Research Article

pubs.acs.org/journal/ascecg

A Renewable Lignin−Lactide Copolymer and Application in Biobased

Composites
Yi-Lin Chung,† Johan V. Olsson,‡ Russell Jingxian Li,‡ Curtis W. Frank,§ Robert M. Waymouth,‡
Sarah L. Billington,† and Elizabeth S. Sattely§,*
†
Department of Civil and Environmental Engineering, Stanford University, Stanford, California 94305, United States
‡
Department of Chemistry, Stanford University, Stanford, California 94305, United States
§
Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
*
S Supporting Information

ABSTRACT: The need for renewable alternatives to traditional

petroleum-derived plastics has driven recent interest in biobased
composite materials that are sourced from carbon-neutral
feedstocks. Lignin, an abundant plant-derived feedstock, has
been a candidate for renewable materials; however, it is often
difficult to blend with other biopolymers. In order to improve the
miscibility of lignin with other bioplastics, we developed a
catalytic and solvent free method for synthesis of a lignin−PLA
copolymer. Graft polymerization of lactide onto lignin catalyzed by triazabicyclodecene (TBD) resulted in a lignin-g-poly(lactic
acid) copolymer; chain length of the PLA is controlled by varying of the lignin/lactide ratio and preacetylation treatment. End-
group analysis reveals high grafting efficiency and preferential grafting on lignin aliphatic hydroxyls over phenolic hydroxyls. The
lignin-g-PLA copolymers display a glass transition temperature range from 45 to 85 °C and multiphase melting behavior. The
lignin-g-PLA copolymers are used as dispersion modifiers in PLA-based materials to enhance UV absorption and reduce
brittleness without a sacrifice in the modulus of elasticity.
KEYWORDS: Green materials, Renewable materials, Bioplastics, Biocomposites, Copolymers, Organocatalyst, Graft polymerization

■ INTRODUCTION
The depletion of fossil fuel resources and the environmental
due to intermolecular association from hydrogen bonding
between the carboxylic acid groups and various ether oxygens
impact of petroleum-based plastic materials have driven a and hydroxyl groups, van der Waals attraction of polymer
strong global interest in renewable biobased polymers and chains, and π−π stacking of aromatic groups.10,11 Modification
composites derived from natural resources.1,2 Lignin is the of lignin by esterification12,13or etherification14 has been used
second most abundant renewable biopolymer in nature and an to improve its dispersion in thermoplastics and thermosetting
inexpensive and currently underutilized3 waste product from materials and leads to improved performance in composite
papermaking and biorefinery industries. These processes materials. Graft polymerization is an attractive approach to
produce a lignin fraction that is often relegated to the low- covalently modify the surface of lignin, resulting in a lignin-
value use of combustion or sold as a natural component of based copolymer that can be used in a broader range of
animal feeds. The development of a way to convert lignin to applications, and allows for the design of novel materials with
new high-value products will have a crucial impact on tailored properties.15−17 Glasser and co-workers have synthe-
biorefinery economics; consequently, the conversion of lignin sized multiphase star-like copolymers of lignin-polycaprolac-
to value-added chemicals and materials is an active area of tone18 and lignin-polystyrene19 that are better dispersed in
research.3,4 Several laboratories have explored the use of lignin poly(vinyl chloride)8 and polystyrene-based19 thermoplastic
as an inexpensive structural filler, surfactant, and additive in materials, respectively, compared to unmodified lignin.
materials applications. For example, lignin is used in biobased Poly(lactic acid) (PLA) is one of the main biodegradable
polymeric composites to modify material properties such as polymers in the current and emerging bioplastics markets;
hydrophobicity, stiffness, and crystallinity relative to neat however, it is not yet considered a direct replacement for
biopolymers.5−7 However, the use of unmodified lignin as a conventional synthetic polymers because of its high cost of
filler in thermoplastic polymers often negatively impacts the production and several undesirable attributes including
mechanical properties of the resulting composite materials.4,6,8,9 brittleness, poor thermal resistance, limited gas barrier
The poor dispersion of lignin in many composites is
attributed to its propensity to self-aggregate. Lignin is an Received: March 19, 2013
irregular polymer made up of substituted phenyl rings and Revised: July 15, 2013
phenolic and aliphatic hydroxyl groups, and aggregation is likely Published: July 26, 2013

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ACS Sustainable Chemistry & Engineering Research Article

properties, and poor UV light barrier properties.20,21 Some integration values of the spectral regions arising from aliphatic
laboratories have tried to address these issues by preparing hydroxyls (149−146 ppm), phenolic hydroxyls (144−137.5 ppm), and
PLA−lignin composites;22,23 however, these materials often carboxyls (136−134 ppm) relative to the internal standard (145.5−
exhibit lower tensile strength and elongation at break than neat 144.5 ppm).
Differential scanning calorimetry (DSC) was performed on a TA
PLA. To improve the dispersion of lignin in PLA, lignin-g-PLA Instruments Q100 and Q2000 DSC using a heating and cooling rate of
copolymers have been synthesized to compatibilize lignin with 10 °C/min and nitrogen flow rate of 50 mL/min. The samples were
PLA.24,25 Our hypothesis is that the introduction of small heated from 0 to 190 °C, cooled to 0 °C, and then heated to 190 °C
amount of well-dispersed lignin-g-PLA copolymers should again. Glass transition temperature (Tg) was determined on the second
improve UV light barrier properties of the composites without heating scan if not otherwise specified.
a sacrifice in flexibility. This approach has been successful for The size exclusion chromatography (SEC) system consisted of a
generating other types of PLA composites, e.g., PLA−talc Shimadzu LC-20AD pump, Shimadzu SIL-20AC HT autosampler,
reported by Narayan et al.26 Because ring-opening polymer- CTO-20A column oven, and Shimadzu RID-10A refractive index
ization (ROP) of lactide is an established method for the detector. A Jordi Gel DVB guard column (500 Å) and three Jordi Gel
DVB analytical columns (500 Å, 104 Å, and 105 Å) were used with
synthesis of PLA, we reasoned this process would enable the
chloroform as the eluting solvent (1 mL/min) and at 40 °C. The
graft polymerization of PLA onto lignin to generate a lignin-g- system was calibrated using polystyrene standards from Varian
PLA copolymer sourced from completely renewable materials. (Calibration Kit S-M2-10, U.S.A.) and Shodex (Showa Denko K.K.,
Furthermore, use of an efficient organocatalytic ROP process27 Tokyo, Japan). Samples (5 mg) were dissolved in chloroform (1 mL)
would leave no metal residues in the resulting biobased and then filtered through a 0.22 μm PTFE membrane before injection
composites. Here, we report a simple metal- and solvent-free into the SEC system.
31
method for organocatalytic graft polymerization of lactide onto P NMR spectra and phosphitylation of lignin and lignin-g-PLA
lignin to produce lignin-g-PLA copolymers using triazabicyclo- copolymer were performed based on modification of the method
decene (TBD) as a catalyst. The PLA chain length can be described by Granata et al.29 A solvent mixture composed of
controlled by using varying ratios of lignin to a lactide deuterated chloroform (CDCl3) and pyridine (1.6/1.0, v/v) was
prepared and dried over molecular sieves prior to use. This solution
monomer. Further control of the grafted PLA chain length is was used for the preparation of relaxation reagent solution (RR,
also accomplished by pre-acetylating the lignin. The ability to chromium(III) acetylacetonate, 5.0 mg/mL) and the internal standard
control the chain lengths of the grafted PLA enables variable solution (IS, cyclohexanol, 10.0 mg/mL). A total of 15.0 mg of oven-
levels of interaction with a surrounding polymer matrix (PLA), dried sample was dissolved in a CDCl3-pyridine solvent (370 μL)
allowing properties of the lignin−PLA composite materials to followed by the addition of RR (50 μL) and IS (50 μL). The resulting
be tuned. We investigated the dispersibility of the grafted solution was left to stand for 1 h to ensure total dissolution. TMDP
lignin−PLA copolymers in a PLA matrix and measured the (30 μL) was then added and let stand for at least 7 h to ensure
impact of the modified lignin on the UV−vis absorption spectra complete derivatization prior to 31P NMR analysis. The phosphityla-
and mechanical properties of the resulting composite. tion of PLA was conducted according to the experimental procedure

■
described above, with a reaction time of 3 days at room temperature.
The phosphitylated PLA polymer was analyzed by in situ 1H NMR
EXPERIMENTAL SECTION (CDCl3) (Figure S2, Supporting Information) and 31P NMR (CDCl3)
Materials. Lignin (Indulin AT, Westvaco, Charleston, SC) was (Figure 3(b)).
dried at 50 °C vacuum for 36 h and stored in a glovebox (N2) prior to Representative Procedure for Synthesis of Lignin-g-PLLA
use. L-lactide (S,S) (LLA) (Purac Biochem, Netherlands) and Copolymers (Lignin:Lactide 10:90). Inside a glovebox (N2), TBD
triazabicyclodecene (TBD) (Aldrich) were used as received and catalyst (100 mg, 1 wt %), lignin (1 g, 10 wt %), and L-lactide (9 g, 90
stored in a glovebox under nitrogen. 2-Chloro-4,4,5,5-tetramethyl- wt %) were weighed into a reaction vial (25 mL) equipped with a stir
1,3,2-dioxaphospholane (TMDP) (Sigma-Aldrich), cyclohexanol (Alfa bar. The vial was sealed, taken outside the box, and immersed into an
Aesar), chromium(III) acetylacetonate (Strem Chemicals), deuterated oil bath at 130 °C for 3.5 h with stirring. The reaction mixture was
chloroform (Cambridge Isotope Laboratories), pyridine (EMD then cooled to room temperature and was subsequently quenched by a
Chemicals), acetic anhydride (EMD Chemicals), N-methyimidazole dichloromethane solution (5 mL) of acetic acid (100 mg). After the
(Acros Organics), p-dioxane (JT Baker), chloroform (Fisher), residue had completely dissolved, an aliquot was taken out and
isopropanol (Fisher), and poly(lactic acid) (2003D) (NatureWorks concentrated in vacuo for 1H NMR analysis (in CDCl3). L-Lactide
LLC, MN) were used as received without further purification. Oven- conversion (83%) was determined by integration of the L-lactide
dried glassware and stir bars were used for all polymerization methide signal (5.03 ppm) against the integration of the PLA methide
experiments. All polymerization reactions were carried out under inert signal (5.16 ppm). The remainder of the crude reaction mixture was
atmosphere (nitrogen). then concentrated on a rotary evaporator to a highly viscous solution
Characterization. 1H-nuclear magnetic resonance (NMR) spectra (approximately 10 mL), which was then precipitated by pipet addition
were recorded at room temperature on a Varian 300 (75), 400 (100), to a stirred methanol solution (1 L). Subsequently, the methanol
or 500 (125) MHz spectrometer, with shifts reported in parts per solution was discarded, and the precipitated polymer at the bottom of
million downfield from tetramethylsilane and referenced to the the beaker was collected by extraction with dichloromethane. Then
residual solvent peak. 31P NMR spectra were obtained on a Varian polymers were concentrated and dried in vacuo to a constant weight,
mercury plus spectrometer, equipped with a four-nucleus switchable yielding (6.90 g, 69% yield) pure lignin-g-PLA copolymer. The PLA
and pulse field gradient probe operating at 162 MHz, using methods chain length average was determined by 1H NMR (CDCl3) end-group
modified from that of Cateto et al.28 Experiments were recorded at 25 integration of the PLA (5.16 ppm) methide proton against the end-
°C in CDCl3. Chemical shifts were calibrated from the sharp 31P NMR group methide proton (4.35 ppm) (Figure 1, Mn = 1800 Da). The
signal at 132.2 ppm arising from the reaction product between residual purified lignin-g-PLA (10/90) copolymer was further characterized by
31
water and TMDP. Spectra were quantitative with proton broad bands P NMR (Figure 3), DSC (Figures 4 and 5), and SEC (Table S1 and
decoupling only during acquisition time. Cyclohexanol was used as an Figure S5, Supporting Information). The theoretical Mn value for PLA
internal standard for the quantitative evaluation of the lignin hydroxyl chains in Figure 2 was calculated by dividing the mmoles of lactide by
group content. 31P NMR spectra were obtained with a 100 kHz mmoles of the lignin−OH functionality (obtained by 31P NMR
spectral width, 128,000 data points, 8 s relaxation delay, 0.64 s analysis). This maximum Mn for grafted PLA chains was then
acquisition time, 8 μs for a 55.4° pulse, and 1 Hz line broadening using multiplied by the observed conversion of lactide in the grafting
128 scans. Content of different hydroxyl groups were obtained by the reaction.

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copolymerization with L-lactide. 31P NMR analysis revealed 75%

degree of acetylation (DA).
Mechanical Properties of PLA−Lignin Composites. A total of
2.1 g PLA was blended with non-modified lignin (0.021−0.105 g) or
lignin-g-PLA copolymer (0.21−0.2625 g) in chloroform (15 mL) at
room temperature for 15 h. Then, the polymer mixture was
precipitated by the addition of isopropanol (100 mL). The
precipitated polymers were dried in a vacuum oven (80 °C) for 3
days prior to use. PLA−lignin composites were obtained by hot
pressing the dried precipitate (PHI-Tulip Model 225H-X6-13, U.S.A.)
at 190 °C using three pressure stages: 0 ton pressure for 30 s, 0.1 ton
for 1 min, and then 0.5 ton for 2 min. The hot-pressed specimen (∼60
mm × 100 mm × 0.25 mm) was then cut into sample strips (10 mm ×
100 mm) using a razor blade for tensile testing. Tensile tests were
carried out using Instron 5565 (TA Instruments) to measure tensile
modulus, strength, and strain of composites. The space between the
grips was 50 mm and served as the gage length for deformation
measurements. A constant deformation speed of 5 mm/min was used.
The specimens were conditioned at room temperature under 54% RH
for 2 days prior to testing. Four to five replicate specimens were tested
and analyzed.
Figure 1. 1H NMR spectrum of lignin-g-PLA copolymers in CDCl3. Optical Properties of PLA−Lignin Composites. A total of 500
mg PLA was blended with unmodified lignin (5 mg) or lignin-g-PLA
copolymer (50 mg) in chloroform (10 mL) at room temperature for 2
h. Then, the polymer mixture was precipitated by methanol (100 mL)
and dried in a vacuum oven (55 °C) prior to use. A total of 50 mg of
PLA−lignin blends were then hot pressed at 180 °C using three
pressure stages: 0 ton pressure for 30 s, 0.1 ton for 1 min, and then 0.5
ton for 2 min into films 0.04−0.05 mm in thickness. The films were
conditioned at room temperature under 0% RH for 3 days prior to
testing. Because poly(ethylene terephthalate) (PET) is a commonly
used material for packaging and and also used for light-sensitive
products because it has good UV light barrier properties,20 we are
interested in comparing the UV light barrier properties of PLA−lignin
composites to PET. The PET materials were obtained from
poly(ethylene terephthalate) (PET) bottles (Fiji bottled water) and
then hot pressed by the same procedure into films with 0.04 mm in
thickness. Optical properties of PLA, PLA−lignin, and PET films were
measured by an Agilent Cary 6000i UV−vis−NIR spectrophotometer.
The specimens were scanned from 200 to 800 nm at room
temperature.
Figure 2. Number-average molecular weight (Mn) of each grafted PLA
chain on the starlike lignin-g-PLA copolymers. The experimental PLA
chain length was determined by 1H NMR end-group integration. The
theoretical value was determined as described in the Experimental
■ RESULTS AND DISCUSSION
Graft Polymerization of PLA onto Lignin via Ring-
Section. Opening Polymerization. The diverse chemical function-
alities of lignin, including a mixture of aliphatic hydroxyls,
phenolic groups, and carboxylic acid etc., presents a challenge
for synthetic modification, both in terms of functional group
The lignin-g-PLA copolymers (30−50 wt % lignin) were tolerance and selectivity. Previously described ring-opening
synthesized as above but were instead purified by dialysis (MW cutoff polymerization (ROP) protocols on lignin with caprolactone18
1000 Da) over methanol (1 L) changed twice over 12 h. The and styrene19 utilized chemical pretreatment (hydroxypropyla-
remaining contents of the dialysis bag were extracted with dichloro- tion), followed by fractionation processes as a method to
methane and concentrated in vacuo, yielding the pure copolymers. convert lignin into a functionally more homogeneous material
General Procedure for Acetylation of Lignin (DA=75%). The
procedure was modified from a previously reported acetylation prior to its use in polymerization. From a practical and
method.13 To 1.0 g of lignin was added acetic anhydride (Ac2O, 2.6 economic standpoint, the need for chemical pretreatment and
mL, 28.0 mmol, 5.5 eq, based on 5.10 mmol OH/g lignin) and diluted purification of lignin prior to use limits the attractiveness of this
to a final volume of 4.0 mL using p-dioxane in a 7 mL scintillation glass approach. Thus, we investigated whether lignin could be used
vial equipped with a stir bar. The reaction was sealed and stirred at 50 directly in graft polymerization reactions for production of new
°C for 2 h. No special care was taken to ensure that the reaction was biobased polymeric materials.
moisture- or air-free. Acetylated lignin was recovered by precipitation In order to create a lignin-g-PLA copolymer that would
initiated by addition of 45 mL of deionized (DI) water to the crude perform well in a PLA composite, we turned to graft
reaction mixture. The resulting suspension was transferred to a 50 mL polymerization of PLA onto an unmodified lignin substrate.
falcon tube and subjected to centrifugation at 4000g for 15 min. The
supernatant was decanted and discarded. The residue was resuspended This approach was especially attractive because there are well-
in an additional 45 mL of DI water and subjected to another round of established methods for ROP of lactide to make PLA. In
centrifugation. After two rounds of centrifugation, the resulting particular, a metal-free approach developed by the Waymouth
product was freeze dried, followed by drying in a vacuum oven (50 and Hedrick laboratories has been used to polymerize L-lactide
°C) prior to subsequent analyses and used as a substrate for (LLA), caprolactone, and valerolactone.30 We discovered that
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Scheme 1. Ring-Opening Polymerization of Lactide (LA) on Lignin Using Triazabicyclodecene (TBD) Catalyst

the organocatalytic ring-opening polymerization of lactide at 146.2−146.5 ppm (shown in Figure 3(b)). The absence of
31
could be done in the melt with catalytic triazabicyclododecene P resonances corresponding to aliphatic and phenolic lignin
(TBD) in the presence of lignin (1−50%) to cleanly generate a OH signals (149−146 and 144−137.5 ppm, respectively) in
novel lignin-g-PLA copolymer (Scheme 1 and Table S1, Figure 3(c) and the presence of 31P resonances corresponding
Supporting Information). to PLA terminal hydroxyls at 146.5 ppm (at 5 wt % lignin)
Analysis of the isolated copolymers by 1H NMR spectros- indicates that all detectable OH groups of lignin are covalently
copy indicated efficient surface modification of lignin (Figure modified by PLA chains in the 5 wt % lignin-g-PLA copolymer.
1). The resonances at 5.3−5.1, 4.4−4.3, and 4.0−3.5 ppm For higher lignin loadings (30%), some lignin phenolic OH
(CDCl3) are assigned to the protons of the PLA repeating unit functionality is unmodified, as indicated by the broad peak at
(HA), end group of PLA (HB), and lignin, respectively. These 140−139.5 ppm (Figure 3(d) and Table S2, Supporting
spectra could also be used to calculate average PLA chain Information). Organocatalytic ROP is efficient with aliphatic
length in the copolymer by 1H NMR end-group integration; as alcohol initiators,30 but less is known on the use of phenolic
the weight fraction of lignin relative to lactide monomer initiators.31 Our study suggests that phenols are slower
increased, the resulting shorter PLA grafted chains decreased in initiators than aliphatic alcohols but are in part acting as
length (shown in Figure 2), suggesting that initiation of PLA initiators in the polymerization. This was also supported by
polymerization at each lignin−OH group effectively competes control experiments of TBD-catalyzed lactide polymerization
with extension of the PLA chain. (130 °C, 4 h, melt) with aliphatic (benzyl alcohol) and
By varying the lignin content from 1 to 50 wt % in the graft phenolic initiator (3-ethyl-phenol) at a target degree of
polymerization process, the chain lengths of the grafted PLA polymerization (DP) of 25 (Table S3, Supporting Informa-
could be controlled from number-average molecular weight tion). Initiation by benzyl alcohol resulted in an observed Mn of
(Mn) 200−11,000 Da (Figure 2). The observed Mn of the 3600 Da, whereas 3-ethyl-phenol as initiator gave a higher Mn
grafted PLA chains were in close agreement with the theoretical (7200 Da). The presence of the phenolic end group was
value predicted from the number of active hydroxyls on lignin confirmed by 1H NMR on the isolated PLA and integrated
determined by phosphitylation of the lignin substrate and (1:1) against the methide alcohol end group (Figure S1(b),
analysis by 31P NMR spectroscopy (Table 1). Supporting Information). This suggests that phenols may be
acting as initiators in the polymerization of LA, using the above-
Table 1. Effect of Pre-Acetylation on Chain Length of Each described conditions, although with lower efficiency than
Grafted PLA Chain of Lignin-g-PLA Copolymers (5 wt % aliphatic alcohols.
lignin) In order to increase the length of PLA chains while keeping
the lignin content high in the copolymer, we hypothesized that
type of Lignin neat lignin pre-acetylated ligninc
a
grafted PLA chain length could be controlled by appropriate
Mn of each grafting PLA chain (Da) 3600 6408
tailoring of the lignin OH content. Thus, we prepared a series
aliphatic OH 149−146 ppmb 2.01 0.66
of lignin samples with varying degrees of acetylation (Table S4
phenolic OH 144−137.5 ppmb 3.10 0.58
and Figure S3, Supporting Information). Lignin (75%
total OH 149−137.5 ppmb 5.10 1.24
acetylated) was used in the synthesis of lignin-g-PLA copolymer
COOH 136−134 ppmb 0.40 0.35
a
(5 wt % lignin). Table 1 shows that a significant increase in
Number-average molecular weight (Mn) is determined by 1H NMR molecular weight of each grafted PLA chain was observed in the
end-group integration. bHydroxyl (OH) group content in units of resulting lignin-g-PLA copolymer (Mn 6408) compared to the
mmol/g. cDegree of acetylation (DA) of the pre-acetylated lignin is
75%. DA is determined by dividing the acetylated OH group content
neat lignin (Indulin AT) (Mn 3600).
(5.10 − 1.24 = 3.86 mmol/g) of the pre-acetylated lignin by that of the The lignin-g-PLA copolymers were found to be soluble in
unmodified lignin (5.10 mmol/g). common organic solvents such as chloroform and tetrahy-
drofuran in contrast to unmodified lignin; a trend of increasing
solubility was observed as the PLA chain length increased.
To assess the efficiency of the grafting method, we Thermal Properties of Lignin-g-PLA Copolymers.
phosphitylated the PLA-grafted lignin and compared the 31P Lignin has a relatively high glass transition temperature (Tg =
NMR spectra to that of phosphitylated lignin and PLA. In 150 °C (Figure S4, Supporting Information)) as compared to
Figure 3(a), the resonances at 149−146, 144−137.5, and 136− commercial bioplastics, e.g., PLLA (63 °C),32 PCL (−60 °C),33
134 ppm (CDCl3) are assigned as the phosphotriesters of the and PHBV (−9−9 °C).34 The condensed rigid phenolic
aliphatic hydroxyl (OH), phenolic OH, and carboxylic groups moieties and strong intermolecular hydrogen bonding inter-
of lignin, respectively.29 The 31P chemical shifts of phospho- actions restrict the thermal mobility of lignin molecules and
triesters derived from the terminal hydroxy group of PLA occur result in its high Tg. The incorporation of lignin into these
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Figure 3. 31P NMR spectrum of (a) lignin, (b) PLA, and lignin-g-PLA copolymers with (c) 5 wt % lignin and (d) 30 wt % lignin, derivatized by 2-
chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane. Int. Std: internal standard (cyclohexanol).

Figure 4. DSC curves of lignin-g-PLA copolymers on the second heating scan (a) and after annealed at 90 °C for 14 h prior to the DSC scanning
from room temperature to 200 °C at 10 °C/min (b).

polymeric materials is expected to affect their thermal 75 °C; at 50 wt % lignin, the transition is sufficiently broad that
properties. DSC analysis of the lignin-g-PLA copolymers clearly it is difficult to identify the Tg. Because lignin is an
shows that the incorporation of lignin significantly influences inhomogeneous waste material, the increase of the lignin
the glass transition temperatures (Tg) of the lignin-g-PLA content resulted in decreased homogeneity of the resultant
copolymers (Figure 4(a)). Glass transition temperatures for copolymers. When the lignin-g-PLA copolymers are annealed at
lignin-g-PLA copolymers ranging from 45−85 °C were 90 °C for 14 h before the DSC scan (Figure 4(b)), an
observed depending on the initial lignin/LA ratio (Figure 5 endotherm is observed with an onset of approximately 110 °C
and Table S1, Supporting Information). for samples containing 1−10% lignin. The endotherm is likely
At low lignin content (1−5 wt %), the measured Tgs do not due to the melting of PLA crystals (Tm of PLA = 90−185
differ significantly from that of polylactide (63 °C). At higher °C).35 The incorporation of lignin in the PLLA structure
lignin content (>10%), where the length of the grafted PLA reduced the crystallization of PLA during annealing treatment.
chains are lower than Mn = 2000 (Figure 2), the Tgs increase as The gradual disappearance of the melting peak could be the
the weight fraction of lignin increases (Figure 5). The lignin result of the decreasing PLA chain length at higher lignin
segment, which possesses a relatively high Tg compared to PLA, content. The PLA chain of the copolymer below the critical
contributes to the increased Tgs of copolymers. For lignin molecular weight of ∼DP14 likely does not form the crystal
contents from 10−40 wt %, the Tgs increase from about 45 to structure.
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Figure 5. Glass transition temperature (Tg) of lignin-g-PLA

copolymers on the second heating scan.
Figure 6. Images of PLA−lignin composites samples suggest increased
dispersion of lignin in composites made from lignin-g-PLA copolymer
Optical and Mechanical Properties of PLA Compo- compared to those made with unmodified lignin: (a) PLA, (b) PLA1L,
sites with Lignin-g-PLA Copolymers. The optical and (c) PLA5L, (d) PLA1C, and (e) PLA5C. The lignin contents for (b)/
mechanical properties resulting from blending the unmodified (d) and (c)/(e) are 0.9−1.0 and 4.4−4.8 wt %, respectively.
lignin and lignin-g-PLA copolymers with commercial PLA were
studied in hot-pressed films. Table 2 illustrates the composition

Table 2. Composition and Abbreviation for PLA−Lignin

Composites
lignin-g-PLA
copolymers (g)
lignina PLA unmodified lignin
abbreviations (wt %) (g) (g) 10:90b 40:60b
PLA 0 100 − − −
PLA1L 1.0 100 1 − −
PLA5L 4.8 100 5 − −
PLA1C 0.9 100 − 10 −
PLA5C 4.4 100 − − 12.5
a
Lignin content in the composites. bLignin:L-lactide weight ratio.

and abbreviation for the PLA−lignin blends. Figure 6 shows Figure 7. UV−vis spectrum for PLA, PET, and PLA−lignin
that the unmodified lignin forms aggregated particles in the composites with unmodified lignin (PLA1L) and lignin-g-PLA
PLA matrix (Figure 6(b,c)). The presence of polar groups on copolymers (PLA1C). The amounts of lignin in the PLA films with
lignin favors self-aggregation because they can form clusters of unmodified lignin (PLA1L) and with lignin-g-PLA copolymers
lignin through hydrogen bonding.10 Grafting PLA chains (PLA1C) are 1% and 0.9%, respectively.
switches the polarity of lignin from hydrophilic to hydrophobic;
thus, lignin-g-PLA copolymer interacts more favorably with a nm) and UV-B (280−315 nm). By adding a low amount of
surrounding hydrophobic PLA matrix and displays increased lignin (0.9 wt %) with PLA grafted on the surface into the PLA
dispersion in the PLA materials (Figure 6(d,e)). The interfacial films, the PLA−lignin films (PLA1C) show UV light barrier
interaction between the grafted chains and polymeric matrix properties, which block nearly all UV-C and UV-B and half of
could be further tailored by varying the species of the grafted UV-A (315−400 nm). The unmodified lignin (PLA1L) did not
monomers and chain lengths to achieve good dispersion of significantly reduce the UV light transmission because of the
lignin particles in a wide range of thermoplastic materials. poor dispersion in the PLA materials. Most of the UV light
The absorption of UV light is an important property for passes through the films without encountering and being
designing packaging materials to protect light-sensitive absorbed by the unmodified lignin. However, the lignin-g-PLA
products from damage during storage. It is reported that PLA copolymer acts as a well-dispersed UV blocker that can
materials have better UV light barrier properties than low potentially be applied in the biocompatible packaging and
density polyethylene (LDPE) but worse than those of PET, surface coating industry for preventing damage and extending
cellophane, and polystyrene (PS).20 We investigated the light shelf life of light sensitive products.
barrier properties of PLA films with unmodified lignin and The mechanical properties of tensile modulus of elasticity,
lignin-g-PLA copolymers and compared those to PET films tensile strength, and strain at ultimate tensile strength of PLA−
(shown in Figure 7). The PLA film shows no ultraviolet (UV) lignin composites were evaluated by tensile tests of hot-pressed
light transmission in the lower range of UV-C (100−230 nm), films (Figure 8). Li et al.23 reported that the tensile strength
while the PET film does not transmit both UV-C (100−280 and elongation at break of PLA−lignin composites decreased
1236 dx.doi.org/10.1021/sc4000835 | ACS Sustainable Chem. Eng. 2013, 1, 1231−1238
ACS Sustainable Chemistry & Engineering Research Article

Figure 8. Mechanical properties of PLA−lignin composites. The lignin content in the PLA1L/PLA1C and PLA5L/PLA5C are 0.9−1.0 and 4.4−4.8
wt %, respectively.

with increasing lignin content, while the Young’s modulus in

tension remained constant up to a lignin content of 20 wt %.
■ CONCLUSIONS
The present study demonstrates that PLA can be directly
Ouyang et al.22 also found that the tensile strength and grafted onto unmodified lignin by ring-opening polymerization
elongation at break decreased with the addition of lignin in a with an organic catalyst. Graft polymerization of lactide onto
PLA matrix but that Young’s modulus in tension increased lignin catalyzed by triazabicyclodecene in the melt provides
(20%) with 20 wt % lignin addition. In the experiments lignin-g-PLA copolymers with controllable PLA chain lengths.
reported here, the incorporation of lignin-g-PLA copolymers End-group analysis by 31P NMR revealed a high grafting
(lignin:lactide 10:90) into PLA (PLA1C) resulted in a modest efficiency and preferential grafting on lignin aliphatic hydroxyls
increase in the tensile strength (+16%) and strain (+9%) over phenolic hydroxyls. The lignin-g-PLA copolymers
without a sacrifice in the tensile modulus (Figure 8). However, displayed increased glass transition temperatures from 45 to
the tensile strength and strain for the PLA composites with 85 °C with increasing lignin content from 10% to 50%. The
unmodified lignin (PLA1L and PLA5L) and lignin-g-PLA PLA composites with a 10% lignin-g-PLA copolymers
copolymers with a higher wt % of lignin (lignin:lactide (lignin:lactide 10:90) addition (PLA1C) block nearly all UV-
40:60)(PLA5C) decreased compared to the neat PLA materials C (100−280 nm) and UV-B (280−315 nm) and half of UV-A
(PLA). The mechanical property results show that lignin-g-PLA (315−400 nm). The incorporation of lignin-g-PLA copolymers
copolymers with appropriate grafted PLA chain lengths can be (PLA1C) shows an increase in the tensile strength (+16%) and
utilized as well-dispersed polymeric plasticizers for improving strain (+9%) without a sacrifice in the tensile modulus. The
flexibility and toughness of brittle PLA materials. synthesized lignin-g-PLA copolymers with appropriate grafted
The tensile modulus of elasticity for PLA−lignin composites PLA chain lengths can be utilized as dispersion modifiers in
was estimated by the rule of mixtures (Table 3). The PLA-based biobased composite materials, improving UV
absorbance as well as mechanical properties.

■
Table 3. Comparison of Estimated and Experimental
Modulus of Elasticity for PLA−Lignin Composites ASSOCIATED CONTENT
experimental modulus of estimated modulus of elasticity *
S Supporting Information
materials elasticity (MPa) (MPa)a Tabulated data related to the structural and mechanical
lignin 4500 − characterization of lignin-g-PLA copolymers. This material is
PLA 2764 ± 111 − available free of charge via the Internet at http://pubs.acs.org.
PLA1L
PLA5L
PLA1C
2586
2886
2968
±
±
±
161
63
116
2780
2843
2779
■ AUTHOR INFORMATION
Corresponding Author
PLA5C 2902 ± 35 2838
a
*Tel: 001-650-724-5928. E-mail: [email protected].
Tensile modulus of elasticity is predicted by the rule of mixtures: Ec =
Notes
EPLAVPLA + EligninVlignin, where Ec is the modulus of the composites,
The authors declare no competing financial interest.

■
EPLA and Elignin are the modulus of PLA (2764 MPa) and lignin (4500
MPa),36,37 and VPLA and Vlignin are the volume fractions of PLA and
lignin. ACKNOWLEDGMENTS
We are indebted to Prof. Craig Criddle and Zach Wright for
insightful discussions on biopolymers and PLA. We thank Dr.
Stephen R. Lynch for the helpful discussion on 31P NMR
experimental modulus of elasticity for both PLA composites experimental setup. J. V. Olsson thanks the Marcus Amalia
with unmodified lignin (PLA1L and PLA5L) and lignin-g-PLA Wallenberg Foundation for postdoctoral funding. Yi-Lin Chung
copolymers with a higher wt % of lignin (lignin:lactide is thankful for the support from Award NSC98-2917-I-564-176
40:60)(PLA5C) were in close agreement with the estimated from the National Science Council (NSC) in Taiwan and Grant
value. The slight positive deviation of modulus of elasticity from CMMI-0900325 from the National Science Foundation (NSF).
the estimated value of PLA1C suggests the lignin-g-PLA R. M. Waymouth acknowledges support from the DOE (DE-
SC00005430). E. S. Sattely acknowledges the generous support
copolymer with appropriate grafted PLA chain lengths might
from start-up funds provided by Stanford University.

■
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