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org/Macromolecules Article

Reactive Micro-Crosslinked Elastomer for Supertoughened

Polylactide
Yingding Qu, Yihang Chen, Xiayan Ling, Jiali Wu, Jiangtao Hong, Hengti Wang,* and Yongjin Li*
Cite This: https://doi.org/10.1021/acs.macromol.2c00824 Read Online

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ABSTRACT: Elastomer toughening of plastics is extensively

acknowledged as a robust route to develop high-performance
materials. However, the drastic sacrifice of tensile strength resulting
Downloaded via INST OF CHEMISTRY on August 8, 2022 at 13:30:54 (UTC).

from overloading of the elastomer remains unresolved. So far, the

elastomers used as toughening agents are mainly non-crosslinked
since linear chains are usually considered to exhibit superiority in
adsorbing the impact energy. Herein, we found that the micro-
crosslinking of a commercially available linear elastomer, ethylene-
acrylic ester-glycidyl methacrylate terpolymer (EGMA), is
significantly beneficial for the toughening of polylactide (PLLA).
The reactive micro-crosslinked EGMA (RMCE) with various
crosslinking densities was feasibly fabricated through melt
processing and used as a more efficient toughener for the brittle
PLLA than the linear elastomer. The notched impact strength of the PLLA/RMCE was 35.9 kJ/m2, which was more than 5 times
that of PLLA/EGMA (7.0 kJ/m2) at the same 15 wt % elastomer loadings. At the same time, the tensile strength and Young’s
modulus kept high values of 51 MPa and 1.4 GPa, respectively. Synergistic effects such as wide domain size distribution, small
ligament thickness, and suitable interfacial adhesion were believed to be main contributors of the increase. The toughening
mechanism was further clarified. This work provides a novel avenue to achieve supertoughened PLLA and new insights into the
toughening mechanism as well. Such a feasible, versatile, and low-cost method should be widely applicable.

1. INTRODUCTION Among various reactive elastomers, ethylene-acrylic ester-

Polylactide (PLLA) is a biobased and biodegradable thermo-
plastic polyester that is considered a promising substitute for
traditional petroleum-based polymers.1−4 Due to its high
strength and modulus, good processability, and competitive
cost,5−11 PLLA has wide prospects in the fields of sustainable
commodity and engineering applications, such as pack-
aging,12−14 biomedical devices,15−17 and disposable consumer
products.18−20 Therefore, growing attention from both
industries and academia has been attracted to modify the
intrinsic brittleness of PLLA. Among various strategies and
technologies, the reactive blending of PLLA with reactive
elastomers, such as glycidyl methacrylate-grafted poly-
(ethylene-co-octene) (GMA-g-POE),21−23 natural rubber-
glycidyl methacrylate (NA-GMA),24,25 maleic anhydride-
grafted styrene−ethylene/butylene−styrene (MA-SEBS),26
epoxide polybutadiene (EPB),27 and polyurethane prepolymer
(PUP),28 is an efficient and convenient method of toughening
PLLA. Numerous factors for the reactive elastomer toughening
of PLLA have been carefully investigated, such as the type and
concentration of the reactive elastomer, particle size and
particle size distribution of the elastomer, interparticle distance
of the dispersed phase, and interfacial adhesion of blend
components.29−33
glycidyl methacrylate terpolymer (EGMA) has been exten-
sively investigated as an excellent toughener for PLLA for both
the low Tg and high reactivity with the PLLA matrix.34−40 The
dispersed rubbery domains adsorb the impact energy trans-
ferred by the good interfacial bonding upon suffering external
impact stress. As reported by Oyama,40 the notched impact
strength of the as-prepared PLLA/EGMA 80/20 was below 10
kJ/m2 with 20 wt % elastomer. They also reported the
increased impact strength of the annealing (crystallization of
the PLLA matrix). Wang et al.41 found similar results for the
binary PLLA/EGMA blends that annealing induced toughen-
ing for the binary PLLA/EGMA blends. Furthermore, EGMA
can toughen PLLA-based multicomponent blends. For
example, Mohanty 42 reported supertoughened PLLA/
EGMA/PEBA ternary blends with unique “multiple-stacked
structure”. Inoue’s group43 prepared supertough PLLA/SEBS/
Received: April 21, 2022
Revised: June 29, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acs.macromol.2c00824

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EGMA and PLLA/PC/SEBS/EGMA systems through reactive Table 1. Fabrication of RMCE with Various Contents of
melt blending. Despite the promise of this strategy, complex DCP
fabricating steps (such as thermal annealing) and a high
code EGMA (g) DCP (g)
content of the elastomer are not practical in scale-up
production. Moreover, drastic sacrifice in the tensile strength EGMA 100 0
and modulus of PLLA often occurs inevitably. It remains RMCE-0.05a 100 0.05
urgent to develop efficient strategies to overcome the RMCE-0.2 100 0.2
RMCE-0.3 100 0.3
limitations of EGMA loading for the high-stiff−tough balanced
RMCE-0.5 100 0.5
PLLA materials.
RMCE-2 100 2
On the other hand, the dynamic vulcanization of elastomers a
in the PLLA matrix during melt blending is also an effective The numbers referred to the concentration (%) of DCP in EGMA/
strategy to increase the impact strength of PLLA. Wang et al.44 DCP blends.
prepared supertough thermoplastic vulcanizates consisting of
PLLA and a crosslinked unsaturated aliphatic polyester Table 2. Fabrication of PLLA/Reactive Elastomer (85/15,
elastomer (VUPE). Interfacial compatibilization occurred w/w) Blends, EGMA or RMCE, with Different Crosslinking
during peroxide-induced dynamic vulcanization. The notched Densities
impact toughness of PLLA was significantly increased, while Code PLLA (g) EGMA (g) RMCE (g)
the tensile strength severely dropped. The in situ formed PLLA/EGMA 42.5 7.5 0
grafting copolymers of PLLA and the elastomer account for the PLLA/RMCE-0.05 42.5 0 7.5
strengthening of the interface and therefore the enhanced PLLA/RMCE-0.2 42.5 0 7.5
impact strength. However, the functions of the crosslinking of PLLA/RMCE-0.3 42.5 0 7.5
the elastomer domains have not been elucidated. PLLA/RMCE-0.5 42.5 0 7.5
Herein, we propose a new strategy to toughen PLLA with a PLLA/RMCE-2 42.5 0 7.5
low content of a toughener using a reactive micro-crosslinked
elastomer (RMCE). The RMCE with various crosslinking 2.3. Instruments and Measurements. 2.3.1. Scanning Electron
densities was first prepared by a simple melt blending strategy Microscopy (SEM). Cryofractured surfaces and impact-fractured
with varying dicumyl peroxide (DCP) contents. The surfaces of blends were sputter-coated with a thin layer of gold and
comparison of the structure and morphology of the toughened then examined using a scanning electron microscope (FE-SEM,
Hitachi S-4800), operating at an accelerating voltage of 3.0 kV.
PLLA with a low elastomer concentration between the original 2.3.2. Transmission Electron Microscopy (TEM). The morpholo-
linear EGMA and RMCE has been made. It was found that the gies of the blends were characterized by TEM (Hitachi HT-
toughness was astonishingly enhanced for the PLLA blend 7700ninstrument). All specimens were pre-ultramicrotomed at
after the simple crosslinking of the elastomer, while it kept −120 °C with a thickness of 80 nm and then stained with RuO4
constant tensile strength and Young’s modulus. We found that for 4 h. The accelerating voltage was 100 kV. The particle sizes of the
the application of the RMCE leads to not only the desirable EGMA phase dispersed in the PLLA matrix were analyzed using Nano
phase morphology but also the suitable interfacial adhesion. Measurer software. The number-average particle size (dn), particle
Such effects benefit the toughening of PLLA significantly. The size distribution parameter (σ), and matrix ligament thickness
between EGMA particles (τ) were calculated from the following
high toughening efficiency of the RMCE for PLLA shown in equations:
this work paves a new way to toughen the rigid plastics.
N
nd
i= 1 i i
dn = N
2. EXPERIMENTAL SECTION n
i=1 i (1)
2.1. Materials. Poly(L-lactide) (PLLA, 4032D, Mn = 8.5 × 104 g/
N
mol, Mw/Mn = 1.7) was obtained from Nature Works. Ethylene- n (ln di
i=1 i
ln d)2
acrylic ester-glycidyl methacrylate terpolymer (EGMA, AX8900) was ln = N
n
i= 1 i (2)
supplied by Arkema (France). GMA and methyl acrylate contents are
8 and 24 wt %, respectively. The dicumyl peroxide (DCP) was 1/3 2 2
purchased from Sinopharm Chemical Reagent Co., Ltd. (China). = dn[( /6 ) exp(1.5 ln ) exp(0.5 ln )] (3)
2.2. Sample Preparation. PLLA and EGMA pellets were where ni is the number of EGMA particles with the diameter of di and
vacuum-dried at 80 °C for 12 h before processing. The modification φ is the volume fraction of the dispersed EGMA phase.45
of EGMA with DCP was carried out in a Haake internal mixer 2.3.3. Differential Scanning Calorimetry (DSC). DSC (Q2000)
(Germany) at 190 °C for 5 min with a rotation speed of 50 rpm. was performed at a heating/cooling rate of 10 °C/min with a
PLLA/EGMA and PLLA/RMCE blends were prepared by reactive temperature range from 25 to 190 °C. A nitrogen atmosphere was
melt blending using a Haake internal mixer at a rotation speed of 50 applied during the measurement.
rpm and 190 °C for 10 min, and the weight ratio of PLLA to 2.3.4. Dynamic Mechanical Analysis (DMA). Samples were
elastomer was fixed at 85/15. The obtained samples were injection- molded to dimensions of 10 mm × 6.3 mm × 0.5 mm (length,
molded into specimens using a Haake Minijet Pro (Thermo width, and thickness) and then tested with a DMA Q-800 (TA
Scientific) at a barrel temperature of 200 °C and a molding Instrument) with a heating rate of 3 °C/min from −80 to 170 °C, a
temperature of 50 °C for impact and tensile tests. The blends were fixed amplitude of 5 μm, and a frequency of 5 Hz.
also hot-pressed into sheets (0.5 mm in thickness) under 10 MPa and 2.3.5. Mechanical Tests. Notched impact testing was conducted
200 °C for 20 min for further characterization. The detailed according to the GB/T 16420-1997 standard with an impact tester
composition of blends is shown in Tables 1 and 2. As a comparison, (SS-3700) and a pendulum energy of 2 J. Tensile properties were
the nonreactive polyolefin elastomer (POE) is chosen as the control measured using an Instron universal material testing system (model
sample. PLLA/POE blends with various DCP contents were also 5966) at a crosshead speed of 10 mm/min. Impact tests and tensile
prepared by blending using a Haake internal mixer at a rotation speed tests were all performed at room temperature. The splines used for
of 50 rpm and 190 °C for 10 min. characterization were prepared using a microinjection molding

B https://doi.org/10.1021/acs.macromol.2c00824
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Figure 1. (a) Torque evolution curves, (b) gel contents, (c) storage modulus, and (d) loss tangent (tan δ) in the dependence of temperature of
RMCE elastomers with the various contents of DCP: (I) EGMA, (II) RMCE-0.2, and (III) RMCE-0.5.

machine (Haake Minijet Pro) at a barrel temperature of 200 °C and a
mold temperature of 50 °C.
2.3.6. Fourier Transform Infrared Spectroscopy (FT-IR). Fourier
transform infrared spectra (FT-IR) were recorded using a Germany
Bruker VERTEX 70v spectrometer with a resolution of 4 cm−1 and an
accumulation of 64 scans.
2.3.7. Dynamic Rheological Analysis. A physical rheometer
(MCR301, Anton Paar Instrument) with a parallel configuration
(diameter 25 mm, gap 1mm) was used for rheology characterization.
Measurements were carried out at 200 °C under the protection of a
dry nitrogen atmosphere. The SAOS (small amplitude oscillatory
shear) tests was performed at 200 °C in a fixed amplitude (γ) of 1%
after ensuring a linear viscoelastic (LVE) region. All tests were
conducted in a N2 atmosphere in the frequency (ω) range from 500
to 0.01 rad/s. The plateau modulus was determined using Rouse
correction using Rheoplus software from the obtained SAOS data.
2.3.8. Gel Content Measurement. Crosslinked EGMA is insoluble
in toluene, so RMCE samples with weight W1 were extracted in a
Soxhlet apparatus at 130 °C for 72 h, and toluene was used as the
solvent. The obtained insoluble products were dried for 24 h at 130
°C in a vacuum oven and weighed (W2). The gel fraction (f) was
calculated via eq 446i.e.,
gel fraction (%) = (W2/W1) × 100 (4)
3. RESULTS
3.1. Formation of Reactive Micro-Crosslinked Elas-
tomers. 3.1.1. Micro-Crosslinking of Linear EGMA Elas-
tomers. RMCE elastomers with various crosslinking densities
were prepared by melt blending of linear EGMA with DCP at
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190 °C. The torque curves of EGMA with various amounts of
DCP are shown in Figure 1a. It was clear that the torque
increased as a function of the mixing time with the addition of
DCP, indicating the crosslinking of EGMA during the mixing.
The crosslinking was initiated by DCP followed by the
coupling of the CH2-CH radicals on the ethylene segments on
the EGMA main chains.47 The fact that the torque value
increased with increasing DCP loadings indicated the
increased crosslinking density with the DCP loadings. It
should be noted that all crosslinked RMCE elastomers were
still thermoplastic in the melt state with less than 1% DCP
loadings. This meant that the crosslinking density of the
RMCE in this work was low at low DCP additions. However,
too much DCP led to the complete crosslinking of EGMA, and
unmolten powder was obtained after the melt blending, as
shown in the abnormal torque curve and the inset picture in
Figure 1a. The gel contents of EGMA after the crosslinking
were measured by solvent dissolving and weighting. As shown
in Figure 1b, gel contents increased with increasing DCP
contents from 0 to 2%. Obviously, the degree of crosslinking
can be easily tuned by varying the DCP content.
The micro-crosslinking of EGMA can further be proved by
the DMA and rheological measurements. Figure 1c,d
elucidates the changes of storage modulus and loss tangent
with increasing temperature for RMCE with the indicated
DCP. The Tg of EGMA increased from −18.9 to −16 °C with
the addition of DCP. This again indicated the chain mobility
confinement by the micro-crosslinking.
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Figure 2. (a) Storage modulus (G′) and (b) complex viscosity (|η*|) as a function of angular frequency (ω) of PLLA, EGMA, and RMCE
elastomers with various contents of DCP.

Rheological analysis can provide valuable crosslinking exhibits reactivity and can be further reacted with PLLA during
information about the elastomer. Shear frequency dependence the following melt blending.
of the storage modulus and complex viscosity for neat PLLA, 3.2. Supertough PLLA/Reactive Micro-Crosslinked
EGMA, and RMCE is presented in Figure 2. Evidently, the Elastomer. 3.2.1. Mechanical Properties. Figure 4a illustrates
storage modulus G′ and complex viscosity |η*| of EGMA were the notched impact strength of PLLA/RMCE (85/15) blends
remarkably increased with increasing DCP concentration. The with different crosslinking densities of the elastomer. The
enhanced elasticity and viscosity of RMCE can be ascribed to virgin PLLA was very brittle with a notched impact strength of
the increasing crosslinking degree. To quantitatively describe only 3.1 kJ/m2. The original EGMA was a good impact
the crosslinking structure, Mc (molecular weight between modifier for PLLA, and the impact strength of the PLLA/
adjacent crosslinks) and υd (network density) were calculated EGMA alloy was 7.0 kJ/m2, which was 2 times that of the neat
with G0N (plateau modulus) and are listed in Table 3. It showed PLLA. Notably, the micro-crosslinking of EGMA led to
that υd increased from 19.0 to 43.5 mol/cm3 with improving astonishing toughening effects for PLLA. The notched impact
DCP content from 0.05 to 0.5% as expected (Table 3). strength of the PLLA/RMCE-0.2 (crosslinked with 0.2%
DCP) blend was as high as 35.9 kJ/m2, which was 5 times that
Table 3. Crosslinking Densities for the Reactive Elastomers of the PLLA/linear EGMA blend. The value was about more
Calculated from SAOS Tests than 11 times higher than that of virgin PLLA, indicating the
supertoughening effects of the RMCE elastomers. However,
sample G0Na (Pa) Mcb (104 g/mol) υdc (mol/cm3)
over-crosslinking of RMCE, i.e., increasing content of DCP,
EGMA 445 5.0 19.0 caused a decrease in the notched impact strength. It was
RMCE-0.05 14 500 3.8 24.6 indicated that there was an optimum DCP content (0.2 wt %)
RMCE-0.2 31 480 3.0 31.5 at which the crosslinking density of the elastomer was most
RMCE-0.3 40 040 2.7 35.0 appropriate and the notched impact strength of the final
RMCE-0.5 61 340 2.2 43.5 composite was highest. The impact strength values of PLLA
a
Plateau modulus (G0N) calculated from SAOS tests. bMolecular using original EGMA and RMCE-0.2 with different blend
weight between adjacent crosslinks calculated as compositions have been compared and are presented in Figure
GN0 =
3
RT
Mc (1 2Mc
Mn ), where ρ EGMA (density of EGMA) = 0.940 g/ S1. Similar tendency of toughening can be achieved. Figure 4b
compares the stress−strain curves of PLLA composites
cm , R = 8.314 J/(mol K), and Mn is the number-average molecular
weight of un-crosslinked EGMA. cNetwork density (υd) calculated as
toughened with linear EGMA and RMCE. The corresponding
mechanical properties of PLLA composites are summarized in
ud = M .48
c Table S1. Pristine PLLA was brittle and rigid with the
elongation at break, Young’s modulus, and tensile yield
strength of 6.2%, 1.6 GPa, and 75.2 MPa, respectively. With
3.1.2. Reactivity of RMCE Elastomers. During melt the incorporation of 15 wt % reactive elastomer, the elongation
crosslinking of EGMA using DCP, the free radicals generated at break of PLLA/EGMA increased to 155.5%, while Young’s
by DCP attacked the olefin chain of EGMA but did not modulus and tensile yield strength decreased to 1.5 GPa and
consume the epoxy groups. FT-IR characterization has been 53.5 MPa, respectively. This could be attributed to the nature
carried out to confirm the existence of epoxide groups after of both the reactivity and elasticity of EGMA. For the PLLA/
melt processing. Notably, all spectra have been normalized RMCE-0.2 blend, the elongation at break was further increased
with the carbonyl group at 1750 cm−1 as a reference group, to 255.8% with almost the same Young’s modulus (1.4 GPa)
which is not involved in the crosslinking reaction. As shown in and tensile yield strength (51.1 MPa). The tensile toughness is
Figure 3, the characteristic peak of the epoxy group (∼910 further calculated by integrating the stress−strain curves
cm−1) was not weakened for EGMA with various DCP (Table S1). The integral area of the PLLA/RMCE blend
contents. This demonstrated the existence of epoxide groups in exhibited a significant enhancement: from 2.9 MJ/m3 (PLLA)
RMCE elastomers. In other words, the prepared RMCE and 49.4 MJ/m3 (PLLA/EGMA) to 80.7 MJ/m3 (PLLA/
D https://doi.org/10.1021/acs.macromol.2c00824
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Figure 3. FT-IR spectra of reactive elastomers with various topologies: (I) EGMA, (II) RMCE-0.2, and (III) RMCE-0.5 (a) in the range of 450−
4000 cm−1 and (b) enlarged FTIR in the range of 840−1000 cm−1.

Figure 4. (a) Notched impact strength and (b) typical stress−strain curves of PLLA and PLLA/reactive elastomer (85/15) blends with various
contents of DCP; (c) digital photographs of representative samples after impact and tensile tests; and (d) comparison of notched impact strength
and tensile strength between this work and other PLLA/RMCE-0.2 (85/15) blends based on PLLA/E-MA-GMA 85/15,49 PLLA/E-MA-GMA/
OMMT 85/15/2,49 PLLA/PCLU 85/15,50 PLLA/GMA-CSS 85/15,51 PLLA/MB-g-GMA 85/15,52 PLLA/BA-EA-GMA 85/15,53 PLLA/EGMA/
PUDA-co-BUDA 85/10/5,54 PLLA/GPOE 85/15,55 and PLLA/GACR 85/15.56

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Figure 5. SEM and TEM micrographs of the PLLA/reactive elastomer (85/15) blends: (a) PLLA/EGMA, (b) PLLA/RMCE-0.2, and (c) PLLA/
RMCE-0.5 blends.

Figure 6. (a) Averaged particle sizes and size distribution parameter σa and (b) ligament thickness of PLLA and PLLA/reactive elastomer (85/15)
blends with various contents of DCP. aSize distribution parameter σ was calculated according to eq 2.

RMCE-0.2). This means that RMCE-0.2 is superior for
toughening PLLA when compared with the linear reactive
elastomer.
Comparison of the mechanical properties (toughness and
strength) of the present materials with the reported PLLA
composites toughened with various reactive tougheners is
shown in Figure 4d. As indicated, this work demonstrates the
optimized comprehensive performance of both notched impact
strength and tensile strength. Toughness−stiffness balance was
realized for the PLLA/RMCE-0.2 blend. This result exhibits
the great potential of reactive micro-crosslinked elastomers in
toughening.
3.2.2. Morphology. It is well-known that the phase
morphology, including the interfacial interactions, particle
size of the elastomer, and size distribution, is a vital factor that
F https://doi.org/10.1021/acs.macromol.2c00824
determines the mechanical properties of polymer composites.
SEM micrographs of cryogenic fractured surfaces of the PLLA/
EGMA (85/15) blends are illustrated in Figure 5. All samples
exhibited “sea-island” morphology, where the elastomer was
found to be well-dispersed in the PLLA matrix. No significant
difference can be observed from SEM images because of the
same rubber loadings. To observe the morphology of the
prepared PLLA blends more clearly, TEM observation was
carried out. Spherical EGMA domains (black) with a thick
interfacial layer (gray) were dispersed in the PLLA matrix
(white) (Figure 5a3). Interestingly, the particle size distribu-
tion notably became wider for PLLA blends toughened with
crosslinked elastomers. Many smaller elastomer droplets with a
diameter of 30 nm were observed, as marked in red circles
(Figure 5b3,c3). The statistical results of the elastomer particle
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Figure 7. (a) DSC heating curves (10 °C/min) from 25 to 190 °C and (b) changes of loss tangent (tan δ) with increasing temperature for PLLA/
reactive elastomer (85/15) blends.

Figure 8. (a) Storage modulus (G′) and (b) complex viscosity (|η*|) as a function of angular frequency (ω) and (c) weighted relaxation spectrum
of PLLA/reactive elastomer (85/15) blends with various contents of DCP: (I) PLLA/EGMA, (II) PLLA/RMCE-0.2, and (III) PLLA/RMCE-0.5
blends.

size and its distribution parameter σ are summarized in Figure
6a. The existence of large particles was attributed to the slight
crosslinking of the EGMA elastomer, which prevented the
breakage of the EGMA phase into fine droplets. According to
Wu’s correlation relating the average diameter of the dispersed
phase (d)57
4 K ±0.84
d=
(5)
m
where α is the interfacial tension, K is the viscosity ratio of the
dispersed phase/matrix phase, γ̇ is the shear rate, and ηm is the
matrix viscosity. The exponent of K is positive for K > 1.
Therefore, increasing the elastomer viscosity by crosslinking
(shown in Figure 2b) resulted in an enhancement of the
particle size of EGMA, and the big droplets are observed in
Figure 5. On the other hand, as for the part of the un-
crosslinked EGMA chains in micro-crosslinked elastomers, a
higher shear force at a constant screw rotation speed generated
numerous small un-crosslinked particles dispersed in the PLLA
matrix. Thus, a large domain size distribution was observed for
the PLLA/RMCE-0.2 and PLLA/RMCE-0.5 blends. In
addition, the matrix ligament thickness (surface-to-surface
G https://doi.org/10.1021/acs.macromol.2c00824
interparticle distance) was also calculated and is given in
Figure 6b. It showed that the PLLA/RMCE-0.2 blend had the
smallest ligament thickness (0.31 μm), and the PLLA/EGMA
blend demonstrated the largest value (0.50 μm). We believe
that large elastomer particles could trigger cavitation during the
impact stress, while small elastomer particles initialize shear
band and enhance matrix shear yielding. The thin ligament was
believed to be favorable to the overlap of the stress fields;
hence, the matrix phase would undergo elevated shear yielding
under impact. This result is in accordance with the results of
notched impact strength.
3.2.3. Thermal Behaviors. DSC experiments were per-
formed to estimate the thermal properties of composites. As
plotted in Figure 7a, all specimens exhibited the same
transitions upon heating: a clear glass transition and a large
cold crystallization exotherm peak and melting peak. The cold
crystallization temperature Tc, the melting temperature Tm,
and the crystallinity of the PLLA matrix Xc for all blends were
also similar (Figure S2 and Table S2). Figure 7b illustrates the
changes of loss tangent with increasing temperature for PLLA/
elastomer blends. Tg values of EGMA in PLLA/EGMA blends
were lower than Tg values of virgin EGMA (shown in Figure
1d). It was ascribed to the negative pressure imposed on the
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Figure 9. Optical micrographs of macroscopic fracture splines and overall impact-fractured surfaces of the PLLA/reactive elastomer 85/15 blends:
(a) PLLA/EGMA, (b) PLLA/RMCE-0.2, and (c) PLLA/RMCE-0.5 blends.

Figure 10. SEM micrographs of impact-fractured surfaces of the PLLA/reactive elastomer (85/15) blends with various contents of DCP: (a)
PLLA/EGMA, (b) PLLA/RMCE-0.2, and (c) PLLA/RMCE-0.5 blends.

dispersed phase, originating from the asymmetric thermal
shrinkages during the cooling process from the melt state.41
Obviously, the micro-crosslinking of the EGMA did not induce
the significant difference in the crystallization behaviors and
the relaxation of the matrix and the domains. The heat
distortion temperatures (HDT) of PLLA/EGMA and PLLA/
RMCE blends were also the same (Table S2). Note that high
impact strength by the RMCE was achieved at the as-injected
PLLA alloys without any further heat treatment or annealing,
as reported in the literature.40,41
3.2.4. Rheological Properties. Figure 8 shows the G′ and
|η*| values of PLLA/RMCE blends with the different
crosslinking densities. It is very interesting to find that the
storage modulus (Figure 8a) and the complex viscosity (Figure
8b) of PLLA/RMCE in the low-frequency region were lower
than those of PLLA/EGMA without crosslinking. This would
be beneficial for the industrial melt processing, such as the
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extrusion or injection molding. The melt weighted relaxation
spectra58 of the blends with various topologies of elastomers
are shown in Figure 8c. The two relaxation peaks at a short
time scale, at 0.01 and 0.4 s, were related to the relaxation of
PLLA and EGMA components, respectively. It was observed
that with the increase of the DCP content, the relaxation peak
of RMCE had more amplitude, indicative of the suppressed
dynamics of RMCE chains due to the internal formation of
crosslinked networks.48,59 On the other hand, the relaxation
processes of PLLA segments of the three blends are quite
different. For the PLLA/RMCE blend, a prominent relaxation
peak of PLLA is observed. This is mainly attributed to the
sufficient in situ grafting reaction between PLLA and EGMA
elastomers. Most of the PLLA chains have been immobilized
on elastomer particles, and thereby, the molecular motion of
PLLA is seriously suppressed. For the two PLLA/RMCE
blends, more free PLLA chains existed since the number of
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Scheme 1. Schematic Diagrams Showing Interfacial Adhesion, Topology of the Elastomer, and Droplet Distribution of PLLA/
Reactive Elastomer Blends with Various Contents of DCPa
a
(a) PLLA/EGMA, (b) PLLA/RMCE-0.2, and (c) PLLA/RMCE-0.5 blends.
reactions with the PLLA matrix is greatly reduced. Therefore,
the molecular motion of PLLA is facilitated, and the relaxation
process of the PLLA component turned negligible. To verify
this assumption, we paid more attention to the relaxation peak
in the longer relaxation time (2−100 s) region. As reported,
the additional long-term relaxation is associated with the form
relaxation process of domains, where the interfacial inter-
actions dominated the dynamics.60,61 It was observed in Figure
8c that the strength (τH(τ)) of interfacial relaxation was
obviously decreased with increasing crosslinking density,
implying the weakened interfacial interactions using RMCE
compared to un-crosslinked EGMA. This can be attributed to
the fact that the exterior epoxide groups were confined upon
the gradual formation of crosslinked RMCE networks.
Therefore, the reactivity and the in situ grafting reaction
between PLLA and EGMA across the interface were reduced,
suitably weakening the interfacial strength across the phase.
Such reduced but suitable adhesion compared with the non-
crosslinked EGMA-toughened PLLA will be beneficial to the
improved toughening efficiency and will be discussed later.
3.3. Fracture Behaviors of the PLLA/RMCE blends.
Figure 9 shows the optical micrographs of the overall impact-
fractured surfaces of blends with the various crosslinking
densities of the reactive elastomer. It was demonstrated that
the area of whitening was directly related to the notched
impact strength. The fractured surface was entirely whitened in
the PLLA/RMCE-0.2 sample (Figure 9b1) with a notched
impact strength of 35.9 kJ/m2. In contrast, the fractured
surfaces of other samples were just partially whitened with a
relatively low impact strength. Stress whitening is generally
caused by microscale damage, such as cavitation, crazing, and
microvoids, which leads to scattering of light.62 The
homogeneous whitening of the blends with a high impact
strength indicated the homogeneous cavitation/crazing during
the fracture. To further observe the micromorphology of the
stress-whitened region, SEM characterization on the fracture
I https://doi.org/10.1021/acs.macromol.2c00824
Article
surface was performed (Figure 10). For PLLA blends
toughened with un-crosslinked EGMA (Figure 10a), rough
surfaces with only fibrillation and few microvoids were
observed. For samples toughened with over-crosslinked
RMCE-0.5 (Figure 10c), the surfaces exhibited debonding
and fibrillation. However, no perceptible plastic deformation of
the matrix was observed. In contrast, cavitation and plastic
deformation of the PLLA matrix prevailed over the fractured
surface of the micro-crosslinked RMCE-0.2-toughened com-
posite (Figure 10b). The results were consistent with the
values of notched impact strength, since matrix shear yielding
was more efficient in dissipating energy as compared with
debonding under an impact pattern.
4. DISCUSSION
Simple crosslinking of a reactive EGMA elastomer induced
significantly enhanced toughening efficiency for the PLLA
matrix. The notched impact strength of the RMCE-toughened
PLLA was as high as 35.9 kJ/m2 without any further heat
annealing. Such a simple binary blend kept a high modulus and
tensile strength. Furthermore, reactivity with PLLA was also
critical to obtain good interfacial adhesion and high toughness.
Micro-crosslinked POE (0.2% DCP) without reactive groups
could not toughen PLLA compared with the PLLA/POE (0%
DCP) 15% blend (shown in Figure S3). It was important to
elucidate the toughening mechanism of the RMCE for PLLA.
We considered that two factors induced by micro-crosslinking
account for the enhancement of the toughening effects. On the
one hand, the micro-crosslinking of EGMA led to the
enhanced viscosity of the elastomer. This therefore induced a
larger rubber domain distribution in the PLLA matrix and
smaller ligament distance between the rubber domains (as also
shown in Figure 6). On the other hand, the micro-crosslinking
led to decreased epoxy group reactivity, and this affected the
interfacial bonding between the rubber domains and the
matrix. As we confirmed in Figure 3, RMCE kept the epoxide
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Macromolecules pubs.acs.org/Macromolecules Article

Figure 11. TEM micrographs of impact-fractured surfaces of the PLLA/reactive elastomer (85/15) blends with various contents of DCP: (a)
PLLA/EGMA, (b) PLLA/RMCE-0.2, and (c) PLLA/RMCE-0.5 blends.

Scheme 2. Possible Toughening Mechanism of the PLLA/Reactive Elastomer with Micro-Crossslinked Topologya

a
(a) Stress concentration of toughened blends upon impact stress and (b) internal cavitation of the elastomer with a suitable interface and the
resulting shear yielding of the PLLA matrix.

groups that reacted with the PLLA matrix during melt
blending, but obviously, the confinement of EGMA chains
by crosslinking impeded the reactions between the EGMA and
the PLLA matrix. This could be further confirmed by the low
increase of torque during processing and strengthened the IR
intensity of epoxy groups for PLLA/RMCE 70/30 blends
(Figure S4). Therefore, proper interfacial adhesion can be
achieved, and this might also be beneficial for the enhancement
of the toughening. Indeed, it is generally accepted that too
strong interfacial adhesion leads to brittleness in polymer
blends/composites.29,63 Based on the above-mentioned dis-
cussion, the effects of crosslinking of EGMA on the PLLA/
EGMA blends can be depicted in Scheme 1.
The morphological change and the proper interfacial
adhesion by the micro-crosslinking of EGMA led to different
toughening mechanisms. The toughening mechanism of the
present reactive micro-crosslinked elastomer mainly included
three aspects. (1) Suitable interfacial adhesion (shown in
Section 3.2.4): An excessively high interfacial adhesion in the
PLLA/original (un-crosslinked) elastomer blend not only
prevented interfacial debonding but also stiffened elastomers
and deprived their elasticity.29,63 By contrast, debonding was
more likely to occur for the PLLA/over-crosslinked elastomer
blend with weak interfacial adhesion under impact force and
J https://doi.org/10.1021/acs.macromol.2c00824
dissipated energy. For the PLLA blend toughened with the
micro-crosslinked elastomer, a suitable interfacial adhesion was
vital to generate internal cavitation of elastomers, which
induces shear yielding of the PLLA matrix and adsorbs massive
impact energy. (2) Larger rubber domain distribution (shown
in Section 3.2.2): The PLLA/micro-crosslinked elastomer
blend was characterized with wide particle size distribution due
to the high viscosity of the crosslinked elastomer. Large
particles were efficient in inducing cavitation, while small
particles were effective in initializing shear band and matrix
shear yielding.29,64 The synergy of large and small elastomer
particles adsorbed massive energy and thereby improved the
impact toughness of the PLLA/micro-crosslinked elastomer
composite. (3) Smaller ligament distance (shown in Section
3.2.2): The ligament thickness of the PLLA/micro-crosslinked
elastomer composite was calculated to be the smallest. Small
matrix ligament thickness was conducive to the overlap of the
stress fields around the dispersed phase. Therefore, the matrix
phase would undergo enhanced shear yielding under impact
force.65,66
TEM micrographs of impact-fractured surfaces of the
PLLA/reactive elastomer (85/15) blends with various
contents of DCP were observed to examine the possible
toughening mechanism. As shown in Figure 11, both internal
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Macromolecules pubs.acs.org/Macromolecules
cavitation (microvoids) and shear yield deformation were
observed for the PLLA/RMCE-0.2 sample, while scarce
cavitation and shear yield were found in the PLLA/EGMA
sample. Overall, as illustrated in Scheme 2, in heterogeneous
polymer systems, the dispersed phase suffers triaxial stress as
the stress concentration point under the external force and
thereby triggers internal cavitation (Scheme 2a). Cavitation
conversely releases the local triaxial stress, which induces shear
band and matrix shear yielding around the dispersed phase
(Scheme 2b). Although cavitation of elastomer particles does
not consume much energy, matrix shear yielding initialized by
cavitation contributes a lot to the adsorption of fracture energy
and is key to obtain ideal supertoughened PLLA.
5. Conclusions. In summary, reactive micro-crosslinked
elastomers (RMCEs) were successfully prepared by simple
melt blending. The crosslinking density of EGMA was
increased from 19.0 to 43.5 mol/cm3 by simply varying the
DCP concentration from 0.05 to 0.5%. All micro-crosslinked
EGMA elastomers were still melt-processable. The prepared
RMCE was then used as the toughening agents for PLLA. A
400% enhancement in notched impact strength for the PLLA/
RMCE-0.2 blend of 35.9 kJ/m2 as compared with that of the
PLLA/un-crosslinked EGMA blend of 7.0 kJ/m2 was achieved,
while tensile strength and Young’s modulus remained almost
unchanged. The drastic improvement in notched impact
strength was explained in three aspects: suitable interfacial
adhesion, small matrix ligament thickness, and synergy of large
and small elastomer particles. These assumptions could be
verified by FT-IR, rheological characterization, and TEM
observation. In general, this study provides a novel strategy to
achieve high-performance plastics and deeper insights into
toughening mechanisms.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.macromol.2c00824.
Notched impact strength of PLLA/EGMA blends and
PLLA/RMCE-0.2 blends with different PLLA/elastomer
compositions from 95/5 and 90/10 to 85/15, DSC
cooling curves (10 °C/min) from 190 °C after being
held at 190 °C for 5 min of PLLA/reactive elastomer
blends, notched impact strength of PLLA and PLLA/
POE (85/15) blends before and after crosslinking by
DCP, torque evolution curves and FT-IR spectra of
PLLA/reactive elastomer (70/30) blends with various
contents of DCP, mechanical parameters of PLLA and
PLLA/reactive elastomer (85/15) blends with various
crosslinking densities of the elastomer, and thermal
parameters of PLLA/reactive elastomer (85/15) blends
with various contents of DCP (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Hengti Wang − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China; orcid.org/0000-0003-1650-0651;
Email: hengti-wang@hznu.edu.cn
Yongjin Li − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
K https://doi.org/10.1021/acs.macromol.2c00824
Article
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China; orcid.org/0000-0001-6666-1336;
Email: yongjin-li@hznu.edu.cn
Authors
Yingding Qu − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China
Yihang Chen − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China
Xiayan Ling − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China
Jiali Wu − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China
Jiangtao Hong − College of Material, Chemistry and Chemical
Engineering, Key Laboratory of Organosilicon Chemistry and
Material Technology, Ministry of Education, Hangzhou
Normal University, Hangzhou 311121 Zhejiang, People’s
Republic of China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.macromol.2c00824
Author Contributions
Y.Q.: methodology, visualization, data curation, and writing�
original draft preparation; Y.C.: resources and validation; X.L.:
resources and validation; J.W.: resources and validation; J.H.:
resources and validation; H.W.: validation; methodology,
writing�reviewing and editing, and funding acquisition; and
Y.L.: supervision, conceptualization, writing�reviewing and
editing, and funding acquisition.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was financially supported by the National Natural
Science Foundation of China (No. 51903071 and U21A2092)
and the Major Project of Natural Science Foundation of
Zhejiang Province of China (LD19E030001).
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