Materials Chemistry and Physics 124 (2010) 163167

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Chemical modication of exible and rigid poly(vinyl chloride) by nucleophilic

substitution with thiocyanate using a phase-transfer catalyst
Tomohito Kameda, Yuuzou Fukuda, Guido Grause, Toshiaki Yoshioka
Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan

a r t i c l e

i n f o

Article history:
Received 28 August 2009
Received in revised form 1 June 2010
Accepted 4 June 2010
Keywords:
Poly(vinyl chloride)
Flexible
Rigid
Nucleophilic substitution
Thiocyanate
Phase-transfer catalyst

a b s t r a c t
The purpose of this study was to examine the effect of a phase-transfer catalyst on the chemical
modication of exible and rigid poly(vinyl chloride) (PVC) by substituting chloride with thiocyanate
(SCN) in order to develop a new process for recycling PVC. The effects of temperature and time on
the reaction of a SCN/ethylene glycol (EG) solution on PVC were investigated in the presence and
absence of tetrabutylammonium bromide (TBAB) as a phase-transfer catalyst. TBAB was found to accelerate the dehydrochlorination of both exible and rigid PVC, thus allowing the reaction to take place
over shorter reaction times. The substitution yield and substitution/dehydrochlorination ratio were
higher in the presence of TBAB than in its absence. By reducing the reaction temperature, the substitution/dehydrochlorination ratio increased, and substitution occurred more rapidly when TBAB was
present. The differences between exible and rigid PVC were negligible. Together, these results indicate that the phase-transfer catalyst TBAB is effective in accelerating the substitution of chloride by SCN.
This two-phase reaction allows for the easy separation of the polymer from the solvent without using
other chemicals or thermal processes.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Poly(vinyl chloride) (PVC), a common commodity plastic, can
be classied according to its plasticizer content into exible and
rigid PVC. Flexible PVC has excellent processability and is commonly used as agricultural foil, wire coating material, and oor
covering. On the other hand, rigid PVC is characterized by its excellent mechanical strength, making it useful for pipes, joints, and as
a construction material. A reasonable percentage of agricultural
foils is recycled into oor coverings, and wire coatings and pipes
can be reused after mechanical recycling. The VINYLOOP process,
developed by SOLVAY in Belgium, uses a solvent for the separation of PVC and additives. However, most of the PVC is landlled,
since thermal processes such as incineration and pyrolysis result
in the release of HCl, which tends to cause corrosion of the facility.
Furthermore, the products of liquid pyrolysis such as oil contain
chlorinated organic compounds, making it impossible to use them
as fuel or feedstock. Accordingly, various methods for separating
the chlorine from organic products have been studied to promote
the recycling of waste PVC [19].
In our laboratory, we have demonstrated wet treatment
processes for waste PVC, using either aqueous NaOH at high

Corresponding author. Tel.: +81 22 795 7211; fax: +81 22 795 7211.
E-mail address: [email protected] (T. Yoshioka).
0254-0584/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.06.011

temperature and pressure [1013] or NaOH/ethylene glycol (EG)

solution under atmospheric pressure [14,15]. In the latter case,
we found that the hydroxide-catalyzed dehydrochlorination reaction occurred due to a combination of E2 and SN 2 mechanisms
(Scheme 1) [14,15]. This discovery allowed us to develop new
polymers from waste PVC by introducing new functional groups
(Scheme 2). In a previous study, we found moderate substitution of
Cl by thiocyanate (SCN) in addition to the elimination of HCl [16].
The obtained polymer is expected to have antibacterial properties.
The reaction time and temperature of this hydroxide-catalyzed
dehydrochlorination can be reduced by employing a phase-transfer
catalyst. Even under mild conditions (70 C and under atmospheric
pressure), we observed considerable dehydrochlorination in aqueous NaOH at a yield of up to 80% [1719]. We also found that the
efciency of the catalyst depended strongly on the size of the catalyst molecule. Since tetrabutylammonium bromide (TBAB) was the
most effective phase-transfer catalyst, we have also used this catalyst in the present work. Thiobenzoate was used as a nucleophile for
investigating the PVC chain conguration [20,21]. Various nucleophiles were used for the surface modication of PVC [2224].
Scheme 3 shows the reaction mechanism for the phase-transfer
catalyzed substitution (e.g. of Cl in PVC by SCN). Since SCN is
unable to penetrate the organic phase due to the size of the solvation shell and its own polarity, a phase-transfer catalyst is used
as a vehicle for the SCN ion. The catalyst is generally the halide of
a quaternary amine or phosphine, bearing lipophilic alkyl groups.

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T. Kameda et al. / Materials Chemistry and Physics 124 (2010) 163167

Table 2
Composition of the rigid PVC used.
(wt.%)
PVC
MBS
Sn stabilizer
Monoglycelide
Processing aid
LDPE
Pigment

Scheme 1. Mechanism for the dehydrochlorination of PVC in a NaOH/EG solution.

82.4
13.2
2.47
0.99
0.82
0.082
0.012

MBS: methyl methacrylate/butadiene/stylene = 15/70/15.

LDPE: low density polyetylene.

2.2. Methods

Scheme 2. Reaction formula for the substitution of Cl in PVC by Nu.

The SCN/EG solution was prepared by dissolving KSCN (molar SCN/ClPVC ratio:
4) in EG. A SCN/EG solution (50 mL) was placed in a 100 mL ask, to which was
added the phase-transfer catalyst tetrabutylammonium bromide (TBAB) (molar
TBAB/ClPVC ratio: 0.25). The ask was heated to the required temperature using
a silicone oil bath under a N2 ow of 100 mL min1 . After reaching the required
temperature, 1.0 g of PVC powder was added to the solution, and the mixture was
stirred for a specied time. After cooling the ask with water, the reaction solution
was ltered. The solid residue was washed with deionized water and methanol, and
dried under reduced pressure.
2.3. Characterization

Scheme 3. Reaction mechanism for the substitution of Cl by SCN in PVC in the

presence of a phase-transfer catalyst.

It can easily penetrate the organic phase with SCN as the counter
ion and replace the Cl , which in turn is transported back into the
liquid phase. This can lead to a reduced reaction time and hence to
an improved substitution yield, since the zipper mechanism [25],
responsible for the fast dehydrochlorination of PVC, does not occur.
This study reports the effect of a phase-transfer catalyst on the
chemical modication of exible and rigid PVC by substituting Cl
with SCN. The effects of the temperature and reaction time on the
dehydrochlorination of PVC in a SCN/EG solution in the presence of
the phase-transfer catalyst TBAB were investigated.
2. Experimental
2.1. Materials
The compositions of the exible and rigid PVC samples used are presented in
Tables 1 and 2, respectively. The exible PVC consisted primarily of PVC, CaCO3 as a
ller, and diisononyl-phthalate (DINP) as a plasticizer. The Cl content was 20.6 wt.%.
The rigid PVC consisted primarily of PVC, methyl methacrylate/butadiene/styrene
(MBS) as an impact modier, and a Sn stabilizer. The Cl content was 46.5 wt.%. PVC
pellets 4 mm in size were ground while being cooled with liquid nitrogen, and then
sieved to obtain particles between 150 and 250 m in size.
The PVCs and other reagents were purchased from Kanto Chemical (Tokyo,
Japan) and Wako Pure Chemical Industries (Osaka, Japan). KSCN was used as the
source for SCN and as a nucleophile.

The Cl concentration of the ltrate was determined by a Dionex DX-100 ion

chromatograph and a Dionex model AS-16A column (eluent: 35 mM NaOH). The
residue was burnt at 850 C under an air ow of 100 mL min1 , and the evolved gas
was quenched by water and hydrogen peroxide water traps. The Cl in the residue
was determined by analyzing the solutions in the traps using ion chromatography.
The contents of C, H, N, and S in the residue were determined by combustion analysis.
The residue was also analyzed by Fourier transform infrared spectroscopy (FT-IR).

3. Results and discussion

3.1. Flexible PVC
Fig. 1 shows the effect of TBAB on the dehydrochlorination yield
for exible PVC in a SCN/EG solution. The dehydrochlorination yield
was calculated as the ratio of the Cl content in the ltrate to that in
the original PVC. The addition of TBAB signicantly accelerated the
reaction. The reaction rate at 150 C was low, resulting in a dehydrochlorination yield of only 7.9% after 24 h. In contrast, after the
addition of TBAB, a dehydrochlorination yield of almost 50% was
achieved after 12 h. Increasing the temperature to 190 C resulted
in further improvement of the dehydrochlorination yield, which
reached 93.4% after 6 h without TBAB and 98.7% after 3 h with
TBAB. Therefore, in the presence of TBAB, nearly complete dehy-

Table 1
Composition of the exible PVC used.
(wt.%)
PVC
CaCO3
DINP
Chlorinated parafn
Alkylbenzene
Pb stabilizer
Calcium stearate
Wax
DINP: C6 H4 (COOC9 H20 )2.

36.8
28.3
23.9
6.99
1.84
1.10
0.74
0.37
Fig. 1. Effect of TBAB on the dehydrochlorination yield of exible PVC in a SCN/EG
solution.

T. Kameda et al. / Materials Chemistry and Physics 124 (2010) 163167

Fig. 2. Effect of TBAB on the substitution of Cl by SCN and the elimination of HCl,
resulting in the dehydrochlorination of exible PVC. Conditions: (a) 150 C, 24 h; (b)
150 C, 12 h + TBAB; (c) 190 C, 6 h and (d) 190 C, 3 h + TBAB.

Scheme 4. Reaction formula for the substitution of Cl by Nu and the elimination of

HCl in the dehydrochlorination of PVC.

drochlorination was achieved within half the time required in its

absence.
As shown in Scheme 1, the dehydrochlorination of exible PVC
is caused by the substitution of Cl by Nu, resulting in the elimination of HCl. Based on the elemental analysis of the residue, the
effects of TBAB on the substitution of Cl by SCN and the elimination
of HCl were examined at 150 and 190 C (Fig. 2). The substitution
and elimination yields were calculated from the ratios of y and z
to n, according to Scheme 4. The sum of the substitution and elimination yields is the dehydrochlorination yield of PVC, expressed
by the ratio of (y + z) to n. The substitution yield in the absence of
TBAB was 3.2% and 22.4% at 150 and 190 C, respectively. The substitution yield rose after the addition of TBAB and reached 24.6% and
26.1% at 150 and 190 C, respectively. It is noteworthy that the presence of TBAB resulted in higher substitution yields independent of
temperature. The ratio of substitution to dehydrochlorination (the
sum of substitution and elimination) increased after adding TBAB
from 0.41 to 0.50 and from 0.24 to 0.26 at 150 and 190 C, respectively. This increase might be caused by the catalytic effect of TBAB,
allowing the substitution to approach equilibrium conditions more
quickly while not affecting the elimination of HCl.

165

Fig. 3. Yields of the substitution of Cl by SCN and the elimination of HCl in the
presence of TBAB, resulting in the dehydrochlorination of exible PVC at low temperatures: (a) at 100 C for 48 h and (b) at 130 C for 24 h.

The results above clearly show that substitution works better at

lower temperatures. Further reductions in the temperature caused
a further rise in the substitution/dehydrochlorination ratio, which
reached 0.75 after 24 h at 130 C and 0.86 after 48 h at 100 C (Fig. 3).
It should be noted, however, that these high yields came at the cost
of signicantly longer reaction times. In both cases, the degree of
dehydrochlorination was low while the substitution ratio was high,
indicating that it is possible to upgrade the PVC and maintain its
original properties.
It is known that increasing the length of the conjugated C C
double bonds results in a change in the color of the product from
white to yellow, orange, red, brown, and black. Fig. 4 shows sample
photographs of a exible PVC and its products obtained after the
reacting the former in a SCN/EG solution in the presence of TBAB
at 100 C (48 h) or 130 C (24 h). The color of the product changed
to dark gray at 130 C (Fig. 4(c)), indicating the presence of conjugated C C double bonds and progress of the E2 reaction. In contrast,
the color of the product obtained at 100 C (Fig. 4(b)) was similar
to that of the original exible PVC (Fig. 4(a)). This indicates the
absence of the zipper mechanism, which is known to be responsible for the formation of conjugated C C double bonds during the
dehydrochlorination of PVC; it corresponds to the decline in the
number of double bonds observed at lower temperatures (Fig. 3)
[21].
Fig. 5 shows the FT-IR spectra of exible PVC and its products obtained after reacting the former in a SCN/EG solution in the
presence of TBAB at 100 C after 48 h and at 130 C after 24 h, respectively. The absorption bands corresponding to the CH stretching
vibration (around 2900 cm1 ), derived mainly from PVC and DINP,
and the C O stretching vibration (around 1700 cm1 ), derived from

Fig. 4. Photographs of (a) exible PVC, as well as its products obtained from reacting the former with a SCN/EG solution in the presence of TBAB: (b) at 100 C for 48 h and
(c) at 130 C for 24 h.

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T. Kameda et al. / Materials Chemistry and Physics 124 (2010) 163167

Fig. 7. Effect of TBAB on the substitution of Cl by SCN and the elimination of HCl
from rigid PVC. Conditions: (a) 150 C, 24 h; (b) 150 C, 24 h + TBAB; (c) 190 C, 6 h
and (d) 190 C, 3 h + TBAB.

Fig. 6 shows the effect of TBAB on the dehydrochlorination yield

of rigid PVC in a SCN/EG solution. Rigid PVC reacted in a way similar
to exible PVC. The addition of TBAB resulted in a more rapid dehydrochlorination. At 190 C, nearly complete dehydrochlorination
was achieved at after 3 h (99.7%) and 6 h (96.7%) in the presence and
absence of TBAB, respectively. The reaction accelerated markedly at
150 C, increasing the dehydrochlorination yield from 2.2% in the

absence of TBAB to 44.5% in its presence after a reaction time of

24 h. Elemental analysis of the residue claried the effect of TBAB
on the substitution of Cl by SCN and the elimination of HCl at 150
and 190 C (Fig. 7). The substitution yield increased robustly from
0.9% in the absence of TBAB to 23.2% in its presence at 150 C, while
only a moderate rise from 23.3% to 28.4% was observed at 190 C.
The substitution/dehydrochlorination ratio also increased slightly
in the presence of TBAB from 0.43 to 0.52 and from 0.24 to 0.28
at 150 and 190 C, respectively. As was the case with exible PVC,
the reaction shifted strongly towards substitution when the temperature was reduced. The substitution/dehydrochlorination ratio
increased to 0.91 at 100 C after 48 h and to 0.74 at 130 C after 24 h
(Fig. 8). The increase in the ratio of substitution was also visible
in the product colors (Fig. 9). The product at 100 C (Fig. 9(b)) was
almost exactly the same color as that of the rigid PVC (Fig. 9(a)).
Even at 130 C (Fig. 9(c)), there was only a slight change in product color; the orange tinge indicated that the zipper mechanism,
responsible for fast dehydrochlorination of PVC [21], did not occur
at this low temperature. That is, the formation of conjugated C C
double bonds was not observed. (For interpretation of the references to color in this text, the reader is referred to the web version
of the article.)
The FT-IR spectra show the substitution of Cl by SCN (Fig. 10).
The absorption bands derived from the SC N group (around
2150 cm1 ) and the N C S group (around 2050 cm1 ) were
present in products obtained at 100 C after 48 h and at 130 C after

Fig. 6. Effect of TBAB on the dehydrochlorination yield of rigid PVC.

Fig. 8. Yields of the substitution of Cl by SCN and the elimination of HCl from rigid
PVC in the presence of TBAB: (a) at 100 C for 48 h and (b) at 130 C for 24 h.

Fig. 5. FT-IR spectra of (a) exible PVC, as well as its products obtained from reacting
the former with a SCN/EG solution in the presence of TBAB: (b) at 100 C for 48 h
and (c) at 130 C for 24 h.

DINP, are visible in all the FT-IR spectra. The FT-IR spectrum of the
product obtained at 130 C (Fig. 5(c)) differs markedly from those
of the exible PVC and the product obtained at 100 C. Fig. 5(a) and
(b) shows the absorption bands of the C C stretching vibrations
(16001750 cm1 ), consistent with the elimination of HCl by an E2
mechanism. The FT-IR spectra also conrm the substitution of Cl by
SCN following an SN 2 mechanism. Both the SC N group (around
2150 cm1 ) and the N C S group (around 2050 cm1 ), obtained
as a result of the isomerization of the SC N group, were observed
in the FT-IR spectra of both products.
3.2. Rigid PVC

T. Kameda et al. / Materials Chemistry and Physics 124 (2010) 163167

167

Fig. 9. Photographs of (a) rigid PVC, and its products after dehydrochlorination in the presence of TBAB: (b) at 100 C for 48 h and (c) at 130 C for 24 h.

Fig. 10. FT-IR spectra of (a) rigid PVC, and its products after dehydrochlorination in
the presence of TBAB: (b) at 100 C for 48 h and (c) at 130 C for 24 h.

24 h. The rising intensities of their absorption bands with increasing temperature can be explained by an acceleration of the SN 2
reaction under these conditions.
4. Conclusions
TBAB was found to accelerate the dehydrochlorination of exible and rigid PVCs in a SCN/EG solution. Both the substitution yield
and the ratio of the substitution to dehydrochlorination increased
in the presence of TBAB. A further reduction of the temperature
caused a shift in the reaction towards one of substitution.
This behavior can be explained by the lipophilic character of the
phase-transfer catalyst; that is, by increasing the catalyst concentration in the PVC phase, the concentration of SCN also increases
(Scheme 3). Although the equilibrium remains unaffected by the
catalyst, this fosters an accelerated exchange between Cl and SCN.
The increase in the substitution/dehydrochlorination ratio in the
presence of the catalyst occurs because the acceleration of substitution is more than that of elimination.
Overall, the phase-transfer catalyst, TBAB, was found to be very
effective in accelerating the substitution of Cl in PVC by SCN.
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