POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2008; 19: 1391–1395

Published online 25 July 2008 in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/pat.1199

A novel depolymerization of nylons in ionic liquidsy

Akio Kamimura* and Shigehiro Yamamoto
Department of Applied Molecular Bioscience, Graduate School of Medicine, Yamaguchi University, Ube 755-8611, Japan
Received 30 April 2008; Accepted 1 May 2008

Treatment of a polyamide such as Nylon-6 in ionic liquids at 300-C resulted in the effective
depolymerization to monomeric amides, which were readily isolated through direct distillation
from the reaction pot. The ionic liquids were recycled and they still worked as good reaction media
after being used five times. The present method provides a new usage of ionic liquids that will serve
as a key material for realizing zero-emission chemical recycling process of plastics. Copyright # 2008
John Wiley & Sons, Ltd.

KEYWORDS: ionic liquids; polyamides; depolymerization; DMAP

INTRODUCTION reactions, special care must be taken to prevent fire. It is

Plastics are indispensable materials for our daily life and are
widely used in many types of products. The advantages of
plastics are that they are light, robust, and nonperishable.
However, after several decades of manufacture, plastics
are increasingly becoming waste materials. Once they are
considered as a waste product, their wonderful merits
turn into formidable demerits for waste treatment. For
example, the merits of lightness and robustness change to
demerits of bulkiness and hardness. It is important to
remember that plastics originally are carbon resources
obtained from petroleum; therefore, they should be treated
in a recycling scheme. There are several methods of plastic
recycling, e.g. material recycling, energy recycling, and
monomer recycling. Among these, monomer recycling is the
best from the viewpoint of preserving carbon resources
because it produces recycled plastics from waste ones.1 For
this purpose, the following three chemical treatments are
needed: depolymerization of waste plastics, purification of
recovered monomers, and polymerization for preparing
recycled plastics. The first reaction is the most important
step.
In general, treatment of polymers at high temperatures
results in depolymerization to give monomers and their
decomposed compounds. Thermolysis,2 high temperature
solvolysis,3 and supercritical fluids4–13 are frequently used
for this purpose. A high boiling point solvent or high-
pressure apparatus is usually required to achieve these
conditions. If organic solvents are employed for these
also important to control the depolymerization reaction in a
selective manner for the effective recycling of waste plastics,
because this is crucial to carry out the subsequent
polymerization successfully. Thus, there remain many
problems to be solved to achieve an ideal depolymerization
reaction.
Ionic liquids are a new reaction medium that has quite
unique features compared to other conventional organic
solvents.14–21 During the course of our study for developing
an efficient method for the depolymerization,21,22 we were
interested in using ionic liquids for these reactions. In
particular, less flammability and non-volatility are very
attractive features that would allow us to perform the
depolymerization reaction under a normal atmosphere in
ordinary glassware. When we launched our research,
no reports on the application of ionic liquids in the
depolymerization reaction had hitherto been published.23,24
Among the plastics or polymers, we examined polyamides
for depolymerization in ionic liquids, because polyamides
such as nylon are one of the most common polymers used in
daily life and are produced in vast amounts each year.
However, only a few successful depolymerization reactions
of polyamides have been reported thus far.25–35 In this paper,
we report full details of an innovative method for the
depolymerization of polyamides in ionic liquids.36
EXPERIMENTAL

*Correspondence to: A. Kamimura, Department of Applied Mol-
ecular Bioscience, Graduate School of Medicine, Yamaguchi
University, Ube 755-8611, Japan.
E-mail: ak10@yamaguchi-u.ac.jp
y
This study was presented at the Second International Congress
on Ionic Liquids (COIL-2), August 2007, Yokohama, Japan.
Contract/grant sponsor: Grant-in-Aid for Scientific Research on
Priority Areas, Science of Ionic Liquids.
General
All 1H and 13C NMR spectra were measured in CDCl3 and
recorded on a JEOL EX-270 (270 MHz for 1H and 67.5 MHz
for 13C) spectrometer. GC-MS analyses were performed with
a Shimadzu QP-2010 GC-MS spectrometer. All of the
reactions mentioned in this paper were performed under a
nitrogen atmosphere unless otherwise stated. Ionic liquids
were purchased from Kanto Chemical Co. Ltd.

Copyright # 2008 John Wiley & Sons, Ltd.

1392 A. Kamimura and S. Yamamoto

The depolymerization of Nylon-6 in [emim][BF4]

Nylon-6 (0.5 g, mean molecular weight ¼ 22,000) was added
to a solution of DMAP (0.025 g) in [emim][BF4] (5 ml) and the
mixture was allowed to heat to 3008C for 5 hr with vigorous
stirring. The reaction mixture became a homogeneous black
oil. After cooling, the reaction mixture was extracted with
ether (10 ml
25) and the ether phase was combined and Scheme 1.
concentrated. A crude product was obtained in 0.3175 g,
which showed the identical retention time and EI-fragment
pattern to those of commercially available caprolactam. The
purity of the crude product was determined to be 67.7% by
GC analysis. The yield of 1 was estimated to be 43% (0.215 g).

General procedures for the depolymerization of Nylon-6

in [PP13][NTf2] by direct distillation Scheme 2.
Nylon-6 (0.2055 g, mean molecular weight ¼ 22,000) was
added to a solution of DMAP (0.0148 g) in [PP13][NTf2] (2 ml) ization would take place. Extraction of the ionic liquid with
and the resulting mixture was heated at 3008C for 1 hr. The ether gave the desired caprolactam 1 in 43% yield (Scheme 1).
reaction mixture became a yellow oil, which was placed in a However, this manipulation was quite problematic, because
Kugel-Rohr apparatus and heated at 3008C under 0.5 mmHg. 25 repeated extractions were required to isolate 1.
The resulting monomerized caprolactam was collected in To improve the yield and manipulation in the isolation
86% yield (0.1762 g). White solid; mp; 65–668C (lit. step, direct distillation of 1 from the reaction pot was
68–718C);37 1H NMR (CDCl3) d 1.82–1.62 (m, 6 H), 2.47 (t, examined. Fortunately, the boiling point of 1 was not very
J ¼ 5.5 Hz, 2 H), 3.21 (dd, J ¼ 5.9, 9.9 Hz, 2 H), 6.08 (br, 1 H); high (lit. 136–1388C/10 mmHg)37 so compound 1 was
13
C NMR (CDCl3) d 23.1, 29.6, 30.5, 36.7, 42.7, 179.4; m/z 113 expected to be vaporized under such high temperature
(Mþ, 100), 85 (Mþ–CO, 52), 55 (87), 42 (60). conditions when the reaction vessel was subjected to reduced
pressure. Ionic liquids were non-volatile and could not be
Repeated use of [PP13][NTf2] for the depolymerization distilled under these conditions. We used a Kugel-Rohr
reaction of Nylon-6 apparatus (bulb-to-bulb distillation) and succeeded in
[PP13][NTf2], which was used in the above-mentioned collecting 1 directly from the reaction pot heated at 3008C.
procedure, was again mixed with Nylon-6 (0.1986 g) and This improvement not only reduced the laborious isolation
DMAP (0.0108 g) and heated in the same manner. Com- work dramatically but also improved the yield of 1.
pound 1 was isolated in 84% yield (0.1678 g). In the third use, With this new experimental procedure in hand, the
the reaction between Nylon-6 (0.2009 g) and DMAP (0.0122 g) depolymerization reaction was examined with various ionic
gave caprolactam 1 in 87% yield (0.1757 g). In the fourth use, liquids (Scheme 2). The results are summarized in Table 1.
the reaction between Nylon-6 (0.2037 g) and DMAP (0.0110 g) The depolymerization of Nylon-6 in [PP13][NTf2] pro-
gave caprolactam 1 in 77% yield (0.1569 g). In the fifth use, ceeded smoothly and 1 was isolated in 86% yield (entry 2).
the reaction between Nylon-6 (0.2004 g) and DMAP (0.0109 g)
gave caprolactam 1 in 78% yield (0.1558 g). Table 1. Depolymerization reaction of Nylon-6 in various
ionic liquids
General procedures for the depolymerization of Nylon-12 DMAP Temp 1; yield
in [PP13][NTf2] by direct distillation Entry Ionic liquid (wt%) (8C) (%)a Limp/LNMRb
Nylon-12 (0.2011 g, mean molecular weight ¼ 22,000) was
1 [PP13][NTf2] 0 300 55
added to a solution of DMAP (0.0114 g) in [PP13][NTf2] (2 ml)
2 [PP13][NTf2] 5 300 86
and the resulting mixture was heated at 3008C for 1 hr. The 3 [PP13][NTf2] 5 270 7
reaction mixture became a yellow oil, which was placed in a 4 [PP13][NTf2] 5 330 55 (8)c
Kugel-Rohr apparatus and heated at 3008C under 0.5 mmHg. 5 [PP13][NTf2] 5 350 6 (7)c
The resulting monomerized 2 was collected in 7% yield 6 [TMPA][NTf2] 5 300 79 0.65
(0.0143 g). 1H NMR (CDCl3) d 1.33 (m, 14H), 1.51 (m, 2H), 1.68 7 [TMPA][NTf2] 5 270 82 0.65
8 [TMPA][NTf2] 5 330 77 (2)d 0.65
(m, 2H), 2.30 (m, 2H), 3.31 (m, 2H), 5.47 (br, 1 H); 13C NMR 9 [TMPA][NTf2] 5 350 61 (6)d 0.65
(CDCl3) d 23.9, 24.7, 24.9, 25.3, 25.7, 26.2, 26.4, 26.8, 28.4, 37.0, 10 [P13][NTf2] 5 300 77
39.1, 173.4; m/z 197 (Mþ, 50), 168 (20), 154 (30), 140 (25), 126 11 [bmim][NTf2] 5 300 35 0.61
(30), 112 (45), 100 (80), 86 (55), 73 (50), 55 (100), 41 (90). 12 [P14][NTf2] 5 300 56 0.70
13 [aeim][NTf2] 5 300 72
14 [DEME][NTf2] 5 300 49
RESULTS AND DISCUSSION 15 [TMPA][Br] 5 300 0
16 [TMPA][BF4] 5 300 0
The first depolymerization reaction for Nylon-6 was carried a
Isolated yield.
out in [emim][BF4]. Treatment of Nylon-6 in this ionic liquid b
Reference 38.
at 3008C for 5 hr resulted in the formation of a homogeneous c
Yield of N-propylcaprolactam in parenthesis.
d
mixture of ionic liquid so we thought that some depolymer- Yield of N-methylcaprolactam in parenthesis.

Copyright # 2008 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2008; 19: 1391–1395
DOI: 10.1002/pat

Figure 1. NMR spectra of [TMPA][NTf2] after being used five times for the depo-
lymerization of Nylon-6.
The presence of 5 wt% of DMAP was important to increase
the yield of 1 (entry 1). It seems that 3008C was the optimum
temperature for efficient reaction; the reaction rate at 2708C
was very slow and almost no depolymerization occurred
(entry 5). On the other hand, the temperatures above 3308C
were too high to allow selective depolymerization (entries 4,
5); the yield of 1 decreased and the formation of N-alkylated
caprolactam was observed in the crude reaction mixture.
Similar results were obtained in the reaction with
[TMPA][NTf2] (entries 6–9). The formation of the side
products indicated that some portion of the ionic liquids
decomposed during the reaction above 3308C. NMR spectra
of [TMPA][NTf2] clearly showed that the decomposition
occurred during the reaction (Fig. 1). The spectra of the ionic
liquids treated over 3308C looked somewhat broader than
those of original [TMPA][NTf2]. This may be partially due to
Figure 2. Yield of 1 in the reaction using recycled ionic liquids for the depolymer-
ization of Nylon-6.
Copyright # 2008 John Wiley & Sons, Ltd.
Depolymerization of nylons in ionic liquids 1393
the high temperature conditions which induced the reaction
between compound 1 and the cationic part of the ionic liquid.
The yields of 1 depended on the cationic part of the ionic
liquid. For example, quaternary ammonium type ionic
liquids usually offered better results of 1 than imidazorium
type ionic liquids (Table 1, entries 10–14). The anionic part
was also important for the reaction. [NTf2] was the best anion
and other anions such as [BF4] and [Br] provided poor results
(entries 15 and 16). Thus, the ionic liquids such as
[PP13][NTf2] and [TMPA][NTf2] were found to be the best
ones for the depolymerization reaction.
We next examined the repeated use of ionic liquids. The
results are summarized in Fig. 2.
Ionic liquids such as [PP13][NTf2] and [TMPA][NTf2]
underwent depolymerization smoothly to give 1 in over 80%
yields throughout the reaction from the first to the fifth use. It
Polym. Adv. Technol. 2008; 19: 1391–1395
DOI: 10.1002/pat
1394 A. Kamimura and S. Yamamoto
Scheme 3.
Table 2. Depolymerization reaction of Nylon-12
[PP13][NTf2]
Times 1 2 3 4
2; yield (%)a 7 10 14 17
a
Isolated yield.
should be mentioned that these ionic liquids were useful
even after exposure to such high temperature conditions. The
reaction with [DEME][NTf2] and [P14][NTf2] proceeded
sluggishly and gave 1 in moderate yields. The yields of 1
were improved as the reaction time increased. For example,
treatment of Nylon-6 in [bmim][NTf2] gave 1 in 35% yield for
the first time, and 80% in the third time. This may be partially
due to the fact that the remaining Nylon-6 or its oligomers in
the ionic solvent were monomerized in the second or later
reactions.
Nylon-12, another widely used polyamide, was examined
for the present depolymerization (Scheme 3). Treatment of
Nylon-12 in [PP13][NTf2] in the presence of catalytic
amounts of DMAP at 3008C under reduced pressure resulted
in the distillation of 2. The results are summarized in Table 2.
Although the desired depolymerization took place, the yield
of 2 was rather low. The ionic liquid could be used five times,
but the yield of 2 remained low.
The depolymerization of polyamide is a type of solvolysis
reaction in which the amide group in the polymer chain
undergoes addition–elimination cleavage by nucleophilic
attack. The reaction rate for these types of reactions is usually
affected by the polarity of the solvent. Thus, a highly polar
solvent is expected to accelerate the reaction rate. An ionic
liquid such as [TMPA][NTf2] shows higher Limp/LNMR
value, an ionicity parameter, is dissociative, and it acts as a
highly polar solvent.38–42 On the other hand, [bmim][NTf2],
which has lower Limp/LNMR value than [TMPA][NTf2], is
associative and less polar than [TMPA][NTf2]. As a result, the
reaction rate of the present depolymerization should be high
in [TMPA][NTf2] and low in [bmim][NTf2]. This is probably
the reason why [TMPA][NTf2] and [PP13][NTf2] promoted
the depolymerization smoothly.
When polyamide is mixed with ionic liquid, there are no
external nucleophilic species that attack the carbonyl carbon
(Scheme 4). Consequently, the terminal amino group in
polyamide is supposed to be the strongest nucleophile in the
reaction mixture. When the amino group attacks the adjacent
carbonyl group, the polyamide chain automatically gives 1
and next terminal amino group, which attacks the next
Copyright # 2008 John Wiley & Sons, Ltd.
in
5
9
Scheme 4.
carbonyl carbon to cleave the polyamide chain succes-
sively.43,44 This is probably a reason why Nylon-6 afforded 1
in good yield. DMAP should catalyze this intramolecular
stepwise cleavage process by attacking the carbonyl group,
resulting in the acceleration of the reaction rate very much.
On the other hand, the depolymerization of Nylon-12 is not
easy because the terminal amino group is hard to attack to
the adjacent carbonyl group due to the macrocyclic
formation. As a result, the depolymerization rate through
this mechanism is slow in Nylon-12 and the yield of 2
remained low.22
CONCLUSION
We have successfully developed a new depolymerization
method for polyamide using ionic liquids. The present
procedure could be performed under normal pressure with
no concerns over fire hazards. It was performed in normal
glassware and never required a high-pressure apparatus.
The monomer, caprolactam, was isolated directly from the
reaction pot, which resulted in the reduction of laborious
isolation work and improved the yield of 1 dramatically. This
simple manipulation also reduced chemicals which were
usually necessary to use during the isolation procedure. Ionic
liquids were reused at least five times, and the yields of
caprolactam were high. All of these features of the present
reaction will provide a new concept toward developing a
zero-emission chemical recycling system, in which ionic
liquids will exhibit their own very unique features that have
never been seen in any other organic solvent.
Acknowledgments
This work was partially supported by a Grant-in-Aid for
Scientific Research on Priority Areas, Science of Ionic Liquids
(2005–2009), from the Ministry of Education, Culture, Sports,
Science and Technology, Japan. We thank Professor
Masayoshi Watanabe, Yokohama National University, for
helpful suggestions.
Polym. Adv. Technol. 2008; 19: 1391–1395
DOI: 10.1002/pat

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DOI: 10.1002/pat