Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 12552−12562 pubs.acs.org/journal/ascecg

Levulinic Acid as a Versatile Building Block for Plasticizer Design

Wenxiang Xuan, Minna Hakkarainen, and Karin Odelius*
Department of Fibre and Polymer Technology, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH
Royal Institute of Technology, Teknikringen 56, Stockholm 100 44, Sweden
*
S Supporting Information

ABSTRACT: The large potential of utilizing green platform

chemicals such as levulinic acid, glycerol, and ethylene glycol
as building blocks for the design of high-performance
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biobased plasticizers was demonstrated. From these green

platform chemicals, esters with ketal or ketone functionalities
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and linear or branched structures were carefully designed and

synthesized via a mild and solvent-free route and characterized
by 1H NMR, 13C NMR, and FTIR. The effect of the structural
combinations on the performance as plasticizers for
polylactide (PLA), including migration resistance, was
followed by a series of characterization techniques. The
levulinates with ketone end-groups exhibited large capability
to lower the glass transition temperature (Tg) of PLA (to 15
°C by 20 wt % plasticizer). Ketal end-groups provided additional thermal stability to the plasticizers, but their ability to lower Tg
was not as good as that of ketone end-groups. Significantly improved flexibility reaching 546% elongation at break was achieved
by the addition of 20 wt % ethylene glycol dilevulinate, as compared to 5% elongation at break for neat PLA. The structural
differences for the plasticizers resulted in different degrees of hydrophobicity, which influenced the migration tendency of the
plasticizers and also the hydrolysis rate of PLA. The branched ester structure with ketal end-groups maintained the processing
window of PLA, but also lowered the hydrolysis rate of PLA in an accelerated migration test. In general, performance
comparable to that of the reference plasticizer acetyl tributyl citrate (ATBC) was demonstrated, offering promise for a family of
plasticizers derivable from green platform chemicals.
KEYWORDS: Plasticizer, Levulinic acid, Polylactide, Migration, Acetyl tributyl citrate

■ INTRODUCTION
For the design of truly sustainable plastics, full life-cycle needs
to be considered including the nature and choice of additives
such as plasticizers. As the potential migration from polymer
matrix and the safety of the plasticizers in the environment is of
importance, both during the service-life and after disposal,
proper choices need to be made. Hence, effort is focused on
developing sustainable plasticizers utilizing renewable sources
for their synthesis, aiming at proper function during use and no
hazardous effects during the entire life-cycle of the materials.
These compounds are of interest, for example, to plasticize
PVC1,2 and PLA.3−5
PLA is a commercial polymer synthesized from renewable
resources and a promising degradable replacement for PS and
PET.6 PLA is employed in several applications including food
packaging.7 However, the glass transition temperature of PLA
is above room temperature, making PLA a rigid and brittle
material. When targeting flexible applications, adding additives
such as plasticizers is considered as a well-accepted solution to
enhance the properties of PLA. Given the ubiquitous calls for
sustainability and environmental impact, biobased plasticizers
are preferred to preserve the inherent fully biobased nature of
PLA.
The plasticizing effect is indicated by the depression of glass
transition temperature (Tg) and increased elongation at break
for the materials. One of the general prerequisites underlying
the decreased Tg and improved strain is good miscibility
between the plasticizer and polymer. The miscibility can be
tuned by the modification of chemical structure and molecular
weight of the plasticizer, by the concentration of the plasticizer
in the material, and sometimes by the processing method and
temperature.8 For example, acetyl triethyl citrate and acetyl
tributyl citrate, which only differ in side chain length but have
the same branched structure, decrease the Tg value of PLA by
29.1 and 42.1 °C, respectively, at 20 wt % addition.9 In
addition, an increased plasticizing efficiency of PLA is observed
with a decrease of the molecular weight of poly(ethylene
glycol) (PEG),10 and phase separation occurs when an
excessive amount of PEG is present.11 The nature of the
end-group is also of large importance as illustrated by
methylation of PEG, which enhances the miscibility between
the PLA matrix and PEG plasticizer.12 A vast variety of
plasticizers have been reported for PLA including aliphatic
Received: May 2, 2019
Revised: June 18, 2019
Published: June 19, 2019

© 2019 American Chemical Society 12552 DOI: 10.1021/acssuschemeng.9b02439

ACS Sustainable Chem. Eng. 2019, 7, 12552−12562
ACS Sustainable Chemistry & Engineering
esters,13−15 phthalate,16 dicarboxylate,17 triacetine,18 cit-
rates,9,19,20 epoxies,3 benzoates,21 glucose esters,22 cardoon
seed oil derivatives,4 esters of tartaric acid,5 and polymeric
substances (e.g., PEG,10,11,23,24 polyesters,25 and lactic acid
oligomers26,27).
In light of the enormous market volume of commodity
plastics, the replacement of petroleum-based plasticizers by
renewable analogues establishes need for the production of
eco-friendly plasticizers, which utilize biobased building blocks
and synthesis routes. The green platform chemicals are
promising raw materials, offering multiple product applicability
and large potential to serve as a platform for the production of
biobased derivatives.28 Several green platform chemicals have
already been converted into value-added green plasticizers for
PLA, including derivatives of xylitol,29 succinic acid,30
glycerol,31 levulinic acid,32 and 2,5-furan dicarboxylic acid.33
The plasticizers can, due to their low molecular weight,
migrate to the surface of the product during their use, thereby
deteriorating the material.34 The migration behavior of a
plasticizer is related to factors such as molecular weight,35,36
chemical composition,19 and structure.37 The aim of this study
was therefore to design a palette of plasticizers from green
platform chemicals, and to evaluate the effect of structural
variations on plasticization efficiency and migration resistance
in PLA blends. Here, the green platform chemicals levulinic
acid and glycerol and ethylene glycol that can be attained from
renewable resources were selected as the building blocks for
the synthesis of ester plasticizers with linear or branched
structures. The chemical composition of plasticizers was
further tuned by ketalization. The results were compared to
those obtained with the commercial reference plasticizer
ATBC.
■
EXPERIMENTAL SECTION
Materials. Ethylene glycol (EG, 99%, Honeywell), glycerol (GL,
GPR Rectapur, VWR), levulinic acid (LeA, 97%, Sigma-Aldrich),
iron(III) chloride (FeCl3, 97%, Sigma-Aldrich), sulfuric acid (H2SO4,
95−98%, Sigma-Aldrich), and p-toluene sulfonic acid monohydrate
(PTSA·H2O, 98.5%, Sigma-Aldrich) were used for the synthesis of
plasticizers. Sodium hydrogen carbonate (GR for analysis, Merck) and
ethyl acetate (analytical reagent grade, Fisher Scientific) were utilized
during the extraction to purify the plasticizers. Dichloromethane
(HPLC grade, Fisher Scientific) and polylactide (5200D, Nature-
Works) were utilized as the solvent and film forming polymer during
solution casting of films with or without plasticizers. Tributyl 2-
acetylcitrate (ATBC, ≥98%, Sigma-Aldrich) was selected as reference
plasticizer. Ethanol (GPR Rectapur, 96 vol %, VWR), acetic acid
glacial (analytical reagent grade, Fisher Scientific), and water
(hypergrade for LC−MS, Merck) were used to prepare simulants
for the migration measurements. Methanol (hypergrade for LC−MS,
Merck) was used for ESI−MS analysis. All chemicals were used as
received.
Synthesis of Plasticizers. To synthesize the plasticizers,
esterification to form ethylene glycol dilevulinate (ED) and glycerol
trilevulinate (GT) was performed. The type of catalyst (H2SO4,
FeCl3, PTSA·H2O), catalyst concentration (0.01, 1.0, 5.0 mol %
toward hydroxyl group), reaction time (0−24 h), and temperature
(110 or 140 °C) were first optimized. The optimum conditions were
considered to be as follows: LeA (70 g, 0.6 mol), one of the polyols
(12 g, 0.2 mol for EG or 0.13 mol for GL), and catalyst PTSA (0.8 g,
0.004 mol) were stirred vigorously in a 250 mL three-necked round-
bottomed flask at 110 °C for 24 h. The reaction was conducted under
a nitrogen atmosphere, and the formed water was collected in a water-
cooled condenser connected to a 25 mL flask. After the reaction was
completed, the mixture was neutralized using saturated NaHCO3 (aq)
to remove the unreacted LeA. The solution was then extracted with
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ethyl acetate. The organic phase containing the products was
collected and further rinsed with deionized water twice to remove
impurities. The solvent was removed by rotary evaporation at reduced
pressure. ED and GT were subsequently modified to form ketalized
ethylene glycol dilevulinate (KED) and ketalized glycerol trilevulinate
(KGT). The optimized reaction variables included time (0−72 h),
temperature (25, 50, and 80 °C), and feed ratio of hydroxyl group to
ketone (2:1, 3:1, and 10:1). The following conditions were
subsequently used: ED (10 g, 0.04 mol) and EG (25 g, 0.40 mol)
or GT (12 g, 0.03 mol) and EG (28 g, 0.45 mol) were stirred
vigorously in a 100 mL three-necked round-bottomed flask at 50 °C
for 48 or 72 h to reach high conversion and to obtain KED and KGT,
respectively. The reaction was conducted in a nitrogen atmosphere,
and the formed water was collected in a water-cooled condenser
connected to a 25 mL flask. After the reaction was completed, the
mixture was dispersed in deionized water and subsequently extracted
using ethyl acetate. The organic phase containing KED or KGT was
collected and further rinsed with deionized water three times to
remove impurities. The solution was concentrated by rotary
evaporation of solvent at reduced pressure.
Solution Casting. Neat PLA film and plasticized PLA films were
obtained by solution casting. The amount of plasticizer (ED/GT/
KED/KGT) blended with PLA was 10 or 20 wt %. The concentration
of neat PLA or the combined concentration of PLA and plasticizer
was 4.0 g in 100 mL of dichloromethane solution. At least 1 h of
magnetic stirring at 22 °C was applied to obtain a homogeneous
solution. The films were dried in Petri dishes (D = 186 mm) in a fume
hood at 22 °C for 7 days, followed by at least 7 days in a drying
chamber at 25 °C and reduced pressure. The average thickness of a
typical film was 0.12 ± 0.02 mm. The neat PLA film was named as
“PLA100”, and the plasticized films were labeled as “10P” or “20P”, in
which the number 10 or 20 symbolizes the plasticizer concentration
(10 or 20 wt %) and P represents the abbreviation of the plasticizer.
Migration Study. According to the EU regulation on plastic
packaging materials,38 the overall migration is assessed in a simulant
liquid after a certain time and conditions (e.g., aging temperature and
choice of simulant), and the testing method is varied depending on
the application scenario. Here, three simulants (water (H2O), 10 vol
% ethanol in water (EtOH), and 3 wt % acetic acid in water
(AcOH)), an aging temperature of 60 °C, and the time points of 1, 5,
and 10 days were selected. For each combination of conditions,
triplicates were prepared by placing each PLA film (around 1 cm × 1
cm) in a 20 mL sealed vial containing 10 mL of simulant. The
triplicate samples of each simulant and blend (or neat PLA)
combination were then aged in a 60 °C oven.
Electrospray Ionization Mass Spectrometry (ESI−MS). The
migrating pattern of the low molecular weight substances from the
films was determined by a Finnigan LCQ ion trap mass spectrometer
in positive mode after 1, 5, and 10 days. The aged liquid sample was
diluted using methanol with a volume ratio of 1:2. The flow rate of
the syringe pump for the dilution was 25 μL/min, and an ion source
operating at 4.5 kV was used with the capillary heater set to 200 °C.
The nebulizing gas was nitrogen.
Mass Loss. The mass loss was measured after 1, 5, and 10 days.
Any simulant on the surface of samples was gently removed using
tissue paper and cotton swabs. The weight of the samples after being
stored in a drying chamber (at least 10 days, 25 °C, reduced pressure)
was recorded as dry weight (w1) and was compared to the initial
weight of the samples (w0). The mass loss was then determined by
w − w1
mass loss (%) = 0 × 100%
w0 (1)
Size Exclusion Chromatography (SEC). The molecular weight
of the neat PLA and 10-day aged PLA films was analyzed by a
GPCMAX (from Malvern) equipped with autosampler, a PLgel 5 μm
Guard column, and two PLgel 5 μm MIXED-D columns. The PLA
was dissolved and carried by chloroform with 2 vol % toluene as an
internal standard. The flow rate was 0.5 mL/min, and the temperature
was at 35 °C. The calibration was created using narrow polystyrene
standards with Mn ranging from 1200 to 400 000 g/mol.
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Figure 1. Scheme of the synthesis route (a), 1H NMR spectra (b), 13C NMR spectra (c), and FTIR spectra (d) of the four synthesized potential
plasticizers.
Fourier Transform Infrared Spectroscopy (FTIR). FTIR
spectra of the plasticizers and their PLA blends were collected on a
PerkinElmer Spotlight 400, equipped with a germanium attenuated
total reflection (ATR) crystal. IR absorption spectra were recorded in
ATR mode from 4000 to 600 cm−1 with 16 scans at 25 °C.
Nuclear Magnetic Resonance (NMR). 1H NMR and 13C NMR
spectra of the plasticizers were measured on a Bruker Avance 400
spectrometer at 25 °C. 1H NMR and 13C NMR spectra were
measured at 400 and 100 MHz, respectively. Chloroform-d (CDCl3)
was used as a solvent, and the internal standard was CHCl3.
Differential Scanning Calorimetry (DSC). Glass transition
temperatures, melting temperatures, and crystallinities of the neat
and plasticized PLA were measured under nitrogen atmosphere by
Mettler Toledo DSC 820 Module. Triplicate samples were analyzed,
and the samples were heated from 25 to 200 °C and then kept at 200
°C for 2 min. The samples then were cooled to −30 °C and kept at
−30 °C for 2 min, followed by the second heating scan to 200 °C.
The cooling and heating rates were 10 °C per minute. The glass
transition temperatures were marked as the midpoint of glass
transition in the second heating scans. The crystallinity (χc) was
obtained by applying eq 2 with cold crystallization and melting
enthalpies. ΔHm, ΔHcc, ΔH0m, and wPLA represent the enthalpy of
melting, the enthalpy of cold crystallization, the enthalpy of melting
for 100% crystalline PLA, and the weight percentage of PLA,
respectively. 93.1 J/g39 was applied as the enthalpy of melting for
100% crystalline PLA.
ΔHm − ΔHcc
χc = × 100%
ΔHm0 × wPLA (2)
Thermal Gravimetric Analysis (TGA). The thermal stability of
the neat plasticizers and PLA blends was evaluated using a Mettler
Toledo TGA/DSC 851e module instrument under nitrogen flow of
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50 mL/min from 25 to 500 °C, at a heating rate of 5 °C per minute.
Triplicate samples were analyzed. The onset temperature at weight
loss with 5% was taken for comparison.
Tensile Test. Tensile test was conducted on an INSTRON 5944
module equipped with pneumatic grips. A load cell, with 500 N as
maximum load, was set at a crosshead speed of 20 mm/min. Samples
were prepared by cutting the films into rectangular specimens with a
constant width of 5 mm and a length of roughly 100 mm. The length
between gauges was 20 mm. All samples were conditioned for 40 h at
RH 50 ± 5% and 23 ± 1 °C, according to ASTM D618-13 (Standard
Practice for Conditioning Plastics for Testing). At least eight
specimens were measured for each sample.
■
RESULTS AND DISCUSSION
The green platform chemicals levulinic acid and glycerol that
are already commonly acquired from biomass transformation
and ethylene glycol that could potentially be attained from
renewable resources, are ideal starting-points in the realization
of biobased plasticizers for PLA for value-added applications
such as in food packaging. Here, a variety of biobased ester-
plasticizers were designed from these three chemicals by
utilizing the possibility to create ketone or ketal functionalities
as end-groups as well as linear and branched ester structures.
The effect of these structural features, influencing the
hydrophobicity of the plasticizers as well as the interactions
with PLA, on the blend properties and migration resistance
was investigated. One of the best-functioning and most
migration-resistant commercialized green plasticizer, ATBC
(structure seen in Figure 2), was chosen as reference plasticizer
for performance evaluation.
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Synthesis and Characterization of Potential Plasti-
cizers. Altogether four potential plasticizers with different
functionalities and structures were synthesized successfully.
Two esters with ketone end-groups, ethylene glycol
dilevulinate (ED) and glycerol trilevulinate (GT), were
obtained through condensation of levulinic acid and ethylene
glycol or glycerol as presented in Figure 1a. The optimized
reaction conditions ensured a conversion of alcohol of 65−
75%, yielding liquid products with slightly yellow color. To
synthesize esters KED and KGT with ketal functionality, the
ketone end-groups in ED and GT esters were ketalized by
ethylene glycol, Figure 1a. Ketalization can be realized under
the presence of a homogeneous catalyst40,41 or a heteroge-
neous catalyst42,43 at high temperature. These common
conditions are similar to those applied during esterification.
However, as observed during the optimization, the ketalization
could be selectively achieved over esterification by tuning the
reaction temperature. Therefore, to achieve a high degree of
ketalization with preserved ester groups, a solvent- and
catalyst-free process was designed and utilized. The conversion
of ketones during ketalization reached 63−88%, and the
obtained KED and KGT were light-yellow viscous liquids.
Chemical Structure of the Plasticizers. To confirm the
structures of the four plasticizer candidates, 1H NMR and 13C
NMR spectra were utilized, Figure 1b,c and Figures S1−8. For
the ketone-esters ED and GT, the ketone end-groups from
levulinic acids were retained, which was proven by the signals
from the adjacent protons at δ = 2.18 ppm (CH3−), 2.59 and
2.75 ppm (−CH2−) in the 1H NMR spectrum, and the ketone
carbonyl carbon signal at δ = 206 ppm in the 13C NMR
spectrum. The formation of ester-bond was verified by the
signals from the ester carbonyl carbon at δ = 173 ppm in the
13
C NMR spectrum. The ketal-esters KED and KGT are
ketalized products of ED and GT. Therefore, the methyl and
methylene groups, previously adjacent to the ketone carbonyl
carbon, shifted to δ = 1.31 ppm (CH3−), 2.01 and 2.40 ppm
(−CH2−) in the 1H NMR spectrum, and also new signals of
the methylene groups from 1,3-dioxolane ring were observed at
δ = 3.97−3.89 ppm. In the 13C NMR spectrum, the signals at δ
= 109.17 ppm and δ = 66.41 ppm correspond to the C-2 and
C-4, C-5 of the 1,3-dioxalane ring, while the signals of ketone
carbonyl carbon vanished.
The esterification and ketalization were further confirmed by
FTIR spectroscopy (Figure 1d). A strong absorption band at
1733−1736 cm−1, in the spectrum of all four esters, confirmed
the existence of ester bonds, and the absorption band of the
ketone groups in ED and GT was observed at 1713 cm−1. The
absence of absorption at 1713 cm−1 in the spectrum of KED
and KGT indicates effective ketalization of ED and GT.
Furthermore, the strong C−O stretching vibration in ED and
GT was indicated by the peaks at 1149−1147 cm−1, while the
corresponding band of ketals exhibits characteristic triple
peaks,44 which were located at 1157, 1131, 1099 cm−1 and
1164, 1130, 1097 cm−1 in the spectra of KED and KGT,
respectively. In addition, the absorption at 3050−2800 cm−1
was assigned to the C−H stretching vibration. In combination
with the NMR characterizations, the ketalization process was
verified, and the presence of ester and ketal functionalities in
the potential plasticizers was confirmed.
Thermal Stability of the Plasticizers. The thermal stabilities
of the four synthesized esters were determined by thermal
gravimetric analysis, Figure 2. The onset temperatures of 5%
weight loss (T5) and maximum weight loss temperatures
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Figure 2. TGA traces of the four synthesized potential plasticizers and
reference plasticizer ATBC.
(Tmax) are listed for comparison (Table S1). The thermal
stability of the plasticizers increased significantly after
ketalization, and KGT exhibited the highest thermal stability.
Comparison of ED and KED showed that, after ketalization,
the T5 increased from 140 to 204 °C and the Tmax increased by
32 °C. Similarly, the T5 increased from 164 to 280 °C for KGT
after ketalizing GT, and the Tmax increased by 34 to 357 °C. As
compared to the reference plasticizer ATBC, KED and KGT
suggested higher thermally stability due to their higher T5 and
Tmax values, and ED was less stable. Although the T5 value of
GT was lower than that of ATBC, the Tmax of GT was 57 °C
higher than the Tmax of ATBC.
Theoretical Prediction of Miscibility of PLA/Esters
Blends. Miscibility is an essential criterion for the selection of
plasticizers to reach, for example, high plasticizing efficiency,
migration-resistance, and long service life. The miscibility for a
certain polymer-plasticizer system is strongly affected by the
temperature,45 chemical structure, and molecular weight of the
plasticizer. Such a system can be viewed as a polymer−solvent
system, in which Hansen solubility parameters have been
successfully used as a tool to predict the theoretical system
miscibility. The plasticizer should have solubility parameters
similar to those of the polymer to ensure miscibility, and the
relative energy difference (RED) number calculated from the
differences in Hansen solubility parameters between plasticizer
and polymer is utilized as a parameter to reflect the possible
miscibility.45
The Hansen solubility parameter components and the
overall solubility parameter of each plasticizer and the
repeating unit of PLA were calculated from group contribu-
tions with the Hoftyzer−Van Krevelen method,46 Table S2.
The calculated overall solubility parameter of PLA was
calculated to be 20.6, which is within the range of the reported
literature values that vary from 20.1 to 21.9 (MJ/m3)1/2.47,48
According to the obtained RED values, which were 0.4, 0.7,
0.5, and 0.7 for ED, KED, GT, and KGT, respectively, all four
synthesized plasticizers and the reference plasticizer ATBC
were in the same range and theoretically predicted to be
miscible with PLA (RED < 1).
Experimental Evaluation of the Miscibility of PLA/
Esters Blends. The neat PLA film (PLA100) and PLA blends
containing 10 or 20 wt % ATBC or the synthesized esters were
prepared from solution casting. The obtained transparent films
were then evaluated by DSC to investigate the effect of
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Figure 3. DSC traces of PLA blended with 10 wt % (a) and 20 wt % (b) synthesized esters or ATBC. The Tg and Tm values were chosen from the
second heating scan.
Figure 4. Thermal stabilities of PLA blends containing 10 wt % (a) and 20 wt % (b) synthesized esters or ATBC.
chemical structure on thermal properties, Figure 3. One glass
transition temperature was detected for each film, and the
increased depression of Tg with higher amount of added esters
was widely observed, from which good miscibility of the esters
in PLA was deduced. These results were in agreement with the
theoretical prediction of the miscibility between the synthe-
sized plasticizers and PLA.
The blends with 10 wt % synthesized esters or ATBC all had
Tg values above room temperature, ranging from 36 to 46 °C,
as compared to 59 °C for PLA100, Figure 3a. The reduction in
Tg was lower for the blends with ketal-esters KED and KGT.
When the content of synthesized esters or ATBC was
increased to 20 wt %, the Tg of the films decreased further
to as low of values as 15 °C for 20ED, Figure 3b. All films
portrayed Tg very close to or below 25 °C except 20KGT (Tg =
33 °C), which is beneficial for flexible applications. In
comparison with previous studies on low molecular weight
plasticizers for PLA, the obtained decrease in Tg is comparable.
For example, for PLA (Mn of 137 000) extruded with 20 wt %
triethyl citrate, tributyl citrate, acetyl triethyl citrate, or ATBC,
the measured Tg values varied from 17.0 to 32.6 °C.9 In
another study, a reduction in Tg to 38.9 °C from solution-
casted PLA was achieved when plasticized with 20 wt % di-2-
ethylhexyl-adipate, which is an approved PLA plasticizer for
materials in food contact.49 Moreover, adding 20 wt % esters of
tartaric acid lowered the Tg of PLA to 39.9 °C.5
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A melting transition was observed for PLA100 and most of
the PLA blends. Cold crystallization was also seen in 10ED,
20ED, 20ATBC, and 20GT, induced by the increased chain
mobility due to the presence of the esters. The peaks of fusion
and cold crystallization became broader and more significant in
the thermograms as the esters content increased, although the
actual crystallinity after reduction of the cold crystallization
peak was generally below 0.5% and was not significantly
affected by the amount of the esters (Table S3). The dual or
“shoulder” fusion peak of 20ED indicated melt crystallization
or the presence of two types of lamellar crystals, α-form and
α′-form. The α-form is usually obtained by conventional
melting crystallization conditions. The α′-form is less perfect
and can be achieved by crystallization under 120 °C.50
Interestingly, there was no cold crystallization in 20KED and
20KGT as compared to the presence of cold crystallization in
20ED and 20GT. Considering the differences in ester
structures and the measured Tg values, it is proposed that
the more bulky ketal groups affected the mobility of the system
less because of steric hindrance and increased the required free
volume needed for chain mobility, thus leading to lower
reduction in Tg and reduced ability for cold crystallization.51
Thermal Stability of PLA/Esters Blends. Thermal
gravimetric analysis was performed on PLA and PLA blends
to evaluate the effect of the different esters on the thermal
stability of the blends, Figure 4 and Table S4. The blends with
branched esters, GT and KGT, had higher T5 temperatures
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Figure 5. Mechanical properties of PLA and PLA blends. (a) Modulus. (b) Elongation at break. (c) Stress at break.
than those with linear esters, ED and KED. The highest T5
value, close to that of PLA100, was observed for the blend with
KGT, that is, the ester with a branched structure and ketal end-
groups. The combination of branched structure and ketal end-
groups has been shown to increase the thermal stability of
PVC.52 The thermal degradation of the blends with ED, KED,
and the reference plasticizer ATBC consisted of two stages, the
degradation or evaporation of the ester itself followed by the
degradation of PLA, Figure 4. The blends with GT and KGT,
independent of their content, portrayed thermal degradation
patterns similar to that of PLA100. A high T5 could be an
advantage during processing, as it enables processing at higher
temperatures without degradation. Interestingly, although the
T5 value of neat GT was quite low as compared to the other
synthesized esters, its blends exhibited superior thermal
stability as compared to blends with ED, KED, and ATBC.
Mechanical Properties of PLA/Esters Blends. The
mechanical performances of the prepared PLA films were
altered, as expected, by the incorporation of low molecular
weight compounds, as illustrated in Figure 5 and Figures S9
and S10. PLA100 demonstrated the highest values for both
modulus and stress at break, but the lowest value of elongation
at break, that is, typical properties for rigid and brittle materials
with poor ductility. On the contrary, due to the enhanced
chain mobility suggested by previous DSC results, the reduced
Young’s modulus and improved elongation at break were
observed for all of the blends, showing that the films were
plasticized. For example, when 10 wt % ED or ATBC was
added, the elongation at break increased from 5% to 487% and
449%, respectively; meanwhile, the Young’s modulus de-
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creased from 2053 to 1299 and 1519 MPa, respectively. In
addition, almost 41% and 34% of tensile stress at break was lost
in the case of 10ED and 10ATBC, respectively, as compared to
PLA100. The increment of plasticizers content to 20 wt %
brought further increase in the elongation at break and
decreased the Young’s modulus. The increased ability for chain
movements was also seen by the lower Tg values of the blends.
The elongation at break for 20 wt % blends ranged from 446%
to 643%, and the modulus distributed between 263 and 1416
MPa. The tensile stress was almost preserved or slightly
improved for most blends. It was clear that all four synthesized
esters had a plasticizing effect.
It has previously been reported that an elongation at break
below 150% and tensile stress of 20 MPa were determined for
PLA plasticized by 20 wt % DEHA, accompanied by a high
Young’s modulus close to 1500 MPa and Tg of 38.9 °C.49 For
PLA plasticized with 20 wt % of glucose hexanoate,22 an
elongation at break of 370%, a stress at break of 21 MPa, and
Young’s modulus of 590 MPa were determined. Thus, the
measured results for PLA blends prepared here were well
comparable. For example, 20KGT had a relatively high Tg (33
°C) and high modulus (1416 MPa), a greater elongation
(446%), and higher tensile stress at break (39 MPa),
approximately equaling to 70% and over 500% of the
corresponding performances of 20ATBC.
Migration Study of the Plasticized PLA Films. The
migrants, including plasticizers and PLA hydrolytic degrada-
tion products (PLA oligomers, LAn), dissolved in each
simulant after predetermined aging periods were fingerprinted
by electrospray ionization mass spectrometry (ESI−MS) to
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Figure 6. Positive-mode ESI−MS spectra of films stored at 60 °C for 10 days in 3 wt % acetic acid, suggesting the presence of migrated plasticizer
and PLA oligomers. (a) PLA100. (b) 20KED. (c) 20GT. (d) 20KGT.
elucidate the effect of plasticizer and aging time on the
migration patterns of plasticized PLA films, and they were
compared to PLA100. The overall results are listed in Table
S5.
Identification of Migrated Plasticizers from Plasticized
PLA Films. Migration of the plasticizers could be observed for
all of the plasticized PLA films after 1 day of aging at 60 °C.
The presence of migrated plasticizers was identified by their
dominant characteristic peaks shown in ESI−MS spectra
(Figures 6 and 7). As an example, the Mw of ATBC plasticizer
is 402.5 g/mol, and therefore the peak (m/z = 425) in the
ESI−MS spectra (Figure 7a−c) was assigned to the mono
sodium adduct of ATBC. Similarly, the mono sodium adducts
of ED (m/z = 425), KED (m/z = 369), and GT (m/z = 409)
were detected by ESI−MS in Figures 6b and 7d−f, Figure 6b,
and Figure 6c,d, respectively. The ketals are classically used as
ketone protecting groups and are susceptible toward
hydrolysis. Therefore, the relative intensity of KED in the
spectra was very low, and the KGT was not even detected;
instead, their hydrolyzed products of ED and GT gave strong
signals in the ESI−MS spectrum of 20KED (Figure 6b) and
20KGT (Figure 6d).
Identification of PLA Oligomers from Plasticized PLA
Films. Within 10 days of aging, no lactic acid oligomers, the
degradation products of PLA, were detected in the ESI−MS
spectra of PLA100 (Figure 6a), regardless of the type of
simulant and aging time. The LAn was detected in 20ATBC
and 20ED after 10 days of aging in each simulant (Figure 7).
However, in the case of 20KED (Figure 6b) and 20GT (Figure
6c), LAn was detected only after aging in acetic acid simulant.
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No LAn was detected by ESI−MS in any 20KGT samples
irrespective of employed simulants.
The main series of PLA degradation products (m/z = 200−
1100) corresponded to linear lactic acid oligomers terminated
by carboxyl and hydroxyl end-groups, with the hydrogen from
the carboxyl group exchanged by a sodium ion. The detected
signals occurred at m/z = (72*n + 1 + 17 + 23*2 − 1), where
n and 72 represent the number and molecular weight of
repeating units in oligomers, respectively. The common
chemical structure for the oligomers is suggested in Figures
6 and 7. Such series of double sodium adducts have been
observed in a few previous studies where the degradation
product patterns of PLA were recorded.53−55 One additional
series of oligomers (m/z = 600−1500) with relative low
intensity was detected in the spectrum of 20ED samples
(Figure 7d−f). This new group of peaks appeared at m/z =
(72*n + 1 + 17 + 23*3 + 18 − 2*1). Two protons were
exchanged by sodium ions in this case, and similar adducts
have been reported in the degradation traces of neat PLA
hydrolyzed in water at 60 °C as well.53 The detection of LAn
with longer chains revealed the constant cleavage of ester
bonds on main chains.55
Mass Loss and Aging-Induced Changes in Thermal
Properties. The mass loss of PLA blends containing 20 wt %
plasticizers after 1, 5, and 10 days of aging revealed that all
plasticized films had an increased mass loss with increasing
aging time as expected (Figure 8a). After 10 days of aging, the
PLA100 portrayed a very minor mass loss, and therefore its
degraded oligomers were undetectable in the ESI−MS
spectrum (Figure 6a). 20ATBC and 20ED exhibited the
lowest and highest mass losses, respectively, among all tested
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Figure 7. Positive-mode ESI−MS spectra showing migrated plasticizers and PLA oligomers leached from films that were aged at 60 °C for 10 days
in three different simulants. (a) 20ATBC in water. (b) 20ATBC in 10 vol % ethanol. (c) 20ATBC in 3 wt % acetic acid. (d) 20ED in water. (e)
20ED in 10 vol % ethanol. (f) 20ED in 3 wt % acetic acid.
samples. 20ED lost more than 30 wt % of mass after 10 days;
that is, at least 10 wt % of PLA was transferred into simulants.
This is in accordance with the intense signals of PLA oligomers
in the ESI−MS spectra (Figure 7d−f). 20KED, 20GT, and
20KGT demonstrated intermediate migration behavior, and
there were no large differences in the mass loss between them.
A previous study has shown that a more hydrophilic plasticizer
commonly leads to faster migration.56 In agreement with this,
the most hydrophilic plasticizer ED, which also had the lowest
molecular weight, had the highest mass loss rate after 1 day.
The changes in the thermal properties of the PLA100 and
the 20 wt % plasticized PLA films in the different aging media
are displayed in Figure 8b−d. After 10 days of aging, the Tg of
PLA100 decreased from 59 to 57, 55, and 52 °C in water,
ethanol, and acetic acid simulant, respectively, which is
explained by the decreasing molecular weight induced by
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hydrolytic aging (Table 1). This can be compared to the
significant increment of Tg for all of the plasticized films
explained by the migration of the plasticizers. For 20ATBC, a
lower Tg was preserved because of its lower migrating rate of
the plasticizer. The aging temperature was set to 60 °C, which
is higher than the Tg of PLA100, and an increase in χc was
therefore observed for all of the aged films. Consequently,
rising melting temperatures were obtained, and thicker crystals
may be formed during hydrolysis.57 Nevertheless, the hydro-
lytic degradation lowered the molecular weight; that is, shorter
PLA chains were formed. Thus, the value of Tm was most likely
determined by the joint effect of the degree of degradation and
crystallization. That effect was demonstrated by the observa-
tion that 20ED and 20ATBC had Tm values very close to each
other in water simulant after aging, while 20ED had a higher
degree of χc and much lower molecular weight than 20ATBC.
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ACS Sustainable Chemistry & Engineering Research Article

Figure 8. Mass loss during aging and thermal properties of PLA films aged 10 days. (a) Mass loss. (b) Glass transition temperatures. (c) Melting
temperatures. (d) Crystallinity (PLA content counted as 100% in calculations). Tg was taken from the second heating scan; crystallinity and Tm
were based on the first heating scan.

Table 1. Changes in Molecular Weight of PLA100 and Plasticized PLA after Aging for Ten Days
sample Mn (g/mol) dispersity sample Mn (g/mol) dispersity
PLA100 (before aging) 118000 1.7
PLA100, H2O 25000 2.2 20ATBC, H2O 34000 1.9
PLA100, EtOH 12000 2.3 20ATBC, EtOH 24000 2.1
PLA100, AcOH 8000 2.3 20ATBC, AcOH 10000 2.1
20ED, H2O 7000 2.4 20KED, H2O 16000 2.1
20ED, EtOH 9000 2.2 20KED, EtOH 14000 2.1
20ED, AcOH 5000 2.2 20KED, AcOH 7000 2.0
20GT, H2O 12000 2.4 20KGT, H2O 26000 1.8
20GT, EtOH 9000 2.9 20KGT, EtOH 21000 1.9
20GT, AcOH 7000 2.0 20KGT, AcOH 8000 2.0

Molecular Weight Changes. The molecular weight of the
initial PLA100 and the 10-day aged blends and PLA100 was
examined by size exclusion chromatography (Table 1).
Generally, the molecular weight decreased with increasing
hydrolysis time for all of the tested films. The degradation of
PLA was indicated by a significant decline in the molecular
weight of PLA100 and the plasticized films. The initial Mn of
PLA100 was 118 000 g/mol, which dropped to 25 000 g/mol
after aging for 10 days in water, at the same time as the
dispersity increased from 1.7 to 2.2. It has been reported that
the Mn of neat PLA fell from 56 750 to 7510 g/mol, and the
dispersity increased from 1.7 to 2.6 after 8 days of aging in
phosphate buffer (pH 7.3) at 60 °C.58 Lower Mn values after
aging were obtained when PLA was plasticized by the three
synthesized plasticizers (ED, KED, and GT) as compared to
12560
the PLA100 because the plasticized systems had higher
mobility and the migrated plasticizers generated more surface
area for hydrolytic attack. However, the hydrolysis rate of PLA
is also governed by the balance of hydrophobicity and
hydrophilicity of the plasticizers.59 Higher Mn and lower
dispersity values were thereby retained in the case of 20ATBC
and 20KGT, which were plasticized by more hydrophobic
plasticizers with larger size. A similar inhibited hydrolysis
process for PLA plasticized by ATBC has been observed
before, and the hydrophobic nature of the plasticizer itself was
believed as the underlying reason for suppressed water
absorption and thus slower degradation rate.60 That was
aligned with the fact that KGT is the most hydrophobic of the
four synthesized plasticizers. Moreover, when a branched
structure or ketal functionality was employed, higher Mn value
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ACS Sustainable Chemistry & Engineering
was achieved after aging when comparing films from 20ED,
20KED, 20GT, and 20KGT.
■
CONCLUSIONS
A family of biobased plasticizers, with ketone or ketal end-
groups and linear or branched ester structures, was successfully
synthesized by utilizing ethylene glycol and the green platform
chemicals levulinic acid and glycerol. The structures of the
synthesized plasticizes were confirmed by 1H NMR, 13C NMR,
and FTIR. All synthesized plasticizers significantly decreased
the Tg of PLA, where ketal and branched plasticizer structures
resulted in less reduced Tg. The thermal stability of the
plasticizer itself was increased by ketal end-groups, and the
thermal stability of plasticized PLA was retained when a
branched structure was employed together with ketal end-
groups. The four synthesized plasticizers ensured comparable
enhancement in ductility and a somewhat higher Young’s
modulus, as compared to PLA with reference plasticizer
ATBC. The ESI−MS analysis suggested fast migration of
plasticizers and PLA hydrolysis during the migration study.
The hydrolysis rate of PLA was decreased by the addition of
branched plasticizer with ketal end-groups. Thus, the
plasticizers designed from levulinic acid and especially the
one with branched structure and ketal functionality demon-
strated good potential to be introduced as a biobased high-
performance plasticizer for PLA.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.9b02439.
NMR spectra of the four synthesized plasticizers, tensile
curves of PLA film and PLA blends with plasticizers,
thermal stability data related to plasticizers and blends,
calculation of solubility parameters, and a summarized
table of ESI−MS results (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: hoem@kth.se.
ORCID
Minna Hakkarainen: 0000-0002-7790-8987
Karin Odelius: 0000-0002-5850-8873
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We gratefully acknowledge The China Scholarship Council
(CSC) for the financial support of this work. Many thanks to
Yunsheng Xu and Geng Hua for the assistance with NMR
analysis.
■
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