Iranian Polymer Journal

https://doi.org/10.1007/s13726-019-00764-w

ORIGINAL RESEARCH

Understanding the effect of chain extender on poly(butylene

adipate‑co‑terephthalate) structure
Alana Gabrieli de Souza1   · Edilene de Cássia Dutra Nunes1   · Derval dos Santos Rosa1 

Received: 10 June 2019 / Accepted: 21 October 2019

© Iran Polymer and Petrochemical Institute 2019

Abstract
We investigated poly(butylene adipate-co-terephthalate) (PBAT), a biodegradable polymer, under the influence of a chain
extender (a multifunctional epoxide oligomer, Joncryl ADR-4370S®, ADR) at different concentrations, and correlated their
properties concerning the molecular interaction between the active sites of the structures. Several studies have used ADR in
poly(lactic acid)-PBAT blends; however, the effect of ADR in terms of chemical and physical interaction with PBAT is not
investigated in-depth, which can limit its applications. The chain extender is usually applied to improve the mechanical and
thermal properties and PBAT resistance to thermal degradation. The developed materials were evaluated by high-resolution
solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), mechanical and thermal
properties, and rheological measurements. NMR and FTIR indicate an interaction between the carboxylic sites of PBAT and
the epoxy sites of ADR. PBAT-2%ADR shows higher tensile properties, probably due to the hydrogen bonds and interactions
of π–π nature between the materials; in this case, the ADR can act as a reinforcing agent. High contents of chain extender
can change the nature of the interaction and influence the final properties of the polymer. The effect of this additive was
found to be strongly dependent on the content used and the polymer processing. It was observed that ADR could act as an
internal lubricant during processing (due to the low molecular weight of this additive), demonstrating the importance of
processing parameters control.

Keywords  Biodegradable polymers · ADR chain extender · Torquerheometry · Polymerproperties · Polymer

characterization

Introduction Recently, poly(butylene adipate-co-terephthalate), PBAT,

The increased consumption of petrochemical-based conven-
tional polymeric materials in recent years has led to a direct
effect on the generation of solid waste, which causes seri-
ous environmental problems [1]. Hence, there is an urgent
need for the development of new bioproducts. Biodegrad-
able materials have become a focus of research and design
because of increasing concerns about environmental pollu-
tion [2]. This class of polymers is an alternative to synthetic
plastic materials, especially for use in short-term and dispos-
able applications, such as packaging [1].
* Derval dos Santos Rosa
dervalrosa@yahoo.com.br
1
Centro de Engenharia, Modelagem E Ciências Sociais
Aplicadas, Universidade Federal Do ABC, Santo André,
SP 09510‑580, Brazil
which is an aliphatic–aromatic copolyester, has been exten-
sively researched in food, pharmaceutical, and agricultural
areas, among others. This polymer is very flexible and has a
wide range of unusual properties, such as high elongation-
at-break and biodegradability [3]. However, the application
of PBAT in some fields is limited due to the high cost and
processing parameters; so, it is common to use some addi-
tives to change specific properties or decrease the costs. To
improve some parameters that facilitate the polymer pro-
cess in conventional equipment (mixers, extruders, injection
molding machines), various strategies were employed [4–6].
Most of them focused on optimizing the molecular structure
of PBAT through chain extension, branching, and controlled
crosslinking.
The modifier is usually a di or multifunctional low-molar-
mass compound, which can react with carboxyl end groups
of PBAT molecules [7, 8]. Many addition-type modifiers
with different types of reactive groups have been reported

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to be effective in improving the properties of PBAT, such as
Joncryl ­ADR® [9], maleic anhydride [10], dicumyl perox-
ide [11], among others. Chain extenders are multifunctional
additives that bind close to the ends of different macromo-
lecular fragments, thus, extending the chain and increasing
the average molar mass of the polymer. Its additive does
not prevent degradation but compensate their effects on the
molar mass of the polymer, and facilitates the processing due
to improvement in polymer properties, such as an increase
in the melt temperature and polymer viscosity [12]. Besides,
as demonstrated by literature, blends of brittle polymer-con-
taining ADR have increased the maximum elongation.
The use of the chain extender in flexible polymers is
not common, and few reports are found in the literature.
The purpose of the addition of this type of additive in ther-
moplastic polymers is the control of the processing condi-
tions of the PBAT, retarding its degradation and increasing
its industrial processability. The interaction between the
Fig. 1  Molecular structure
of the PBAT and ADR, with
the carbon positions related
to the 13C NMR resonance
peaks (indicated by the letters)
and the final product
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Iranian Polymer Journal
polymer and the additive, and the dispersion, are factors
that can affect processing. The additive can also act in the
dispersion of a reinforcing phase in composites, acting as
a compatibilizer. In this case, it is important to know the
additive-matrix behavior before adding a third component
to the system. Some studies show that the chain extender can
avoid the agglomeration of the fillers [13, 14].
In this study, a multifunctional epoxide oligomer, Joncryl
ADR-4370S®, was used in the PBAT matrix. The molecular
structures of PBAT and ADR are shown in Fig. 1.
The physicochemical interaction between ADR and
PBAT matrix was investigated using various PBAT/ADR
mass ratios (from 1 to 10 wt%). The reactivity and efficiency
of ADR were evaluated regarding the interactions with the
polymer by Fourier transform infrared spectroscopy (FTIR)
and high-resolution solid-state nuclear magnetic resonance
spectroscopy (NMR). Mechanical and thermal proper-
ties were evaluated to verify the advantages of ADR in
Iranian Polymer Journal
improving PBAT properties. Finally, torque rheometry was
applied to understand the influence of ADR in the process-
ability of PBAT, inferring information about the interaction
and molar mass of the materials.
Experimental
The poly(butylene adipate-co-terephthalate) (PBAT) (aver-
age molecular weight mass of 66,500 g mol−1) and Joncryl
ADR ­4370S® chain extender (average molecular weight
mass of 6800  g  mol−1 and epoxy equivalent weight of
285 g mol−1) were produced and supplied by BASF Brazil.
The samples were prepared using a quick K-Mixer homog-
enizer (MH—100, MH Equipment Ltd, Brazil) and molded
into sheets by compressing at 190 °C and 40 MPa for 5 min
using a hot compression-molding machine. The initial con-
centrations of ADR investigated were 0, 0.5, 1, 2, 5, and
10 wt%. FTIR and NMR measurements were conducted
only on samples with 0, 1, 5, and 10 wt% of ADR because
there are no significant changes to the other compositions.
Mechanical, thermal, and rheological properties were con-
ducted in all the samples, to present a more detailed descrip-
tion of these properties as a function of concentration.
Fourier transform infrared spectroscopy
Identification of functional groups in the chemical structures
of materials was carried out by Fourier transform infrared
spectroscopy (FTIR), using the equipment Frontier 94,942
(PerkinElmer, USA). Using ATR accessory, the spectra were
recorded in the range of 400–4000 cm−1 and 64 scans.
Nuclear magnetic resonance spectroscopy
13
C 1H cross-polarization (CP)1 experiment was conducted
in a Varian VNMRS 500 MHz spectrometer (USA) operat-
ing at the resonance frequency of 125.7 (13C) and 500 MHz
(1H) at magic angle spinning (MAS) of 15 kHz for the pre-
cursors and the PBAT-1% ADR, and 10 kHz for PBAT-5%
ADR and PBAT-10% ADR using a tpm decoupling pulse
sequence on the 1H channel during the free induction decay
acquisition. The CP-MAS experiments were performed,
instead of single-pulse ones, because the first enhances the
signal–noise ratio on the 13C spectrum due to the shorter
relaxation time of the protons in comparison to the carbons.
Typical acquisition parameters were 1H π/2 pulse length of
2.5 µs and the relaxation delay of 8 s, with the contact time
of 1.0 ms. Chemical shifts are reported relative to tetrame-
thyl silane (TMS) at 0 ppm using adamantane as a secondary
reference with the ­CH2 carbon at 38.5 ppm.
Mechanical properties
Tensile tests were performed in a universal testing machine
(Instron 5900) (Instron S/A Ind. e Com. Ltd. Brazil) accord-
ing to ASTM D638-V. The dimensions of the specimens
were: 2 mm of thickness, 25.4 mm of the distance between
grips, 63.5 mm of length, and 7.62 mm of parallel section
width strong. The cross-head movement speed of 50 mm/
min was used as recommended by the standard, at room
temperature. The samples were pre-conditioned in a des-
iccator, to avoid moisture absorption. The elastic modulus
(E), ultimate tensile strength (σmax) and elongation-at-break
(εmax) were evaluated.
Thermal properties—DSC analysis
The differential scanning calorimetry (DSC) was performed
using a TA Instrument DSC Q200 (Texas, USA). The sam-
ples were heated from − 50 to 200 °C, cooled to − 50 °C
and reheated up to 200 °C, with a heating/cooling rate of
10 °C.min−1. Only the thermal transitions of the cooling
and the second heating were considered in this study. The
total percent crystallinity (Xc) of the samples was calculated
according to Eq. 1 [12, 15]:
ΔH m
Xc (1)
ΔH 100% WPBAT
where ΔHm is the sample melting enthalpy, ΔH100% is the
theoretical value of a 100% crystallinity PBAT (114 J/g), and
WPBAT is the matrix fraction in the composite.
Rheological measurements
The rheological measurements were done using a torque
rheometer Plastograph EC (Brabender) (New Jersey, USA)
with a rotation speed of 60 rpm for 10 min at 150 °C.
Results and discussion
Fourier transform infrared spectroscopy
Figure  2 shows the FTIR spectra of neat PBAT, neat
ADR, and PBAT-ADR with different contents. The main
IR peaks of PBAT are at 2958, 2875, 1392, 1168, 1122
and 940 cm−1, in agreement to Cai et al. [16]. The bands
at 2958 and 2875 cm−1 for PBAT are assigned to the C ­ H3
and ­CH2 stretching modes; 1457 cm−1 ­CH2 in-plane bend-
ing mode; 1409 cm−1 bending mode of O–CH2; 1390 cm−1
out-plane bending mode of ­CH2; 1271, 1168 and 1104 cm−1
C–O stretching mode; 1018 cm−1 in-plane bending mode
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Fig. 2  a Full FTIR spectra of neat PBAT and the modified polymers with different concentrations of ADR and b zoom of the region 1500–600
indicative of the main peaks presented in the text

of =C–H in benzene ring; 940 cm−1 benzene substitutes and

875 cm−1is assigned to the out-plane bending mode of =C–H
in benzene ring [12, 16, 17].
After the addition of ADR, it can be verified that PBAT-
5% ADR and PBAT-10% ADR show a little increase in
intensity on the peak at 758 cm−1, which corresponds to the
presence of an aromatic ring of ADR in the blend. Similar
results were also observed in the PBAT-PLA-lignin bio-
composite with ADR [18]. The formation of a new peak at
731 cm−1 (indicated by the red square in Fig. 2b) is an indi-
cator of a possible interaction between the functional groups
of both materials. This peak represents a new conformation
of PBAT/ADR samples possibly changed the vibration of
the –CH2– groups. It also justifies the small variations of
intensity in other peaks in the spectrum, reached by the elon-
gation vibrations [10, 19]; the samples with higher amount
of ADR show more intense peaks. It indicates that only
high amounts of ADR (5 and 10 wt%) present a significant
interaction between the PBAT and the chain extender, which
reflect in changes in the molecular vibration of the chemical Fig. 3  13C{1H} CP-MAS NMR of PBAT, ADR and PBAT modified
structure of the materials; this does not mean that the other with 1, 5, and 10 wt% of ADR. Labels at the resonance peaks indicate
samples had no interaction, but rather that due to the low their assignments specified in Fig. 1, according to references [19–21].
content of incorporated ADR, the IR analysis did not detect Asterisks indicate spinning sidebands
significant variations in the spectrum.
to the molecular structure of the PBAT and ADR which are
Magnetic resonance spectroscopy indicated in Fig. 1. Concerning potentially interacting sites,
PBAT has the carboxylic groups at the end of the polymer
Figure  3 shows the 13C{1H} CP-MAS NMR spectra of chain, represented at 173 ppm. This peak is identified as
PBAT, ADR, PBAT-1%ADR, PBAT-5%ADR, and PBAT- a protonated carboxylic acid, and, as the carboxylic acid
10%ADR. The labels on the resonance peaks correlate them becomes more deprotonated, its resonance peak shifts to

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higher frequencies (~ 185 ppm) [20] (the PBAT-ADR peaks Table 1  Mechanical properties of PBAT modified with ADR
showed a slight shift). Sample Young’s Elongation-at-break Tensile
In the ADR, the principle is the same, and a peak referred modulus (E) [%] strength
to the carboxylic site is observed at 176 ppm, which is char- [MPa] [MPa]
acteristic of the ADR structure. Additionally, the epoxy
PBAT 51.0 ± 1.6 1269.3 ± 147.6 25.1 ± 1.2
sites, representing around 45 ppm, are also potential inter-
PBAT-0.5%ADR 52.4 ± 0.6 1837.2 ± 54.0 22.1 ± 1.0
acting sites. For instance, an epoxy-proton donor reaction
PBAT-1%ADR 59.1 ± 3.2 1556.4 ± 103.6 28.9 ± 0.4
mechanism, observed as propagation steps in a polymeriza-
PBAT-2%ADR 79.4 ± 2.3 1008.4 ± 83.2 32.0 ± 0.8
tion process, shifts the resonance peaks of the epoxy carbons
PBAT-5%ADR 51.0 ± 0.2 1014.1 ± 42.0 24.6 ± 0.8
to 70 ppm, now as ethers or alcohol [21].
PBAT-10%ADR 50.4 ± 1.1 1633.7 ± 28.1 26.9 ± 0.8
The PBAT-1%ADR shows a spectrum identical to the
pure PBAT. This behavior was expected due to the low
concentration of ADR; it means that the presence of small
amounts of ADR and the copolymer processing does not Table 2  Thermal properties of PBAT modified with ADR in the sec-
trigger intermolecular interactions or decomposition and ond heating run
confirms the results observed in FTIR analysis. On PBAT- Sample Tg (°C) Tm (°C) ∆Hm (J/g) Tc (°C) Xc (%)
5%ADR, ­the13C spectrum is still dominated by the PBAT
PBAT − 33.7 124.6 15.0 58.5 14.0
peaks, which is the main component of the composition. The
PBAT-0.5%ADR − 30.6 124.6 14.8 58.9 13.0
peaks at 25 and 130 ppm, attributed to the PBAT, feature
PBAT-1%ADR − 31.3 122.9 16.2 62.9 14.3
small shoulders at 20 and 125 ppm that are related to the
PBAT-2%ADR − 31.1 122.8 20.3 55.9 18.2
ADR. Also, this spectrum shows spinning sidebands at 63,
PBAT-5%ADR − 28.8 122.6 17.4 49.5 16.0
85 and 94 ppm, which are due to carbonyls d, attached to the
PBAT-10%ADR − 27.3 120.9 13.1 45.0 12.8
benzene, and the γ and γ′, attached to the aliphatic carbons
(this measurement was performed at slower MAS, 10 kHz,
in comparison to the experiments for the pure compounds
and the PBAT-1%ADR, 15 kHz). The sample PBAT-2%ADR showed a significant increase
The PBAT-10%ADR spectrum is dominated by the ADR, in E and σ values; the other samples just presented a slight
in a proportion of, at least, 2:1. Although cross-polarization increase in elastic modulus and in tensile strength. The
experiments are not quantitative as performed in this man- remarkable increase in σ of PBAT at relatively low con-
ner, the use of high contact time (1 ms) should provide a centration of ADR (1 and 2%) can be attributed to different
spectrum that resembles the quantitative spectrum. The fact factors [19]: probably, the ADR resulted in a variation in the
that the ADR dominates the 13C{1H} CP-MAS spectrum is relative Mw of the sample [2]; and the main reason is related
an unexpected result. One possibility for this behavior is that to the glass transition (Table 2) of the samples, that even
at higher concentrations (~ 10%), the presence of the ADR with slight increase reflects in the polymer properties. In this
in the thermo-mechanical mixture induces linkage break case, the ADR action probably occurs by physical interac-
in the PBAT polymer structure; in this case, it is possible tions, since there are no significant changes in the PBAT-
that, due to the scission suffered by PBAT chains, the ADR ADR FTIR and NMR spectrum for 1 wt%. The improve-
has greater interaction with new PBAT “interaction points”, ment of mechanical properties like elongation-at-break and
which induces a more efficient chain extension effect, as tensile strength is due to the effect of the interaction between
presented in the next sections. the materials [12, 19]. A different mechanical behavior was
observed in PBAT-5%ADR and PBAT-10%ADR. In these
Mechanical properties samples, the ADR action is different from its action in the
samples with low contents. As more ADR was added, the
The tensile mechanical properties (tensile modulus - E, ten- tensile strength decreased. Two hypotheses justify this
sile strength - σ, and elongation-at-break- ε) of PBAT and change: (1) ADR particles can act as stress concentra-
PBAT modified with ADR are summarized in Table 1. The tors; (2) ADR acting as a chain extender at 5 and 10%. We
results showed that the elongation-at-break increases from believe that the second hypothesis is the more coherent, and
around 1200 to 1770% after the addition of chain extender, it can be justified because, as a chain extender, the materials
as expected, since it reacts with terminal groups of poly- show indicative of chemical interactions by the vibrational
meric chains, approximating each other. Adding different changes observed in the FTIR and NMR analysis.
contents of ADR changes the mechanical properties because Similar results were observed by Wang et al. (2016)
the intermolecular forces and polar–polar interactions prob- after the addition of ADR into poly(propylene carbonate)
ably are formed. matrix. In this case, the authors observed that the addition

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of 1 wt% was the best ADR content [2]. This substantial
difference in the best ADR content can be attributed to the
high poly(propylene carbonate) matrix fragility, which is
another widely used material, or because of the low reac-
tivity between ADR and PBAT.
The composition with the best mechanical properties
is PBAT-2% ADR. Considering the mathematical models
to which the acquired data on mechanical properties were
fitted (Fig. 4), the elastic modulus presented a maximum
value at an ADR concentration of 3% [22]. For any higher
ADR content, lower values were achieved, as observed
in our results of 5 and 10%. According to Cardoso et al.
(2017), the arrangement of PBAT molecular shows three
molecular CH bonds. Those points are undermined due to
the modifier action, which reduces the elastic modulus and
tensile strength after the maximum point [10]. In our case,
the maximum point is ~ 2 wt%.
This mechanical behavior indicates the suitability of the
PBAT-ADR for application in thin films, biodegradable
package, and other forms requiring significant stretching
without breakage [19]. It is important to note that PBAT
is a high-cost material and increasing its mechanical
strength and stiffness can give greater functionality to
its application, resulting in a more resistant and higher
added value material. The three intermediary situations
and their expected behavior are shown in Fig. 5. The ran-
dom branched sites were generated during processing, due
to the shear suffered by the polymer.
Fig. 4  Elastic modulus of PBAT-ADR samples as a function of the
ADR content
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Thermal Properties—DSC analysis
Table 2 shows the DSC results: glass transition temperature
(Tg), melting temperature (Tm), cold crystallization tempera-
ture (Tc) and degree of crystallinity (Xc) of PBAT without/
with the ADR addition. The curve obtained for the second
heating run and cooling is presented in Fig. 6. The Tg val-
ues were determined in the second heating scan to evaluate
the changes after the ADR addition. PBAT showed Tg of
− 33.7 °C, which agreed with a reported value of − 30 °C
for PBAT in the literature [1]. After the addition of ADR,
the Tg values ranged from − 31 to − 27 °C, according to the
content of ADR added and its interaction with PBAT matrix.
With the addition of 0.5 wt % ADR, the Tg was increased
from − 33.7 to − 30.6 °C. This small variation is justified by
the low interaction between PBAT and ADR, due to the low
content incorporated, which results in few available active
sites.
Just after the addition of 5 and 10% of ADR, the increase
in Tg values was more significant. In this case, as verified
by FTIR and NMR results, chemical reaction between the
active groups of ADR and carboxylic groups of PBAT prob-
ably occurred, changing the molecular weight of the copoly-
mers formed.
Even at low ADR concentrations, the Tg of the samples
increased. It occurred because, with the introduction of the
benzene ring of ADR to the main chain of PBAT, the rigidity
of the molecular chain was increased. When polar groups
were introduced, Tg of the PBAT was increased because of
the increment inactivation energy of internal rotation and
intermolecular forces [2]. The variations in Tg, although
small, agree with the one observed in the literature for other
materials modified with ADR [2].
Tg and Tm are essential factors to consider because they
give information on the level of association between poly-
mer chains. The stronger the intermolecular bonds between
polymer chains, the higher the values of Tg. In this study,
as presented, the addition of 5 and 10% ADR resulted in
significant changes in the glass transition and melting tem-
peratures, which indicates the strong interaction between
PBAT and ADR.
The ­Xc of the PBAT was 13%. According to Li et al. the
crystallinity values are strongly dependent on the prepara-
tion method, and to the source of raw material, it may vary
between 10.0 and 18.0% [1]. Bastarrachea et al. verified a Xc
of 10.0% for the solvent-cast PBAT films [23]. The crystal-
linity of PBAT increased with the addition of ADR in most
cases, which is due to the increase in ∆Hm observed for
PBAT-1%ADR, PBAT/2%ADR, and PBAT/5%ADR. This
phenomenon may be due to the induced heterogeneous crys-
tallization from the ADR particles [24]. The increased crys-
tallinity corroborates the mechanical results, mainly for the
sample PBAT/2%ADR. In the case of PBAT/10%ADR, the
Iranian Polymer Journal
Fig. 5  Schematic representation of PBAT and ADR interaction
excess of ADR, which has lower chain flexibility, probably
restricts the mobility of the PBAT chains, hampering the
molecular organization and decreasing the Xc values [19].
In samples PBAT/ 2%ADR and PBAT/5%ADR, the crys-
tallization temperature of PBAT decreased, which can be
attributed to the ADR particles that leads to slow crystal-
lization. In these samples, the ADR probably does not act
as a nucleation agent, different from those observed for the
other samples [24]. In the samples that the Tc increased, its
samples probably have a slow rate and over a wide range of
temperature of crystallization.
In high amorphous structures, the overlapping of poly-
mer chains may not take place entirely, and some regions
will not crystallize due to chain entanglements. When the
PBAT is heated, its chains will start moving and will find
an opportunity to interact with each other. Due to the struc-
tural characteristics and the distribution of polymer chains,
crystallization occurs slowly and over a wide range of tem-
perature, as described before [23].
The changes in thermal properties with the addition of
ADR can be used to describe variations in the tensile prop-
erties of PBAT and the interactions observed in the FTIR
and NMR results.
Rheological measurements
Rheological tests carried out by torque rheometry on PBAT
with and without ADR are shown in Fig. 7. The experiment
was conducted to evaluate the evolution of ADR reaction
with PBAT over the mixing time in the molten state. It was
verified that the ADR did not change the time of the maxi-
mum torque, which occurred at about 0.5 min. From 5 to
10 min processing time, the polymer appears to be fully
molten [25]. The observed results show a slight difference
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Fig. 6  a Second heating run and b cooling of DSC thermograms obtained for all the samples

Fig. 7  Torque rheometry for PBAT with and without ADR a temperature versus time and b torque versus time

with the literature due to the adopted procedure. Costa et al.
[9] incorporated the additive after 8 min of processing time,
while, in this article, we added the additive at the same time
as that of the PBAT.
After 2 min, the temperature increased for all the samples,
but it was more significant for 5% ADR. In the same time,
the torque decreased in all, and again the PBAT/5% ADR
displayed a different behavior. In the case of 2% ADR, there
is a slight increase, while for 5% ADR, the change is very
significant, revealing an increase in viscosity resulting from
the chain extension reaction. Costa et al. [9] observed that
only for high levels of additive, the molar mass has a high
increase (up to 8%). For the other samples, other authors
observed a similar behavior, which can be explained that
ADR has limited solubility in the PBAT melt. When added
in low contents, it can act as a lubricant, reducing viscous
stresses in the matrix and improving the dispersion process.
However, as in low contents the PBAT chains suffered low

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scission, the chemical reaction was not triggered in the sys-
tem, resulting in non-expected results. More intense mixing
may be necessary in these cases to react both components,
even at the risk of increasing degradation during process-
ing. This phenomenon must be taken into consideration in
automated inline testing systems [9].
It is known that the torque increase is related to molten
polymer viscosity increase, which is caused by molecular
weight variation [19]. However, in our work, the viscosity
of neat PBAT is higher than the viscosity of some com-
pounds (unexpected). A likely explanation (but, of course,
not a proof) of these observations is based on the matrix
instability: PBAT starts to degrade during processing and
degradation is profoundly affected by the filler (ADR, in this
case) and the filler content. The first point to observe is that
the presence of the filler has a very strong effect on thermal
degradation, especially to the sample PBAT-10%ADR. So,
the results show a slight, but significant, thermal degradation
during processing [9].
By doing a joint analysis of the mechanical and rheom-
etry results, probably the sample with 5% of ADR was the
only one that presented the effect of chain extension. The
high concentration, as already mentioned, is due to the low
incompatibility between additive and matrix. This sam-
ple shows a good interaction between the PBAT and ADR
(observed by FTIR and NMR), and this interaction between
reactive end groups probably increased the molar mass
of the compounds, avoiding degradation [25]. Yang et al.
(2017) investigated the torque rheometry of PET-ADR and
verified a distinct behavior with low ADR content. In this
case, both compounds have excellent interaction, and ADR
undergoes fast reactions with PET [26].
It is important to note that the torque rheometry simu-
lates processing using shear and temperature. So, this study
is essential to estimate incipient polymer degradation dur-
ing processing. The procedure takes advantages of the high
sensitivity of melt viscosity changes in molar mass. Also,
this method is fast and may be implemented in different pro-
cessing equipments to obtain real-time estimates of polymer
degradation [25]. This analysis must be taken into considera-
tion in automated inline testing systems.
Conclusion
A multi-functional epoxide oligomer, Joncryl A ­ DR®, was
used to improve the mechanical and thermal properties of
PBAT. The interaction between active sites of PBAT and
ADR was verified by FTIR and NMR. It was observed that,
for the samples with 5 and 10% ADR, the carboxylic groups
of PBAT tended to interact with epoxy groups of ADR. How-
ever, to the samples with low ADR contents, no chemical
interaction was observed. Possibly, at low concentrations, or
chemical interaction between samples was low, or there was
only physical interaction, and ADR may have acted as a rein-
forcing agent. After ADR addition, the samples presented an
enhancement in mechanical properties due to intermolecular
forces; there was a remarkable increase in tensile strength
and elastic modulus of PBAT at the relatively low concentra-
tion of ADR (2 wt%). The sample PBAT-5%ADR showed
a decrease in the tensile strength, probably due to the more
efficient action of the chain extender. This was not verified
for the other contents.
Regarding thermal behavior, the observed changes indi-
cated a strong interaction between the PBAT and ADR. The
rheological results showed that ADR could act as an internal
lubricant during processing, which demonstrates the impor-
tance of processing parameters controlling. To industrial
applications, it may be necessary more intense mixing to
disperse ADR in PBAT matrix, even at the risk of increas-
ing degradation during processing. Other different mixing
processes could achieve better results.
This study is important because it brings knowledge about
the interaction between PBAT and ADR. Several studies use
ADR in PLA-PBAT blends; however, the effect of ADR in
terms of interaction with PBAT is not investigated in depth.
It is also important to minimize the risk of degradation and
to increase the processability and commercial applications
of PBAT and its blends.
Acknowledgements  The authors thank the Thiago Branquinho de
Queiroz for the help with the NMR analysis, UFABC, REVALORES
Strategic Unit, Capes  (Code 001), CNPq (nº 306401/2013-4  and
305819/2017-8) and Multiuser Central Facilities (UFABC).
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