J. Coat. Technol. Res.
, 7 (5) 603–613, 2010
DOI 10.1007/s11998-010-9241-x
Soy-based UV-curable thiol–ene coatings
Zhigang Chen, Bret J. Chisholm, Radhika Patani,
Jennifer F. Wu, Shashi Fernando, Katie Jogodzinski,
Dean C. Webster
 FSCT and OCCA 2010
Abstract Novel soy-based thiols and enes were syn-
thesized and characterized. Then, soy-based thiol–ene
UV-curable coatings were formulated and their coat-
ing physiochemical properties were investigated in
detail. The use of biorenewable resources, combined
with environmentally friendly UV-curable technology,
provides a ‘‘green + green’’ solution to the stricter
regulations in the coatings industry. Novel soy-based
thiols and enes were synthesized through the Lewis
acid-catalyzed ring opening reaction of epoxidized
soybean oil with multifunctional thiols or hydroxyl
functional allyl compounds. FTIR and NMR confirmed
the formation of the target compounds. The soy-based
thiols and enes were formulated with petrochemical-
based enes and thiols, respectively, to make thiol–ene
UV-curable coatings. Typical coating film properties,
thermal properties, and photopolymerization kinetics
of these coatings were studied. Soy-based thiol–ene
coatings having lower functionality thiols and enes
have poor UV curability and coating properties, which
was attributed to the lower crosslink density. Soy-
based thiols and enes with higher functionality can be
UV-cured in combination with petrochemical-based
enes or thiols even without the presence of free radical
photoinitiators. Better coating film properties were
obtained from these higher functionality thiol–ene
systems that were toughened by commercial hyper-
branched acrylates.
Z. Chen, B. J. Chisholm, R. Patani, J. F. Wu,
S. Fernando, K. Jogodzinski, D. C. Webster
Center for Nanoscale Science and Engineering,
North Dakota State University, PO Box 6050, Fargo,
ND 58108, USA
B. J. Chisholm, D. C. Webster (&)
Department of Coatings and Polymeric Materials,
North Dakota State University, PO Box 6050, Fargo,
ND 58108, USA
e-mail: dean.webster@ndsu.edu
Keywords Biobased, Soybean oil, UV curable,
Coating, Thiol–ene
Introduction
The anticipated depletion of fossil oil reserves and
rising oil prices make the utilization of renewable raw
materials a necessary step toward sustainable develop-
ment.1 Soybean oil (SBO) is a bio-renewable resource
with a high annual production in the US.2 Research on
soybean utilization has been of long-term interest in
the chemical industry in order to meet the need for bio-
based materials.3–6 Commercialized SBO derivatives
such as epoxidized soybean oil (ESBO, generic struc-
ture shown in Fig. 1) are important starting materials
for the development and production of biobased
industrial products such as adhesives, coatings, plast-
icizers, lubricants, and composites.2,7–14
Curing of polymers by radiation is an efficient way
to turn suitable liquid, low viscosity reactive materials
into solid materials having good properties, for appli-
cations such as coatings, inks, adhesives, and dental
materials.15,16 Curing by light (either visible or ultra-
violet, UV) is a form of radiation curing and is also
known as photopolymerization. Compared to conven-
tional curing mechanisms, radiation curing technology
features extremely fast cure (within minutes or even
seconds, compared to hours or days for conventional
systems), very low energy consumption, and more
importantly, is a solventless, ‘‘green’’ process. It is an
environmentally friendly technology experiencing
rapid development and a rapid increase in market
share. Free radical radiation-curable technology based
on acrylate/methacrylate chemistry comprises over
90% of the radiation-curable materials market. How-
ever, a major drawback of acrylate/methacrylate
chemistry is the inhibition of the photopolymerization
by ambient oxygen.15,17 Fortunately, thiol–ene chemistry
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J. Coat. Technol. Res., 7 (5) 603–613, 2010
has been developed that enables rapid photopolymer-
ization through a unique step-growth polymerization
mechanism, during which ambient oxygen can be
turned into a reactive species, as illustrated in
Scheme 1. Consequently, thiol–ene photochemistry is
insensitive to oxygen inhibition.15–17 This feature, in
addition to the excellent mechanical and physical
properties of the resultant polymers, has attracted
extensive research interest in thiol–ene photochemistry
and materials in recent years.16,18–20 UV-curable thiol–
ene materials have been explored as protective coat-
ings, inks, and adhesives.17,19 Furthermore, the extraor-
dinarily high refractive index of thiol–ene materials
enable high value-added applications such as coatings
for optical lenses and fibers, and as adhesives for
photonic and electronic components.18,20,21
It is highly desirable to incorporate bio-renewable
materials into the ‘‘green’’ UV-curable technologies.
Such a combination provides a ‘‘green + green’’ solu-
tion to the stricter environmental regulations that the
coating industry is facing. SBO-based materials such as
acrylated SBO and ESBO have been investigated in
UV-curable materials.7,22–24 However, no previous
research has been found on the utilization of SBO in
thiol–ene photochemistry. The incorporation of SBO
into thiol–ene-based materials is expected to provide
bio-renewable, lower cost, UV-curable materials with
interesting properties and little or no environmental
impact. This paper reports progress in the synthesis
and characterization of soy-based UV-curable thiol–
ene coating materials.
O O O
O ( C H 2)7
O O
O ( C H 2)7 ( C H 2)7
O ( C H 2)7
O O O 50 lm thickness, followed by UV curing using a
ESBO
Fig. 1: Generic structure of epoxidized soybean oil (ESBO)
RS
.
RS .
+ +
R' R'
Scheme 1: Illustration of free radical step-growth polymerization and oxygen scavenging mechanism of thiol–ene
photopolymerization17
604
Experimental procedure
Materials used
The chemicals used, abbreviations, and their sources
are listed in Tables 1 and 2. All chemicals were used as
received.
Synthesis and characterization
Soy-based multifunctional thiols and enes were syn-
thesized by reacting ESBO with thiols (GDMP,
TMPMP, and PETMP, respectively) or enes (AA
and TAE, respectively), in acetone, using 1 wt% BF3
solution as an acid catalyst. The reactions were
conducted at room temperature with magnetic stirring.
The reactant mole ratio of ESBO to thiols or enes was
1:4.4 in order to react all of the epoxy groups on the
ESBO. A typical synthesis procedure using the GDMP
and ESBO reaction as an example is: 4.54 g ESBO,
4.76 g GDMP, and 4.65 g acetone were charged into a
conical flask under magnetic stirring. Then, 0.093 g BF3
solution was mixed with 4.65 g acetone in a beaker,
and then this BF3 acetone solution was slowly charged
into the conical flask. The completion of the reaction
was determined by the disappearance of the epoxy
peaks of ESBO in the FTIR spectrum at 823 and
843 cm 1. It took approximately 16 h for the comple-
tion of GDMP and ESBO reaction, and 6–7 h for other
reactions. After reaction, the acetone and BF3 solution
were stripped off using a rotary evaporator, under
vacuum, at 50C.
UV-curable coating formulation and
( C H 2)4
characterization
To form films for coating physical property testing, the
liquid materials were cast on aluminum Q-panels with
( C H 2)4
a wire-wound drawdown rod to form a thin film with
Fusion LC6B Benchtop Conveyor with an F300 UVA
lamp (UVA, intensity 1180 mW/cm2 measured by
UV Power Puck II from EIT Inc.), in air, at
O2 RS OO . RSH RS OOH
RS
R' R'
RSH
RS H
.
+ RS
R'
 J. Coat. Technol. Res., 7 (5) 603–613, 2010

Table 1: Chemicals used

Name Abbreviation Source Structure and description
O
Vikoflex 7170 ESBO Arkema Inc. O O
O ( C H 2)7 ( C H 2)4
O O
O ( C H 2)7 ( C H 2)7

O ( C H 2)7 ( C H 2)4
O O O

epoxidized soybean oil, MW 1000 g/mol,

Oxirane oxygen 7% min, 4.4 epoxy
groups per ESBO molecule

THIOCURTM PETMP Evans Chemetics LP O

O CH2CH2SH
PETMP O O
HSCH2CH2 O O CH2CH2SH

O CH2CH2SH
O
Pentaerythritol tetra-3-mercaptopropionate

THIOCURTM TMPMP O
O CH2CH2SH
TMPMP O
O CH2CH2SH

O CH2CH2SH
O
Trimethylolpropane tri-3-mercaptopropionate

THIOCURTM GDMP O
HSCH2CH2 O
GDMP O CH2CH2SH
O
Glycol di-3-mercaptopropionate

Allyl alcohol AA Aldrich

OH

O
Allyl triazine AT
N N

O N O

Allyl isocyanurate AI O

N N

O N O

Tri-allyl ether TAE O

HO
O
O

O
Tris[4-(vinyloxy) VE
O
butyl] trimellitate O
O O
O O
O O

Boron trifluoride BF3 O

dibutyl etherate BF3
Lewis acid solution

Irgacure 2022 PI Ciba Specialty 1:4 (by weight) photoinitiator blend of Phenylbis(2,4,
Chemicals 6-trimethylbenzoyl)-phosphine oxide) and
2-Hydroxy-2-methyl-1- phenyl-1-propanone

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J. Coat. Technol. Res., 7 (5) 603–613, 2010
Table 2: Branched/hyperbranched polyester acrylate
oligomers from Sartomer Company Inc.
Abbreviation Acrylate Acrylate Surface
functionality equivalent tension
weight (mN/m
(grams/mol) at 25C)
CN2300 A8 8 163 32.6
CN2301 A9 9 153 38.4
CN2302 A16 16 122 37.8
CN2303 A6 6 194 40.3
CN2304 A18 18 96 32.6
RH  25%. The general curing protocol was 1 pass
through the lamp with a conveyor belt speed of
10 in./min. The coatings were tested after being condi-
tioned under ambient laboratory conditions for at least
24 h. An automated surface energy measurement unit,
manufactured by Symyx Discovery Tools, Inc. and First
Ten Angstroms, was used to measure the water contact
angle on the UV-cured thin film materials. Droplets of
water were deposited on the film surface. A CCD
camera was used to image the droplets. Automated
image analysis was used to determine the contact angle.
Three drops of water were used for each measurement
and the average contact angle values were reported.
The standard deviation of water contact angle mea-
surements is ca. ±2.
Hardness testing was performed using a BYK
Gardener pendulum hardness tester in König mode.
The hardness was reported in seconds. Methyl ethyl
ketone (MEK) double rubs were used to assess the
solvent resistance of the cured coatings. A 26 oz
hammer with five layers of cheesecloth wrapped
around the hammerhead was soaked in MEK for
rubbing. After 100 double rubs, the cloth was re-wetted
with MEK. The number of double rubs needed to mar
the coating surface and to expose the substrate were
recorded and reported. Falling weight, direct impact
testing was carried out according to ASTM D2794 with
a 2 lb weight. The starting height was increased until
the film was damaged. The maximum height at which
the film was intact was recorded. The results were
reported in inch-lbs. Tensile tests were performed
using an Instron 5542 testing system (Instron Corp.,
Norwood, MA). ASTM D412-D dumbbell specimens
were used. The strain rate was 0.2% s 1.
Dynamic mechanical thermal analysis (DMTA) was
performed using a TA Instruments Q800 DMA in
rectangular tension/compression geometry. Free films
of the cured materials were obtained by removing the
material from the aluminum substrate using a razor
blade. The sample size was 10 9 5 mm2. The film
thickness was measured using a Micromaster micro-
meter. The analysis was carried out from 50C to
200C at a frequency of 1 Hz and a ramp rate of 3C
min 1. Tg was obtained from the maximum peak in the
tan d curves. The crosslink density (me) was calculated
606
according to equation: E¢ = 3 meRT. The E¢ value was
determined in the linear portion at a temperature that
was at least 50C greater than the Tg. DSC experiments
were performed utilizing a TA Instruments Q1000
DSC with a heat-cool-heat cycle. The sample size
ranged from 4.5 to 5.5 mg. The temperature was
ramped from 50C to 200C at 10C min 1 in
nitrogen.
The real-time FTIR (RTIR) method provides a
straightforward way of examining the photopolymer-
ization behavior of UV-curable materials.10,11 The
RTIR experiments were performed using a Nicolet
Magna-IR 850 spectrometer Series II with detector
type DTGS KBr, with a UV optic fiber mounted in a
sample chamber. The light source was a LESCO Super
Spot MK II 100 W DC mercury vapor short-arc lamp
with a UVA bulb. Such a setup directly monitors the
functional group conversion as the photopolymeriza-
tion proceeds. Samples were spin-coated onto a KBr
plate at 3000 rpm for 15 s, followed by exposure to UV
radiation in the FTIR beam for 60 s. Spectra were
taken over a 120 s period at 2 spectra/s. The resolution
was 4 cm 1. The UV intensity was 36 mW/cm2
(UVA) as measured by UV Power Puck II from
EIT Inc. The experiments were performed in air at
25 ± 1C. The thiol, ene, and acrylate conversion of
7170-T, AT, and HBA were calculated from the
percent peak height decrement at 2570 cm 1, 3086
cm 1, and 810 cm 1, respectively. The functional
group conversion at 120 s was reported and compared.
NMR spectra were obtained in deuterated chloro-
form using a JEOL 400 MHz ECA400 spectrometer,
equipped with a 24 position autosampler. Spectral
analysis was facilitated using Delta software. MALDI-
TOF spectra were obtained using a Bruker Daltonics’
Ultraflex Series II Matrix Assisted Laser Desorption/
Ionization Time-of-Flight (MALDI-TOF) Mass Spec-
trometer equipped with a 337-nm nitrogen laser. The
samples were dissolved in THF (1%) and mixed with a
solution of the MALDI-TOF matrix, alpha-cyano-4-
hydroxycinnamic acid (HCCA). Trifluoroacetic acid
(0.1% in water) was used as obtained as the dopant.
Results and discussion
Synthesis and characterization of novel soy-based
thiols and enes
Four novel soy-based thiols and enes were synthesized
according to the procedures described in Section 2.2.
The synthesis routes, using reactions of ESBO with
trifunctional thiol and allyl alcohol, respectively, as
examples, are illustrated in Scheme 2. GDMP and
TMPMP-functionalized ESBOs (7170-G and 7170-T,
respectively) are clear, colorless low-viscosity liquids.
The TAE and AA-functionalized ESBOs (7170-TAE
and 7170-AA, respectively) are clear, light yellow
liquids. The overlay of FTIR spectra for the ESBO,
 J. Coat. Technol. Res., 7 (5) 603–613, 2010

SH

SH R'
(a) O
HS
R 2' R' R 2'
HS
" S
SH
R2
O OH
R 1' S "
" R2 OH
R1 R R 1' SH
O "
R1 R
n S
R3 + R' BF3, acetone OH
R3 R'
"
"
HS
SH S
ESBO O O R' HO SH
M ultifunctional thiols R 3'
HS HO
R 3' (n=num ber of oxirane SH
S
per E S B O m olecule)

R'

HS
SH

(b)
R 2'
O
R2' O
"
OH "
R2 OH O OH
O R2
BF3, acetone R 1' "
" R1 R
R1 R
O + n HO O
R 1'
R3 R3
" "
allyl alcohol HO
O
ESBO O O (n =number of oxirane
per ESBO molecule) R3'
HO
O
R 3'

Scheme 2: Synthesis of thiol and ene functionalized ESBO through reaction of epoxy ring opening by (a) multifunctional
thiols; and (b) hydroxyl functional enes

7170-G, and 7170-T is shown in Fig. 2a. After reaction, to intermolecular ring opening by the multifunctional
the epoxy peaks of the ESBO at 823 and 843 cm 1 thiol TMPMP.
disappeared. A thiol peak at 2575 cm 1 and a much
stronger hydroxyl peak at around 3450 cm 1 appeared.
These indicated the successful ring opening of the Preliminary observations of UV-cured soy-based
epoxy by the thiols. Figure 2b shows the FTIR spec- thiol–ene coatings
trum overlay of the ESBO, 7170-AA, and 7170-TAE.
The spectral changes are similar to those seen for 7170- The synthesized soy-based thiols (7170-G, 7170-T) and
G and 7170-T; the exception being that a double bond enes (7170-AA and 7170-TAE) were combined with
peak at 1648 cm 1 appeared instead of the appearance either soy-based or petroleum-based enes and thiols
of the thiol peak, indicating that the attachment of enes according to theoretical stoichiometric ratios, followed
to the ESBO molecule was completed. In Figs. 3a and by UV curing with and without 3 wt% PI. A general
3b, the NMR and MALDI-TOF spectra of reaction trend was observed that coatings composed of lower
product 7170-T are shown. In the NMR spectrum, the functionality soy-based thiols and enes (such as 7170-G
characteristic epoxy peaks of ESBO, at 2.75–3.15 ppm, and 7170-AA) could only be UV-cured to a tacky state
diminished and were overlapped by the characteristic even with the aid of a photoinitiator. Higher function-
peaks of the thiol TMPMP. The FTIR and NMR data ality soy-based thiol–ene coatings could be cured to a
indicated the completion of the epoxy ring opening tack-free film with one pass through the UV lamp
reaction of ESBO. Figure 3b shows the MALDI-TOF without photoinitiator. However, the coating film prop-
spectrum of 7170-T. The data indicate that the final erties such as solvent resistance, hardness, etc., were
product 7170-T was a mixture composed of a group of poor, and the glass transition temperature for these
TMPMP and ESBO reaction products with films are all lower than 10C (from DSC, data not
TMPMP:ESBO ratios ranging from 1 to 5, as indicated shown). The poor film properties are attributed to the
by the molecular mass peak distribution. It was flexible SBO structure and the flexible C–S-C bond
concluded from these data that although all of the formed in the crosslinked network. In addition, the
epoxy groups of ESBO were reacted as determined by existence of modified ESBO molecules with lower
FTIR and NMR, the product obtained possessed functionalities, as shown by the MALDI-TOF analysis,
various functionalization degrees, which may be due will not only lower the crosslink density, but also

607
J. Coat. Technol. Res., 7 (5) 603–613, 2010

2.0 (a)
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
Absorbance

0.9
Disappearance
0.8 of epoxy peak
0.7 Appearance
0.6 of thiol peak
0.5 7170-T
0.4
0.3
0.2
0.1
–0.0
7170-G
–0.1
–0.2
–0.3
ESBO
–0.4

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm–1)

0.60 (b)
0.55

0.50

0.45

0.40
Disappearance
0.35 of epoxy peak
Absorbance

0.30
Appearance
0.25
of double
0.20 bond peak
0.15
7170-TAE
0.10

0.05
7170-AA
–0.00

–0.05
ESBO

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm–1)

Fig. 2: Overlay of FTIR spectra of (a) ESBO, 7170-G, and 7170-T; (b) ESBO, 7170-TAE, and 7170-AA

plasticize the crosslinked network. When soy-based Hyperbranched acrylate-toughened, UV-cured,

thiols and enes were combined with petroleum-based
enes and thiols, as listed in Table 1, tack-free coatings
could be obtained after one pass under the UV lamp,
and the coating properties were better than those
obtained with the all soy-based combinations. Quan-
titative physical and thermal analysis of the coatings
revealed that UV curing 7170-T with enes such as AT,
AI, TAE, and VE generated coatings with better
properties. The best films were obtained from a coating
composed of 7170-T, AT, and 3% PI as a result of the
more rigid ring structure and lower allyl equivalent
weight of AT. However, these film properties were still
not satisfactory for practical applications.
soy-based, thiol–ene coatings
In order to enhance further the soy-based thiol–ene
coating film properties, a set of five different commer-
cial hyperbranched acrylates (HBAs) with polyester
polyol cores were incorporated into the soy-based
thiol–ene coatings. These HBAs have various degrees
of acrylate functionality and surface tension. HBAs
have been reported to have high reactivity, give lower
photopolymerization shrinkage, and yield better adhe-
sion to the substrates.25 A UV-cured thiol–ene–
acrylate ternary system has been explored previously.
It has been shown that the acrylate gives a higher

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 J. Coat. Technol. Res., 7 (5) 603–613, 2010

(a)

7170

TMPMP

7170-T

(b)

+ 1 TMPMP

+ 2 TMPMP

+ 3 TMPMP

+ 4 TMPMP

+ 5 TMPMP

Fig. 3: (a) NMR spectrum of 7170-T; (b) MALDI-TOF spectrum of 7170-T

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J. Coat. Technol. Res., 7 (5) 603–613, 2010

photopolymerization rate and a higher homopolymer-

transparent
glossy film
SOY-T + 20
ization tendency than reaction with thiols as an ene.26

wt% A18
SOY-18

Tack-free
Due to the greater tendency of HBAs to form higher

14/19
crosslinked UV-cured networks, it was expected that in

160
the 7170-T + AT + HBA system, two networks com-

49

98
posed of homopolymer of HBAs and soy-based thiol–
ene–HBAs would be formed after UV irradiation.
transparent These two networks were expected to have enhanced
glossy film
SOY-T + 20

inter-network adhesion due to the potential reaction

wt% A16
SOY-16

Tack-free

between residual acrylate groups and soy-based thiols.

Five HBAs were formulated with the 7170-T + AT

18/26
100 (the reference formulation) together with a PI. The
160
30

compositions of these formulations are given in Table 3.

The soy-based thiol–ene coatings, cured with and without
the aid of PI, yielded soft coating films with good adhesion
transparent

and impact resistance, but very poor solvent resistance, as

Table 3: Reference formulation and HBA-toughened formulations and corresponding coating physical properties

glossy film
SOY-T + 20

compared to a fully petroleum-based thiol–ene coating

SOY-9

wt% A9
Tack-free

made of TMPMP and AT, which did not show any change
30/55

at more than 400 MEK double rubs. The poor solvent

160
62

93

resistance of the soy-based thiol + AT coating could be

due to the loosely crosslinked network arising as a result
of the higher thiol equivalent weight of the 7170-T
(theoretically 312.5 g/mol for 7170-T vs 133 g/mol for
transparent
glossy film
SOY-T + 20

TMPMP). In addition, the hazy cured film indicated a

SOY-8

wt% A8
Tack-free

certain degree of incompatibility between the oil-based

thiol and the AT, which also contributes to the poor
45/59
160

solvent resistance of the film. As to the HBA-toughened

81

98

coatings, the six acrylate functional A6 does not have

good compatibility with the soy-thiol, as evidenced by the
translucent film with poor coating properties. Otherwise,
translucent
glossy film

the other four HBAs all gave good compatibility with the
SOY-T + 20
SOY-6

wt% A6

soy-based thiol, resulting in transparent films. The

Tack-free

enhanced compatibility of these HBAs with the soy-

20/24

based thiol may be due to the result of the more polar

21

80

acrylate ester and more branched structures in the

2

molecules, increasing the solubility of these HBA oligo-

mers. Because of the better compatibility, these coatings
all gave enhanced hardness and solvent resistance
7170-T + AT + 3

compared to those of SOY-T no PI and SOY-T. In

SOY-T

addition, their adhesion and impact resistance were not

hazy film
Tack-free
wt% PI

sacrificed.
The tensile test results and the glass transition
160

temperature and crosslink density data determined from

2/4
26

92

DMA are shown in Figs. 4 and 5, respectively. For the

7170-T + AT samples, the addition of the PI accelerated
the thiol–ene reaction during photopolymerization, gen-
7170-T + AT

erating a coating material with greater modulus, crosslink

without PI
SOY-T no

hazy film
Tack-free

density, and glass transition temperature, but less elon-

PI

gation. When the HBAs were incorporated into the

7170-T + AT formulations, it was found that A8, A9, and
160

1/2
25

98

A18 increased the glass transition temperature, crosslink

density, tensile modulus, and elongation of the coatings.
However, A16 and A6 did not impart significant coating
speed 10 ft/min,

property improvements to the soy-based thiol–ene coat-

UV curability (Belt

MEK double rubs

(mar/substrate)
Forward impact

ings. This observation may be a consequence of the lower

adhesion (%)
hardness (s)
Formulations

acrylate functionality and poor compatibility with the

Cross-hatch
Description

Pendulum

soy-based thiol for A6.

1 pass)

(in.-lbs)

The gloss and water contact angle values for the

HBA-toughened soy-based thiol–ene coatings were
measured, and the data are shown in Fig. 6. All of the

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 J. Coat. Technol. Res., 7 (5) 603–613, 2010

HBA-toughened coatings have water contact angles The thermal weight loss profiles for the HBA-
around 70. In addition, most of the coatings have a toughened soy-based thiol–ene coatings are shown in
high 20 gloss value, the exception being SOY-T-8, Fig. 7. Comparison of coatings SOY-T and SOY-T no
which had a value of approximately 85. PI shows that SOY-T has a slightly higher thermal
decomposition temperature than SOY-T no PI. This
observation can be explained by the presence of
Tensile modulus (MPa) Strain at break (%)
enhanced crosslinking and the resultant higher glass
10 60
transition temperature caused by the addition of 3%
9
50
PI. The HBA-toughened coatings all have higher
8 thermal decomposition temperatures than SOY-T,

Strain at break (%)

Modulus (MPa)

7
40 which is a direct result of the improved crosslink
6 density and the diluted fatty acid ester concentration in
5 30 the cured film.
4 Real-time FTIR experiments were conducted to
3
20 evaluate the photopolymerization kinetics of the soy-
2
based thiol–ene–HBA ternary systems, in comparison
10 to soy-based thiol–ene formulations, with and without
1
the addition of 3 wt% PI. The functional group
0 0
SOY-T no PI SOY-T SOY-6 SOY-8 SOY-9 SOY-16 SOY-18 conversion curves for SOY-T no PI, SOY-T, and
SOY-T-8 are shown in Fig. 8, and the 120 s functional
Fig. 4: Tensile modulus and elongation data for HBA- group conversion for different formulations are shown
toughened soy-based thiol–ene coatings in Table 4. From Fig. 8 and Table 4 it can be seen that,
while the soy-based thiol–ene formulation can be
16 40
UV-cured to a tack-free film, the conversions of thiol
Glass transition tem perature (°C)

Crosslink density and ene during photopolymerization are low, which

Crosslink density (m m ol/cm 3)

14 Glass transition temperature 35

contributes to the poor cured film properties. With the
12 30 addition of 3 wt% PI, the thiol and ene conversions
25 were significantly improved. The ene conversion
10
20
reached 100% almost instantaneously, while the thiol
8 conversion reached 80%. The greater conversion of the
15
6
ene than the thiol is attributed to homopolymerization
10 under radical conditions.26 When the HBAs were
4 5 added to the soy-based thiol–ene formulations, the
2 0
photopolymerization kinetics changed. HBA has been
reported to have greater homopolymerization ten-
0 -5
SOY-T no PI SOY-T SOY-6 SOY-8 SOY-9 SOY-16 SOY-18 dency via free radical addition than copolymerization
with thiol via a thiol–ene step-growth mechanism.
Fig. 5: Glass transition temperature and crosslink density Further, such homopolymerization was accelerated
data for HBA-toughened soy-based thiol–ene coatings due to the elimination of oxygen inhibition because

140 20° gloss water contact angle 90

80
120
70
Water contact angle (°)

100
60
20° gloss

80 50

60 40

30
40
20
20
10

0 0
SOY-T no PI SOY-T SOY-6 SOY-8 SOY-9 SOY-16 SOY-18

Fig. 6: Gloss and water contact angle for HBA-toughened soy-based thiol–ene coatings

611
J. Coat. Technol. Res., 7 (5) 603–613, 2010

1.4
SOY-T no PI
SOY-T
SOY-T-18
SOY-T-8
SOY-T-9

Deriv. Weight (%/°C)

SOY-T-16
SOY-T-6
0.9

0.4

-0.1
0 100 200 300 400 500 600
Universal
Temperature (°C)

Fig. 7: TGA weight loss derivative curves for HBA-toughened soy-based thiol–ene coatings

1 1

0.9 0.9

0.8 0.8
Conversion (x100%)

0.7 Conversion (x100%) 0.7

0.6 0.6

0.5 0.5

0.4 0.4

0.3 0.3

0.2 0.2 allyl triazine-SOY-T no PI

thiol-SOY-T no PI allyl triazine-SOY-T
0.1 thiol-SOY-T 0.1 acrylate-SOY-8
thiol-SOY-8 allyl triazine-SOY-8
0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (s) Time (s)

Fig. 8: Thiol (left), ene and acrylate (right) conversion curve in RTIR experiments for formulations SOY-T no PI, SOY-T, and
SOY-8

Table 4: Functional group conversion at 120 s in RTIR experiments for different soy-based thiol-ene-HBA ternary
formulations
SOY-T no PI SOY-T SOY-6 SOY-8 SOY-9 SOY-16 SOY-18

Acrylate – – 100 100 100 100 100

Thiol 22.5 79.5 100 99.2 99.4 98.8 97.2
Allyl triazine 45.3 100 84.9 86.6 87 71.9 90.8

of the chain transfer mechanism that was induced by thiol–ene copolymerization step. It was noticed that
the thiol.27 This is evidenced by the lack of an SOY-16 had a lower ene conversion compared to the
induction period for the acrylate conversion as indi- other HBA-toughened formulations. This observation
cated in the RTIR conversion curve, shown in Fig. 8. may explain why no significant film property (solvent
The chain transfer mechanism also further consumes resistance, hardness, tensile strength, and glass tran-
and improves the thiol conversion (>95% for HBA sition temperature) improvements were observed
added formulations) in the soy-based thiol–ene–HBA, compared to SOY-T. In conclusion, the addition of
as shown in Table 4. However, the ene conversion in HBA to the soy-based thiol–ene system seemed to
such ternary formulation systems is generally lower have a synergistic effect which resulted in very high
than that in the thiol–ene system due to the con- final conversions of the acrylate, thiol, and ene
sumption of thiol in the acrylate homopolymeriza- functional groups in the formulation, during photo-
tion stage and reduced system mobility in the later polymerization.

612

Conclusions
Soy-based thiols and enes were synthesized by the
acid-catalyzed ring opening reaction of ESBO by
multifunctional thiols or hydroxyl functional enes, as
evidenced by FTIR and NMR. Due to the low Tg
feature of the soy-based thiols and enes, tack-free
UV-curable coating films with better film properties
were obtained only by formulating higher functionality
soy-based thiols with allyl triazine. The photopolymer-
ization conversion and the coating film properties such
as solvent resistance, modulus and elongation, glass
transition temperature, and thermal degradation tem-
perature could be further enhanced by the addition of
multifunctional, hyperbranched acrylates A8, A9, and
A18.
Acknowledgment We would like to thank the North
Dakota Soybean Council for sponsoring this research.
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