Polymers2013, 5, 344-360; doi:10.

3390/polym5020344
OPEN ACCESS

polymers ISSN 2073-4360

www.mdpi.com/journal/polymers
Article

Esterification of Condensed Tannins and Their Impact on the

Properties of Poly(Lactic Acid)
Warren J. Grigsby *, James H. Bridson, Cole Lomas and Jaime-Anne Elliot

Biopolymer Network Ltd and Manufacturing & Bioproduct Development, Scion, Rotorua, 3046, New
Zealand; E-Mails: [email protected] (J.H.B.); [email protected] (C.L.);
[email protected] (J.-A.E.)

* Author to whom correspondence should be addressed; E-Mail: [email protected];

Tel.: +64-7-343-5899; Fax: +64-7-348-5507.

Received: 25 February 2013; in revised form: 6 March 2013 / Accepted: 11 April 2013 /
Published: 19 April 2013

Abstract: Reported is a study evaluating the potential of esterified tannins as plastic

additives in poly(lactic acid) (PLA). Tannin esterification using anhydrides was
investigated as a route to synthesize tannin esters possessing varying ester chain length
and degree of substitution (DS). Esterification decreased the tannin UV absorbance,
predominately in the UVB region. However, tannin materials with longer ester chain
lengths exhibited melt behaviors suitable for processing in plastics. On compounding into
PLA, tannin hexanoate esters lowered the PLA glass transition by 5–6 °C. Shorter chain
length tannin esters had a reduced effect on PLA polymer properties. The PLA flexural
properties were significantly altered with stiffness decreases of up to 15% depending on
ester chain length and loading. Artificial weathering of modified the PLA samples suggests
the presence of tannin esters may confer a protection role to PLA on extended exposure.
Overall, results suggest scope for the use of tannin esters possessing longer ester chain
length as plastic additives.

Keywords: condensed tannins; polyphenolics; esterification; poly(lactic acid) (PLA);

plastic additives
Polymers2013, 5 345

1. Introduction

Application and market growth of renewable polymers has been driven by sustainability as much as
the emergence and scale of technology to produce these materials. Poly(lactic acid) (PLA) is one
bioplastic which has gained market share due to recent increases in production capacity [1]. In the
lucrative plastic additives market, sustainable options remain less developed, particularly those
additives being both renewable and biodegradable [2]. Plastic additives contribute a range of
functionality and processability to plastics including plasticization, nucleation, flame retardancy, heat
stability and impact modification [3]. Research evaluating bio-derived plastic additives has included
fermentation products [4] and modified vegetable oils [5] to those based on polyphenols such as
lignin [6,7]. In contrast, use of polyphenolic tannins remains relatively unexplored with few examples
of these compounds blended with plastics [8–10]. Condensed tannins are polyphenolic oligomers
based on a flavanyl repeat unit (Figure 1) and are ubiquitous in leaves, bark and wood of trees and
plants. In plants these compounds offer a range of protective roles, inhibiting pathogens, oxidation and
UV degradation [11]. Potentially, these tannin attributes could also be imparted to plastics, and in the
case of bioplastics, potentially enhancing performance as well as sustainability credentials.

Figure 1. Reaction scheme showing the procyanidin structure repeat unit common in
condensed tannins [12] and various routes to tannin ester formation including (i) acid
anhydride with acetic anhydride [18]; (ii) acyl chloride with stearoyl chloride [19]; and (iii)
transesterification with vinyl laurate [20].
OAc

OH CH3 O CH3 AcO O

4'
OAc
8
B 3' O O
HO O OAc
1' OH
2
7 2'
A C 3
i. anhydride OAc
6
5 4 OH
Cl (CH2)16CH3
OH (CH2)10CH3
O O ii. acyl chloride
O O (CH2)16CH3
iii. transesterification O
O (CH2)10CH3 HO O
O (CH2)16CH3
O
HO O O
OH OH
O
OH (CH2)16CH3
OH O

Condensed tannins are commonly available in industrial quantity due to their historical use in
leather tanning and adhesives [12]. While there is potential as plastic additives (antioxidant, light and
thermal stability), tannins are inherently hydrophilic, being unsuited to many industrial applications.
This necessitates chemical modification, for which tannin etherification and esterification have long
been known [12]. In the latter case, this is usually limited to acetylation, but longer chain esters have
been used in specific applications [13–16] as have di-acids for crosslinking [17]. Tannin esterification
Polymers2013, 5 346

can be achieved by several routes including conventional approaches such as acyl chlorides and
anhydrides to those involving transesterification (Figure 1) using a range of bases as catalysts. Within
the literature, there is still opportunity to learn how tannin esterification can be applied, controlled and
optimized to target certain properties and direct their application.
In the current paper, various tannin esters have been synthesized and compounded into PLA to
evaluate their potential as plastic additives. Anhydride esterification has been used to prepare these
tannin esters. This anhydride esterification route is contrasted with other esterification methods
comparing ease of preparation with ester chain length, yield and degree of polyphenolic substitution.
The impact of tannin ester chemistry on the physical, UV absorption and molecular mobility properties
of tannin moieties is investigated. Changes to PLA plastic properties compounded with tannin and
esterified tannin additives are compared with ester chain length and after exposure to artificial
weathering of the plastic.

2. Experimental Section

2.1. Materials

Tannin was extracted from the bark of Pinus radiata using hot water (90 °C) which was
subsequently spray dried and further dried under vacuum before use. Acetic, propanoic, butyric and
hexanoic anhydrides and 1-methylimidazole were all general purpose grade reagents (>98%) and used
as received. Poly(lactic acid) (3001D injection molding grade) was obtained from Natureworks (USA).

2.2. General Method for the Preparation of Tannin Esters

Tannin (5 g–10 g) was dispersed in 2-pentanone (20 mL) and acid anhydride (acetic, propionic,
butyric or hexanoic anhydride) added at varying ratios with or without 1-methylimidazole as catalyst
(Table 1). The reaction mixture was heated to 70 °C for 4 h with stirring, allowed to cool and poured into
cold water (300 mL). In the case of acetylation, the product was collected by filtration and washed
(water) until the pH was ≥ 4. For longer chain esters, the aqueous phase was decanted from the quenched
reaction mixture, ethanol added and the mixture gently heated (60 °C, 30 min). The product was isolated
by either precipitation into water (propionate and butyrate) or extraction into chloroform (hexanoate).
To prepare tannin hexanoate acetate, tannin (10 g) and hexanoic anhydride (14.5 mL) were
combined in acetone (50 mL) and 1-methylimidazole (1 g) added. The reaction was heated in an oil
bath at 60 °C for 4 h. Acetic anhydride (12.5 mL) was then added and the reaction continued for a
further 2 h. After this time, the acetone solvent was distilled from solution. The reaction contents were
then cooled with an iced water bath and 100 mL 10% sodium hydroxide solution poured in the flask
with rapid stirring. The product was allowed to settle and then filtered. The product was washed with
water (2 × 50 mL) before drying under vacuum.
Polymers2013, 5 347

Table 1. Ratios and isolated yields for tannin esterification reactions using acid anhydrides
and 1-methylimidiazole as catalyst. The degree of substitution present in tannin ester
products is calculated using NMR integration.
Product Acid anhydride ratio Catalyst level (%) Yield (%)≠ Degree of substitution
1:1 10 1.2
1:2 10 2.5
1:3 10 3.9
1:4 10 4.7
Tannin acetate
Excess 0 88 4.2
Excess 1 134 5.3
Excess 3 131 5.3
Excess 10 127 5.3
Excess 0 37 -
Tannin propionate
Excess 1 136 -
Excess 0 31 -
Tannin butyrate
Excess 10 152 -
1:2 10 104 2.0
Tannin hexanoate Excess 0 0
Excess 10 147 -
Tannin hexanoate
§ 10 176 5.3
acetate
§ two equivalents of hexanoic anhydride, followed by excess acetic anhydride; ≠ isolated yield based on
weight % increase on tannin used.

2.3. Compounding and Injection Molding

Tannin or tannin esters were combined with PLA to form a master batch using an OMC EBVP
19/30 high-speed twin-screw extruder. The temperature of the extruder head was 170 °C and the
heating zones across the extruder barrel ranged between 170 °C and 185 °C [supplementary material].
Each extruded plastic blend was pelletized creating either 5 or 10% tannin ester PLA master batches.
Injection molding of plastic test specimens was undertaken using a BOY 15S injection molder.
Nozzle and heating zones ranged between 195–205 °C and 170–190 °C, respectively and operated
with a mould temperature of 32 °C, injection time of 6 sec and cooling time of 22 sec [supplementary
material]. Using each master batch, PLA blends were prepared containing 0%, 0.5%, 1.0%, 5.0% and,
for selected samples, 10% w/w tannin ester. At least 10 tensile test specimens and 20 flexural bars
were prepared for each combination.

2.4. Flexural and Tensile Testing

Flexural and tensile testing was undertaken on an Instron 5566 universal testing machine. Prior to
testing, samples were conditioned at 23 °C and 50% relative humidity for at least 7 days. Flexural
testing was undertaken according to ASTM D790-00 with 10 specimens (123 × 13 × 3 mm) evaluated
per sample. Tensile testing was performed to ASTM D638-01 using type I test specimens with a test
speed of 5 mm.min −1. Generally 10 specimens were tested per sample.
Polymers2013, 5 348

2.5. Accelerated Weathering

Testing employed an accelerated weathering tester from Q-Panel Lab Products operating with
UVA-340 lamps at an irradiance of 0.77 W/m2/nm. Flexural test specimens (123 × 13 × 3 mm) were
exposed to a UV light and water regime according to ASTM D4329-99 with the detailed exposure
cycle (Table 2). Samples were randomly rotated every 169 h and were exposed for a total of 504 h.
Prior to, and at the completion of accelerated weathering, samples were weighed and CIE L*a*b*
color measurements taken using a Konica Minolta Chroma CR-400 color meter to evaluate any
changes to exposed samples. Flexural testing was also conducted on weathered samples after
conditioning at 23 °C and 50% relative humidity.

Table 2. Exposure cycle conditions used for the accelerated weathering of PLA plastic samples.

Step Condition Temperature (°C) Time (h)

Step 1 UV 45 8
Step 2 Water spray 25 0.5
Step 3 Condensation 40 2
Step 4 Water spray 25 0.5
Step 5 Condensation 40 2

2.6. Characterization

Solid state 13C NMR spectra were obtained on a Bruker Avance DRX 200 instrument with a 7 mm
doubly tuned 1H/X MAS probe (Bruker). Samples were packed into a zirconia rotor fitted with a Kel-F
cap and spun at 5 kHz. A cross polarisation-magic angle spinning (CP-MAS) pulse program was used
with a 1H preparation pulse of 5 µs, 1H decoupling field of 47 kHz, and an acquisition time of 50 ms.
Hartmann-Hahn matching was conducted using glycine to allow semi-quantitative analysis. Integration
of spectra for degree of ester substitution determination is further described in the supplementary
material. Spin locking experiments and variable contact time experiments were run to determine the
molecular spin relaxation measurements of selected samples. T1H values were calculated from signal
intensity and contact times using methodology and protocols published elsewhere [21].
Differential Scanning Calorimetry (DSC) was undertaken on a Thermal Analysis Instruments Q1000
DSC. Samples (4–8 mg) were placed in standard aluminum pans and then initially heated to 120 °C at
a heating rate of 10 °C/min. The samples were then cooled (5 °C/min) below 0 °C and heated in a
second heat ramp to 200 °C.
Dynamic mechanical thermal analysis (DMTA) used a Rheometrics DMTA V in three point bending
mode. Samples (65 × 10 × 3 mm) were acquired from injection molded flexural specimens. Testing was
undertaken using a 3 °C/minute heating rate and employed 1 Hz frequency and strain rate of 0.05%.
Ultraviolet (UV) absorbance measurements employed a Cary 300 BIO UV/Vis spectrophotometer.
Samples soluble in either water or chloroform were diluted to 0.25% solids whereas the tannin
hexanoate and tannin hexanoate acetate samples were dissolved in dimethylformamide solvent at
0.02% concentration. Measurements were made between 200–450 nm in 5 nm increments using the
appropriate solvent as a blank.
Polymers2013, 5 349

Confocal laser scanning microscopy (CLSM) was undertaken on a Leica TCS instrument analyzing
flexural test specimens. Filters were used to separate the natural fluorescence of the tannin component
into green light. Images were obtained using a 20 × 0.5 dry lens. The images were acquired at a size of
512 × 512 pixels and a total field of view of 500 × 500 μm, yielding a resolution of ~1 pixel/μm. Scans
in the z-direction were recorded at 5 μm intervals to a depth of ca. 80 μm. Images from the different
depths were then combined to produce a 2D projection of a 3D image. Some 10–20 images were
acquired using CLSM. Projected 2D images were then subjected to image analysis to determine the
size of residual tannin esters domains in the plastic employing a custom written macro using V++
software (Digital Optics V.4.0). The size of tannin ester features were defined by the image analysis
program and their area calculated and expressed as frequency distributions of sizes ranging from 40
and >3000 μm2.

3. Results and Discussion

3.1. Esterification by Anhydride Treatment

Peracetylation using acetic anhydrides is a simple and common approach to alter hydrophobicity of
polyphenolics [22]. In the current study, tannin was reacted with varying levels of acetic anhydride and
1-methylimidazole catalyst to determine any control of the anhydride reaction (Table 1). Isolation and
work up of various tannin acetates revealed products as pale brown powders with yields varying from
modest to excellent. The limited solubility of some products necessitated characterization by solid state
NMR which was also utilized to determine the average degree of substitution (DS). Generally, it was
observed that with a greater acetic anhydride ratio there were corresponding increases in the carbonyl
(169 ppm) and methyl (20 ppm) peaks of pendant acetate groups (Figure 2). Upon esterification the
tannin C-3’ and C-4’ (145 ppm) and C-5, 7, 9 (160 ppm) signals [23] split and moved upfield (2–5
ppm). This was more pronounced for the A-ring signals (Figure 1). While this may indicate
substitution was occurring preferentially at the A-ring phenols (hydroxyl sites), only at high anhydride
ratio was there evidence for these phenols being fully esterified. The degree of tannin esterification
could be controlled by the level of anhydride addition (Table 1). A maximum DS of 5.3 was achieved
with excess acetic anhydride and was indicative of full esterification of all hydroxyls of the pine bark
tannin flavanyl unit [24]. Lastly, the degree of acetylation gave no relationship to the resulting tannin
acetate solubility. The presence of both free phenol hydroxyls and acetate groups gives a relatively
insoluble product compared to either full esterification (organic solvent soluble) or native tannin
extract (water soluble). This suggests a minimum DS is required to permit a change in solubility
(hydrophilic to hydrophobic) or greater ester chain length for hydrophobicity.
Esterifying tannin with varying catalyst content and differing chain length anhydrides can give
variable results (Table 1). With acetylation, the use of only 1% w/w 1-methylimidazole catalyst proved
equally effective as use with 10% catalyst. However, with higher chain length anhydrides, a 10%
catalyst was required to maximize both DS and yield. With progressively higher chain length esters,
isolated yields decrease, being less than anticipated for full esterification. NMR also suggests lower
DS values were achieved with increasing anhydride chain length (Figure 3). This was visually evident
with the relative intensity of the ester carbonyl and methyl peaks decreasing across products isolated
Polymers2013, 5 350

from acetic to hexanoic anhydride treatments. For example, excess anhydride produces a tannin
hexanoate only partially esterified with a DS < 3 when compared with acetylation (Figures 2 and 3).
This result indicates esterification via anhydride treatment may become sterically inhibited at some
phenol centers with greater chain length. Practically, it was also found using a longer chain anhydride
requires a more involved isolation step to remove the corresponding acid by-product (Figure 1)
compared with acetic acid and acetylation. Overall, these results suggest anhydride treatments should
be tailored to deliver only two long chain ester groups via anhydride treatment with full esterification
achieved by subsequent acetylation. This was demonstrated by preparing tannin hexanoate acetate
(Table 1). This mixed ester approach enabled efficiencies in ester product work up, isolated yield with
the additional benefits of minimizing reagent use and improved solvent miscibility, as similarly
achieved with tannin-fatty acid conjugates [15].

Figure 2. Comparison of solid state 13C NMR CPMAS spectra of various pine bark tannin
acetate products formed with differing molar ratio of tannin:acetic anhydride and
1-methylimidazole catalyst (cat).

(1:excess, cat.)

(1:4, cat.)

(1:3, cat.)

(1:2, cat.)

(1:1, cat.)

Tannin

150 100 50 ppm

In comparison to anhydride treatment, acyl chlorides are preferable for the synthesis of longer chain
length esters (Figure 1), due to the relative unavailability of such anhydrides, atom efficiency and ease
of product work up [19,20]. As with anhydrides, control of the tannin:acyl chloride ratio can give
Polymers2013, 5 351

defined DS values. Moreover, full esterification of the flavanyl unit phenols was achievable with long
alkyl chain length acyl chlorides [19] compared to anhydride use (Table 1). This result, and the
relatively high yields, suggests acyl chloride reactions with tannins are not subject to steric hindrance
as observed with longer chain anhydride treatments (Table 1). However, if a lower stearic acid chloride
ratio is employed, the tannin stearate product tends to be only partially soluble [15,19] as found with
acetylation (Table 1, Figure 2). As above, partial esterification and inherent insolubility may be
overcome by acetylation of residual phenols, giving the respective mixed ester tannin stearate acetates,
which are soluble in organic solvent [15]. Transesterification is an alternative approach to synthesize
tannins with high specificity for substitution of the tannin flavanyl B-ring [20]. This method can be
performed in several solvents, does not require anhydrous conditions and offers efficiencies in product
workup. However, typically, transesterification achieves a DS < 1, being independent of the ester chain
length and this, together with long reaction time employed, may not suit industrial application.

Figure 3. Comparison of solid state 13C NMR spectra of isolated products from anhydride
treatments with 10% 1-methylimidazole catalyst. (a) tannin acetate; (b) tannin propionate;
(c) tannin butyrate and (d) tannin hexanoate.

3.2 Tannin Ester Properties

While tannin esterification may enhance hydrophobicity and miscibility in oils [15], chemical
modification may alter fundamental tannin properties including reduced antioxidant activity [20],
ultraviolet (UV) light absorption or those associated with tannin macromolecular behavior. For
Polymers2013, 5 352

example, evaluation of various tannin esters (Table 1) found a range of UV absorption profiles, with
key differences observed in the UVB (285–315 nm) and UVA (315–385 nm) regions (Figure 4). In
general, unmodified pine bark tannin has the highest absorption over the UVA and UVB region which
decreases upon esterification as evident for tannin acetate (DS = 5.3, TanAc). This decrease in UV
absorption upon esterification correlated with the level of substitution. Tannin hexanoate (DS = 2,
TanHex) retains good absorption in the UVB range similar to unmodified pine bark tannin, but this
absorption diminishes in the UVA region. However, despite differing levels of substitution, the various
tannin esters show potential as UVB absorbers.

Figure 4. UV absorbance profiles of various tannin esters. Tannin (in water, pH7, blue),
tannin acetate (in chloroform, red), tannin hexanoate (in dimethyl formamide, green) and
tannin hexanoate acetate (in DMF, black).
Absorbance

250 300 350 400 450

Wavelength (nm)

Tannin esterification and ester chain length can alter the relative molecular mobility within the
polyphenolic flavanyl unit and tannin oligomers. By employing solid state NMR and comparing native
tannin with tannin propionate (TanPr, DS = 5.3), differing molecular motion characteristics were
determined about the tannin flavanyl unit (Figure 5). Spin-lattice relaxation (T1ρH) values show the
relative molecular motion of some carbons increase on adding propionate ester groups to the flavanyl
unit. This increase was most significant at C-2,3, C-5,7,9 and C6’. This suggests the presence of
propionate groups has increased the molecular mobility about these carbon centers. This characteristic,
together with introduced hydrophobicity, has the potential to influence compatibility and polymer
properties when integrated into a plastic.
An evaluation of tannin ester properties by differential scanning calorimetry (DSC) was undertaken
to assess the potential melt processing and polymer properties of modified tannins. DSC analysis
revealed thermal behaviors were dependent on ester chain length (Figure 6). Both tannin and tannin
acetate do not have obvious melt features nor physically melt [18]. However, modified tannins bearing
longer chain esters show melt features, decreasing both in broadness and temperature with longer chain
length. This broadness in the melt feature may be associated with the range of tannin oligomers present
in the extract [25] together with extent and randomness of esterification about the tannin flavanyl unit.
Polymers2013, 5 353

In the case of ester chain lengths of 4 to 6 carbons, a board melt occurs between 80 °C and 160 °C.
Such melt behavior is generally below typical plastic melt processing temperatures [3]. In contrast,
tannins bearing ester groups with 12 to 18 carbons melt below 50 °C [19]. These melt behaviors are at
physiological temperature and also suited for application in unsaturated resin systems [15]. Overall,
DSC analysis revealed tannins bearing ester chain lengths greater than propionate were likely suitable
for processing into plastics.

Figure 5. A comparison of the spin relaxation T1ρH values for flavanyl unit carbons of tannin
and tannin propionate using NMR spin locking experiments. ■ Tannin and ■ tannin propionate.

25

20
T1p(H) (ms)

15

10

0
C2,3 C5,7,9 C 1' C 3',4' C 6'

Figure 6. DSC thermograms of various tannin esters. Tannin acetate (orange), tannin
propionate (blue), tannin hexanoate (DS = 2, red), tannin hexanoate acetate (black), tannin
stearate (DS = 1, green) and tannin stearate (DS = 5, purple) with exo up.

0.1

‐0.1
Heat Flow (W/g)

‐0.3

‐0.5

‐0.7

‐0.9
0 50 100 150 200
Temperature (C)

3.3. Tannin Ester Modified Poly(Lactic Acid)

Based on the relative ease of anhydride treatments and their favorable properties, tannin esters with
C2 to C6 chain lengths were compounded into poly(lactic acid) (PLA) at varying levels from 0.5% to
10% (w/w, Table 1). Generally, the presence of these tannin additives color PLA, with this dependent
on the ester and concentration in the plastic [supplementary material]. Analysis of the compounded
Polymers2013, 5 354

plastic by fluorescence microscopy revealed the relative dispersion of each tannin ester (Figure 7). In
the case of TanAc this was retained as relatively distinct domains within the plastic matrix indicative
of poor miscibility or phase separation. These domains were present across the TanAc concentration
range (0.5%–5%). In contrast, TanHex appeared fully dispersed within the plastic. In progressing from
tannin acetate to hexanoate, it was evident the ester chain length determined how the tannin ester
dispersed into the plastic. Tannin propionate and butyrate derivatives respectively show progressive
dissolution and diminishing particle domains within the PLA compared to tannin acetate.

Figure 7. Confocal microscopy images of plastic containing 5% loadings of tannin esters

observing the inherent autofluorescence of tannin particles distributed in the plastic
(top). TanAc (left), TanPr, TanBu and TanHex (right, with each image 500 × 500 μm).
Representative particle size distributions of tannin esters in PLA. TanAc (bottom, left) and
TanBu (bottom, right).

30% 60%
Average Frequency of PLA TAc 5% Average Frequency of PLA TBu 5%
25% 50%

20% 40%
Frequency

Frequency

15% 30%

10%
20%

5%
10%

0%
0%
40

120

200

400

750

1250

1750

2500

>3000

40
80
120
160
200
300

400
500

750
1000
1250

1500
1750
2000

2500
3000
>3000

Particle Size Bins (in µm 2)

Particle Size Bins (in µm2)

To evaluate any effect the tannin esters have on PLA thermal properties, both DSC and dynamic
mechanical analysis (DMTA) were conducted on injection molded samples. Analysis revealed 10%
TanHex and TanHexAc contents in PLA reduce the PLA glass transition (Tg) but does not impact the
PLA melt (Table 3 and Figure 8). DMTA revealed both tannin esters significantly lowered the Tg
onset compared to unmodified PLA (ca. 50 °C). However, shorter chain length esters and lower
quantities of tannin ester gave a reduced impact on PLA thermal properties [supplementary material].
The observed reduction in PLA Tg with tannin hexanoate while significant was less than that which
can be achieved (≤ 38 °C) when blending PLA with poly(ethylene glycols) (PEGs) or citrates [26,27].
DSC analysis of the modified PLA samples was consistent with DMTA, showing a decrease in Tg of
6–7 °C upon addition of TanHex or TanHexAc and no change in the melt temperature (ca. 168 °C).
The onset temperature of crystallization within samples decreased with greater tannin ester content
(Figure 9, Supplementary Material).
Polymers2013, 5 355

Table 3. Results of DSC analysis of selected PLA samples modified by tannin, TanHex
and TanHexAc (see supplementary material).
Cycle 1 Cooling Heating Cycle 2
Additive
Tg (°C) Crystallization (°C) Tg (°C) Melt (°C)
PLA 58.5 155.7 64.3 167.7
1% TanHex 58.0 155.9 63.8 168.0
5% TanHex 56.1 145.0 63.6 167.3
10% TanHex 54.7 139.3 57.3 167.2
1% TanHexAc 59.6 155.9 63.7 168.3
5% TanHexAc 56.1 144.9 59.6 167.1
10% TanHexAc 53.8 139.1 57.8 166.7
1% Tannin 58.6 - 63.5 168.2
5% Tannin 58.3 - 64.4 168.2
10% Tannin 57.6 - 64.5 167.9

Figure 8. DMTA of PLA modified with 10% loadings of tannin hexanoate and tannin
hexanoate acetate. PLA (red), TanHex (green) and TanHexAc (blue).

1.E+10 2.5

1.E+09
2.0
Storage Modulus (Pa)

1.E+08
1.5
tan 
1.E+07
1.0
1.E+06

0.5
1.E+05

1.E+04 0.0
30 40 50 60 70 80
Temperature (C)

A comparison of PLA flexural and tensile properties show the presence of the tannin esters can
impact PLA mechanical properties contributing up to 15% decreases in PLA stiffness (Table 4 and
supplementary material). On addition of tannin acetate, similar modulus of elasticity (MOE) values as
PLA (3894 MPa) were observed with up to 5% TanAc content. With longer ester chain length the
MOE values decreased with greater tannin ester contents. For TanPr and TanBu, only 5% loadings
achieved a significant decrease in PLA stiffness (<3800 MPa). However, both TanHex and TanHexAc
exhibit decreases in MOE values across their entire loading range (0.5% to 10%). At 10% loading,
decreases in MOE of up to 15% were achieved with TanHex (3480 MPa) and TanHexAc (~3400 MPa),
respectively. Typically more significant decreases in PLA stiffness are observed with plasticizing
additives such as PEGs or citrates [27,28]. In the case of adding unmodified tannin, this had a contrasting
effect, stiffening PLA with increased MOE values at higher tannin contents (3915 MPa). This result
indicates the native tannin likely acts as a filler, as observed with unmodified lignins in PLA [6,7]. The
Polymers2013, 5 356

flexural strength decreased upon addition of all tannin esters compared with PLA (133 MPa). This was
related to tannin modifier content for C2–C4 chain length esters, but appeared independent of loading for
TanHex samples. Tensile testing revealed the presence of tannin modifiers in ≥1% loading decrease PLA
tensile modulus values. For 5% TanHex, the tensile modulus was lowered by some 15%. Similarly, PLA
tensile strength values were also reduced, with values dependent on tannin modifier loading.

Figure 9. Representative DSC thermograms of PLA and PLA modified with 5% TanHex
before and after artificial weathering exposure (exo up). PLA (red), PLA-exposure (green),
TanHex (blue) and TanHex-exposure (purple).

0.2

‐0.2
Heat Flow (W/g)

‐0.4

‐0.6

‐0.8

‐1

‐1.2
0 50 100 150 200
Temperature (C)

Table 4. Flexural testing results of modified PLA samples before and after artificial weathering.
Prior to artificial weathering Post artificial weathering
Sample with tannin
Modulus Strength Modulus Strength
ester loading
(MPa) StdDev (MPa) StdDev (MPa) StdDev (MPa) StdDev
PLA 3894 33 113 1 3903 129 114 2
0.5% TanAc 3902 25 111 1 - - - -
1% TanAc 3826 38 111 1 3922 22 110 1
5% TanAc 3868 62 104 2 3929 61 107 1
0.5% TanPr 3904 16 105 1 - - - -
1% TanPr 3872 41 107 1 3896 33 112 0
5% TanPr 3787 21 104 1 3835 127 105 2
0.5% TanBu 3879 39 108 2 - - - -
1% TanBu 3885 44 108 2 3903 77 111 2
5% TanBu 3770 34 105 2 3855 161 106 1
0.5% TanHex 3846 14 105 1 - - - -
1% TanHex 3749 27 104 0 3753 171 106 2
5% TanHex 3605 19 95 1 3532 121 96 1
10% TanHex 3480 19 85 0 3160 263 80 4
1% TanHexAc 3771 25 104 1 3785 88 107 2
5% TanHexAc 3654 16 95 1 3614 86 97 1
10% TanHexAc - - - - 3429 223 69 16
1% Tannin 3805 34 104 1 3807 121 109 1
5% Tannin 3915 23 99 1 3895 110 101 4
10% Tannin - - - - 3996 74 92 2
Polymers2013, 5 357

3.4. Artificial Weathering

Although PLA is unsuited to exterior application [29], the PLA samples were subjected to
accelerated weathering as a means to artificially age the plastic and evaluate any retention of PLA
properties due to the presence of tannin esters. This test included both water condensation and UV
irradiation (Table 2) with samples expected to exhibit some degradation due to PLA hydrolysis and
UV-promoted oxidation [7,29]. Results reveal that after 500 h of artificial weathering, the PLA
flexural modulus increased, but this was not statistically significant due to high variability between test
specimens (Table 4). This variability marred all test specimens after aging. Flexural modulus values
for aged TanAc, TanPr and TanBu modified PLA samples were similar to original values, but this did
not differ to PLA at the 95% confidence level. For the TanHex and TanHexAc samples, a 5% loading
led to retention of flexural properties after exposure. This result suggests both TanHex and TanHexAc
may confer a protection role which may be as a UV absorber within PLA. Evaluation by DSC analysis
revealed aged samples lose crystallinity, but retain similar Tg and melt temperatures (Figure 9).
Results also show any changes in sample weights after accelerated weathering were negligible.
The results from the colorimetric analysis of tannin ester-modified PLA after accelerated
weathering are shown in Table 5. This revealed some variability in color stability with samples
typically lightening in color. Unmodified PLA showed the smallest change in ∆E, a likely consequence
of this polymer being transparent with little scope for significant color change. Of the modified PLA
samples, those modified with TanAc had the highest variability and may be linked to the dispersal of
TanAc (Figure 7). TanHex offered the best color stability of the samples which was probably due to
the even dispersion of TanHex throughout the PLA matrix (Figure 7).

Table 5. Results of colorimetric analysis after artificial weathering exposure.

Sample ∆L ∆a ∆b ∆E
PLA 0.26 0.34 1.43 1.49
TanAc 1% 4.60 7.51 2.14 9.06
TanAc 5% 12.43 1.36 1.48 12.59
TanPr 1% 6.75 0.57 6.08 9.10
TanPr 5% 9.58 0.19 0.31 9.59
TanBu 1% 4.89 3.75 4.14 7.42
TanBu 5% 9.32 0.61 0.65 9.36
TanHex 1% 5.08 0.58 3.56 6.23
TanHex 5% 5.42 0.89 3.69 6.62

4. Conclusions

Esterification of tannin by acid anhydrides is a preferred synthetic route to enhancing tannin

hydrophobicity. In this study, tannin esterification by anhydride treatment was dependent on the level
of catalyst and anhydride chain length employed. An absence of catalyst gives a reduced degree of
substitution, with this more apparent with increasing ester chain length. While preparation of tannin
acetate with 1% catalyst achieved maximal substitution, synthesis of higher chain length tannin esters
Polymers2013, 5 358

becomes increasingly difficult. This was likely due to increased steric hindrance about the tannin
flavanyl unit within oligomer chains. In contrast, esterifying tannins via acyl chlorides is not subject to
steric hindrance with longer ester chains. The current study also shows the degree of ester substitution
can be controlled by modifying the tannin:anhydride ratio as demonstrated with acetic anhydride. In
the case of tannin hexanoate (TanHex), only 2 equivalents of hexanoic anhydride was sufficient to
modify tannin properties and increase its miscibility with plastic.
Modifying tannin with increased ester substitution and ester chain led to some changes in
fundamental tannin properties, none more so than solubility. Esterification reduced UV absorbance in
the UVB region with the extent of this shift dependent on the tannin DS. Tannin esterification also
alters the relative molecular mobility within the tannin flavanyl unit as well as polymer properties.
NMR spin-lattice relaxation (T1ρH) measurements show increased molecular motion about the flavanyl
unit on esterification with relatively short chain propionate groups. More significantly, esterification of
tannins can lead to melt behavior. A range of melt behaviors can result with this primarily dependent
on ester chain length, but also DS. Typically, a lower temperature melt feature was observed with
longer ester chain length. An implication for this work is those tannin esters bearing chain lengths
greater than three carbons melt below common plastic processing temperatures. This potential for
processing into plastic, coupled with retention of UVB absorption and antioxidant properties and
mobility introduced by alkyl ester chains, make tannin esters attractive as plastic additives.
Compounding tannin esters into PLA led to modification of some plastic properties including color.
Thermal analysis revealed minor changes to PLA Tg values with the Tg onset lowered some 5–6 °C
when modified with C6 ester chains (TanHex and TanHexAc). While there were no appreciable
differences in PLA melting, the onset of PLA crystallization was dependent upon the presence and
quantity of tannin ester. Evaluation of the PLA mechanical properties show the flexural properties of
PLA were significantly altered on the addition of tannin esters. A decrease in flexural modulus with
increasing chain length (Ac to Hex) and loading was evident. A 10% TanHexAc loading achieved a 15%
reduction in PLA stiffness. In contrast, addition of unmodified tannin acts as a plastic filler, stiffening
PLA. Flexural strength values reveal addition of all tannin esters led to reduced flexural strength.
PLA samples were subjected to accelerated weathering to determine any potential protection role
offered by the presence of tannin esters. After 500 h of artificial weathering, the PLA flexural modulus
increased, but was marred by high variability between test specimens. While flexural modulus values
for aged TanAc, TanPr and TanBu modified PLA samples were similar to original values, there was no
statistical difference to PLA. With both TanHex and TanHexAc modified samples, the flexural
properties were retained upon weathering. This suggests as plastic additives, tannin esters may act to
reduce PLA stiffness as well as confer a protection role to PLA. Overall, this study reveals significant
scope for the use of longer chain tannin esters as plastic additives, with on-going evaluations in other
plastics still to be reported.

Acknowledgements

The authors are grateful for the confocal microscopy assessments contributed by Carmen Schrade, a
visiting intern from the Department of Applied Chemistry, Reutlingen University. This work was
supported by Biopolymer Network Ltd., through funding by the New Zealand Ministry of Business,
Polymers2013, 5 359

Innovation and Employment. JB, CL and JAE are each grateful to studentships provided by Scion
through BSc(Tech) placements (University of Waikato).

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