1.0

refined polyol 1
References
refined polyol 2
0.5
unrefined polyol 1
[1] Morgan RE, Dean GH. Polyurethane World Congress. Nice, France;
unrefined polyol 2
1991. p. 120.
0.0 [2] Law WK, Patel T. Polym Recycl 1997/1998;3:269.
0 20 40 60 80 100 [3] Modesti M. Adv Urethane Sci Technol 1996;13:237.
Content of unrefined / refined polyol (wt%) [4] Campbell GA, Meluch WC. J Appl Polym Sci 1977;21:581.
[5] Simioni F, Bisello S. Cell Polym 1983;2:281.
Fig. 9. The tensile strength of the reclaimed elastomer with unrefined or re- [6] Xue S, He F. Kobunshi Ronbunshu 1993;50:847.
fined polyol. [7] Ulrich H, Odinak A, Tucker B. Polym Eng Sci 1978;18:844.
[8] Japanese Urethane Industrial Institute. Polyurethanes recycle & recovery.
Technical report; 1993. p. 4.
increase in proportion to the content of unrefined/refined pol- [9] Kanaya K, Takahashi S. J Appl Polym Sci 1994;51:675.
yol. On the other hand, the elongation decreases as the content [10] Satoh S, Kubota N. Japan Tokkyo Koho 1968;PS43-14959.
of unrefined/refined polyol increases. [11] Iwata T. Polyurethane resin handbook. Nikkan Kogyo Shimbun; 1987.