Accepted Manuscript

Zinc-catalyzed ester bond cleavage: Chemical degradation of polyethylene

terephthalate

Yuqi Wang, Yao Zhang, Hongyan Song, Yingxiong Wang, Tiansheng Deng, Xianglin
Hou

PII: S0959-6526(18)33133-0
DOI: 10.1016/j.jclepro.2018.10.117
Reference: JCLP 14519

To appear in: Journal of Cleaner Production

Received Date: 11 May 2018

Revised Date: 9 October 2018
Accepted Date: 10 October 2018

Please cite this article as: Wang Y, Zhang Y, Song H, Wang Y, Deng T, Hou X, Zinc-catalyzed ester
bond cleavage: Chemical degradation of polyethylene terephthalate, Journal of Cleaner Production
(2018), doi: https://doi.org/10.1016/j.jclepro.2018.10.117.

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 ACCEPTED MANUSCRIPT

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Chemical degradation of polyethylene terephthalate was developed to produce terephthalic acid
and ethylene glycol via selective cleavage of ester bonds.

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Zinc-Catalyzed Ester Bond Cleavage: Chemical Degradation of Polyethylene Terephthalate
Yuqi Wanga, Yao Zhangb, Hongyan Songa, Yingxiong Wanga, Tiansheng Denga,* and Xianglin Houa,*
a. Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese
Academy of Sciences, Taiyuan, 030001, People’s Republic of China.
b. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, 79 West
Yingze Avenue, Taiyuan, 030024, People’s Republic of China.

Corresponding author: Xianglin Hou.

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E-mail: houxianglin@sxicc.ac.cn

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Key words: selective cleavage; controlled degradation; coordination catalysis; chemical recycling;
polyethylene terephthalate.

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Abstract
Polyethylene terephthalate (PET) materials were recycled by physical methods for a long
time. Chemical degradation and recycling of PET materials draw more and more attention in

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recent years. In this work, PET materials were degraded and recycled via selective cleavage of
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ester bonds using ZnCl2 as catalysts in aqueous solution. Degradation system 70% ZnCl2/H2O
presented excellent catalytic properties due to the coordination catalysis of Zn2+. Monomers
terephthalic acid (TPA) was reclaimed at 180 oC for 8 h. The yield of TPA reached up to 98.31%,
and the purity of TPA was up to 97.14%. The degradation system ZnCl2/H2O solution was recycled
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and reused for 3 times, and the degradation ratio of PET materials was still up to 100%. In the
degradation process, no organic solvent was added. The work provides a green and sustainable
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strategy to recover high-value-added chemicals (TPA) from waste PET materials in aqueous
phase.
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1 Introduction
Over the last few decades, polyethylene terephthalate (PET) materials were extensively
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utilized in plastic products, and their accumulation in the environment has attracted more and
more attention. About 56 million tons of PET materials were produced worldwide in 2013 alone,
prompting further industrial production of their monomers, terephthalic acid (TPA) and ethylene
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glycol (EG), both of which are derived from raw petroleum. Large quantities of PET materials have
been introduced into the environment through their production and disposal, resulting in the
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accumulation of PET materials in ecosystems (Yoshida et al., 2016). PET materials have the
highest recycling rates among all plastics. Most recycling methods were physical recycling. For
example, waste PET materials from mineral water bottles were recycled and used for carpet
manufacturing via physical methods rather than new mineral water bottles. Chemical
degradation and recycling of PET materials draw more and more attention in recent years. PET
materials were degraded into TPA and EG which can be used to produce new PET materials, and
the new PET can be used to produce new mineral water bottles. The main purpose of chemical
degradation was to recover monomers from waste PET materials.
Chemical degradation and recycling techniques of PET materials mainly include alcoholysis,
hydrolysis, aminolysis and so forth (George and Kurian, 2014). Among them, glycolysis is one of
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most important alcoholysis methods using EG as solvent. Various ionic liquids (ILs) and deep
eutectic solvent (DES) were used as catalysts in degradation process. For example, the Lewis
Based Ionic Liquid [Bmim][OAc] was used to degrade PET in glycol (Al-Sabagh et al., 2014);
Suojiang Zhang’s group realized the glycolysis of PET using fist-row transition metal-containing
ionic liquids as catalysts (Wang et al., 2015a), and the glycolysis of PET was also performed using
DES (urea/ZnCl2) as catalysts (Wang et al., 2015b). The primary degradation product of PET
materials is bis(2-hydroxyethyl) terephthalate (BHET) via glycolysis methods. During the glycolysis
process, other catalysts were also used as catalysts, for example, metal salts (zinc acetate, sodium

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carbonate), solid acid, metal oxides and polyoxometalate. For example, solid acid (SO42-/Co3O4)
was used as catalyst to realize the glycolysis of PET (Zhu et al., 2012); the glycolysis of PET was
carried out using K6SiW11MO39 as catalysts at 185 oC (Geng et al., 2015). Subcritical and

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supercritical glycolysis was also used to produce BHET (Imran et al., 2010). Supercritical
methanolysis is another important alcoholysis method, and the major degradation product of
PET is dimethyl terephthalate (Yang et al., 2002). Supercritical ethanol was also utilized to

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degrade PET using [Bmim][BF4] as catalyst, and diethyl terephthalate can be reclaimed (Nunes et
al., 2014). Hydrolysis of PET materials was performed using solid acid or metal salt as catalyst in
aqueous solution. For example, Zn(CH3COO)2 was used to decompose PET in hot compressed

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water (Liu et al., 2012). PET materials were hydrolyzed into TPA and EG in hydrolysis process.
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Aminolysis methods were also utilized for the degradation and recycling of PET materials
(Fukushima et al., 2013). In Zhen Leng’s work, the aminolysis of PET was performed in
ethanolamine, and the product was used to modify asphalt (Leng et al., 2018a). In Zhen Leng’s
another work, the aminolysis of PET was carried out in triethylenetetramine, and the product was
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also applied to improve the performance of bituminous mixtures (Leng et al., 2018b). The
degradation products were amides compounds, and further reaction was necessary to obtain
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monomers. Except for alcoholysis, hydrolysis and aminolysis methods, other unconventional
approaches were applied for the recycling of PET materials. For example, bacterium (Ideonella
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sakaiensis 201-F6) was used to degrade PET materials (Yoshida et al., 2016). Alkylol amines were
applied for the degradation of PET materials as solvent, for instance, ethanolamine (Tawfik and
Eskander, 2010). Tuan Amran Tuan Abdullah’s group produced hydrogen using waste PET as
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starting material via steam reforming catalyzed by Ni/Pd-promoted Al2O3-La2O3 catalyst (Nabgan
et al., 2017).
Based on above discussion, it can be seen that most degradation methods of PET need
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organic solvent. The degradation products of them are not monomers which were used to
synthesize PET. PET materials are synthesized via polycondensation reaction of TPA and EG. TPA
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primarily derived from p-xylene (PX). PX was oxidized into TPA in acetic acid solvent using
Co(CH3COO)2 as catalyst (Tomas et al., 2013). The manufacture process of PX is complicated, and
the production cost of TPA is relatively high. The reclaiming of TPA from waste PET materials is of
great significance. In our previous work, high concentration ZnCl2 aqueous solution exhibited
excellent catalytic property for the degradation of artificial polymer materials. For instance,
polyurethane was decomposed via selective cleavage of C-N and C-O bonds in ZnCl2/H2O solution
(Wang et al., 2018). IL and DES were used as catalysts in the ethylene glycol solvent. For example,
SuoJiang Zhang’s group explored the glycolysis of PET materials using IL and DES as catalysts. The
degradation product of glycolysis was BHET. Some ILs have good solubility for PET and BHET (Sun
et al., 2018), but the separation of BHET was hard. The prices of ILs are more expensive than
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ZnCl2. Meanwhile, this work was carried out in the aqueous phase, and water was the most
green, sustainable and cheap solvent. TPA was easily precipitated from ZnCl2/H2O system when
the temperature cooled to room temperature, which was beneficial for the separation of TPA.
High concentration ZnCl2/H2O system is a more green and sustainable strategy to recycle waste
PET materials because water is the most green and environment friendly solvent. This
degradation process was a cleaner production process. In this work, PET materials were degraded
by high concentration ZnCl2/H2O system via selective cleavage of C-O bonds, and monomer TPA
was reclaimed. The possible degradation mechanism was proposed for the degradation of PET

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materials catalyzed by zinc chloride catalyst.

2 Material and methods

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2.1 Materials
PET materials were PET mineral water bottles collected from household garbage. ZnCl2,
dimethyl sulfoxide (DMSO) and deuterated DMSO (DMSO-d6) were purchased from TCI (Shanghai,

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China) Development Co. LTD and utilized without further treatment.
2.2 Experimental section
General degradation procedure of PET materials is shown as follows. 35 g of ZnCl2 and 15 g

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of H2O was mixed in a 500 ml of beaker, stirring about 5 min, and a transparent 70% ZnCl2/H2O
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solution was formed. 1 g of PET was added into a 100 ml of kettle, and 50 g of 70% ZnCl2/H2O
solution was poured into the kettle. Then, the kettle was sealed using hydrothermal reactor, and
heated in homogenous reactor at 180 oC for 8 h, generally. After completing reaction, the
degradation products were cooled down to room temperature. After filtration, the TPA was
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separated due to the low solubility in 70% ZnCl2/H2O solution. The TPA was washed two times
using 30 ml of water, and dried in drying oven. The recycled ZnCl2/H2O solution was reused to
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degrade PET materials.

2.3 Characterization and testing
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Degradation process and products were characterized by nuclear magnetic resonance

(NMR), scanning electron microscope (SEM), Fourier transform infrared (FT-IR), elemental
analysis (EA) and thermogravimetric analysis (TGA). To explore the chemical structure of
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degradation products, 13C-NMR, 1H-NMR and heteronuclear single quantum correlation (HSQC)
spectrum were monitored by an AVANCE ⅢTM (Bruker, Switzerland) spectrometer (400 MHz).
Deuterated solvents used for NMR were DMSO-d6 and water-d2. Surface morphology of samples
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was observed by SEM (JSM-7001F, Japanese electronic). To probe the changes of functional group,
FT-IR spectra were collected on a Vertex 80V (VRUKER, Germany) spectrometer in the range of
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4000 – 400 cm-1 wavenumber. The resolution was 4 cm-1, and 40 times scan were accumulated to
form 1 spectrum. Elemental composition of samples was characterized by EA (Vario EL CUBE,
ELEMENTAR, Germany). Thermal stability was measured by TGA (SETSYS EVOLUTION TGA 16/18,
SETARAM, France). Under an argon (Ar) atmosphere, samples were heated from room
temperature (22 oC) to 1000 oC at a heating rate of 5 oC·min-1. Purity of products was determined
by high performance liquid chromatography (HPLC, SHIMADZU, LC-10AT, UV-VIS DETECTOR).
Chromatographic column: Shim-pack CLC-ODS, mobile phase: acetonitrile, flow velocity: 1.0
mL/min, column temperature: 40 oC, injection volume: 2.5 μL, detector: UV-254 nm.

3 Results and Discussion

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3.1 Optimization of degradation conditions of PET materials
The degradation conditions were optimized as shown in Table 1. The degradation reactions
were repeated three times at different condition, and the standard deviation was provided as
shown in Table S1. The factors including catalyst concentration, temperature and reaction time
were explored. The influence of concentration was investigated at 180 oC for 8 h (Table 1, Entries
1-3). With the increasing of concentration from 50% to 70%, the degradation ratio increased from
46.54% to 100%. The degradation ratio also reached to 98.42% in 40% concentration solution
prolonging the reaction time to 24 h (Table 1, Entry 4). Then, the temperature was inspected in

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70% ZnCl2/H2O system for 8 h (Table 1, Entries 5-6). It can be seen that the temperature play an
important role in degradation of PET. The degradation of PET was hardly carried out at 160 oC.
When the temperature rose to above 180 oC, the PET materials can degrade completely. The

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effect of reaction time was also considered in 70% ZnCl2/H2O system at 180 oC (Table 1, Entries
7-8). The degradation ratio increased with the reaction time, and the complete degradation of
PET required at least 8 h at 180 oC. As a result, the optimal degradation conditions were

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determined (70% ZnCl2/H2O system, 180 oC, 8 h). The ZnCl2/H2O degradation system can be
recycled and reused (Table S2). The degradation ratio of PET still reached to 100% after recycled
and reused 3 times. The degradation ratio decreased to 94.20% and 91.80% after reused 4 and 5

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times. The decrease of catalytic effect was caused by biochar.
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Table 1. Degradation of PET materials under different reaction conditions in ZnCl2/H2O system.[a]
Entry Concentration/% Temperature/oC Time/h Degradation ratio[b]/%
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1 70 180 8 100
2 60 180 8 67.02
3 50 180 8 46.54
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4 40 180 24 98.42
5 70 170 8 42.18
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6 70 160 8 0.03
7 70 180 6 86.38
8 70 180 4 45.23
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[a] Mass ratio of PET to ZnCl2/H2O solution was 1:50. [b] Degradation ratio = (W0-W1)/W0. Where,
W0 is the mass of raw materials, and W1 is the mass of PET residue after degradation and
dissolving in DMSO.
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3.2 Characterization and analysis of degradation products

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3.2.1 NMR characterization

The chemical structure of solid degradation products was characterized by 13C-NMR and
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H-NMR spectroscopy (Figure 1 and Figure 2). The peak at 167.12 ppm was attributed to carbon
signal of carbonyl (C-1 of TPA). The peak of C-2 of TPA appeared at 134.96 ppm. And 129.98 ppm
was designated to C-3 of TPA. The result of 1H-NMR was accordance to 13C-NMR. The peak of H-1
of TPA appeared at 8.04 ppm. And the weak signal of 13.32 ppm was belonged to H-2 of carboxyl
of TPA. The HSQC results indicated that the H at 8.04 ppm was connected to the C at 129.98 ppm,
and both of them belonged to benzene ring (Figure S1). The chemical structure of liquid products
dissolved in ZnCl2/H2O solution was also tested by 13C-NMR and 1H-NMR spectroscopy (Figure S2,
Figure S3). The peak of 62.55 ppm was ascribed to C-1 of EG (Figure S2). The peak of 3.52 ppm
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was designated to H-1 of EG (Figure S3). Thus, it can be concluded that the solid degradation
products are TPA and the liquid degradation products are EG. EG was dissolved in 70% ZnCl2/H2O
solution after degradation of PET. The separation of EG was hard when the concentration of EG
was low. The reasons are as following. The boiling temperature of EG is 197.3 oC which is high;
then, the EG can coordinate to Zn2+. When the concentration of EG was high, part of EG can be
separated from ZnCl2/H2O/EG solution. For example, ZnCl2/EG/H2O (mass ratio 2:1:1) solution
was prepared, and part of EG was separated from the solution by reduced pressure distillation
under certain conditions (160 oC, -0.09 MPa, 2 h) (see Figure S4).

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O 3 3 O

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HO C C OH
1 2 2 1
3 3
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1
2
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200 150 100 50 0

Chemical shift/ppm
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Figure 1. 13C-NMR spectrum of solid degradation products. (Deuterated reagent: DMSO-d6)

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1
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O 1 1 O
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HO C C OH
2 2

1 1
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14 12 10 8 6 4 2 0
Chemical shift/ppm

Figure 2. 1H-NMR spectrum of solid degradation products. (Deuterated reagent: DMSO-d6)

3.2.2 SEM images

The degradation process of PET materials could be seen distinctly from the SEM images
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(Figure 3). The surface of PET materials was clean and tidy (Figure 3a). The PET materials turned
up cracks at 160 oC (Figure 3b), but they were hardly degraded at this temperature. When the
temperature rose to 170 oC, the PET materials were decomposed to bulk particles (Figure 3c).
When the temperature was up to 180 oC, the PET materials were completely decomposed, and
the insoluble TPA formed poriform framework (Figure 3d). The solid degradation products were
purified by recrystallization, and uniform particles were obtained (Figure 3e). Interestingly, when
the concentration of catalyst deceased to 40% from 70%, TPA crystal formed at 180 oC for 24 h
(Figure 3f). With the decreasing of catalyst, the viscosity of ZnCl2/H2O solution decreased

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obviously, which benefits mass transfer and crystal formation of TPA.

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Figure 3. SEM images of solid degradation products of PET materials at different temperature.
(a) PET materials (PET bottle); (b) PET residue, 160 oC; (c) PET residue, 170 oC; (d) solid products,
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180 oC; (e) purified solid products, 180 oC; (f) crystals of solid products, 180 oC.
Reaction conditions: (a)-(e) 70% ZnCl2/H2O, 8 h; (f) 40% ZnCl2/H2O, 24 h.
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3.2.3 FT-IR characterization

FT-IR analysis was further carried out to verify the functional group changes of PET materials
in the degradation process. As shown in Figure 4a, the peak at 1712.68 cm-1 was ascribed to the
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stretching vibration of C=O bonds of PET materials, and the peak 1250.42 cm-1 was assigned to
the stretching vibration of C-O of ester bonds. The peaks at 1576.02, 1509.95 and 1406.86 cm-1
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were attributed to the stretching vibration of C=C skeleton of benzene ring. The in-plane bending
vibration of C-H of benzene ring appeared at 1119.31 and 1092.76 cm-1. The peaks of ester bonds
and benzene ring remained intact at 160 oC (Figure 4b). When the temperature raised up to 170
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C, the peak of at 1712.68 decreased slightly and the peak at 1671.72 cm-1 appeared, and the
new peak belonged to the stretching vibration of C=O of TPA. Meanwhile, the peak of C-O of
ester bonds shifted to 1278.20 cm-1 which was attributed to the COOH of TPA (Figure 4c). When
the temperature rose to 180 oC, the C=O bonds of ester bonds disappeared nearly. And the C=O
bonds of TPA appeared at 1671.72 cm-1. At the same time, the peak at 1250.42 cm-1 shifted to
1278.20 cm-1. Due to the influence of COOH, the peak at 1406.86 cm-1 of benzene ring shifted to
1421.86 cm-1 (Figure 4d). In the FT-IR curves of purified degradation products and crystals of solid
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products (Figure 4e and 4f), the peaks at 1671.72 cm-1 and 1278.20 cm-1 were attributed to COOH
of TPA; the peaks of 1576.02, 1509.95 and 1421.86 cm-1 were designated to benzene ring of TPA.
For comparison, the FT-IR spectrum of pure TPA was added (Figure 4g). The results of FT-IR
suggest that the ester bonds were completely cleaved, and COOH of TPA formed at condition of
70% ZnCl2/H2O, 180 oC, 8 h.

C=O C-O
C=C C=C

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C=C
a

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c

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d

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g C=O C-O
=C-H
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2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700
-1
Wavenumber/cm
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Figure 4. FT-IR spectrum of solid degradation products of PET materials at different temperature.
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(a) PET materials (PET bottle); (b) PET residue, 160 oC; (c) PET residue, 170 oC; (d) solid products,
180 oC; (e) purified solid products, 180 oC; (f) crystals of solid products, 180 oC; (g) Pure TPA.
Reaction conditions: (a)-(e) 70% ZnCl2/H2O, 8 h; (f) 40% ZnCl2/H2O, 24 h.
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3.2.4 EA characterization
To obtain elements information, elemental analysis was also conducted (Table 2). The raw
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material PET was consisted of C, H and O elements. The content of C, H and O was 62.36, 4.21
and 33.42. The total content was up to 99.99% (Table 2, Entry 1). The content of C decreased
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from 61.19% to 48.85% with the increasing of temperature from 160 oC to 180 oC. The content of
H decreased from 4.19% to 3.97%. The content of O increased from 33.49% to 37.64%. The
overall content of C, H and O decreased from 98.87% to 90.46% (Table 2, Entry 2-4). The
degradation ratio increases with the increasing of temperature ranging from 160 oC to 180 oC,
meanwhile, the content of ZnCl2 in degradation products also increased. Thus, the obtained TPA
at 180 oC was purified, and the distribution of C, H and O was shown in Table 2, Entry 5.
Interestingly, the TPA crystals could be obtained in 40% ZnCl2/H2O at 180 oC for 24 h, and the
content of C, H and O was displayed in Table 2, Entry 6. For comparison purpose, the element
composition of pure TPA was listed in Table 2, Entry 7. It can be seen that the element content of
purified TPA and TPA crystal was similar to pure TPA; and the content of C, H and O was close to
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57.83%, 3.61% and 38.55%; and the total content of C, H and O reached up to 99.07 and 99.73.
The conclusion means the obtained purified TPA and TPA crystal are very pure. The purity of
purified TPA and TPA crystal were 97.14% and 98.75%, which was determined by HPLC (Table S3).
The mass balance calculations were provided as shown in Table S4.

Table 2. Elemental analysis of solid degradation products of PET at different temperature.

Entry[a] C/% H/% O/% Total/%
1 62.36 4.21 33.42 99.99

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2 61.19 4.19 33.49 98.87
3 58.66 4.02 33.58 96.26
4 48.85 3.97 37.64 90.46

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5 57.59 3.74 37.74 99.07
6 57.72 3.59 38.42 99.73

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7 57.83 3.61 38.55 99.99
[a] 1. PET materials; 2. Solid residues, 160 oC; 3. Solid residues, 170 oC; 4. Solid products, 180 oC;
5. Purified solid products, 180 oC; 6. Crystals of solid products, 180 oC; 7. Pure TPA.

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Reaction conditions of Entry 2-5: 70% ZnCl2/H2O, 8 h; Entry 6: 40% ZnCl2/H2O, 24 h.
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3.2.5 TGA characterization
TGA was utilized to characterize the thermal stability of PET and solid degradation products
(Figure 5). PET materials started to decompose at 370 oC, and the remaining weight remained
about 14.06% unchanged from 500 oC to 1000 oC (Figure 5, (a)). The solid residue of PET at 160 oC
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also began to decompose at 370 oC, and the weight loss process was similar to PET materials. The
remaining weight was about 16.67% which was higher than PET materials’ due to the penetration
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of catalyst (Figure 5, (b)). When the temperature rose to 170 oC, the decomposing temperature of
solid degradation products was advanced to about 250 oC. The remaining weight of PET residue
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at 170 oC was about 12.09% from 500 oC to 1000 oC (Figure 5, (c)). When the temperature of
degradation process rose to 180 oC, the decomposing temperature of solid degradation products
was also advanced to about 250 oC, and the weight loss process was accelerated. The remaining
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weight was about 8.49% from 500 oC to 1000 oC (Figure 5, (d)). The remaining weight of purified
TPA was 3.94% from 440 oC to 1000 oC (Figure 5, (e)). Interestingly, the remaining weight of TPA
crystals remained unchanged from 350 oC, and the remaining weight was about 1.45% (Figure 5,
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(f)). For comparison, the TGA curve of pure TPA was added (Figure 5, (g)). The TGA results
indicate that the PET materials could not be degraded at 160 oC for 8 h; part of PET materials
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were degraded at 170 oC; PET materials were completely degraded at 180 oC; especially, the TPA
crystals was obtained in the degradation condition of 40% ZnCl2/H2O, 180 oC and 24 h.
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(a)
100 (b)
(c)
(d)
80 (e)
(f)
(g)
Remaining weight/%

60

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40

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20

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0

-20

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100 200 300 400 500 600 700 800 900 1000
o
Temperature/ C
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Figure 5. TGA of solid degradation products of PET materials at different temperature.
(a) PET materials (PET bottle); (b) PET residue, 160 oC; (c) PET residue, 170 oC; (d) solid products,
180 oC; (e) purified solid products, 180 oC; (f) crystals of solid products, 180 oC; (g) Pure TPA.
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Reaction conditions: (a)-(e) 70% ZnCl2/H2O, 8 h; (f) 40% ZnCl2/H2O, 24 h.

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3.2.6 Degradation kinetics

With the increasing of catalyst concentration, the degradation reaction of PET was
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accelerated. Thus, the degradation kinetics in various concentration ZnCl2/H2O solutions was
investigated. The degradation kinetics of PET materials in 70% ZnCl2/H2O solution was explored
as shown in Figure 6. The degradation reaction of PET is first-order reaction, and the kinetic
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equation is kt = ln(1/(1-x)). The slopes of (a), (b) and (c) are k values at 170 oC, 180 oC and 190 oC.
Arrhenius equation is k = e-Ea/RT, and take the ln of both sides, lnk = lnA – Ea/RT. The slope of (d)
equals to -Ea/R = -6080.49 K-1 (R = 8.314 J·mol-1·K-1), and the intercept equals to lnA = 11.79.
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Activation energy Ea = 50.55 kJ·mol-1, and pre-exponential factor A = e11.79. For comparison, the
degradation kinetics in 40%, 50% and 60% ZnCl2/H2O solutions were also examined as shown in
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Figure S5, S6 and S7. The activation energy of degradation reaction is 98.73 kJ·mol-1, 75.76
kJ·mol-1 and 62.62 kJ·mol-1 in 40%, 50% and 60% ZnCl2/H2O solutions. The results show that the
activation energy of degradation reaction decreases obviously as the increase of catalyst
concentration. In the other word, the catalyst in various concentrations is different due to the
different coordination number of Zn2+ (see Table S5), and the unsaturated coordination Zn2+
presents excellent catalytic activity.
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(a) (b)
1.0
Equation y = a + b*x Equation y = a + b*x
Weight No Weighti 1.2 Weight No Weighti
Residual 0.00138 Residual 0.00175
Sum of Sum of
0.8 Squares Squares
0.99893
Pearson's r 0.99827 1.0 Pearson's r
Adj. R-Squa 0.99481 Adj. R-Squa 0.99681
Valu Standard Er Value Standard Er
B Intercept 0.01 0.02198 C Intercept 0.005 0.02475
0.6 B Slope 0.14 0.00587 0.8 C Slope 0.202 0.00661
ln(1/(1-x))

ln(1/(1-x))
0.6
0.4

0.4

0.2
0.2

0.0

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0.0

0 1 2 3 4 5 6 0 1 2 3 4 5 6
t/h t/h
(c) (d)
1.8
Equation y = a + b*x y = a + b*x
-1.3 Equation
Weight No Weighti
1.6 Weight No Weight

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Residual 0.00978
Sum of Residual 4.04529E
Squares Sum of -4
1.4 Pearson's r 0.99643 -1.4 Squares
0.98931 Pearson's -0.99884
Adj. R-Squ
Valu Standard E Adj. R-Squ 0.99536
1.2 Value Standard E
D Intercept 0.01 0.05851 -1.5
D Slope 0.26 0.01564 F Intercept 11.79305 0.64717
1.0 F Slope -6080.49 293.1899
ln(1/(1-x))

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-1.6
0.8

lnk
0.6 -1.7

0.4
-1.8
0.2
-1.9

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0.0

-0.2 -2.0
0 1 2 3 4 5 6 0.00216 0.00218 0.00220 0.00222 0.00224 0.00226
t/h 1/T
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Figure 6. The degradation kinetics of PET in 70% ZnCl2/H2O solution. The linear relationship
between ln(1/(1-x)) and t at (a) 170 oC, (b) 180 oC, (c) 190 oC; (d) the linear relationship between
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lnk and 1/T. Where, x is degradation ratio, t is degradation time, T = t1 + 273.15K (t1 is the
Fahrenheit temperature, and T is the Kelvin temperature).
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3.3 Proposed degradation mechanism of PET materials

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The ZnCl2/H2O degradation system was investigated by FT-IR (Figure S8). The peak of 3281
cm was attributed to the stretching vibration of O-H bonds, and 1637 cm-1 was ascribed to the
-1

bending vibration of O-H. The bending vibration of O-H obviously shifted to low wavenumber
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1611 cm-1 with the increasing of ZnCl2 concentration, and the peak intensity was strengthened.
The FT-IR results show that the proton of water was activated by coordination effect of Zn2+ in
high concentration ZnCl2/H2O solution.
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The effect of Zn2+ for the ester bonds was explored using ethyl acetate as model compound
(Figure S9). The peak at 1738.08 cm-1 was designated to stretching vibration of C=O of ethyl
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acetate, and 1231.53 cm-1 was attributed to C-O-C of ethyl acetate (Figure S9, (a)). The addition
of ZnCl2 brought about the shift of absorption peaks of ester bonds due to the coordination effect
of Zn2+. The absorption peak of C=O shifted to 1645.43 cm-1, and the absorption peak of C-O-C
shifted to 1312.12 cm-1. The peak intensity of C=O and C-O-C decreased obviously as the
concentration of ZnCl2 increased from 5% to 50%. The peak intensity of emerging C=O and C-O-C
bonds increased with the increasing of catalyst concentration (Figure S9, (b)-(e)). The FT-IR
results indicate that the Zn2+ can intensely coordinate with ester bonds, which results in the
obvious shift of absorption peaks of C=O and C-O-C bonds.
Based on above discussion and related reference (Sun et al., 2018), the possible degradation
mechanism was proposed (Figure 7). The Zn2+ attacked the O of C=O, promoting the electronic
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cloud shift to O. And the O of water attached to the C of C=O due to the positive charge of C in a
substitution nucleophilic 2 (SN2) manner. Then, one proton of water molecule transferred to O of
C-O, which resulted in the cleavage of C-O bonds. The C-O bonds were cleaved, and TPA and EG
were obtained.

O O O O
H2 H2 H2 H2
HO C C O C C O C C O C C OH
n

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ZnCl2/H2O

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Zn2+ Zn2+ Zn2+

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O O O O
H2 H2 H2 H2
HO C C O C C O C C O C C OH
n

O O O

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H H H H H H
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C-O bonds cleavage

O O
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H2 H2
HO C C OH + HO C C OH
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Figure 7. Possible degradation mechanism of PET via selective cleavage of ester bonds using ZnCl2
as catalyst.
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4 Conclusions
In summary, chemical degradation and recycling of PET materials was realized via selective
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cleavage of ester bonds using ZnCl2 as catalyst. The optimal degradation conditions are
performed in 70% ZnCl2/H2O at 180 oC for 8 h. The monomer TPA was reclaimed, and the yield
was up to 98.31%, and the purity of TPA reached to 97.14%. The high concentration ZnCl2/H2O
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catalysis system exhibited high selectivity on cleavage of ester bonds, which benefits the
controlled degradation process, and degraded PET materials into monomer TPA. The degradation
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solution was easy to separate and reuse. The obtained TPA could be reused in manufacture of
new PET materials. The degradation of PET was performed in aqueous solution, and no organic
solvents were added. The degradation is a cleaner production process because water is more
green and eco-friendly solvent than organic solvent. This work provides a promising strategy for
the recycling and recovery of PET materials.

Acknowledgement
This work was supported financially by the National Natural Science Foundation of China
(No. 51703237) and the Applied Fundamental Research Project of Shanxi Province (No.
201701D221053).
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Chemical degradation of PET material was achieved via selective cleavage of ester bonds.

The coordination catalysis of Zn2+ accelerated the hydrolysis process of ester bonds.

High value-added chemicals were recovered from waste PET materials.

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