Depolymerization of PET waste to potentially applicable aromatic

amides: Their characterization and DFT study

Meenu Teotia, Nazia Tarannum , Rakesh Kumar Soni
Department of Chemistry, Chaudhary Charan Singh University, Meerut 250 004, India
Correspondence to: M. Teotia (E - mail: teotiameenu@gmail.com)

ABSTRACT: Poly(ethylene terephthalate) waste has been depolymerized to a series of potentially applicable aromatic amides through
aminolysis with different amines such as methylamine, ethylenediamine, ethanolamine, and butylamine at ambient conditions of tem-
perature and pressure. The amides prepared were characterized by different techniques like Fourier transform infrared (FTIR), UV-
Visible spectroscopy, nuclear magnetic resonance (NMR), elemental analysis, mass spectrometry, powdered X-ray diffraction (XRD),
Raman spectroscopy, and thermal analysis. Further more, an attempt is being made to insight the physical parameters of the aromatic
amides using ab initio DFT (Density Functional Theory) study. DFT calculations were performed at Becke’s three parameter function-
al and Lee–Yang–Parr functional (B3LYP) level of calculation with 321-G basis set. The atomic orbital energy (HOMO and LUMO)
and energy gap is also represented. The vibrational frequencies optimized by DFT were in agreement with the experimental FTIR
data. An efficient conversion of PET waste to amides was achieved without catalyst through environment friendly clean approach. V C

2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45153.

KEYWORDS: aminolysis; aromatic amides; degradation; DFT; recycling; vibrational frequency

Received 2 February 2017; accepted 23 March 2017

DOI: 10.1002/app.45153

INTRODUCTION hydroxyethyl terephtalate, diols, polyols, dimethylterephthalate, etc.,

PET has become the need of the day as a packaging material but
the excessive consumption of synthetic wastes like PET is a threat
of serious monitoring as well. The statistic suggests that more
than 13 million tonnes of PET wastes are consumed every year
worldwide and so is the waste created in same proportion.1
Thereby the need for the degradation of these wastes arises. Sever-
al reports are available in literature on depolymerization of PET
waste through chemical methods such as hydrolysis,2–5 alcoholy-
sis,6–8 glycolysis,9–13 ammonolysis,14,15 and aminolysis.16–18
Sinha et al. (2010) have reviewed extensively the different chemical
methods used for depolymerization of PET waste.19 PET waste recy-
cling through alkaline, acid and neutral hydrolysis involves high
temperature and pressure and also suitable purification methods
are needed to get purified end products. Methanolysis of PET waste
gives dimethyl terephthalic acid (DMA) in the presence of metal
salts used as catalysts. Temperatures up to 310 8C along with high
pressures and also super critical state of methanol have been used
to increase the yield of DMA. Depolymerization of PET waste
through glycolysis method is extensively investigated by the
researchers. This method also requires temperature range of 180–
250 8C and metal salt catalysts. PET glycolysis products such as bis-
find potential applications as precursors for acrylate terminated oli-
goesters,11,20 polyurethanes,21 plasticizers,22 dyestuffs,23 and other
value added products.
Among all these methods limited work has been reported about
depolymerization of PET waste through aminolysis. N-substituted
terephthalamides are the end products of aminolysis method and
have a very little industrial and commercial exposure till now. Few
reports are available exploring the applications of terephthalamide
derivatives as plasticizers,24 UV curable adhesion promoters,25 chelat-
ing agents,26 thiazolidinone derivatives,27 polyurethanes,28 and anti-
fungal agents.29 N,N 0 -Dihydroxoethyl benzene 1,4-dicarboxamide, an
aminolysis end product of PET waste with ethanolamine is the most
investigated terephthalamide and is synthesized using different cata-
lytic systems and elevated temperatures.30–33 Microwave-assisted ami-
nolytic depolymerization in presence of catalysts has also been
reported.34,35 It can be converted into a number of value added
organic derivatives and hence possess huge synthetic potential appli-
cation which can be devoted to the presence of hydroxyl moieties at
both ends. Literature survey investigates the use of metal catalysts
owing to their cationic properties which facilitates the generation of
electron deficient centers for the aminolytic depolymerization.36,37
N,N 0 -Diaminoethyl benzene 1,4-dicarboxamide, another monomer

Additional Supporting Information may be found in the online version of this article.
C 2017 Wiley Periodicals, Inc.
V

WWW.MATERIALSVIEWS.COM 45153 (1 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153


ARTICLE WILEYONLINELIBRARY.COM/APP
obtained through depolymerization of PET waste with ethylene
diamine also exhibits extraordinary properties that make it enticing
for various applications.38,39 Exhaustion of energy and efforts are the
main disadvantages associated with depolymerization reactions at
high temperature and pressure and in presence of catalytic systems.
This article highlights economical and environment friendly
approach for chemical degradation of PET waste into N,N 0 -
dimethyl benzene 1,4-dicarboxamide (I), N,N 0 -diaminoethyl
benzene 1,4-dicarboxamide (II), N,N 0 -dihydroxoethyl benzene
1,4-dicarboxamide (III), and N,N 0 -di-n-butyl benzene 1,4-dicar-
boxamide (IV) by aminolysis method. All the amides have been
prepared at ambient conditions without the use of any catalyst.
The aminolysed end products were well characterized using
FTIR, UV-visible spectroscopy, NMR study, elemental analysis,
mass spectrometry, powdered XRD, Raman and thermal analy-
sis. The ab initio study of the synthesized aromatic amides has
been carried out to investigate the physical parameters.
EXPERIMENTAL
Materials
The postconsumed PET wastes of soft drink and mineral water
bottles were collected and chopped into small flakes (8 3 8 mm)
after removing cap. The flakes were cleaned thoroughly by wash-
ing with soap water and then with distilled water. The cleaned
PET waste flakes were dried at 80 8C for 5 h. Methylamine (40%
aqueous solution) was procured from Thomas Baker and ethyl-
ene diamine (99%), ethanolamine (98%), and butylamine (99%)
were procured from Qualigens. All of these amines were used as
received. Dimethyl sulfoxide (DMSO) (99%), dimethyl formam-
ide (DMF) (99%), tetrahydrofuran (THF) (99.8%), chloroform
(99.5%), methanol (99.8%), carbon tetrachloride (99%), acetoni-
trile (99%), benzyl alcohol (99%), dioxane (99%), acetone
(99%), carbondisulfide (99%) were of LR grade from Loba
Chemie and used as received. HPLC grade acetonitrile (99.8%),
acetic acid (99.8%), and water were used for HPLC analysis.
Computational Method
The computer simulations are done using GAUSSIAN 03 pro-
gram package.40 Density functional theory (DFT)41–43 calcula-
tions were performed at Becke’s three-parameter functional and
Lee-Yang-Parr functional (B3LYP) level of calculation and the 6–
21 G basis set was used for ground state geometry optimization.
Synthesis of Aromatic Amides
A series of aromatic amides were prepared from PET waste via
chemical degradation method. The synthesis involves depolymer-
ization of PET waste through an economical and environment
friendly approach to synthesize a series of terephthalamides with
different amines. The depolymerization of PET waste has been
carried out at ambient conditions of temperature and pressure
and also the use of catalyst is strongly avoided. The amines
required for aminolysis were selected on the basis of need of end
groups at the amide linkages. The experimental set up was repeat-
ed thrice to confirm the formation of products. All the amides
were recrystallized from DMSO and subjected to various charac-
terization techniques and thermal analysis.
N,N 0 -Dimethyl 1,4-Benzene Dicarboxamide (I). A reaction of
properly washed and dried PET waste flakes with aqueous
WWW.MATERIALSVIEWS.COM 45153 (2 of 10)
10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
methylamine (40% w/w) was carried out in a ratio of 1:10
respectively.44 10 g of PET flakes with 100 mL of aqueous
methylamine was poured into amber colored bottle and sealed
properly to ensure any escape of amine. The white colored pre-
cipitates started appearing after few hours. After 45 days, 100%
conversion was achieved; the precipitates were filtered, washed
several times with hot distilled water to remove excess of amine
and then dried in vacuo at 60 8C for 36 h. The molecular for-
mula for the expected amide is C10H12O2N2 with theoretical
elemental compositions, C (62.50%), H (6.25%), O (16.67%),
and N (14.58%). Analytical percentages are, C (62.46%), H
(6.21%), O (16.79%), and N (14.54%) which strongly supports
its structural formula.
N,N 0 -Diaminoethyl 1,4-Benzene Dicarboxamide (II). Cleaned
and dried PET waste flakes were subjected to degradation with
ethylenediamine in a ratio of 1:10, respectively, at ambient con-
ditions of temperature and pressure. 10 g of PET flakes with
100 mL of ethylenediamine was poured into amber colored bot-
tle and was sealed properly. After 10 days (100% conversion),
the precipitates were collected, washed with hot distilled water
and then dried in vacuo at 60 8C for 36 h. The molecular for-
mula of the monomer is C12H18O2N4 with theoretical elemental
compositions, C (57.60%), H (7.20%), O (12.80%), and N
(22.40%). Analytical percentages are C (57.80%), H (7.10%), O
(12.89%), and N (22.21%).
N,N 0 -Dihydroxoethyl 1,4-Benzene Dicarboxamide (III). Properly
washed and dried PET waste flakes were depolymerized with
ethanolamine in a ratio of 1:14, respectively, in similar manner
(10 g, PET; 140 g ethanolamine) at ambient conditions of tem-
perature and pressure. After 85 days (99% conversion), the pre-
cipitates were collected, washed with cold distilled water and
dried in vacuo at 60 8C for 36 h. The molecular formula of the
expected monomer is C12H16O4N2 with theoretical elemental
compositions, C (57.14%), H (6.35%), O (25.40%), and N
(11.11%). Analytical percentages are C (57.31%), H (6.30%), O
(25.30%), and N (11.09%) supporting the structural formula.
N,N 0 -Di-n-Butyl 1,4-Benzene Dicarboxamide (IV). Compound
IV was also synthesized by treating properly washed and dried
PET waste flakes with n-butylamine in a sealed amber colored
bottle in a ratio of 1:10 respectively at ambient conditions of
temperature and pressure. After 45 days (100% conversion), the
precipitates were collected, washed, and dried in vacuo at 60 8C
for 36 h. The molecular formula of the monomer is C12H16O4N2
with theoretical elemental composition C (69.56%), H (8.69%),
O (11.56%) and N (10.14%). Analytical percentages are C
(69.50%), H (8.79%), O (11.66%), and N (10.04%).
Characterization
Elemental analysis was performed using Thermo Scientific (FLASH
2000) CHN Elemental Analyser. 1H NMR spectra of the amides
were recorded on FTNMR Spectrometer model Avance-II (Bruker)
using DMSO solvent at field strength 9.4 T (1H frequency, 400
MHz). FTIR spectra of the samples were recorded on Agilent
FTIR Spectrometer (ATR module of Cary 630 FTIR, Agilent Tech-
nologies) from 600 to 4000 cm21. UV-visible spectra were
recorded on UV double beam spectrophotometer Systronics 2201,
with bandwidth 2 nm in DMSO solvent from 200 to 800 nm.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153
 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

Table I. Chemical Degradation of PET Waste into Different Amides using Amine Compounds and Catalyst/Temperature (with Reference)

Amine used Catalyst/temperature Year Reference

Diethylenetriamine, triethylenetetramine, 200–210 8C 2001 30
Hydrazine hydrate Lead acetate/66 8C 2004 45
Methyl amine Quaternary ammonium salts/ambient 2005 16
Ethanolamine Glacial acetic acid, Sodium acetate and Potassium sulfate 2006 31
Ethanolamine DBTO/190 8C 2010 32
Primary, secondary, and Organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) 2011 46
asymmetric amines
Ethanolamine Sodium acetate/170–200 8C 2011 34
Ethanolamine/hydrazine hydrate Imidazolium ionic liquids 2012 47
3-amino 1-propanol Sodium acetate, Potassium sulfate/reflux 2013 48
Hydrazine hydrate Nickel chloride, Magnesium chloride/reflux 2013 49
Ethylene diamine 100 8C 2013 50
Ethanolamine Sodium acetate, Zinc acetate 2014 33
Diethanolamine/ethanolamine Deep eutectic solvents (choline chloride-zinc 2016 51
chloride and choline chloride-urea)

Thermogravimetric analysis (TGA/DTA) were performed using products may alter the chemical properties of the obtained
Perkin Elmer, Diamond TG/DTA at 20.00 8C/min in nitrogen amides, etc., polymerization reactions, simultaneous degradation
atmosphere. Powder X-ray diffraction studies were done on Pana- of the products, and their hydrolysis at high temperatures.
lytical’s X’Pert Pro X-ray diffractometer, Scan axis, gonio, Anode Solubility
Material, Cu, K-Alpha1 [Å] 1.54060, K-Alpha2 [Å] 1.54443, K- The typical solubilities of the amides in different solvents have
Beta [Å] 1.39225. Mass spectra were recorded on Waters, Q-TOF been listed in Table II. The aminolysed end products were dis-
Microma SS (LCMS) mass spectrometer. Raman spectra were solved in excess of the solvents at room temperature
recorded on indigenously designed Raman spectrometer, RI Instru-
ments & Innovation India. High-performance liquid chromatogra- Table II. Solubility of Compounds (I, II, III, IV) in Different Solvents
phy was performed on Shimadzu LC2010CHT HPLC instrument
equipped with SPOLAR-C18 column [4.6 mm diameter, 250 mm
Solvent I II III IV
length and 5lm particle size].
DMSO J J J J
- - - -
-

-
RESULTS AND DISCUSSION DMF J ⍜* J J
- - -
-

-
Synthesis Distilled water A A J* A
-

-
The four amide (I, II, III, and IV) derivatives synthesized herein Benzene A A A ⍜*
have been obtained by depolymerization of PET waste via ami- Chloroform A A A A
nolysis reaction with methylamine, ethylenediamine, ethanol-
Acetone A A A A
amine and butylamine. The structures of these amides are given
THF J* J* J* ⍜*
in Figures 3 and 4. In aminolysis reaction, the nitrogen of - - -
-

Methanol A A ⍜* A
amine behaves as a nucleophile and attacks the carbonyl carbon
of the ester linkages. Further nitrogen atom loses hydrogen ion Carbon tetra chloride A A A A
to carbonyl oxygen (rearrangement) and amide linkages are 1,2-Dichloroethane A A A ⍜*
formed at the ester groups present in PET by expulsion of Carbon disulfide A A A A
hydrogen ion to glycol units. The byproduct in these reactions Triethylamine A A A A
is ethylene glycol which can be recovered from the filtrate and Acetonitrile A A A A
utilized for other useful chemical conversions. The degradation Dioxane A A A A
reaction proceeds slowly but all the folds were cleaved within Benzyl alcohol A A A A
the reported timescales. The literature review suggests that ami-
0.1N HCl J* J* J* A
- - -
-

nolysis of PET can also be carried out by refluxing PET with

0.1N NaOH A A A A
amines in presence of catalysts which makes the carbonyl car-
Toluene A A A A
bon more electrophilic thus facilitating the attack by nitrogen
atom as shown in Table I. Although the use of catalyst has Acetic acid J* J J* ⍜*
- - -
-

reduced, the aminolysis reaction time but has added to several Acetone (30%) 1 methanol (20%) A A A A
disadvantages as well.16,30-34,45–51 The major disadvantages of J, soluble, ⍜, sparingly soluble; not more than 40%. A, insoluble *, solu-
-
-

these reactions involves oxidation of ethylene glycol; oxidation bility on heating.

WWW.MATERIALSVIEWS.COM 45153 (3 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 1. FTIR spectra of aromatic amides (I, II, III, and IV). [Color figure can be viewed at wileyonlinelibrary.com]

(31 6 4 8C), stirred and kept for 12 h. The amides are fairly sol-
uble in DMSO and DMF, on heating these can also be dissolved
in THF. Compound II has good solubility in acetic acid; howev-
er, I and III are soluble on heating. Compound III is partially
soluble in water but completely soluble in hot water.
Characterization
FTIR Spectra. FTIR spectra of the aromatic amides were
recorded in solid state on attenuated total reflection module
shown in Figure 1. The vibrational frequencies (cm21) of
amides (I, II, III, IV) corresponding to important functional
groups experimentally and theoretically are given in Table III.
All the compounds are showing a strong absorption due to
NAH stretch in the region 3354.74–3283.39 cm21 and a very
prominent absorption in the range of 1629.78–1618.05 cm21,
characteristic of amides (Amide I band). Amide II band (NAH
bending trans to carbonyl oxygen) cannot be seen in the spectra
as it is being merged up to amide I band (solid state of
sampling). Compound III (N,N 0 -dihydroxoethyl benzene 1,4-
dicarboxamide) possesses primary alcoholic groups at both
ends, band at 3358.09 cm21 is attributed to OAH stretch and
also a very strong absorption is observed at 1050.19 cm21
(CAO stretch). The absence of peak at 1715.63 cm21, corre-
sponding to C@O stretch of ester linkage in all spectra indicates
complete aminolysis of PET flakes. Raman spectra study of the
amides has further supported the vibrational frequency data.
The details of the data obtained from Raman spectra have been
provided in the supporting information (Figure S1).
UV-Visible Absorption Spectra. UV-Visible spectra of the com-
pounds were recorded by irradiating solutions of amides in
DMSO at the same concentration in 1 cm path quartz cell. The
compounds showed strong absorption in the range of 250–
320 nm. The kmax value for all the compounds is nearly same,
as the chromophoric group (-HNCO-C6H4-CONH-) undergo-
ing p-p* transition is common in all four amides (Figure 2).

Table III. Comparison of Experimental and Theoretical Vibrational Frequencies of Aromatic Amides (I, II, III, and IV)

I II III IV
Amides/vibration Experimental DFT study Experimental DFT study Experimental DFT study Experimental DFT study
NAH Stretch 3352.80 3348.79 3343.73; 3345.90; 3283.39 3285.75 3313.35 3308.04
3284.73 3285.01
C@O stretch 1629.78 1620.37 1627.46 1626.42 1618.24 1620.07 1623.45 1629.06
(amide I band)
C@C stretch 1550.77; 1560.02; 1541.16; 1544.64; 1550.98; 1555.57; 1535.40; 1533.48;
1490.12 1480.37 1446.15; 1444.20; 1459.95; 1450.16; 1497.81 1500.00
1408.94 1410.71 1429.77 1427.25
CAN stretch 1166.96 1165.05 1113.76; 1109.38; 1157.41 1154.02 1157.96 1187.50
1164.30 1165.80
CAH out of plane 867.10 867.85 854.58 852.65 866.33 863.83 860.38 863.84
bending (Ar-ring)

WWW.MATERIALSVIEWS.COM 45153 (4 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 2. Characteristic UV-visible absorption spectra of amides I, II, III,

and IV. [Color figure can be viewed at wileyonlinelibrary.com]
Figure 4. 1H NMR with splitting pattern and structure of amides III, and IV.
1 [Color figure can be viewed at wileyonlinelibrary.com]
NMR Characterization. H NMR spectra of amides I and II
and III and IV are shown in Figures 3 and 4, respectively. The
peaks obtained in 1H NMR spectrum for compound I are protons are not coupled to neighboring OH proton. The peak
attributed as; a sharp singlet at 7.88 d is typical for the four Ar- at 3.3 d (residual water) is missing in the spectrum as the pro-
H protons (symmetrical parasubstituted aromatic ring), peak at tons are being chemically exchanged to OH protons of the com-
8.4 d as a broad low hump due to CO-NH protons, a doublet pound, absorbing at 4.67 d (2H; singlet), uncoupled to CH2
at 2.84 d accounts for N-CH3 protons.52 A strong absorption at
3.3 d is due to the presence of residual water in DMSO and a
very weak absorption at 2.5 d is attributed to residual d5
DMSO in the sample. 1H spectrum of compound II shows typi-
cal resonances at 2.79 d, mean value (a fine quartet; observed
from resolved spectra) attributed to 4 H, ANH2 protons, two
multiplets at 3.44 d (b) merged up with residual water and at
3.54 d (c) are typical resonances of two sets of protons of meth-
ylene groups-CH2(c)CH2(b)NH2.50 Aromatic protons resonate
at 7.92 d and a triplet at 8.5 d is due to ACONH (2H) protons.
Amide III shows a quintet (4H) at d value 3.40 (mean value)
due to ANH–CH2- protons; however, a very fine triplet at 3.59
d is attributed to -CH2-OH(4H) protons indicating that these

Figure 3. 1H NMR with splitting pattern and structure of amides I and II. Figure 5. Powdered-XRD of amides I, II, III, and IV. [Color figure can be
[Color figure can be viewed at wileyonlinelibrary.com] viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45153 (5 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

ions forming cluster of peaks that result from [M 1 nH]1,

[M 1 Met]1, and their dimers [2M 1 H]1, [2M 1 Met]1, etc.53
The high resolution mass spectra show molecular ion peaks ion-
ized by H1 and also at m/z corresponding to their metal adducts.
The exact molecular masses of the compounds in numerical order
are 192.09, 250.09, 252.09, and 276.14 as observed from their MS
spectrum. The main peaks for compound I are at m/z 215.06
[base peak], 193.09, 175.12, 162.11, and 136.18 for [M 1 Na]1,
[M 1 H]1, [M-2H-CH3]1, [M-NHCH3]1, and [M-2H-CON-
HCH3]1, respectively. The MS spectrum of compound II provides
peaks at m/z 308 [M-3H 1 Na 1 K]1; base peak, 274.26

Figure 6. Mass spectra of aromatic amides I, II, III, and IV.

protons. A typical resonance of Ar-H(4H) is at d value 7.92 and

ANH- proton resonates at 8.41 d(2H; fine triplet). Proton
NMR spectrum of compound IV shows a very fine triplet at
0.931 d (CH3), two sextets for methylene units adjacent to
methyl group at 1.36 d and 1.55 d (mean values), a fine quintet
at 3.28 d attributed to CH2 unit directly linked to nitrogen
atom, slightly overlapped with residual water signal at 3.30 d,
Ar-H(4H) resonates at d value 7.89 and –NH- proton at 8.42
d(2 H; very fine triplet).
Powdered X-ray Diffraction Study. The typical powdered XRD
patterns for the compounds are shown in Figure 5. The picto-
grams indicated crystalline nature of compounds I, III, and IV;
however, a semicrystalline nature of the compound II was
observed.
Mass Spectral Analysis. Mass spectra (MS) were recorded on Figure 7. Thermogravimetric analysis (TGA) and differential thermal
waters Q TOF micromass LCMS spectrometer using electrospray analysis (DTA) of amides I, II, III, and IV. [Color figure can be viewed at
ionization technique. ESI mass spectra involve multiple charged wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45153 (6 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

Table IV. Data Obtained from Simultaneous DTA/TGA Analysis of Compounds I, II, III, and IV

Compound Peak temperature (8C) (DTA curve) DH (J/g) % Weight loss (TGA curve)
I 319.37; 397.56 165.36; 195.63 —; 96
II 178.13 281.42 16
III 196.69; 238.16 76.35; 87.46 —; —
IV 224.26 105.07 —

[M 1 H1Na]1, 250.09 [M]1, 249.09 [M-H]1, 247.09 [M-3H]1; destruction of intermolecular hydrogen bonding and strong
base peak, 218.21 [M-CH2NH2]1. The peaks for Compound III, dipole–dipole interactions leading to melting of the amide.32
are at m/z 275.06 [base peak], 253.09, 232.15, 192.08, and 150.12 TGA thermogram of compound III suggests degradation in
for [M 1 Na]1, [M 1 H]1, [M-3H-OH]1, [M-NHCH2CH2OH]1, three steps, first peak involves 14.9% weight loss, however,
and [M 1 3H-NHCH2CH2OH and -CH2CH2OH]1. Peaks in the 11.12% weight loss was observed for second peak which may be
MS spectrum of compound IV are at m/z 299.12 [base peak], attributed to loss of two water molecules and a molecule of
277.14 and 250.15 which corresponds to [M 1 Na]1, [M 1 H]1, ethene, respectively followed by degradation of rest of the mole-
and [M 1 2H-C2H4]1, respectively. MS data of the compounds is cule. The weight of the amide IV is constant for the peak
quite similar to the previous studies16,32 and confirm complete resolved in DTA curve with maxima at 224 8C, DH 5 105.07 J/g
degradation of the PET waste. The corresponding MS spectra for clearly tells its meting point, which is in coherence with the
amides are given in Figure 6. results obtained through DSC studies of the amide by Soni
et al. 2010.44 Thermal analysis results conclude significant ther-
High-Performance Liquid Chromatography Study. The pres-
mal stability of the amides (I, III, and IV) except for (II) which
ence of ANH2 group in the side chain of Compound II can
undergoes transamidation at higher temperature.
lead to transamidation reaction of the monomer to form a,x-
aminoligo and other higher homologues as reported in refer- Apart from thermal stability, the compounds showed storage
ence.50 The synthesis of compound II at ambient conditions stability. This was confirmed by comparing the FTIR spectra of
may raise the question whether the formation of higher homo- the compounds observed at different storage time intervals.54
logues is accompanied with monomer. To check out the pres- There was no significant change observed in the spectra of
ence of high molecular weight oligomers, HPLC of the
compound II was performed. Since compound II is soluble in
acetic acid, analysis was carried out by injecting 10 lL of the
sample solution (2 mg in 30 mL of acetic acid). Mobile phase
used was acetonitrile and buffer solution (pH 5 3) in a 60:40
ratio at a flow rate of 0.4 mL/min. The buffer solution was pre-
pared by dissolving 1.7 g of potassium dihydrogen phosphate in
500 mL of water and the pH was maintained by adding phos-
phoric acid. The total ion chromatogram supported the absence
of transamidation products and clearly depicts that N,N 0 -diami-
noethyl 1,4-benzene dicarboxamide monomer is the main con-
stituent eluted at 2.804 min. The chromatogram of compound
II is given in the supporting information for reference (Figure
S2).
Thermal Characterization. Thermogravimetric analysis (TGA)
and differential thermal analysis (DTA) thermograms of the
depolymerized aminolysates were analyzed to observe their
physical characteristics and behavior at high temperature (Fig-
ure 7). The data obtained from simultaneous TGA/DTA ther-
mogram of the compounds I, II, III, and IV has been tabulated
in Table IV. DTA thermogram of compound I indicates melting
of amide at 319.37 8C and peak at 397.56 8C suggests thermal
decomposition of amide in a single step degradation process
(TGA curve). The broad endothermic peak in DTA curve of
compound II with maxima at 178.13 8C may be referred to
melting with intermolecular transamidation of amide as this
reaction proceeds at higher temperature, followed by decompo-
sition.50 Two endothermic peaks were resolved in DTA curve of Figure 8. Geometrically optimized structure of amides I, II, III, and IV.
compound III at 196.69 and 238.16 8C which may be referred to [Color figure can be viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45153 (7 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

 10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ARTICLE WILEYONLINELIBRARY.COM/APP

Table V. Theoretically Optimized Physical Parameters of Aromatic Amides I, II, III, and IV

Dipole moment Zero point vibrational

Amides (Debye) Point group Energy (a.u.) Degree of freedom energy (kcal/mol)
I 4.27 C1 2644.70 72 130.03
II 5.15 C1 2832.98 102 188.39
III 6.56 C1 2872.48 96 170.38
IV 6.26 C1 2879.33 126 241.91

Table VI. Energy Parameters Calculated for the Series of Amides Using II, III, and IV is shown in Figure 8. Several calculated thermo-
DFT Study dynamic parameters at ground state like dipole moment, point
group symmetry and zero point vibrational energy of the com-
EHOMO ELUMO HOMO-LUMO pound is represented in Table V. The presence of groups like
Amide (a.u) (a.u) energy gap h AOH pulls the electrostatic field thereby increasing a dipole
I 20.322 20.241 20.081 0.041 moment for compound as in amide III (N,N 0 -dihydroxoethyl
II 20.196 20.038 20.158 0.079 benzene 1,4-dicarboxamide). The molecule shows C1 symmetry
representing lowest energy at all levels. The total energy of the
III 20.233 20.102 20.131 0.065
molecule is the sum of the translational, rotational, vibrational,
IV 20.232 20.098 20.134 0.067
and electronic energies. The vibrational frequency of aromatic
amides have been optimized by DFT and compared with experi-
compounds as per the data. Hence, it can be concluded that the mental FTIR. The experimental and theoretical vibrational fre-
synthesized compounds have storage stability over prolonged quencies were found to be in close relation with each other as
period of time. shown in Table III.
The electronic property of the aromatic amides was also stud-
Density Function Theory (DFT) Study ied. The highest occupied molecular orbital (HOMO) and low-
DFT calculations were performed at B3 LYP level of calculation est unoccupied molecular orbital (LUMO) help to determine
with 321-G basis set for optimization of ground state geometry the interaction of molecule with other species. The low HOMO
of four amides. Geometrically optimized structure of amides I, and LUMO energy gap supported the possibility of charge

Figure 9. HOMO-LUMO energy level representation and energy gaps of respective amides. [Color figure can be viewed at wileyonlinelibrary.com]

WWW.MATERIALSVIEWS.COM 45153 (8 of 10) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153


ARTICLE WILEYONLINELIBRARY.COM/APP
transfer interactions within the molecules.55 A decrease in the
kinetic LUMO energy gap indicates decline in kinetic stability
and an augmentation in the polarizibility and chemical reactivi-
ty.56,57 h is associated with chemical hardness and their stabili-
zation through hyperconjugative interactions58 as shown in
following equation:
ðELUMO 2EHOMO Þ
h5 (1)
2 11, 79.
The EHOMO, ELUMO, HOMO–LUMO energy gap and h of the
amides studied is calculated as per the DFT calculations and
shown in Table VI. The pictorial presentation of HOMO and
LUMO atomic frontier orbitals is shown in Figure 9. HOMO-
LUMO energy gap for amide I is lowest among the other three
amides predicting an easy charge transfer within molecule.
CONCLUSIONS
Keeping in mind the huge synthetic potential devoted to depoly-
merization of PET waste to number of applications, the catalyst
free synthesis of amide derivatives can be a stepping stone toward
sustainable development. The paper highlights economical, envi-
ronment friendly, and easy approach for chemical degradation of
PET waste into N,N 0 -dimethyl benzene 1,4-dicarboxamide, N,N 0 -
diaminoethyl benzene 1,4-dicarboxamide, N,N 0 -dihydroxyethyl
benzene 1,4-dicarboxamide, and N,N 0 -n-butyl benzene 1,4-dicar-
boxamide by aminolysis method. All the amides have been pre-
pared at ambient conditions without the use of any catalyst. The
four derivatives (I-IV) possess dimethyl, diaminoethyl, dihydrox-
oethyl, and di n-butyl moieties respectively which were confirmed
through FTIR, Raman, NMR, UV-visible, mass spectrometric anal-
ysis, and elemental analysis. All the techniques established the pres-
ence of characteristic functional group in the respective structures
of derivatives. The structures were established further by geometry
optimization using DFT study and the theoretical vibrational fre-
quencies were correlated with the experimental vibrational
frequency data. The vibrational frequencies optimized by DFT
were in agreement with the experimental FTIR data. Further, an
attempt has been made to study the physical parameters and
atomic orbital energy levels of the aromatic amides using DFT
study. HOMO-LUMO energy gap for compound I was found of
the order of 20.081 a.u. which is lowest among the amide deriva-
tives however highest energy gap was observed for compound III
(20.158 a.u.) and also the highest dipole moment (6.56 Debye).
The series of synthesized derivatives may have potential application
in the field of photocuring, pharmaceutical coating, and material
research. The article will definitely prove to be a useful guide for
upcoming researchers keen to develop new materials from amino-
lysed end products of PET waste. Catalyst free and economic
chemical degradation of PET waste will enhance the industrial via-
bility of recycling process.
ACKNOWLEDGMENTS
The authors thankfully acknowledge DST (DST/TSG/Ceramic/
2011/77-G) for the financial assistance. Authors acknowledge SAIF
Centre, Punjab University, and Cochin for carrying out Powdered
XRD, NMR, MS, and TGA/DTA analysis.
WWW.MATERIALSVIEWS.COM 45153 (9 of 10)
10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
REFERENCES
1. George, N.; Kurian, T. Ind. Eng. Chem. Res. 2014, 53,
14185.
2. Namboori, C. G. G.; Haith, M. S. J. Appl. Polym. Sci. 1968,
12, 1999.
3. Paszun, D.; Spychaj, T. Ind. Eng. Chem. Res. 1997, 36, 1373.
4. Mishra, S.; Goje, A. S.; Zope, V. S. Polym. React. Eng. 2003,
5. Mishra, S.; Zope, V. S.; Goje, A. S. J. Appl. Polym. Sci. 2003,
90, 3305.
6. Yang, Y.; Lu, Y.; Xiang, H.; Xu, Y.; Li, Y. J. Polym. Degrad.
Stab. 2002, 75, 185.
7. Goto, M.; Koyamoto, H.; Kodama, A.; Hirose, T.; Nagaoka,
S. J. Phys. 2002, 14, 11427.
8. Genta, M.; Iwaya, T.; Sasaki, M.; Goto, M.; Hirose, T. Ind.
Eng. Chem. Res. 2005, 44, 3894.
9. Goje, A. S.; Mishra, S. Macromol. Mater. Eng. 2003, 288,
326.
10. Shukla, S. R.; Harad, A. M. J. Appl. Polym. Sci. 2005, 97,
513.
11. Nikles, D. E.; Farahat, M. S. Macromol. Mater. Eng. 2005,
290, 13.
12. Karayannidis, G. P.; Achilias, D. S. Macromol. Mater. Eng.
2007, 292, 128.
13. Abdelaal, M. Y.; Sobahi, T. R.; Makki, M. S. I. Constr. Build.
Mater. 2011, 25, 3267.
14. Aguado, J.; Serran, D. Feedstock Recycling of Plastic Wastes.
Royal Society of Chemistry; London, UK, 1999.
15. Jain, A.; Soni, R. K. J. Polym. Res. 2007, 14, 475.
16. Soni, R. K.; Singh, S. J. Appl. Polym. Sci. 2005, 96, 1515.
17. Shamsi, R.; Abdouss, M.; Sadeghi, G. M. M.; Taromi, F. A.
Polym. Int. 2009, 58, 22.
18. Tarannum, N.; Agrawal, R.; Soni, R. K. Der. Pharm. Chem.
2016, 8, 137.
19. Sinha, V. K.; Patel, M. R.; Patel, J. V. J. Polym. Environ.
2010, 18, 8.
20. Farahat, M. S.; Nikles, D. E. Macromol. Mater. Eng. 2002,
287, 353.
21. Zeltins, V.; Cabulis, U.; Abolins, A.; Gaidukovs, S. IOP Conf.
Ser. Mater Sci Eng, Conf. 2016, 1,111.
22. Perez Amaro, L.; Coiai, S.; Ciardelli, F.; Passaglia, E. Waste
Manage. 2015, 46, 68.
23. Li, M.; Huang, Y.; Yu, T.; Chen, S.; Ju, A.; Ge, M. RSC Adv.
2014, 4, 46476.
24. Soni, R. K.; Dutt, K.; Jain, A.; Soam, S.; Singh, S. J. Appl.
Polym. Sci. 2009, 113, 1090.
25. Soni, R. K.; Teotia, M.; Dutt, K. J. Appl. Polym. Sci. 2010,
118, 638.
26. Soni, R. K.; Bhardwaj, M. J. Ind. Chem. Soc. 2016, 93, 229.
27. Palekar, V. S.; Damle, A. J.; Shukla, S. R. Eur. J. Med. Chem.
2009, 44, 5112.
28. Sadeghi, G. M. M.; Shamsi, R.; Sayaf, M. J. Polym. Environ.
2011, 19, 522.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153

ARTICLE WILEYONLINELIBRARY.COM/APP
29. Agrawal, R.; Tarannum, N.; Mishra, S.; Soni, R. K. Der.
Pharm. Chem. 2016, 8, 132.
30. Spychaj, T.; Fabrycy, E.; Spychaj, S.; Kacperski, M. J. Mater.
Cycles Waste Manage. 2001, 3, 24.
31. Shukla, S. R.; Harad, A. M. Polym. Degrad. Stab. 2006, 91, 1850.
32. Tawfik, M. E.; Eskander, S. B. Polym. Degrad. Stab. 2010, 95, 187.
33. More, A.; Kute, R. A.; Mhaske, S. Iran. Polym. J. 2014, 23, 59.
34. Achilias, D. S.; Tsintzou, G. P.; Nikolaidis, A. K.; Bikiaris, D.
N.; Karayannidis, G. P. Polym. Int. 2011, 60, 500.
35. Parab, Y. S.; Shah, R. V.; Shukla, S. R. Curr. Chem. Lett.
2012, 1, 81.
36. Kobayashi, S.; Mori, Y.; Yamashita, Y. Comp. Coord. Chem.
II 2004, 9, 399.
37. Sabot, C.; Kumar, K. A.; Meunier, S.; Mioskowski, C. Tetra-
hedron Lett. 2007, 48, 3863.
38. Sulkowski, W. W.; Borek, J.; Danch, A.; Radon, A.;
Sulkowska, A.; Toborowicz, A.; Bernatek, A. J. Therm. Anal.
Calorimetry 2004, 77, 363.
39. Sharma, P.; Lochab, B.; Kumar, D.; Roy, P. K. ACS Sustain.
Chem. Eng. 2016, 4, 1085.
40. Frisch, M.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.;
Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.
Gaussian 03, revision D. 01. Gaussian Inc.: Wallingford,
CT, 2004; p 26.
41. Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, 864.
42. Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, 1133.
43. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
44. Soni, R. K.; Swati, S.; Dutt, K. J. Appl. Polym. Sci. 2010, 115,
3074.
WWW.MATERIALSVIEWS.COM 45153 (10 of 10)
10974628, 2017, 31, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.45153 by Chief Librarian Jadavpur University, Wiley Online Library on [09/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
45. Goje, A. S.; Thakur, S. A.; Diware, V. R.; Chauhan, Y. P.;
Mishra, S. Polym. Plast. Technol. Eng. 2004, 43, 407.
46. Fukushima, K.; Coulembier, O.; Lecuyer, J. M.; Almegren,
H. A.; Alabdulrahman, A. M.; Alsewailem, F. D.; Mcneil, M.
A.; Dubois, P.; Waymouth, R. M.; Horn, H. W.; Rice, J. E.;
Hedrick, J. L. J. Polym. Sci. Part A: Polym. Chem. 2011, 49,
1273.
47. Palekar, V. S.; Shah, R. V.; Shukla, S. R. J. Appl. Polym. Sci.
2012, 126, 1174.
48. Shah, R. V.; Borude, V. S.; Shukla, S. R. J. Appl. Polym. Sci.
2013, 127, 323.
49. Parab, Y. S.; Shukla, S. R. Waste Biomass Valor. 2013, 4, 23.
50. Hoang, C. N.; Dang, Y. H. Polym. Degrad. Stab. 2013, 98,
697.
51. Musale, R. M.; Shukla, S. R. Int. J. Plast. Technol. 2016,
20, 106.
52. Gutowsky, H. S.; Holm, C. H. J. Chem. Phys. 1956, 25,
1228.
53. Cheng Ning, Y. Structural Identification of Organic Com-
pounds with Spectroscopic Techniques; Willey-VCH: Wein-
hem, 2005.
54. Smidt, E.; Meissl, K. Waste Manage. 2007, 27, 268.
55. Liou, G. S.; Hsiao, S. H.; Su, T. H. J. Mater. Chem. 2005, 15,
1812.
56. Fleming, I. Frontier Orbitals and Organic Chemical Reac-
tions; Wiley: New York, 1976.
57. Sinha, L.; Prasad, O.; Narayan, V.; Shukla, R. Mol. Simul.
2011, 153.
58. Valencia, F.; Romero, A. H.; Kiwi, M.; Ramirez, R.; Toro-
Labbe, A. Phys. Lett. 2003, 371, 267.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45153