European Polymer Journal 100 (2018) 178–186

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European Polymer Journal

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Poly (L-lactide)/PEG-mb-PBAT blends with highly improved toughness and T

balanced performance
⁎
Ruoyun Lia, Linbo Wua,b, , Bo-Geng Lib
a
State Key Laboratory of Chemical Engineering at ZJU, College of Chemical & Biological Engineering, Zhejiang University, Hangzhou 310027, China
b
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical & Biological Engineering, Zhejiang University, Hangzhou 310027, China

A R T I C L E I N F O A B S T R A C T

Keywords: PEG-mb-PBAT (EB, for simplicity) multiblock copolymers were synthesized via chain extension/coupling of poly
Poly(L-lactide) (ethylene glycol) (PEG) and poly(butylene adipate-co-terephthalate) (PBAT) diols, and used as modifiers to
Plasticization prepare blends of commercial poly(L-lactide) (PLLA) and EB via melt blending. The EB copolymers were char-
Toughening acterized by 1H NMR and DSC, and the PLLA70/EB30 blends were characterized by DSC, SEM, tensile and
Multiblock copolymers
impact testing. The PEG segments in EB show greatly depressed crystallization as compared with PEG pre-
Mechanical properties
polymer, therefore, exhibit excellent plasticization effect on PLLA. Furthermore, they also compatibilize the
PBAT microphase with PLLA matrix. Owing to strong interfacial adhesion, the PBAT micro-phases induces highly
oriented shear yielding during impact process and therefore act as efficient tougheners of PLLA. Therefore, the
blends possess highly improved toughness (impact strength 44 kJ/m2) and excellent ductility (elongation 160%),
and at the same time, retain sufficient stiffness. Furthermore, the L/EB blends show superior mechanical per-
formances than the L/EP (PLLA/PEG-mb-PPA) blends reported by us previously.

1. Introduction [11,19–21]. Therefore, satisfactory plasticizers with high enough molecular

Biobased and biodegradable polymers have attracted much attention
from academy and industry for decades because of unsustainability of pet-
roleum resources and daily increasing concerns about the environment [1].
Poly(L-lactide) (PLLA) is regarded as the most important biobased biode-
gradable polymer and has been used as an excellent substitute for traditional
petroleum-based non-degradable polymers. It is a semi-crystalline polyester
with characteristic polymorphs and stereoisomerism, excellent biocompat-
ibility, biodegradability, transparency [2–4] and high stiffness, and has been
extensively applied to the fields of biomedical materials, packaging materials
and other disposal products [5–10]. However, PLLA also has inherent
shortcomings like poor ductility and impact toughness, with elongation at
break lower than 10% [11] and izod impact strength less than 5 kJ/m2
[12,13]. These shortcomings severely limit its applications as materials with
highly demanded end-use performance [14].
Mixing with a plasticizer is an efficient way to improve the ductility or
tensile toughness of PLLA, and the impact toughness can sometimes be
improved as well. A variety of plasticizers have been reported for PLLA
plasticization, including epoxy soybean oil [15], citrate esters and its deri-
vatives [16–18], poly (ethylene glycol) (PEG), poly (propylene glycol) [14].
Among them, low molecular weight plasticizers tend to migrate from PLLA
matrix, as a result, the plasticized PLLA materials get brittle again soon
weight were employed to depress migration [22–24]. On the other side, as
an inherent drawback, plasticization is often achieved at the expense of
sacrificing material stiffness. Furthermore, plasticized PLLA did not achieve
satisfactory impact toughness in some reports [21,25,26].
Blending with rubber-like modifiers is widely used for PLLA
toughening. In order to maintain its biodegradability, various flexible
biodegradable polymers, especially aliphatic polyesters or aliphati-
c–aromatic copolyesters, have been employed to toughen PLA
[12,13,27–31]. However, it is often difficult to achieve excellent duc-
tility and toughness at the same time via blending with only elastomers
and even in the presence of pre-made or in-situ formed compatibilizers
which are necessary to enhance the interfacial adhesion [32–34].
Therefore, it is quite desirable to modify PLA to achieve good balance
among ductility, impact toughness and stiffness.
In our previous study, multiblock copolymers (PEG-mb-PPA) com-
posed of miscible PEG segment and immiscible flexible poly(1,2-pro-
pylene adipate) (PPA) were designed and used as modifiers for PLLA.
The resulting PLLA/PEG-mb-PPA blends have much more balanced
mechanical properties than PLLA/PEG or PLLA/PPA blends [35].
However, some of the blends exhibit second yielding/necking phe-
nomenon and therefore relatively low strength at break. Poly(butylene
adipate-co-terephthalate) (PBAT), as a biodegradable flexible

⁎
Corresponding author at: State Key Laboratory of Chemical Engineering at ZJU, College of Chemical & Biological Engineering, Zhejiang University, Hangzhou 310027, China.
E-mail address: wulinbo@zju.edu.cn (L. Wu).

https://doi.org/10.1016/j.eurpolymj.2018.01.037
Received 9 November 2017; Received in revised form 27 January 2018; Accepted 29 January 2018
Available online 31 January 2018
0014-3057/ © 2018 Elsevier Ltd. All rights reserved.
R. Li et al.
copolyester, can be used as a modifier of PLLA to improve its ductility
and/or toughness [28,32]. As a PLLA modifier, PBAT has some favor-
able factors vs. aliphatic polyesters like PPA, including semi-ar-
omaticity and relatively low cost. For this consideration, in this study,
PBAT was used instead of PPA to synthesize PEG-mb-PBAT multiblock
copolymers which acted as more efficient and economical modifiers to
prepare PLLA/PEG-mb-PBAT blends with better performance.
2. Experimental section
2.1. Materials
Poly(L-lactide) (PLLA, 4032D, NatureWorks), hexamethylene diiso-
cyanate (HDI, Aladdin), polyethylene glycol (PEG6000, Mn 6000 g/mol,
Sinopharm, China) were all used as received. 1,4-Butanediol (BDO) and
terephthalic acid (TPA) were provided by Sinopec Yizheng Chemical
Fiber Co. Adipic acid (AA) and commercial liquid titanium-based cat-
alyst were kindly provided by Zhejiang Xinfu Pharmacy Co.
2.2. Synthesis of PBAT diol prepolymer (B)
BDO, AA, TPA (AA/TPA molar ratio 55/45, diol/diacid molar ratio 2/1)
and catalyst (0.1 wt% based on all monomers) were mixed in a 1000 mL
four-necked round bottomed flask under stirring. The esterification reaction
was carried out under nitrogen atmosphere at 200–220 °C until no water
was distilled out. Additional catalyst (0.1 wt%) was added and then the
pressure was reduced to below 150 Pa and the temperature was raised to
230 °C, and melt polycondensation was conducted under these conditions
for 12 h. White OH-terminated PBAT prepolymer was obtained after cooling
to room temperature under N2 protection.
2.3. Synthesis of multiblock copolymers (EB)
PEG (70, 50, 20 wt%) and PBAT (30, 50, 80 wt%) prepolymers were
mixed in a 100 mL three-necked flask, heated to 140 °C and kept at the
temperature under stirring and pressure below 100 Pa for at least 2 h in
order to remove the moisture in them. Then, HDI (NCO/OH molar ratio
1.05:1) was added into the mixture to start the chain extension/cou-
pling reaction under nitrogen atmosphere at 140 °C until clear
Weissenberg effect appeared at a stirring rate below 30 rpm. Finally, the
resulting multiblock copolymer PEG-mb-PBAT was cooled and stored in
a dessicator after taking out from the flask. For simplicity, the copoly-
mers are denoted as EB30, EB50 and EB80, respectively.
2.4. Preparation of PLLA/EB (L/EB) blends
PLLA (100-x part) and an EB modifier (x part) were melt blended in
a Brabender Torque Rheometer (Brabender Technology, Germany) with
a rotor speed of 60 rpm at 180 °C for 10 min. PLLA was dried in a va-
cuum oven at 80 °C and the EB modifiers at 40 °C for at least 24 h before
blending. PLLA blends with PEG6000 (E) or PBAT4000 (B) were also
prepared for comparison. For simplicity, the obtained blend was sym-
bolized as “Mx”, where M represents the modifier (EB; E; B;), x re-
present the weight percentage of the modifier in the blend.
The obtained blends were injection molded using HAAKE MiniJet II
(Thermo Electron, Germany) to prepare dumbbell-shaped (narrow
section dimension: 20 × 4 × 2 mm3) and rectangular specimens
(80 × 10 × 4 mm3) for tensile and impact testing, respectively. The
blends were first melt in the cylinder at 180 °C, and then injected into a
mold preheated to 35 °C at an inject pressure of 850 bar for 30 s. Neat
PLLA was also processed under the same condition and used as a blank
sample to make a reference.
2.5. Characterization
1
H NMR spectra of the PBAT prepolymer and the EB multiblock
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European Polymer Journal 100 (2018) 178–186
copolymers were recorded with a Bruker AC-80 400 MHz NMR spec-
trometer using CDCl3 as solvent and tetramethylsilane as internal
standard. Intrinsic viscosity was measured at 25 °C with an automatic
viscosity tester (ZONWON IVS300, China) equipped with an Ubbelohde
viscometer (inner diameter 0.36 mm), using CHCl3 as solvent (solution
concentration 5 mg/mL).
Thermal transition behaviors were recorded with differential scan-
ning calorimetry TA-Q200 (TA Instrument, America). The blend sam-
ples were first heated to 200 °C at 40 °C/min and kept for 3 min, and
then cooled to −110 °C at −80 °C/min. After keeping at −110 °C for
3 min, the samples were reheated to 200 °C at 10 °C/min. For the pre-
polymers and multiblock copolymers, the DSC measurements were
carried out at the same heating and cooling rates but different tem-
perature range, −70 to 100 °C for PEG6000 and −110 to 180 °C for
PBAT prepolymer and EB.
Tensile properties of the blends were measured with a universal
testing machine Zwick/Roell Z020 (Zwick, Germany) at 25 °C according
to ASTM D638. The test was carried out at a crosshead speed of 10 mm/
min with a gauge length of 25 mm. Notched Izod impact testing was
carried out according to ASTM D256 using a CEΛST Resil impact tester
(CEΛST, Italy) with a pendulum of 4 J. All samples were conditioned at
room temperature for at least 48 h before testing. Five replicates were
tested for each sample.
Impact fracture surface of the blends was observed with an Utral 55
(Carl zeiss, Germany) scanning electron microscope at an acceleration
voltage of 5 kV. The impact fracture surface was coated with a thin gold
layer prior to observation.
3. Results and discussion
3.1. Synthesis and characterization of PEG-mb-PBAT (EB) multiblock
copolymers
The poly(butylene adipate-co-terephthalate) (PBAT) prepolymer
was synthesized via melt polycondensation of BDO, AA and TPA, as
shown in Scheme 1. It appears to be a white solid at room temperature.
Its 1H NMR spectrum is given in Fig. 1, along with the corresponding
chemical shift assignments. The chemical shift assignments of PBAT are
consistent with those reported in the literatures [36–38]. Among them,
the signals at 4.44 ppm (d), 4.38 ppm (i), 4.15 ppm (h) and 4.09 ppm (f)
are attributed to the chemical shifts of the protons in the two methylene
groups in the BDO moiety linked to the ester bonds, respectively. The
signal at 3.74–3.68 ppm (a′) is ascribed to the methylene linked to
terminal hydroxyl group. Based on the peak area ratio
(Ad + Ai + Ah + Af)/Aa′, the number average molecular weight (Mn) of
PBAT was determined to be 4000 g/mol. The hydroxyl value (VOH)
calculated from Mn is of 28.1 mg KOH/g. The intrinsic viscosity (IV) is
of 0.26 dL/g (CHCl3, 25 °C).
PEG-mb-PBAT (EB, for simplicity) multiblock copolymers were syn-
thesized by chain extension/coupling of PEG6000 and PBAT4000 diols
using HDI as an extension/coupling agent. The products appear to be white
to slight yellow solids. The IV of EB30, EB50 and EB80 reached 2.05 dL/g,
2.00 dL/g and 0.76 dL/g, respectively as collected in Table 1, which are
much higher than the prepolymers. From the 1H NMR spectrum of EB50
shown in Fig. 1, it can be seen that the characteristic signals of PBAT and
PEG methylene (q, 3.64 ppm) remained, and some new peaks attributed to
the methylene protons in the HDI moiety appeared at 3.15 ppm (n),
1.49 ppm (s) and 1.33 ppm (t). EB30 and EB50 showed similar 1H NMR
spectra (data not shown). From the much higher IV (vs. IV of prepolymers),
clear Weissenberg effect during chain extension/coupling reaction and the
results of 1H NMR spectra, it can be concluded that chain extension/cou-
pling occurred and high molecular weight EB multiblock copolymers had
been successfully synthesized.
PLLA blends with EB as well as PEG6000 and PBAT4000 were
prepared in a Brabender mixer at 180 °C. The appearances of these
blends are shown in Fig. 2. PLLA itself and the L/E blends (E20, E30)
R. Li et al. European Polymer Journal 100 (2018) 178–186

Scheme 1. Schematic diagram of synthesis of PEG-mb-

PBAT (EB) multiblock copolymers and preparation of
PLLA/EB blends.

in Table 2. The PEG prepolymer showed quite a sharp melt crystal-

lization peak around 29 °C with an enthalpy of 162 J/g even at a high
cooling rate of 80 °C/min, and melt at 60 °C with an enthalpy of 172 J/g
in the second heating scan at 10 °C/min, indicating its strong crystal-
lizability. The PBAT prepolymer presents to be poor crystallized and it
showed melt crystallization at 21 °C and melting at 114 °C, but the
crystallization and melting enthalpies are much lower (12.8 J/g and
24.6 J/g). PBAT showed clear glass transition around −40 °C, but PEG
showed no glass transition because of its strong crystallization.
As the melt crystallization peaks of PEG and PBAT prepolymers overlap
to certain extent, the melt crystallization peak of EB is the contribution of
both segments. As PEG prepolymer showed much stronger crystallizability
than PBAT prepolymer, it can be deduced that the contribution of PEG
segment is dominant in EB30 and EB50, but both segments contribute im-
portantly in EB80. The melt crystallization peak broadens and the melt
crystallization enthalpy decreases as the content of PBAT segment increases.
Fig. 1. 1H NMR spectra of the PBAT prepolymer (Mn 4000 g/mol) and the EB50 multi-
This result indicates that the crystallization of both segments in EB was
block copolymer. depressed due to the constraint of each other. Similar results have been
reported in other poly(ether-ester urethane)s [39]. As a result, cold crys-
tallization of PEG segment appears in EB50 and EB80 in the second heating
scan, and the melting temperature (Tm) and enthalpy (ΔHm,PEG, J/gPEG) of
Table 1
Molecular characteristics of PEG, PBAT prepolymers and EB multiblock copolymers.
PEG segment decreases with increasing the content of PBAT segment. Such
a crystallization depression is desirable for EB when it is used as a plasticizer
Sample Composition (wt%) Mn (g/mol) VOH (mg KOH/g) [η] (dL/g) for PLLA. Besides, both segments show independent melting peaks and the
glass transition temperature (Tg) of PBAT segment keeps almost unchanged,
B E
suggesting that the two segments are incompatible and micro-phase se-
PEG (E) 0 100 6000 19.4 0.23 paration morphology exists.
PBAT (B) 100 0 4000 28.1 0.26 Fig. 4 shows the DSC thermograms of neat PLLA and its blends, and
EB30 30 70 – – 2.05 Table 3 summarizes the thermal transition properties in the second
EB50 50 50 – – 2.00
heating scan. As expected, neat PLLA did not show observable melt
EB80 80 20 – – 0.76
crystallization. But the crystallization of PLLA in E20 and E30 blends
The number average molecular weight (Mn) of PEG used here was according to the was clearly promoted because of the plasticizing effect of PEG. It dis-
provider. The Mn of PBAT prepolymer was calculated from its 1H NMR spectrum shown in played melt crystallization (Tc 83.3–104.4 °C, ΔHc 26.1–36.1 J/gPLLA)
Fig. 1: Mn(PBAT) = 210 × (Ad + Ai + Ah + Af)/Aa’ + 92. The hydroxyl values (VOH) of even at cooling rate of 80 °C/min, no cold crystallization but sharp
PEG and PBAT were calculated from their Mn values. melting peak (ΔHm 34.4, 36.4 J/g). On the other hand, the crystal-
lizability of PEG in E20 and E30 seemed to be depressed to certain
extent. It displayed melt crystallization only in E30 and melting in both
are colorless and transparent, but the L/B (B20, B30) and L/EB (EB3030, blends. But the melting enthalpies are lower than that of PEG pre-
EB5030, EB8030) blends appear to be white or slight yellow and opaque. polymer (44 J/gPEG and 95.7 J/gPEG vs. 172 J/gPEG).
In comparison with neat PLLA, the PLLA in B20 and B30 blends
3.2. Thermal transition behaviors of EB and PLLA blends showed no melt crystallization but earlier cold crystallization (94–96 °C
vs. 110 °C). The melting enthalpies were almost unchanged when in-
Fig. 3 shows DSC thermograms of the two prepolymers and the creasing the PBAT content from 20% to 30%. Therefore the
three EB copolymers. The thermal transition properties are summarized

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R. Li et al. European Polymer Journal 100 (2018) 178–186

Fig. 2. Appearances of various PLLA blends.

Fig. 3. DSC thermograms of the prepolymers PEG (E), PBAT (B) and EB multiblock copolymers. (A) cooling scan at 80 °C/min; (B) 2nd heating scan at 10 °C/min.

Table 2
Thermal transition properties of PEG (E), PBAT (B) and EB multiblock copolymers.

Sample Cooling: 80 °C/min 2nd heating: 10 °C/min

Tc (°C) ΔHc (J/g) Tg,PBAT (°C) Tcc,PEG (°C) ΔHcc,PEG (J/g) Tm,PEG(°C) ΔHm,PEG (J/g) ΔHm,PEG (J/gPEG) Tm,PBAT (°C) ΔHm,PBAT (J/g)

PEG (E) 28.8 161.9 – – – 60.4 171.8 171.8 – –

EB30 16.6a 71.5a −39.6 – – 52.7 80.6 115.1 101.6 3.8

EB50 16.3a 47.3a −33.4 −9.7 2.3 50.7 53.3 106.6 100.2 6.1
EB80 40.4a 18.3a −52.4 −24.0 4.7 33.9 13.3 66.5 99.9 11.5

PBAT (B) 20.6 12.8 −40.2 – – – – – 114.3 24.6

a
The melt crystallization peak of EB multiblock copolymers is attributed to both PEG and PBAT segments as both crystallize from melt at overlapped temperature range, therefore, the
enthalpy is the sum of both segments.

Fig. 4. DSC thermograms of L/E, L/EB, L/B blends. (A) cooling scan at 80 °C/min; (B) 2nd heating scan at 10 °C/min.

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Table 3
Thermal transition properties of L/E, L/EB and L/B blends in the second heating scan.

Sample PEGa (w Tg,PBATb (°C) Tg,PLLA/Tgc,PLLAc Tcc,PLLAd (°C) ΔHcc,PLLAe (J/ Tm,PEGf (°C) ΔHm,PEGg (J/ Tm,PLLAh (°C) ΔHm,PLLAi (J/ γc,PLLAj (%)
%) (°C) gPLLA) gPEG) gPLLA)

PLLA 0 – 61.6/56.0* 110.4 30.8 – – 168.8 34.2 3.6

E20 20 – – – – 48.8 44 167.3 43.0 45.9

E30 30 – – – – 54.2 95.7 167.2 52.0 55.6

B20 0 −41.6 59.5/56.0 93.8 25.0 – – 166.6 32.8 8.3

B30 0 −42.4 59.0/53.1 95.6 26.1 – – 166.7 33.0 7.4

EB3030 21 −39.8 −/34.1 73.7 22.0 50.3 57.6 166.6 39.6 18.8
EB5030 15 −41.4 −/43.0 79.5 24.1 48.8 44.0 166.7 37.1 13.9
EB8030 6 −45.3 56.8/49.4 92.6 24.9 33.7 10.0 167.2 32.4 8.0

a
Weight percentage of PEG segment in the blends. estimated from the modifier percentage in the blends and PEG percentage in the modifier, for an example, 30%*(1–80%) = 6% for
EB8030.
b
Tg of PBAT segment in the blends.
c
Tg of PLLA in the blends determined from 2nd heating and cooling scans respectively.
d,e
Cold crystallization temperature and enthalpy of PLLA in the blends.
f,g
Melting temperature and enthalpy of PEG segment in the blends.
h,i
Melting temperature and enthalpy of PLLA in the blends.
j
Crystallinity of PLLA in the blends, calculated from the equation (ΔHm,PLLA − ΔHcc,PLLA,)/ΔHm0,PLLA where ΔHm0,PLLA is equal to 93.6 J/g.

crystallization promotion effect of PBAT is much weaker than PEG.
PLLA showed slightly decreased Tg (62–59 °C) and PBAT showed un-
changed Tg, indicating very weak miscibility between them.
In the three L/EB blends, PLLA did not show clear melt crystallization
either, but much earlier cold crystallization and enhanced melting peak, as
compared with neat PLLA. Glass transition of PLLA was observed in EB8030
but not in EB3030 and EB5030 because it was overlapped with the melting
peak of PEG segment in EB30 and EB50. For this reason, the glass transition
temperature in the cooling scan (Tgc,PLLA) is used instead to discuss the
plasticization effect of PEG segment on the blends. As seen in Fig. 5, although
Tgc,PLLA is slightly lower than Tg,PLLA, they both decrease with the content of
PEG segment in the blends, indicating that its plasticization effect does exist
in the blends. It can be seen that the cold crystallization temperature and
enthalpy of PLLA (Tcc,PLLA and ΔHcc,PLLA) decrease with PEG content, and the
melting temperature (Tm,PLLA) keeps unchanged but the enthalpy (ΔHm,PLLA)
increases. This result reveals that the PLLA chain mobility and crystallizability
was enhanced as a consequence of the plasticization effect of PEG segment.
The crystallinity of PLLA in L/EB blends is lower than that in L/E blends but
increases with PEG content, suggesting that PEG segment in EB retains its
crystallization promotion effect on PLLA to certain extent. The dependences
of some other thermal transition properties on the content of PEG segment
were also given in Fig. 5. The Tg of PBAT keeps almost unchanged, suggesting
that PBAT is immiscible with PEG and PLLA.
3.3. Mechanical properties
Fig. 6 shows the tensile curves of L/E, L/B, and L/EB blends and neat
PLLA, and Table 4 summarizes the mechanical properties. Clearly,
according to the tensile and impact testing results, PLLA exhibits as a typical
rigid and brittle polymer with very low elongation at break (3.1%) and
impact strength (2.4 kJ/m2). Elongation and impact resistance was sig-
nificantly improved to 200–250% and 4.5–13.8 kJ/m2 respectively after
blending with 20–30 wt% PEG because of the excellent plasticization effect
of PEG. However, a remarkably decline of tensile modulus from 3.4 GPa to
0.6–0.2 GPa and strength from 64.6 MPa to 25.6–19.5 MPa occurred at the
same time. This was reported to be an inherent drawback of PEG plastici-
zation on PLLA [9,15,40,41]. In comparison with L/E blends, the L/B
blends containing 20–30 wt% PBAT prepolymer show higher tensile mod-
ulus (2.3–1.6 GPa) and strength (39.4–25.0 MPa) but inferior ductility
(1.8–2.2%) and toughness (5.2–4.1 kJ/m2). In comparison with PLLA, the
blends show even lower elongation but doubled impact strength, revealing
that PBAT itself can be a toughener but not a plasticizer. Furthermore, it is
found that the mechanical properties of L/B in this study is quite different
from the one reported by Zhang et al. [32], in which the PLLA/PBAT blend
display comparable impact strength (4 kJ/m2) but relatively superior
elongation (> 200%). It is possibly because of the much higher molecular
weight of the commercial PBAT used in their research. Differently, the L/EB
blends show superior and more balanced mechanical properties. As a
whole, the elongation (160–220%) is comparable to L/E blends, the tensile
modulus (1.2–2.0 GPa) and strength (24–31 MPa) are comparable to L/B
blends, and the impact strength (10–44 kJ/m2) is higher than both L/E and
L/B blends. Furthermore, different from the PLLA/PEG-mb-PPA (L/EP)
blends reported previously, there was no “second yielding/necking” phe-
nomenon observed during tensile testing of the L/EB blends. In conclusion,
EB can be an excellent modifier to toughen and plasticize PLLA at the same
time without deteriorating tensile strength and tensile modulus a lot.

Fig. 5. Dependences of thermal transition properties of PLLA blends on the weight percentage of PEG segment in the blends.

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Fig. 6. Strain-Stress curves of PLLA/PEG (L/E), PLLA/PBAT (L/B) and PLLA/EB (L/EB)
blends and neat PLLA.
To further compare the mechanical properties of these blends and
analyze the role of PEG and PBAT prepolymers or segments in the
blends, the dependences of the mechanical properties on the contents of
PEG and PBAT in the blends are plotted and shown in Fig. 7. It can be
seen from Fig. 7A that the elongation increases with PEG content in
both L/EB and L/E blends, but decreases in L/EB blends and keeps
unchanged in L/B blends with PBAT content. From these results, it can
be concluded that it is PEG but not PBAT plasticizes PLLA because PEG
is miscible with PLLA but PBAT is not. PEG is found to be an excellent
plasticizer of PLLA. In L/E blends, 10–20% PEG is needed to reach
elongation as high as 150%. However, very interestingly, the elonga-
tion of EB8030 reaches 160% although the PEG content in it is only 6%.
Depressed crystallization and therefore improved plasticization of PEG
segment in EB multiblock copolymers may account for the result. In this
sense, the existence of PBAT segment in the EB multiblock copolymers
is helpful to enhance the plasticization effect of PEG segment on PLLA.
The tensile strength of the blends decreases with both PBAT and
PEG contents. But the deterioration effect of PEG is more remarkable
because PEG chain is more flexible than PBAT and is miscible with
PLLA. As far as the EB30 blend is concerned, the strength increased
with PBAT content. EB30 blends contain less PEG than the E30 blend,
therefore higher tensile strength was achieved for EB30 blends. For
EB8030 which contains 6% PEG and 24% PBAT, it can be seen from
Fig. 7B that its strength is close to an imaginary B24 blend, but it has
much higher elongation and impact strength than B20 and B30. Similar
variation tendency can be found for the tensile modulus of the blends as
exhibited in Fig. 7C. The L/EB blends show higher modulus than L/E
blends with same PEG content. This result indicates that the existence
of PBAT segment is helpful to reduce the employment content of PEG
on the one side, and on the other side it can retard the decrease of
strength and modulus to certain extent.
The impact strength increases with PEG and PBAT contents in L/E
and L/B blends (see Fig. 7D), respectively. Although PEG shows more
favorable toughening effect in L/E than PBAT in L/B blends and E30
shows higher impact strength than B30 because of the plasticizing effect
of PEG, the impact strength of L/EB blends increases with PBAT seg-
ment content but decreases with PEG segment content. These results
suggest that PBAT but not PEG segment in EB plays a role of toughener
role. But the PEG segment also plays a key and necessary role in
toughening in L/EB blends. Although PBAT is a flexible prepolymer, the
L/B blends show poor impact strength because of the incompatibility of
PLLA and PBAT leading to the weak interphase interaction between
them. When an EB multiblock copolymer is used instead of the PBAT
prepolymer, the PEG segment will diffuse into the PLLA phase and
enhances interphase interaction between PLLA and PBAT. Therefore
remarkable toughening can be achieved. Clearly, superior toughening
has been achieved in L/EB than in L/E and L/B blends.
In summary, the miscible PEG segment in EB acts as plasticizer and
compatibilizer and therefore endows L/EB blends with improved duc-
tility and enhances the interphase adhesion between PBAT segment
with PLLA, the flexible immiscible PBAT segment is compatibilized by
PEG and therefore acts as an effective impact modifier and provides
highly improved toughness. On the other hand, the presence of PBAT
segment in EB depressed the crystallization of PEG segment and en-
hanced its plasticization effect consequently. In other words, PLLA can
be effectively plasticized at lower content of PEG segment and therefore
L/EB blends can retain higher modulus and strength. Because of the
synergistic effect of both segments, the EB multiblock copolymers can
plasticize and toughen PLLA effectively at lower content of PEG and
PBAT segments. In this way, L/EB blends with superior and balanced
mechanical properties including ductility, toughness, strength and
modulus is successfully prepared.
The mechanical behaviors of L/EB blends are similar to those of
PLLA/PEG-mb-PPA (L/EP) blends which were reported in our previous
study [35]. Fig. 8 gives a comparison of the mechanical properties of
the two kinds blends with the same composition and content of EB and
EP. It can be seen that, for the L/EP blends, only EP3030 with high PEG
content (21%) exhibits high elongation, but all the three L/EB blends
(PEG 6–21%) show elongation higher than 150%. The impact strength
of both kinds of blends increases with the content of flexible (co)
polyesters, but the increase is more rapidly with PBAT content.
Therefore, EB30 has much higher impact strength than EP30 (44 kJ/m2
vs. 33 kJ/m2). Furthermore, all the three L/EB blends show higher
tensile strength than the L/EP blends, and their tensile modulus is also
higher or comparable. In addition, although the undesired “second
yielding/necking” phenomenon appears during tensile testing of L/EP
blends, it does not occur in L/EB blends. Therefore, the L/EB blends
show superior mechanical properties as compared with L/EP blends.
The semi-aromaticity and weak crystallizability of PBAT segment in EB
might account for the higher performance of L/EB blends. In contrast,

Table 4
Mechanical properties of PLLA/PEG (L/E), PLLA/PBAT (L/B) and PLLA/EB (L/EB) blends and neat PLLA.

Sample Composition (wt%) E (MPa) σy (MPa) σb (MPa) εb (%) σimp (kJ/m2)

PBAT (B) PEG (E) PLLA

PLLA 0 0 100 3360 ± 30 71.4 ± 0.8 64.6 ± 1.4 3.1 ± 0.2 2.4 ± 0.3

E20 0 20 80 608 ± 127 13.6 ± 0.5 25.6 ± 0.5 199.2 ± 6.9 4.5 ± 1.6
E30 0 30 70 203 ± 70 – 19.5 ± 0.8 254.2 ± 9.4 13.8 ± 2.9

B20 20 0 80 2300 ± 94 57.9 ± 0.7 39.4 ± 0.6 1.8 ± 0.6 5.2 ± 0.2
B30 30 0 70 1600 ± 93 27.0 ± 0.2 25.0 ± 1.2 2.2 ± 0.7 4.1 ± 0.2

EB3030 9 21 70 1240 ± 165 21.4 ± 1.3 23.9 ± 1.5 221.5 ± 8.8 10.2 ± 1.7
EB5030 15 15 70 1290 ± 72 26.0 ± 1.1 26.4 ± 0.6 205.1 ± 16.2 17.2 ± 1.4
EB8030 24 6 70 2000 ± 87 36.1 ± 0.5 30.9 ± 1.9 158.8 ± 10.8 43.7 ± 2.9

E: tensile modulus; σy: stress at yield; σb: stress at break; εb: elongation at break; σimp: impact strength.

183
R. Li et al.
Fig. 7. Mechanical properties of PLLA blends as a function of the content of PEG or PBAT content in the blends.
Fig. 8. Comparison of the mechanical properties of PLLA/PEG-mb-PBAT (L/EB) and
PLLA/PEG-mb-PPA (L/EP) blends.
the PPA segment in EP is fully aliphatic and amorphous. Therefore, it is
important to reasonably select the flexible polyester when designing
PLLA blends modified with PEG-mb-polyester copolymers.
3.4. Micro-phase morphology
Impact fracture surface of L/EB and L/B blends were investigated
with scanning electron microscopy to make clear the toughening me-
chanism. The results were shown in Fig. 9. The surface of B30 shows
spherical PBAT dispersed particles (0.5–2 μm) with apparent phase in-
terface with PLLA matrix and voids formed by interfacial debonding
cavitation, indicating the incompatibility and weak interfacial adhesion
between PBAT particles and PLLA matrix. Because of weak interfacial
adhesion, the toughness of B30 is only slightly improved though some
PLLA fibrillation is observed which often occurs during ductile fracture
process [42–44]. In comparison with B30, less cavitation is observed
but clear shear yielding appears in EB3030. The size of dispersed PBAT
particle of EB3030 is smaller and the phase interface is obscure because
184
European Polymer Journal 100 (2018) 178–186
of the compatibilization effect of PEG segment. And the PBAT particles
are elongated to certain extent. Such elongated morphology of elas-
tomer particles was reported to be helpful for polymer toughening [13].
Increasing the content of PBAT segment in EB, shear yielding de-
formation oriented along the impact direction (see the arrow) appears
in EB5030. In EB8030, highly oriented yielding deformations of PLLA
matrix are observed. Oriented yielding deformation was also observed
in highly toughened (49 kJ/m2) PLLA blends with in-situ reactive
compatibilized sliding graft copolymer [45] and with a bioelastomer
[46].
In general, impact fracture of rubber-toughened polymer blends
strongly depends on the interfacial interaction between the two phases.
The rubber particles act as stress concentrators in the matrix. When the
interfacial adhesion is poor, debonding of the dispersed phase occurred
during impact fracture, resulting in apparent cavitations as shown in
B30, whereas when there is adequate interfacial adhesion, shear
yielding is initiated via destruction inside the dispersed particles.
Considerable fracture energy can be absorbed when there is debonding
or shear yielding during impact fracture process, while the latter con-
tributes more to energy absorption [47]. Therefore, the impact tough-
ness of L/EB blends is higher than L/B as more shear yielding can be
observed in L/EB blends. Shear yielding intensifies and highly orients
with increasing the content of PBAT segment in EB, leading to much
higher impact toughness.
4. Conclusions
High molecular weight PEG-mb-PBAT (EB for simplicity) multiblock
copolymers containing 30%, 50% and 80% PBAT were synthesized via
chain extension/coupling of OH-terminated PEG6000 and PBAT4000
prepolymers, and used to plasticize and toughen PLLA simultaneously.
In the resulting PLLA/EB blends, the miscible PEG segments diffuse into
PLLA matrix to plasticize PLLA and/or locate at the PLLA-PBAT inter-
face to compatibilize the PBAT micro-phase and PLLA matrix, the im-
miscible PBAT segments in EB aggregate to form compatibilized micro-
R. Li et al.
phases and act as effective toughener of PLLA. Therefore, the blends
possess highly improved toughness and excellent ductility, and at the
same time, retain sufficient stiffness. The excellent impact toughness
comes from highly oriented shear yielding induced by compatibilized
PBAT particles due to strong interfacial adhesion. Furthermore, the L/
EB blends exhibit superior mechanical performances as compared with
our previously reported PLLA/PEG-mb-PPA (L/EP) blends, because of
different natures and micro-phase morphologies of modifiers in these
blends.
Acknowledgements
This work was supported by the National Key Research and
Development Program (2016YFB0302402), the National Nature
Science Foundation of China (51373152, 51773177) and 151 Talents
Project of Zhejiang Province.
185
European Polymer Journal 100 (2018) 178–186
Fig. 9. SEM micrographs of the impact fracture surface
of B30, EB3030, EB5030 and EB8030.
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