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Degradation of PVC waste into a flexible polymer

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by chemical modification using DINP moieties†

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Cite this: RSC Adv., 2019, 9, 28870

Lihui Lu,a Shogo Kumagai,a Tomohito Kameda,a Ligang Luo *b

and Toshiaki Yoshioka*a

In consideration of the toxicity and high migration capacity of plasticizers, the possibility to obtain flexible
PVC via chemical modification of PVC was investigated for feedstock recycling. In this work, some Cl atoms
of PVC were substituted with fragments of the common plasticizer DINP (diisononyl phthalate) in the
presence of K2CO3 (potassium carbonate) or DIEA (N,N-diisopropylethylamine), and the simultaneous
elimination of PVC was suppressed. 1H NMR (1H nuclear magnetic resonance spectroscopy) and 1H–1H
COSY (1H–1H correlation spectroscopy) were used to evaluate the substitution while a novel method of
calculating the substitution and elimination ratios was developed using a combination of 1H NMR and
elemental analysis. A maximum substitution rate of 35.7% was achieved using thiophenol as
a nucleophile in the presence of DIEA, while the corresponding elimination of HCl was just 4.4%. In
addition, the thermal stability of the modified PVCs was very close to that of pure PVC, which suggested
Received 4th July 2019
Accepted 27th August 2019
that the main characteristics of PVC were preserved. Moreover, the Tg values of all the modified PVCs
were less than that of PVC, which means it is feasible to improve the plasticity of PVC via substituting
DOI: 10.1039/c9ra05081g
some Cl on PVC with DINP moieties. Therefore, an alternative approach for feedstock recycling of PVC
[Link]/rsc-advances by chemical modification was developed in this work.

chlorinated organic during pyrolysis treatment, which was

Introduction limited various recycling demands.8 Therefore, a series of
Plastics are inexpensive, lightweight, durable and corrosion- strategy were investigated on the migration of Cl, such as
resistant, with high thermal and electrical insulation proper- thermal degradation,4,9–11 chemical modication,12–14 hydro-
ties. The diversity of polymers and the versatility of their prop- thermal process in supercritical or subcritical water,15–18 near-
erties are used to make a vast array of products that bring critical methanol process for dechlorination of PVC and addi-
medical and technological advances, energy savings and tives recovery,19 and near-critical aqueous ammonia process.20
numerous other societal benets.1–3 A world without plastics Among them, chemical modication of PVC is a famous tech-
seems unimaginable today. However, plastic waste is a growing nique that allows addition of new functionalities to PVC while
social problem, because of loss of natural resources, depletion maintaining its primary characteristics by substituting some Cl
of landll space, and environmental pollution, especially for the atoms with various nucleophilic reagents.21–24 In previous study,
marine environment.4,5 Therefore, fuel and feedstock recycling the properties of gas transport,21 luminescence,22 antibacte-
of plastic wastes has attracted widespread attention around the rial,23 and plasticity24 have been improved by graing different
world. functional groups to substitute Cl atoms on PVC. In particular,
As one of the most important chlorinated plastics, PVC has P. Jia et al. investigated self-plasticization of PVC materials via
been widely used in manufacturing pipes,3 cable insulation,4 chemical modication with phosphorus containing castor oil
lms,5 building materials,6 medical materials7 and so on. based derivatives,14 cardanol groups,24 aminated tung oil methyl
However, it is a great challenge to treat with PVC waste due to its ester,25 and mannich base such as cardanol butyl ether13 and
chlorine content of ca. 58%. Nowadays, the treatment of PVC waste cooking oil methyl ester.26 These ndings transformed
was suffered on the products of corrosive HCl and harmful the traditional plastic processing technology to obtain cleaner
production of internally plasticized PVCs. Therefore, this tech-
a
nique has a great potential to be used for PVC recycling because
Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba,
Aramaki-aza, Aoba-ku, Sendai, Miyagi 980-8579, Japan. E-mail: yoshioka@[Link].
it can convert waste PVC into value-added materials with
[Link]; Fax: +81-22-795-7212; Tel: +81-22-795-7212 improved properties, which can be referred to “upgrade
b
College of Life Science, Shanghai Normal University, 100 Guilin Road, Shanghai recycling”.
200234, China. E-mail: luo_ligang@[Link] Without plasticizer, PVC is a rigid polymer at room
† Electronic supplementary information (ESI) available. See DOI: temperature. Nevertheless, PVC products are normally obtained
10.1039/c9ra05081g

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from the combination of PVC with additives which provides our This was suggested that the thiophenol group was successfully
desired properties to the material.27 The plasticizers, which act graed on PVC backbone, which means the nucleophilic
as spacer between molecules of the polymer, are mainly used to substitution of PVC and thiophenol was efficient in the pres-
reduce the melt viscosity, to decrease the transition temperature ence of K2CO3 as a base.
or to lower the elastic modulus of PVC as it weakens the inter- Subsequently, the 1H NMR spectra was used to identify the
molecular bonds of the polymer which facilitate its process- PVC and the modied PVC with thiophenol. In Fig. 2, one of
ing.27 The most commonly used plasticizer were terephthalate common signal of the chemical shi between 2.25–2.52 ppm is
species, such as diisononyl phthalate (DINP), diethylhexyl attributed to hydrogen atoms a, and the other common signal of
phthalate (DEHP), diisobutyl phthalate (DIBP), di-n-butyl the chemical shi between 4.35–4.52 ppm is attributed to
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phthalate (DBP), and diisodecyl phthalate (DIDP).28 hydrogen atom b.22 Compared to the spectrum of PVC
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However, most of these plasticizers have been banned in the (Fig. 2(A)), there were new peaks of hydrogen atoms c and e
last decades due to their high migration capacity and strong observed in Fig. 2(B). It is obviously noted that a single sharp
toxicity.29,30 Therefore, the possibility to produce exible PVC by peak of the chemical shi appeared around 3.66 ppm, which is
chemical modication using common plasticizer DINP moieties as attributed to the hydrogen atom c of the new produced group
nucleophiles (Fig. 1), which was investigated in this work for (–CH–S–) of the modied PVC with thiophenol. It was suggested
feedstock recycling. The obtained products are environmentally- that a portion of chlorine atoms were already substituted by
friendly while compared with a mixture of PVC and plasticizer. thiophenol and the nucleophilic substitution occurred. More-
However, the main problem is the elimination reaction simulta- over, the signals of hydrogen atoms e are also observed at the
neously occurring with a strong base such like sodium hydroxide chemical shis between 7.25–7.50 ppm.
(NaOH),31 which have effect on the properties of PVC and causes On the other hand, the peak of hydrogen atoms d (CH]CH)
a blackish color, which will narrow the applicability of the recycled is not obviously observed in Fig. 2(B), which was suggested that
PVC. As a result, the effect of potassium carbonate (K2CO3) and the simultaneous elimination of PVC was suppressed under the
N,N-diisopropylethylamine (DIEA) were investigated as a weak reaction condition. Therefore, the rate of dechlorination was
inorganic base and organic base on substitution and elimination, consistent with the ratios calculated from elemental analysis,
respectively. The substitution was evaluated by 1H nuclear which was according to the previously reported methods,32 and
magnetic resonance (1H NMR). Moreover, a novel method of then the corresponding elimination rate could be obtained.
calculating the substitution and elimination rates based on 1H Nevertheless, substitution ratio was calculated from their 1H
NMR and elemental analysis was developed, which is simpler and NMR spectra. In Fig. 2(B), it was showed that the chemical shis
more accurate than the methods used in previous study.32 between 7.25–7.50 ppm is attributed to the hydrogen atoms e
(ve hydrogen atoms) which are from thiophenol before the
reaction, while the chemical shis between 1.95–2.35 ppm is
Results and discussion attributed to the hydrogen atoms a (two hydrogen atoms) which
Conrmation of the substitution of PVC with thiophenol are from PVC before the reaction. Therefore, the substitution
ratio was dened as eqn (1):
At rst, the FT-IR spectra were employed to investigate the
structure between PVC and the modied PVC with thiophenol Substitution ratio [%] ¼ (x/m)/(y/n)  100% (1)
(Fig. S1†). The sharp peaks of PVC at 2969, 2920, 1436 and
606 cm
1 are belong to the alkane C–H stretching vibration, where x and y are the integrals of the corresponding hydrogen
–CH2 deformation vibration and C–Cl stretching vibration, atoms shown in Fig. 2(B), and m ¼ 5 and n ¼ 2 when PVC was
respectively.13,33 Compared to the curve of PVC, it was observed
that several new peaks at 3075, 1575 and 1552 cm
1 were
appeared, which are attributed to C–H stretching vibration of
arene and the skeleton vibration of benzene ring, respectively.34

Fig. 2 1H NMR spectra of PVC and the modified PVC using thiophenol
as a nucleophile (400 MHz, THF-d8, 329.9 K. Reaction conditions:
Fig. 1 Structures of DINP and the nucleophiles investigated in this 500 mg PVC, 1.0 eq. thiophenol, 0.1 eq. K2CO3, 40  C, 50 mL DMF as
work. solvent, 3 h).

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substituted with thiophenol. The elimination ratio was deter-

mined by subtracting the substitution ratio from the dechlori-
nation ratio, as shown in eqn (2):

Elimination ratio [%] ¼ dechlorination ratio [%]
substitution

ratio [%] (2)

To further conrm the substitution of PVC with thiophenol, Scheme 1 Substitution reaction of PVC with thiophenol in the pres-
1
H–1H COSY was also performed for characterization of the ence of K2CO3 or DIEA.
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products. In Fig. 3, the correlation peaks (marked with red

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circles) between hydrogen atoms a and c are observed obviously.

It was indicated that hydrogen atoms a and c were correlated respectively. This was because their corresponding substitution
each other and hydrogen atom c was bonding with the adjacent rates were just 6.5% and 6.3%, respectively. While using DIEA as
carbon of hydrogen atoms a, which was demonstrated that the a base, the degree of substitution for isooctyl thioglycolate was
structure of C6H5–S–CH–CH2– was successfully formed. just 3.7% (Table 1, entry 4), and there was no reaction using 1-
According to the above results, it was considered that thio- octanethiol (Table 1, entry 6), which was showed lower efficiency.
phenol was attacked to the a-position carbon of PVC to replace Therefore, the efficiency condition of substitution was using
Cl atom and produce HCl, which is corresponding with the thiophenol as the nucleophile because the nucleophilic group
previous literature.9,12 Nevertheless, the produced HCl could be C6H5S– is more easily formed under the reaction condition due to
neutralized by the base of K2CO3 or DIEA. Therefore, one part of the conjugation of the benzene ring. In addition, it was suggested
Cl atoms in PVC were successfully substituted by thiophenol, that the effect of isooctyl thioglycolate was shown better than that
which is in accordance with the experimental result from 1H of 1-octanethiol as the nucleophile when both organic and
NMR spectrum in Fig. 2(B) and Scheme 1. inorganic bases were used, probably due to the positive inuence
of electron-withdrawing carbonyl group (C]O). Furthermore,
Characterization of the modied PVCs when thiophenol was the nucleophile, a better performance was
Subsequently, isooctyl thioglycolate and 1-octanethiol were con- obtained using the organic base DIEA, whereas the inorganic
ducted as nucleophilic reagents to modify the PVC sample. And base K2CO3 was a better base when isooctyl thioglycolate and 1-
the dechlorination degrees of PVC using the three different octanethiol were used, as shown in Table 1. Finally, all the
nucleophiles in DMF using K2CO3 or DIEA as bases were elimination ratios of the modied PVC were lower than their
summarized in Table 1. When taking thiophenol as a nucleo- corresponding substitution ratios, probably due to the relatively
phile, the rate of dechlorination was 20.2% in the presence of weak basicity of K2CO3 and DIEA in comparison with NaOH.17
K2CO3 (Table 1, entry 1), while the dechlorination rate was 40.1%
with DIEA as a base (Table 1, entry 2). This was attributed to the
Thermal stability of PVC and the modied PVCs
corresponding high substitution ratios of 17.5% and 35.7%,
respectively. However, when using isooctyl thioglycolate and 1- For conrmation of the thermal stabilities of pure PVC and the
octanethiol in the presence of K2CO3, the dechlorination ratios modied PVC with different nucleophilic reagents using DIEA
were 7.0% (Table 1, entry 3) and 10.7% (Table 1, entry 5), as a base, the thermo-gravimetric and differential thermal
analysis (TG-DTA) of PVC sample were conducted in Fig. 4. At
rst, it was observed that the PVC used in these experiments
showed a weight loss of 5 wt% at an onset temperature (TD-onset)
of 269  C. This may be led by dehydrochlorination of PVC in the
temperature range of about 250–350  C in the main reaction of
the rst stage, which is corresponding with the literature.4
However, a weight loss of 63.1 wt% was observed for unmodi-
ed PVC aer the rst degradation stage, suggesting that the
formed polyene chain could also decomposed during the rst
stage. This is because that ca. 57 wt% of weight loss was ex-
pected from the complete elimination of PVC. As shown in
Fig. 4, it was indicated that the thermal degradation of the
modied PVCs with different nucleophilic groups and dechlo-
rination ratios were showed the similar trend as that of pure
PVC, which also include two distinct stages. Moreover, the
product modied by thiophenol with 40.1% dechlorination
ratio showed a similar degradation character to unmodied
Fig. 3 1H–1H COSY of PVC and the modified PVC with thiophenol
PVC during the rst stage. And its TD-onset is 261  C and the
(400 MHz, THF-d8, 353.0 K. Reaction conditions: 500 mg PVC, 1.0 eq. weight loss of the rst stage is 63.1%. However, it showed
thiophenol, 0.1 eq. K2CO3, 40  C, 50 mL DMF as solvent, 3 h). a different degradation behavior during the second degradation

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Table 1 Degrees of dechlorination, substitution and elimination for the chemical modification of PVC using different nucleophiles and basesa

Elimination
Entry Nucleophile Base Dechlorinationb (%, EA) Substitutionc (%, 1H NMR) (%)

1 Thiophenol K2CO3d 20.2 17.5 2.7

2 DIEAe 40.1 35.7 4.4
3 Isooctyl thioglycolate K2CO3d 7.0 6.5 0.5
4 DIEAe 5.1 3.7 1.4
5 1-Octanethiol K2CO3d 10.7 6.3 4.4
DIEAe
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6 1.0 0 1.0
a
Reaction conditions: 500 mg PVC, 1.0 eq. appropriate nucleophiles, 0.1 eq. K2CO3 or 1.0 eq. DIEA, 40  C, 50 mL DMF as solvent, 3 h. b Results were
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from elemental analysis. c Results were from 1H NMR analysis. d Reaction temperature: 40  C. e Reaction temperature: 110  C.

stage, the temperature range of PVC modied by thiophenol the sample with 17.5% substitution ratio did not have a PVC-
with 40.1% was around 350–480  C, while the temperature like character, which might be attributed to the effect of the
range of the second stage on PVC was approximate 350–525  C, different substituted rates or aromatic nucleophilic group
which was corresponding with the cracking and decomposition (C6H5S–) itself. Then, the sample with 17.5% substitution also
of the dehydrochlorinated PVC.4 The possible cause might be has a signicant degradation in the third stage.
the high substitution ratio (35.7%) and the maximum rate of In Fig. 6, the thermal stability of both 1-octanethiol-
dechlorination (40.1%) resulted from it. Simultaneously, the substituted PVCs slightly reduced in comparison with that of
thermal stability of the products modied by isooctyl thio- PVC during the rst stage, resulting in their TD-onset of 236  C
glycolate and 1-octanethiol with the corresponding dechlori- and 235  C. However, the product with no substitution rate
nation ratio of 5.1% and 1.0% were slightly reduced, resulting showed the similar trend as PVC during the second stage, while
in the TD-onset of 241  C and 236  C, respectively. It is worth the modied PVC product with 6.3% substitution rate was
noting that their degradation behaviors remained identical with showed easily degradable. It was implied that the thermal
that of pure PVC during the second stage, probably due to their stability was slightly decreased on PVC modied with graing
low dechlorination concentration. an aliphatic nucleophilic group.
To further investigate the effect of the substituted concen-
tration on thermal stability, the PVC substituted with thio-
Glass transition temperature (Tg) of PVC and the modied
phenol and 1-octanethiol were also conducted by TGA analysis.
PVCs
As shown in Fig. 5, it showed that the same degradation char-
acter was observed during the rst stage (250–350  C) for both In addition, the glass transition temperature (Tg) of PVC and
thiophenol-substituted PVCs, even with 17.5% and 35.7% modied PVCs were also detected using DSC measurements,
substitution rates, respectively. Nevertheless, the trends for and the results were summarized in Table 2. It was observed
those degradation had a signicantly difference during the that the Tg of pure PVC with a stiff backbone is at around 82  C
second stage (350–480  C), which the sample with 17.5% (Table 2, entry 1). The addition of plasticizer into PVC polymer
substitution has loss over 20 wt% weight. It was because that will increase the distance of PVC chains and make the

Fig. 4 TG analysis of PVC and the modified PVCs with different Fig. 5 TG analysis of PVC and the modified PVCs with thiophenol
nucleophiles using DIEA as a base (testing conditions: sample, 10 mg; using K2CO3 or DIEA as a base (testing conditions: sample, 10 mg;
heating temperature, 50–800  C; heating rate, 10  C min
1; 50 heating temperature, 50–800  C; heating rate, 10  C min
1; 50
mL min
1 N2 flow). mL min
1 N2 flow).

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Experimental
Materials
PVC powder (Mw ¼ 68 750), K2CO3, DIEA, thiophenol, isooctyl
thioglycolate and dimethylformamide (DMF) were purchased
from the Wako Pure Chemical Industries, Ltd (Japan). Tetra-
hydrofuran (THF), 1-octanethiol and methanol were acquired
from the Kanto Chemical Co., Inc. (Japan). Thiophenol, isooctyl
thioglycolate, and 1-octanethiol were used as nucleophilic
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reagents. Water was used the ultrapure water in the experi-

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ments. All other reagents and solvents were used without

further purication.

Fig. 6 TG analysis of PVC and the modified PVCs with 1-octanethiol

Experimental procedure
using K2CO3 or DIEA as a base (testing conditions: sample, 10 mg;
heating temperature, 50–800  C; heating rate, 10  C min
1; 50 In a type experiment, PVC powder (500 mg, 8 mmol equivalent
mL min
1 N2 flow). monomer), an appropriate nucleophile (1.0 eq.), and a base
(either K2CO3 (0.1 eq.) or DIEA (1.0 eq.)) were added to 50 mL of
DMF in a three-neck ask while stirring. The reaction mixture
macromolecular structure polymer easy to move, increase the was heated respectively up to 40  C or 110  C using a silicone oil
free volume of PVC and reduce the Tg.13 Obviously, the Tg of all bath for 3 h. Aer reaching the required reaction time, the
the modied PVCs are less than that of pure PVC, as shown in solution was ltered and washed with methanol to obtain
Table 2. This indicates that internally plasticized PVCs can be a precipitate. The precipitate was ltered off and dissolved in
obtained via chemical modication of PVC with appropriate THF to remove impurities. This was poured into methanol for
nucleophilic reagents (DINP moieties). In addition, the Tg of the recrystallization, aer which the white solid was ltered off and
modied PVCs with thiophenol slightly decreased compared to dried under reduced pressure to further analyze. Each experi-
pure PVC. Nevertheless, the modied PVC with 35.7% substi- ment was repeated at least 2 times (in duplicate) unless other-
tution ratio has a lower Tg (Table 2, entry 3) in comparison with wise noted.
the one with 17.5% substitution ratio (Table 2, entry 2), which
suggests high substitution efficiency can be conducive to Product analysis
improving plasticity of PVC. Moreover, the Tg of the modied The puried products were analyzed by 1H NMR (Bruker
PVCs with long carbon chain nucleophiles (isooctyl thio- DPX400, 400 MHz), and deuterated solvents were THF-d8 and
glycolate and 1-octanethiol) distinctly decrease to 65.8 and DMF-d7. In addition, elemental analysis of the products was
65.6  C (Table 2, entries 4 and 6), respectively. It means that the performed using a CHN-coder MT6 (Japan Yanaco New Science
effect of long carbon chain group on improving the plasticity of Inc.). Fourier transform infrared spectrometry (FT-IR) was
PVC are evidently better than that of thiophenol group. There- recorded on a NICOLET iS10 Fourier transformed infrared
fore, these results illustrate that the nucleophiles of DINP spectrophotometer. The thermal stability of the products (10
moieties can play an internally plasticized effect on PVC mg) was measured using a TG/DTA 6200 (Japan Seiko Instru-
through replacing partial Cl atoms on PVC. Besides, the factor ments) by heating from 50–800  C at a heating rate of
for decreasing Tg is mainly caused that the substituting of Cl 10  C min
1 under N2 ow (50 mL min
1). Glass transition
atoms with nucleophiles will increase distance between PVC temperature (Tg) was characterized using a NETZSCH DSC 200
chains and reduce intermolecular force.24–26 PC analyser (differential scanning calorimeter measurements)
under N2 atmosphere. The temperature was over a range of
50
to +120  C with a heating of 10  C min
1. Approximately 10 mg
Table 2 DSC and TGA data of PVC and modified PVCs of PVC materials were weighed and sealed in a 40 mL aluminum
crucible and immediately detected using DSC measurement.
Entry Samples (SN2) Tga ( C) TDb ( C) The DSC data was collected from a rst cycle of heating.25,26
1 PVC 82.1 269
2 PVC-thiophenol-17.5% 77.7 263 Conclusions
3 PVC-thiophenol-35.7% 75.2 261
4 PVC-isooctyl thioglycolate-6.5% 65.8 265 In this paper, thiophenol or long carbon chain groups in the
5 PVC-isooctyl thioglycolate-3.7% 75.6 241 presence of an inorganic base (K2CO3) and an organic base
6 PVC-1-octanethiol-6.3% 65.6 236
(DIEA) were successfully employed to remove the Cl in PVC,
a
DSC testing conditions: each sample, 10 mg; heating temperature, which convert waste PVC into value-added products to improve

50 to +120  C; heating rate, 10  C min
1; under N2 atmosphere. its plasticity for feedstock recycling. The maximum substitution
b
TGA testing conditions: sample, 10 mg; heating temperature, 50–
800  C; heating rate, 10  C min
1; 50 mL min
1 N2 ow. TD: ratio reached up to 35.7% when using thiophenol in the pres-
temperature of weight loss of 5 wt% for a sample. ence of DIEA, which was probably attributed to the easily

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formed nucleophilic group (C6H5S–). Meanwhile, the elimina- 10 M. Sadat-Shojai and G.-R. Bakhshandeh, Polym. Degrad.
tion ratio was just 4.4% due to the use of a weak base. It was Stab., 2011, 96, 404.
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of all the modied PVC during the rst degradation stage when Proc. Combust. Inst., 2013, 34, 2321.
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some Cl atoms by DINP moieties reagents because the Tg of all 14 P. Jia, L. Hu, M. Zhang, G. Feng and Y. Zhou, Eur. Polym. J.,
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15 Y. Qi, J. He, F. Xiu, W. Nie and M. Chen, J. Cleaner Prod.,

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Conflicts of interest 2018, 196, 331.

16 Z. Yao and X. Ma, Bioresour. Technol., 2018, 247, 504.
There are no conicts to declare. 17 P. Zhao, Z. Li, T. Li, W. Yan and S. Ge, J. Cleaner Prod., 2017,
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Acknowledgements 18 N. Huang, P. Zhao, S. Ghosh and A. Fedyukhin, Appl. Energy,
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This work was supported by the Natural Science Foundation of 19 Y. Qi, J. He, Y. Li, X. Yu, F. Xiu, Y. Deng and X. Gao, Waste
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