Materials Letters 71 (2012) 6365

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Novel polyethylene glycol-based polyester-toughened polylactide

Zongyan Gui, Yuanyuan Xu, Yun Gao, Chong Lu, Shujun Cheng
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

a r t i c l e

i n f o

Article history:
Received 24 October 2011
Accepted 9 December 2011
Available online 14 December 2011
Keywords:
Biomaterials
Polymers
Polylactide
Blend
Toughen

a b s t r a c t
Polyethylene glycol (PEG) is an excellent plasticizer for polylactide (PLA) and can signicantly enhance the
elongation at break of PLA. However, the impact resistance of PLA/PEG blend is very limited. In this study,
PLA was toughened by blending with a novel PEG-based polyester, poly (polyethylene glycol-co-citric
acid) (PEGCA), synthesized by a condensation reaction between PEG and citric acid. PLA and PEGCA were
partially miscible. The PEGCA phase was dispersed in the continuous PLA phase. The PLA/PEGCA (85/15 w/
w) blend showed much better mechanical properties in comparison to the PLA/PEG (85/15 w/w) blend.
With the addition of 15% PEGCA, the elongation at break reached 242%, whereas the impact resistance
reached 103 J/m.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Polylactide (PLA) is a biodegradable and bio-based polymer. It has
the advantages of high modulus, high strength, thermoplasticity,
transparency, and biocompatibility, when compared to other biopolymers such as starch. PLA has attracted increasing interest in various
industries, such as the packaging, textile, medical, and automotive industries. PLA is a very promising, eco-friendly alternative to traditional petroleum-based polymers [1,2]. However, PLA also has the
drawbacks of inherent brittleness and poor toughness, which impede
its wide application. Hence, modication processes that toughen PLA
have drawn great attention [35]. Blending with exible polymers is
the method most extensively used to improve the mechanical properties of PLA. However, many of these blends are immiscible and have
poor mechanical properties. For example, compatibilization is necessary to enhance the elongation at break and the impact resistance of
PLA/poly (butylenes adipate-co-terephthalate) blends due to their
poor miscibility [6]. Plasticization is an economical and easy method
of modifying PLA. Polyethylene glycol (PEG) is an excellent plasticizer
for PLA because of its good miscibility [7]. The elongation at break of
PLA increases in the presence of PEG, but the impact resistance remains poor. The miscible blends lack dispersed particles that act as
stress concentration points in the matrix which initiate crazing and
shear banding, thus absorb energy and hinder crack growth under a
strong external shock [8].
Citric acid is a bio-based, inexpensive, non-toxic, and multifunctional monomer, isolated from citrus fruits. The novel highly
branched polyester, poly (PEG-co-citric acid) (PEGCA) is based on

Corresponding author. Tel.: + 86 21 64776909; fax: + 86 21 64776549.

E-mail address: chshj2003@hotmail.com (S. Cheng).
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.12.045

citric acid and PEG. PEGCA can potentially improve the exibility of
PLA. PLA and PEGCA are supposed to be highly compatible given the
PEG segment in PEGCA. In the present study, PEGCA was synthesized
by a condensation reaction between PEG and citric acid, without a
catalyst. PLA and PEGCA blends with different compositions were
also prepared using an internal mixer. The objective was to investigate the mechanical properties of the PLA/PEGCA blends in comparison with PLA/PEG blends.
2. Experimental
PEG (Mw = 1000 g/mol) and citric acid were obtained from the
China Chemical Reagent, Co. PLA (4032D, density = 1.25 g/cm 3) was
purchased from Natureworks LLC (USA).
PEGCA was synthesized by a direct esterication reaction. Equimolar amounts of PEG and citric acid were placed in a four-neck,
round-bottom ask. The ask was tted with inlet and outlet
adapters, and was immersed in a silicone bath, preheated and xed
at 130 C. After the melting process, the mixture was allowed to
react by stirring under nitrogen for 10 h, and under reduced pressure
of 10 kPa for another 50 h. Subsequently, a viscous, transparent, oillike liquid was obtained. The resulting polymer was poured into a
glass ask, which was cooled to room temperature. The samples
were dried by lyophilization before use.
Before blending, PLA was dried in a vacuum at 80 C for 8 h. Neat
PLA, PLA/PEGCA blend (85/15 w/w) and PLA/PEG blend (85/15 w/w)
were prepared by using a KCCK XSS-300 rheometer equipped with
a 60 ml mixing chamber (KCCK, China) at 180 C for 6 min. After
blending, the samples were hot-press molded into a 1 mm-thick
plate, followed by quenching to room temperature. The pressing temperature was 180 C, and the pressing time was 2 min, with a pressure of 10 MPa.

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Z. Gui et al. / Materials Letters 71 (2012) 6365

Differential scanning calorimetry (DSC) measurements were performed with a modulated DSC2910 (TA Instruments, USA) in a nitrogen atmosphere. The sample weights were approximately 8 mg.
Samples were rst heated from room temperature to 200 C, and
then held for 3 min to eliminate the thermal history. They were
then cooled to 50 C at 10 C/min. After holding for another
3 min, the samples were reheated to 200 C at 10 C/min. Only the
second heating curves were measured.
The fracture surfaces were studied under a JSM-6360LV (JEOL,
Japan) scanning electron microscopy (SEM) instrument. The samples
were submerged in liquid nitrogen and broken down. The fracture
surfaces were studied by SEM after all surfaces were sputtered with
gold.
The tensile testing was carried out using a universal testing machine (CMT6104, Sans, China) at a crosshead speed of 10 mm/min
with a gauge length of 25 mm. Notched Izod impact tests were carried out according to ASTM D256A procedures using a standard impact tester (JJ-20, China). All samples were stored under ambient
conditions (23 C and 50% relative humidity) for 48 h before testing.
Each sample included ve to seven tested replicates, to obtain a reliable mean and standard deviation.
3. Results and discussion
Fig. 1 shows the 1H NMR spectrum of citric acid, PEG and PEGCA.
In PEGCA spectra, the peaks around 2.93.1 ppm were assigned to
the underlined protons in \CH2\ from citric acid, which were shifted
towards higher values in comparison to the NMR spectrum of pure
citric acid (peaks around 2.72.9 ppm). The peaks around 4.3 ppm
were attributed to the protons signal of esteried \COOCH2\ groups
in PEG segments. All these peaks indicated the formation of ester
bonds [9,10].
Fig. 2 shows the SEM images of neat PLA and PLA/PEGCA blend.
The blend sample exhibited a phase-separated morphology. The
PEGCA phase was spherical or elliptical, and was dispersed in the continuous PLA phase. This nding meant that PLA and PEGCA were not
miscible.
Fig. 3 shows the DSC heating curves of neat PLA and PLA/PEGCA
blend. The neat PLA curve showed three transitions upon heating: a
PLA glass transition, a cold-crystallization exothermic peak, and a
melting endothermic peak. The blend curve showed an additional
melting endothermic peak around 30 C, regarded as the melting
peak of PEGCA. The PLA/PEGCA blend exhibited a lower glass transition temperature of 51.5 C than neat PLA of 61.0 C. The DSC and
SEM data indicated that PLA and PEGCA were partially miscible, and
that some molecular interactions existed between the two components. The interaction may have originated from the miscibility

between the PLA molecular chain and the PEG segment of PEGCA.
Some PEGCA molecules were soluble in the PLA matrix. The shifted
glass transition temperature represented the improved segmental
mobility of the PLA segment.
The tensile and impact properties of neat PLA, PLA/PEGCA blend as
well as PLA/PEG blend are shown in Fig. 4. Neat PLA was typically
rigid and brittle. It had high tensile modulus and strength, as well as
very limited elongation at break and impact resistance. After the addition of PEGCA or PEG, the tensile strength and modulus of the
blend dropped, whereas the elongation at break signicantly increased. PEG had no effect on the toughness of PLA. However, the
PLA/PEGCA blend shows signicantly higher impact resistance than

Fig. 1. 1H NMR spectra of citric acid, PEG and PEGCA.

Fig. 3. DSC curves of neat PLA (P0) and PLA/PEGCA (85/15 w/w) blend (P15).

Fig. 2. SEM images of (a) neat PLA and (b) PLA/PEGCA (85/15 w/w) blend.

Z. Gui et al. / Materials Letters 71 (2012) 6365

65

Fig. 4. Tensile and impact properties of neat PLA, PLA/PEGCA blend (85/15 w/w) and PLA/PEG blend (85/15 w/w).

the other samples due to the dispersed phases in the matrix of PLA
[8]. Therefore, the PLA was successfully toughened after the addition
of PEGCA.
4. Conclusions
PEGCA can toughen PLA and make it exible. PEGCA was partially
miscible in PLA, as shown by SEM and DSC analyses. Glass transition
temperature of PLA decreased with the addition of PEGCA. The PLA/
PEGCA (85/15 w/w) blend showed much improved mechanical properties when compared to the PLA/PEG (85/15 w/w) blend. With the
addition of 15% PEGCA, the elongation at break reached 242%, whereas the impact resistance reached 103 J/m.
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