J. Chil. Chem. Soc.
, 62, Nº 4 (2017)
DEGRADATION OF POLY(ETHYLENETEREPHTALATE) WASTE TO OBTAIN OLIGOMERS
USING A ZINC COMPLEX AS CATALYST
A. A. OVALLE-SÁNCHEZ; P. ELIZONDO-MARTÍNEZ; N. A. PÉREZ-RODRÍGUEZ;
E. HERNÁNDEZ-FERNÁNDEZ; M. G. SÁNCHEZ-ANGUIANO*
1
Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas; Av. Universidad S/N Ciudad Universitaria,
San Nicolás de los Garza Nuevo León CP 66451, México.
ABSTRACT
Thermal degradation of Poly(ethylene terephthalate) (PET) bottles waste was carried out by glycolysis using triethyleneglycol (TEG) as nucleophilic agent
and N1,N2-bis(2-aminobenzyl)-1,2-diaminoethane zinc(II) (ABEN), in order to test this compound as catalyst in the degradation of PET until to obtain short chains
of polyester (oligomers). The depolymerization processes was tested at 180, 190 and 210 °C, and two molar ratios of PET:TEG (1:1.3 and 1:2.6), the amount of
catalyst used was fixed at 1% in relation to PET, the best experiment of PET glycolysis was found at 190 °C during two hours in a mass relation PET:TEG 1:1.3.
All products were analyzed by Fourier transform infrared spectroscopy (IR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC),
the behavior of the reaction rate was studied for the best experiment by measuring the amount of degraded PET at different glycolysis time. The degradation of PET
was favored with the use of ABEN, which accelerates the reaction, obtaining oligomers in the absence of an organic solvent or reaction medium, this is the most
efficient catalyst found so far. The oligomers were obtained with molecular weight between 900 and 1500 g mol-1 depending on the reaction time, 60 min was the
less time of the total glycolysis of PET. Also was found that the molecular weight of the oligomers increased along the glycolysis, due to the recombination with
TEG and ethylene glycol produced in degradation.
Keywords: Poly(ethyleneterephthalate), degradation, catalyst, chemical recycling, glycolysis
INTRODUCTION by Pingale and Shukla with ethylene glycol (EG) and zinc chloride as catalyst,
molar ratio PET:EG 1:14 and 8 hours under reflux16. This is a very long reaction
PET is a thermoplastic material that presents good thermal and mechanical time; a large amount of nucleophile agent is also required. Ghaemy et al. studied
properties; it is mainly used in the textile industry and the fabrication of bottles for PET degradation using zinc acetate as catalysts to evaluate its influence on the
carbonated drinks. The PET bottles are discarded in huge quantities, originating degradation level at different temperatures: 135, 160, 200 and 210 ºC until
a serious ecologic problem because they accumulate in the environment, such BHET obtained. The highest yield was obtained after 8 hours in reflux at 200
as, sewer system obstruction and its accumulation in green areas prevents the ºC and a mole ratio of 1/1.2 (PET/EG)17. Glycolytic depolymerization of PET
natural growth of plants. Therefore, there is a growing interest in recycling bottle waste was attempted using excess ethylene glycol in the presence of zinc
PET by degradation as a partial solution to the solid waste problem, PET acetate, sodium carbonate, sodium bicarbonate, sodium sulphate and potassium
waste degradation consists of the decomposition by chemical agents to obtain sulphate. The highest yield was achieved with zinc acetate as catalyst at 196 ºC,
monomers and oligomers as raw materials for the syntheses of polyesters or but EG:PET molar ratio between 5.4:1 and 7.6:118.
employed as precursors for high molecular weight polyurethanes1, polyester2 Zinc acetate as catalyst has been widely studied in kinetics aspects on the
and other specific uses3. PET can be recycled by chemical depolymerization degradation of PET process, using 1,4-butanediol and triethylene glycol, it was
using diols, alcohols, water and even ethanolamine4,5 and diethanolamine as found that the glycolyzed product consist mainly of BHET and dimer at 190 ºC
depolymerizing agents6. Particularly, degradation by glycolysis is a process and 4 hours as reaction time19. In similar researches on glycolysis of PET, the
by transesterification between ester and OH groups in excess, to obtain bis(2- reaction has been achieved with different glycols: propylene, diethylene and
hydroxyethyl terephtalate) (BHET)7. Some previous works associated to the triethylene, using catalysts such as manganese acetate, zinc acetate and lead
optimal conditions to carry out the glycolysis of PET have been published, acetate. Again the reaction conditions such as time, temperature and amount
depending of the reaction conditions were obtained BHET, dimers, trimers or of glycol are high, compared with those reported in the present study20,21. The
oligomers8, 9, the high polydispersity of these products is not suitable for use degree of degradation of PET in glycolysis depends on the type of catalyst,
in any particular application. Glycolysis of PET is an environmentally friendly ionic liquids have also been used for this purpose22,23. But their synthesis
reaction because it does not generate residues, because the obtained product is is long and complicated, for this reason they are more expensive than the
used in other processes, and the molecular weight of the oligomers produced metallic compounds regularly used as catalysts. In addition to the conventional
can be controlled by adjusting some reaction conditions as temperature, time, catalyst, some researches have been working with titanium phosphate and 1,5,7
catalyst type and glycol amount. Metal acetates of zinc, lead, cobalt, cupper triazabicyclo[4,4,0]dec-5-ene as catalyst in PET degradation, at 120 and 190
and manganese have been used as catalyst in the glycolysis of PET waste with ºC with glycolysis time of 6 hours, was reported that these catalysts influenced
ethylene glycol; the most efficient was zinc acetate10. the rate of depolymerization to obtain oligomers and 78% yield of BHET24 and
Carta et al. reported that temperature, time, amount of glycol and the hydrotalcite with ethylene glycol as solvent at 2 hours and 198 ºC was complete
catalyst in the process of glycolysis are the most important factors that affect the degradation25. The combination of microwave irradiation and ionic liquid has
degradation. They found also that an improvement on the degradation of PET allowed more efficient degradation, environmental friendly and economically
could be achieved by increasing the reaction time and the amount of the glycol, feasible, although it is difficult to develop industrially26. Industrial interest of
producing BHET as the main degradation product11. When manganese acetate PET degradation is obtaining oligomers that can be used in the manufacture of
was used as catalyst, the glycolysis conversion rate increases significantly with other products such as polyurethanes or unsaturated polyester resins27,28.
temperature, time and the amount of catalyst12; for example, at 200 ºC and 3 In the most of the papers reported so far, has been used an excess of glycol
hours of reaction were obtained oligomers with 500 g mol-1 13. Our research or high temperature, time and catalyst to reach a high yield of degradation.
group team evaluated several catalysts: chloride aluminum, lead acetate, zinc The main objective in this work was used a new complex as catalyst in order
acetate, cadmium sulphate, calcium sulphate and lithium hydroxide; using to obtain oligomers, that can be used as raw material in the synthesis of
triethylene glycol as nucleophile agent, 180 °C and two hours of reaction, the unsaturated polyester resin. The N1,N2-bis(2-aminobenzyl)-1,2-diaminoethane
amount of degraded PET varied between 8 and 95 % depending of the catalyst zinc(II) complex was synthesized using the methodology reported29. Figure
used, being lead acetate the best catalyst. However, due to the toxicity of this 1 shows the structure of the complex ABEN, it´s an alternative to metallic
compound, many researchers have chosen to use mainly zinc acetate14,15. compounds containing zinc in its structure in order to obtain mild reactions
The depolymerization of PET obtaining close to 74% BHET was reported conditions for producing oligomers from PET degradation.
J. Chil. Chem. Soc., 62, Nº 4 (2017)
and each 20 min during the second hour, in order to studied the relationship
between the glycolysis conversion of the waste PET and reaction time. The first
six samples were treated with THF to separate the oligomers (degraded PET)
from the PET flakes that did not react (residual PET), which was dried at 80 °C
by 6 hours and by a gravimetric method the residual PET was calculated by the
equation 1. The fraction soluble in THF was separated in a rotary evaporator;
the product was dried at 80 °C by 24 hours and weighted to obtain the oligomer
mass.
The aliquots taken during the second hour of reaction were not treated with
THF because after 80 min of glycolysis the PET was totally degraded, thus
these samples were treated with 30 mL of water at 60 °C to extract the residual
Figure 1. Structure of the N1,N2-bis(2-aminobenzyl)-1,2-diaminoethane TEG produced during the degradation and separate it from the produced
zinc(II) complex used as catalyst. oligomer.
EXPERIMENTAL RESULTS AND DISCUSSION
Materials Results of the degraded PET obtained in glycolysis carried out at different
The PET was obtained from post-consumed bottles that were cleaned and temperatures and molar ratios PET/TEG are shown in Table 1. The yields
chopped in small pieces of 3 mm, washed with hot water (at 60 ºC) and rinsed of glycolysis reactions were high in all cases, even at 180 °C, the lower
with acetone, dried at 70 ºC during 24 hours in a vacuum oven. Triethylene temperature used in this work, taking in account some references that report
glycol (99.8%), THF (99.8%) and acetone (99.9%) were acquired from Aldrich 74% of degradation as maximum [18]. Increasing only 10 °C the temperature
and were used without further purification. to reach 190 °C caused a 100 % of degradation in the PET, thus 190 °C and a
Glycolysis molar ratio PET/TEG 1/1.3 (Experiment 3) are the best conditions to carry out
4.0 g of PET (0.025 mol), 0.04 g of ABEN, 5.0 or 10.0 g of TEG (0.033 or these reactions.
0.066 mol) were mixed in a round flask of 100 mL equipped with a thermometer
and a reflux condenser and heated at 180, 190 or 210 °C during two hours under Table 1. Yield of PET degraded at different reaction conditions.
constant stirring. After each glycolysis experiment was completed, the flask
was removed from the hot plate and the product washed three times with 30 Molar Ratio PET/ Temperature
Experiment Yield (%)
mL of distilled water at 60 ºC, stored in a refrigerator at 4 °C for 24 hours, and TEG (°C)
filtered to extract the remaining TEG and EG produced from PET. 1 1/1.3 180 75
The remaining product was mixed with 10 mL of THF, the PET not
degraded was collected by decantation, dried at 80 °C for 24 hours and weighed; 2 1/2.6 180 87
the conversion percentage for the glycolysis of the PET waste was defined as 3 1/1.3 190 100
equation 1. The fractions of oligomers were determined as the difference in
mass between initial mass of PET and the mass of the solid residue extracted 4 1/2.6 190 100
with THF.
5 1/1.3 210 100
Equation 1 6 1/2.6 210 100
Where A = g of PET at the beginning of the reaction, B= g of residual PET The IR spectrum of the product obtained from Experiment 3 is shown in
The residual product obtained after decantation with THF (oligomers) Figure 2, the bands at 3420 cm-1 and 2870 cm-1, absent in the spectrum of the
were dried 80 °C for 2 h and analyzed by IR using a Thermo Scientific IR200 original PET (without degraded), are present in the product from this experiment
ATR (SeZn crystal) FTIR, 32 scans per analysis, from 650 to 4000 cm-1using a due to the formation of chains with termination OH and C-H produced during
Thermo Scientific IR200 ATR (SeZn crystal) FTIR, 32 scans per analysis, from glycolysis. The functional groups shown in IR spectrum are the first indicative
650 to 4000 cm-1 using a Thermo Scientific IR200 ATR (ZnSe crystal), 32 scans of polyester oligomer formation from glycolysis of PET. The other common
per analysis from 650 to 4000 cm-1using a Thermo Scientific IR200 ATR (SeZn characteristics bands of polyester resins are observed at 1714 cm -1 (C=O
crystal) FTIR, 32 scans per analysis, from 650 to 4000 cm-1 using a Thermo stretching), C-O stretching at 1050 cm -1, 727 cm-1 corresponding to –CH2.
Scientific IR200 ATR (SeZn crystal) FTIR, 32 scans per analysis, from 650 to
4000 cm-1using a Thermo Scientific IR200 ATR (SeZn crystal) FTIR, 32 scans
per analysis, from 650 to 4000 cm-1; DSC using a TA Instrument model MDSC
2920, heating rate of 20 ºC/min from 20 to 300 ºC in nitrogen atmosphere and
GPC in a HP equipment (1100 model) under the following conditions: 10 µL
were injected from a 6 mg/mL glycolyzed PET solution into a PL Gel 106 A°
10µm (400K-40M), 105 A° 5µm (40K-4M), 103 A° 5µm (1K-40K) column,
at 40 °C, THF as mobile phase, flow rate 1.0 mL/min. The products obtained
from Experiments 2 and 3 were determined the hydroxyl values according to
ASTM E 1899-08. A summary of the methodology of glycolysis is shown in
Scheme 1.
Figure 2. IR spectra of oligomer obtained from Experiment 3: PET/TEG
1/1.3 ratio and 190°C.
Scheme 1. Methodology used in glycolysis of PET.
Figure 3 shows the DSC thermogram of the product from Experiment 3,
Influence of time on average Mw of oligomers it shows a broader peak with a principal signal at around 78 ºC, this signal
From the experiment realized with 1/1.3 PET/TEG ratio and 190 °C, can be related with the fusion of a oligomers obtained and the entire peak
samples were taken during the glycolysis, each 10 min during the first hour could indicate that the oligomers consist mainly of short and mobile chains
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J. Chil. Chem. Soc., 62, Nº 4 (2017)
that apparently are modified at low temperature before melting. Since the glass electrophilic and therefore more susceptible to attack by the nucleophile agent.
transition temperature of undegraded PET is 84 ºC and melting temperature is The mechanism proposed is showed in the Scheme 2.
around 260 °C.
Influence of time on average Mw of oligomers
A detailed study of the reaction in Experiment 3 was carried out to
establish the rate of PET degradation under the glycolysis conditions used.
Samples were taken at different reaction times and each sample was analyzed to
evaluate de amount of degraded PET and its molecular weight. Table 3 shows
the results of this study, at 60 min of reaction the PET was totally degraded, and
the oligomer resulted in an average molecular weight about 1467. After two
hours of reaction, the molecular weight (1544 g/mol) indicates that oligomers
are formed by seven ethylenterephtalate units on average.
Table 3. Average molecular weight along glycolysis time of Experiment
3.
PET Degraded
Time (min) Mw Mn D
(%)
10 21 1199 921 1.302
20 40 1218 1010 1.206
30 82 1227 1009 1.216
40 87 1260 1015 1.241
Figure 3. DSC scan of product obtained from Experiment 3 product. 50 97 1354 1078 1.256
The GPC results of the products obtained after glycolysis are presented 60 100 1467 1114 1.318
in Table 2. Can be observed a lower molecular weight in the product obtained
80 100 1295 1060 1.222
from Experiment 2 as an effect of the amount of TEG used (See Table 1),
and more cleavage points caused by the OH groups of TEG, the 87% of the 100 100 1385 1082 1.280
PET degraded contains smaller chains with a size uniform, therefore the
polydispersity is lower. 120 100 1544 1147 1.346
In experiments 3 to 6 (carried at 190 and 210 ºC) the entire PET sample
was degraded demonstrating that the temperature is a more important factor Figure 4 shows the data presented in Table 3. The cleavage of PET chain is
than the amount of TEG used. The molecular weights were around 1,200 g/ a random phenomenon, the amount of TEG available at the beginning suffered
mol indicating that the resulting oligomers are formed in average of seven a drastic diminution because it is grafted in the oligomers produced during
repetitive units of ethylenterephtalate, this unit has a theoretical molecular the reaction, but the liberation of ethylene glycol from the PET originate a
weight of 196 g/mol. The hydroxyl values after glycolysis were 252.1 for the recombination reaction of these oligomers, thus, the glycolysis is a reversible
product obtained in Experiment 2 and 199.4 for the Experiment 3. The OH process that can originate a slightly increase in the molecular weight, this
value reported of BHET is 441.5 and 251.3 for the dimer30. These results also behavior has already been reported31.
suggest that the products obtained are mainly formed by oligomers instead pure
BHET, dimers or trimers. This represents an advantage since products with a
high content of OH groups are unsuitable for use in some applications such as
waterproofing or synthesis of polyurethanes.
Table 2. Average molecular weight of the products obtained from the
glycolysis.
Exp Mw Mn Mp Mv D
1 1,314 1,093 832 1,267 1.201
2 919 875 597 897 1.050
3 1,153 1,013 837 1,121 1.138
4 1,162 1,012 853 1,126 1.148
5 1,435 1,164 875 1,380 1.233
Figure 4. Molecular weight distribution of oligomers resulted from PET
6 1,246 1,047 874 1,773 1.190 degradation along glycolysis time in Experiment 3.
The obtained results demonstrate the effectiveness of ABEN as catalyst Figure 5 indicates the relationship between the degraded PET and the gly-
in glycolysis of PET. In references reported so far, it has been degraded colysis time. The amount of degraded PET increase along the glycolysis time
completely PET using various catalysts; but to achieve this, high temperature approached a steady conversion after 60 minutes, after that time the PET is
is required (above 198 °C), solvent or excess agent. In addition, under these completely degraded.
conditions the degradation product obtained is a mixture of BHET, terephtalic
acid, dimers, trimers and oligomers8. In the Experiment 3 the signal intensity at 3400 cm-1 corresponding to OH
Complex ABEN increased the velocity of degradation of PET to get group was analyzed by IR, in samples acquired each 20 min during the reac-
oligomers of short chains. It appears due to the catalytic activity of ABEN like tion. Figure 6 shows the spectra for each sample. The intensity of OH signal
as Lewis acid. The zinc interacts with the oxygen of the carbonyl group of PET, increases with the reaction time until it reaches a maximum at 80 min, which
increasing the electron deficiency of carbon, this encourages the nucleophilic confirms the formation of oligomers with OH termination during the degrada-
attack. In this sense, other research group have reported the use of ZnOAc tion. A decrease in the signal can be observed in 100 and 120 min spectra
like catalyst in the glycolisis of PET, revealing that the process needs higher probably because the OH groups are occupied in the recombination process.
temperature, reaction time or excess glycol that when ABEN is used7-9. This
could be explained because the zinc in ABEN makes the carbonyl carbon more
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J. Chil. Chem. Soc., 62, Nº 4 (2017)
Scheme 2. Proposed mechanism of the glycolysis of PET catalyzed by ABEN.
Figure 5. Relationship between PET degraded and the glycolysis time in Figure 6. The IR spectroscopy of the product from Experiment 3 along
Experiment 3. reaction time.
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J. Chil. Chem. Soc., 62, Nº 4 (2017)
CONCLUSIONS 11- D. Carta, G. Cao, C. D`Angeli, Environ. Sci. Pollut. R. 10, 390, (2003)
12.- Ch. H. Chen, J. Appl. Polym. Sci. 87, 2004, (2003)
The degradation of PET is favored with the use of N1,N2-bis-(2- 13.- B. Geyer, G. Lorenz, A. Kandelbauer, Express Polym. Lett. 10, 559,
aminobenzyl)-1,2-diaminoethane zinc(II) as catalyst, which accelerates the (2016)
reaction obtaining oligomers with PET/TEG molar ratio of 1:1.3, reaction 14.- M.E. Viana, A. Riul, G.M. Carvalho, A.F. Rubira, E.C. Muniz, Chem.
temperature of 190 °C for two hours and in the absence of an organic solvent Eng. J. 173, 210, (2011)
as reaction medium. 15.- N. George, T. Kurian, Ind. Eng. Chem. Res. 53, 14185, (2014)
According the presented results it can be concluded that 60 minutes is the 16.- N.D. Pingale, V.. Palekar, S.R. Shukla, J. Appl. Polym. Sci. 115, 249,
optimal time to degrade PET under the reaction condition here showed. At this (2010)
time the PET is completely degraded. During the glycolysis of PET are obtained 17.- M. Ghaemy, F. Behzadi, Iran. Polym. J. 11, 77, (2002)
oligomers with molecular weight depends on the time of reaction, due to the 18.- R. López-Fonseca, I. Duque-Ingunza, B. Rivas, S. Arnaiz, J. Gutierrez-
recombination of the oligomers with ethylene glycol produced in degradation. Ortiz, Polym. Degrad. Stab. 95, 1022, (2010)
The amount of TEG is an important factor, since can be modulated to control 19.- M.E. Viana, A. Riul, G.M. Carvalho, A.F. Rubira, E.C. Muñiz, Chem.
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materials in the formulation of adhesive and paints, contributing in this way to (2011)
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22.- H. Wang, Y. Liu, Z. Li, X. Zhang, S. Zhang, Y. Zhang, Eur. Polym. J. 45,
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