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Compatibilization www.ms-journal.de

Effect of the Joncryl1 ADR Compatibilizing Agent in

Blends of Poly(butylene adipate-co-terephthalate)/
Poly(lactic acid)
Edilene de C. D. Nunes, Alana G. de Souza, and Derval dos S. Rosa*

Mixtures of PLA with flexible polymers,

The growing search for biodegradable products contributes to the develop- such as PBAT, are studied to improve the
ment of new materials. In this work, the effect of the Joncryl1 ADR chain mechanical properties of PLA, mainly
extender on poly(butylene adipate-co-terephthalate)/poly(lactic acid) blends regarding their toughness.[10,11] PBAT
and PLA, when used together, are consid-
was investigated. The mechanical, thermal, and morphological properties and
ered complementary due to the elastomeric
the contact angle of the blends were also studied. The addition of the chain properties of the PBAT and brittleness of
extender can either improve the adhesion between the phases or act as a the PLA.[12,13] However, the PBAT/PLA
stress concentrator, depending on the proportion of PLA present in the blend. blend is considered to be immiscible.
However, in all samples, the elongation at break was increased. This behavior Therefore, achieving good interface com-
patibility between PBAT and PLA is essen-
is also observed in the morphology of the blends, changing the shape of the
tial to obtain a mixture with satisfactory
PLA particles, from spherical to ellipsoid phase. However, in the proportion properties.[12] The use of chain extenders is
used (0.5 wt%), the chain extender was not enough to increase the adhesion an alternative to improve the compatibility
between the phases of the blends, just the dispersion of the PLA particles. of these blends, as long as these are
Besides, it is possible to observe that the higher the PLA content in the PBAT additives that improve melt strength and
mixture, the lower wettability surface of the blends is reached. thermal stability. Chain extenders enable
re-linking polymer chains that have broken
down due to any degradation reaction. The
resulting reactions depend on the func-
tionality of the chain extender used and its
1. Introduction concentration on the polymer. For the polyesters, such as PBAT,
several searches have used the types containing epoxy groups
The large use of plastics in the packaging industry in recent which can react with the hydroxyl and carboxyl groups in the
years has increased the interest in polymers with biodegradable polyester chain-ends.[13] The Figure 1 shows the structure of
and compostable characteristics to replace conventional PBAT, PLA, and ADR.
polymers in order to reduce the impact caused by the This paper investigates the effects of a chain extender as
inappropriate disposal of these materials in the environ- compatibilizer agent, aiming the increase of the interface in
ment.[1–7] One of the biodegradable and compostable polymers PBAT/PLA blends, and better mechanical, thermal, and
that has commercial potential use is the poly(butylene adipate morphological properties. Besides, this paper presents an
co-terephthalate), PBAT, an aliphatic aromatic copolyester alternative to overcome the high cost of PBAT, maintaining
manufactured from petroleum based resources. It has a high the biodegradability of the polymer.
elongation at break, high ductility, and low modulus of
elasticity.[8] However, PBAT has some disadvantageous proper-
ties that restrict the large-scale industrial applications, such as
2. Experimental Section
poor mechanical properties and high production cost. To
overcome these limitations, PBAT can be blended with another The poly (butylene adipate-co-terephthalate) (PBAT) was
biodegradable polymers to extend the range of applications and produced and supplied by BASF with an average molecular
improve their properties. mass weight of 66 500 g mol
1. The poly(lactic acid)
PLA
Poly(lactic acid)
PLA is a thermoplastic polymer, also produced by Ingeo, 3801-X (batch 653-89-01), kindly provided
biodegradable, with high tensile modulus and strength.[9] by Cargill Agricola SA (Minnetonka, USA). BASF Joncryl1
ADR 4370S chain extender (CE), average molecular mass
E. C. D. de Nunes, A. G. de Souza, D. S. dos Rosa weight of 6800 g.mol
1 and epoxy equivalent weight of
Engineering Center, Modeling and Applied Social Sciences 285 g mol
1.
Federal University of ABC (UFABC) The composites were prepared according to Table 1 using a
Santo Andre 09210-580 SP, Brazil quick K-Mixer homogenizer (MH
50Hir). The samples were
E-mail: dervalrosa@yahoo.com.br; derval.rosa@ufabc.edu.br
molded into sheets by compressing at 190  C and 8 MPa for
DOI: 10.1002/masy.201800035 5 min using a hot compression-molding machine.

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Figure 1. Structures of (a) PBAT, (b) PLA, and (c) chain extender ADR.

2.1. Mechanical Properties
Tensile tests were performed in a universal testing machine
(Instron 5900) (Instron S/A Ind. e Com. Ltda.) according to
ASTM D638. The cross-head movement speed of 50 mm min
1
was used as recommended by the standard. The elastic modulus
(E), ultimate tensile strength (σmax), and elongation at break
(emax) were evaluated.
2.2. Thermal Properties
in the blend, H0m is the melting enthalpy of 100% crystalline
PBAT, and the value used is 114 J g
1.[13] For PLA, the melting
enthalpy of 100% crystalline is 93 J g
1.
2.3. Morphological Properties
The morphologies of the fractured samples were examined
through a JEOL, JCM-6000 SEM, at an acceleration voltage of
10 kV. The samples were sputtered with gold to 20 nm thickness
using a Leica EM ACE 200 sputter coater.

The tests were performed using a TA Instrument DSC Q200.

The sample was heated from
50 to 200  C, cooled to
50  C and
reheated up to 200  C, with 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
Equation (1):


X c ¼ ðΔHm
ΔHcc Þ= W PBAT  H0m  100
2.4. Water Contact Angle (WCA)
Tests were performed using a Dynamic contact angle tensiome-
ter (DCAT) with three phases (air/water/sample) to determine
the static contact angle (θest) and dynamic contact angle (θdin)
according to the Young-Laplace equation with droplets of 4.00 mL
for 300 s.[14]
ð1Þ

where ΔHm is the sample melting enthalpy, ΔHcc is the PLA cold
crystallization enthalpy, WPBAT is the mass fraction of the PBAT
3. Results
3.1. Tensile Properties
Table 1. Prepared PBAT/CE/PLA compositions with their
nomenclature. Table 2 shows results for tensile strength, elongation at break
and modulus of elasticity for all studied formulations.
Sample PBAT [wt%] PLA [wt%] CE [wt%] Considering neat PBAT, the chain extender (CE) led to increase
PBAT 100
–
from 1269.3% to 1848.7% in elongation which corresponds to a
45.6% increase. The increase in elongation at break may be
PBAT/CE 99.5 – 0.5
related to the chain extender behavior after the interaction with
PBAT/PLA 80/20 80 20 – the polymer chain end.[13] However, there was a reduction in
PBAT/PLA/CE 80/20 79.5 20 0.5 tensile strength at break from 25.1 to 19.9 MPa (20% decrease).
PBAT/PLA 70/30 70 30 – Similar results are observed for neat PLA. Yan et al studied the
PBAT/PLA/CE 70/30 69.5 30 0.5 influence of ADR in poly(ethylene terephthalate) and observed
that ADR increased the elastic phenomenon, as verified. This
PLA – 100 –
high elasticity is related to the molecular structure of the
PLA/CE – 99.5 0.5
modified materials.[15]

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Table 2. Mechanical properties of neat PBAT and PLA and their blends with and without CE.

Sample Tensile strength [MPa] Elongation at break [%] Young’s modulus [MPa]

PBAT 25.1  1.2 1269.3  147.6 51.0  1.6

PBAT/CE 19.9  1.0 1848.7  66.2 51.9  2.1
PBAT/PLA 80/20 13.9  0.8 609.3  99.0 71.8  2.7
PBAT/ PLA/CE 80/20 20.6  0.3 753.9  16.8 76.8  4.5
PBAT/PLA 70/30 9.0  0.2 183.1  40.9 93.5  2.3
PBAT/ PLA/CE 70/30 8.6  1.0 214.2  18.2 71.9  5.6
PLA 58.1  1.6 6.4  0.6 2068.0  27.7
PLA/CE 71.8  3.3 6.7  0.2 2417.0  44.9

For the PBAT/PLA 80/20 blend, the addition of CE increased
the elastic modulus and elongation at break. Also, the blend
PBAT/PLA/CE 80/20 showed a slight increase in tensile
strength. This is because of, as the compatibility and interfacial
adhesion between the PBAT and PLA phases were improved, the
tensile and strain properties could be more efficiently
transferred from the PBAT matrix to the PLA domains after
the addition of the chain extender.[16,17] According to Li et al. the
ADR addition resulted in the reaction between the carboxylic
acid group of PBAT/PLA blends and the CE.[18]
Similar results were observed by Tang et al. which added
0.5 wt% of Joncryl ADR and observed an improve in tensile
strength and flexural strength from the studied blend (POM/
TPU).[19] It is possible to note that the increase in the amount of
PLA in the blend composition results in larger modulus of
elasticity, because when a weakly conducting polymer with high
tensile strength is added as the dispersed phase, it is expected
that there should be an increase in the elastic modulus,
satisfying the additivity rule.[13]
For the PBAT/PLA 70/30 blend, the addition of the CE caused
a small reduction in the modulus of elasticity, which may be
justified by a structural change occurring in the mixture,[13]
where the PLA phase appeared as ellipsoids, as deformed
droplets with low aspect ratio and possibly acting as stress
concentrators in the PBAT matrix. These results were observed
by Arruda et al. in their study.[12] In addition, it possibly occurs in
consequence of numerous cavities and/or cracks formed during
deformation.[15] Interestingly, the ductility of all samples can be
significantly improved by incorporation of a small amount of CE
(0.5 wt%.).[14]
3.2. Thermal Properties
The thermal properties of the PBAT, PLA, and their blends with
and without CE are studied by using differential scanning
calorimeter (DSC). Table 3 shows the cold crystallization
temperature (Tcc) and enthalpy (ΔHcc), melting temperature
(Tm), melting enthalpy (ΔHm), and the degree of crystallinity (Xc)
of the samples related to the first heating scan. The glass
transition temperature (Tg) values were determined in the
second heating scan to evaluate the miscibility of the systems.
PLA showed a double endothermic peak (melting temperature)
at 149 and 157.6  C. This double peak is common in polyesters,
and the literature justifies its presence by a melt/recrystalliza-
tion/re-melt mechanism.[16,20]
For the PBAT/PLA blends, there was an overlap between the
PBAT melting region and the PLA cold-crystallization region.
Consequently, it was difficult to determine the cold crystalliza-
tion temperature (Tcc) and enthalpy (ΔHcc), besides PBAT
melting temperature for PBAT/PLA/CE 80/20 blend. It was
reported that this behavior occurs because of the crystals melted
at different temperatures had the similar structure but different
lamellar thickness, which results in double endothermic

Table 3. DSC data of PBAT, PLA, and PBAT/PLA blends with and without CE.

Sample Tga [ C] Tgb [ C] Tcc [ C] ΔHcc [J g
1] Tma [ C] Tmb [ C] ΔHm [J g
1] Xc [%]

PBAT
31.0 – 58.6 17.6 122.9 – 15.6 13,7

PBAT/CE
30.8 – 59.1 16.3 122.4 – 14.8 13.0
PLA – 60.4 104.0 28.4 – 147.7/156.9 15.4 16.6
PLA/CE – 60.1 103.4 22.3 – 147.4/156.0 11.5 12.4
PBAT/PLA 80/20
31.0 59.7 98.6 0.8 120.6 155.5 8.2 8.1
 
PBAT/PLA/CE 80/20
31.3 60.0 125.6 148.7 2.2 2.5
PBAT/PLA 70/30
32.1 59.4 106.0 4.9 124.7 148.4/156.5 2.9 3.7
PBAT/PLA/CE 70/30
31.4 60,7 111.3 1.8 127.1 148.9 0.9 1.2

Tga is the glass temperature of PBAT, Tgb is the glass temperature of PLA, Tma is the melting temperature of PBAT, Tmb is the melting temperature of PLA.

It was not possible to determine the Tcc and ΔHcc in this blend.

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Figure 2. Scheme and micrographs of the fractured neat PBAT, neat PLA, and their blends with and without CE.

peak.[16,20] In all blends, the variation on the Tmb probably is due
to the increase in the organization of the polymers chains due to
the high crystallinity of PLA.
All the blends showed two distinct glass transition temperature,
and no change occurred in this transition, indicating that the
formed blends are thermodynamically immiscible.[13] Further-
more, the presence of the chain extender did not lead to changes in
this transition temperature (Tg), but it decreased the ΔHcc, and
slightly increased the melting temperature for the blends. The PLA
phases in the blends reduced the degree of crystallinity from 13.7%
in the neat PBAT to 8.1% and 3.7%, respectively, in the blends with
20% and 30% PLA. This occurred because PLA has lower chain
flexibility and a higher viscosity, and that restricts the PBAT
molecular reorganization and the chains mobility in the blend,
which decreases the degree of crystallinity.[13]
3.3. Morphological Analysis
The morphologies of neat PBAT and PLA and their blends with
and without CE are shown in Figure 2. The morphology of
immiscible polymers blends is the result of the interaction
between process variables as well as temperature, deformation
types, and shear rate and blend components properties (phases
percentage, interfacial tension, viscosity ratio, and the elasticity)
and the final morphology is the combination of all factors.[13]
The addition of the CE did not cause any visible morphological
changes to neat PBAT, which is an indication that the CE acted
just as a chain extender. The same behavior is observed for PLA
and PLA/CE. However, when analyzing the morphology of the
blends without the CE, a characteristic of immiscible blends with
low adhesion is observed. In the PBAT/PLA 80/20 without chain

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Figure 3. Contact angle for the neat PBAT and their blends with and without CE.

extender, voids are observed in the matrix, where “beads” of PLA samples, the addition of CE can promote biodegradation and/or
were pulled out from the polymer matrix. The spheres dispersed hydrolysis, being indicative of increased biodegradability.[25] In
in the continuous phase are a characteristic of reinforcement the case of the blends, there is an opposite behavior, and it is
morphology for rubber tenacification.[12] possible to observe that higher PLA content in the mixture with
After the addition of the CE, the voids presented smaller PBAT/CE resulted in greater WCA (higher degree of
diameter (according to Figure 2), and the sample was more hydrophobicity).
homogeneous. The CE can act as a compatibilizer and lead to
the reduction of interfacial tension that stabilizes the dispersed
phase in smaller sizes, leading to the refinement of the 4. Conclusions
dispersed phase.[13] This behavior can be seen in the PBAT/
Both the neat PBAT and the studied blends showed, after the
PLA/CE 80/20, corroborating the results of the mechanical
CE addition, an increase in the elongation at break, while the
tensile tests.
elastic modulus slight increased in the neat PBAT and PBAT/
In the case of the PBAT/PLA/CE 70/30 blend, the addition of
PLA 80/20 and decreased into the PBAT/PLA 70/30 blend.
the CE presented a dispersed phase in the form of oriented
This decrease probably occurs due to the change in the form of
ellipsoids, which possibly acted as stress concentrator, which
the PLA particles dispersed in the PBAT matrix, from spherical
justifies the decrease of the mechanical properties, as shown
to ellipsoid phase, that may have acted as a stress concentrator.
previously.
The addition of CE caused an increase in tensile strength,
which is an indicator of the compatibilizer behavior of the
chain extender, as expected. All the samples showed a slight
3.4. Water Contact Angle (WAC)
variation in the melting temperature after the blending,
resulted in the changes in the organization chains. However,
The water contact angle value is used as an indicator of surface
the thermal behavior of the neat PBAT, PLA, and their blends
hydrophilicity or hydrophobicity of polymers, and for PBAT was
did not present significant changes. By the morphological
in the range of 69–73 , depending on the preparation method.[21]
analysis, it can be concluded that the chain extender, in the
Also, according to Smith and Verbeek, the variation in the
content added in this work, was not enough to increase the
contact angle can be justified by the dispersion between the
adhesion between the phases, but significantly altered the
minor phase and major phase.[22] Figure 3 shows the behavior of
dispersion of the PLA phase. After the addition of the CE, neat
the water droplet for the PBAT surfaces and their blends.
PBAT and PLA showed a higher hydrophilicity degree.
Generally, a surface is considered hydrophobic when the
However, in the blends, there is a contrary behavior, with a
WCA is greater than 65 . It is possible to observe that both
higher degree of hydrophobicity. The addition of the chain
PBAT and PLA have a hydrophobic character, and their behavior
extender can either improve the adhesion between the phases
is close to the hydrophilic-hydrophobic transition limit, so, the
or act as a stress concentrator, depending on the proportion of
degree of hydrophobicity is not so high.[21] With the addition of
PLA present in the blend. However, in both PLA concen-
PLA in the PBAT matrix there was a decrease in contact angle,
trations, CE acts in the dispersion of PLA particles.
as long as when PLA content is increased, the WCA increases
too. The results indicate that the hydrophilicity of the PBAT
samples can be tuned by blending with PLA.[23] These results
are due to the variation on the chains length and force field of Acknowledgements
the contacting solid.[24] After CE addition, there was an The authors thank CNPq (n 830094/2008-3, 306401/2013-4, 47180/
inversion in the behavior of neat PBAT and neat PLA, wich 2014-2), REVALORES Strategic Unit, and Multiuser Central Facilities
in both cases, the hydrophilic character growth. For these (UFABC) for the support.

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Keywords
blends, chain extender, compatibilization, differential scanning
calorimetry (DSC), mechanical properties
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