Plasticization effects of dihydroxyl soybean oil improve flexibilities of

epoxy-based films for coating applications

Jonggeun Sung, Yonghui Li, Xiuzhi Susan Sun
Bio-Materials and Technology Lab, Department of Grain Science and Industry, Kansas State University, 1980 Kimball Ave., BIVAP
Bldg., Manhattan, Kansas 66506
Correspondence to: X. S. Sun (E - mail: [email protected])

ABSTRACT: Novel bio-based coating materials were developed through cationic ring-opening photopolymerization of dihydroxyl soy-
bean oil (DSO) with commercial epoxy monomers [i.e., epoxidized soybean oil (ESO) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-
hexanecarboxylate (ECHM). The ether cross-linking and post-polymerization of the polymeric network were observed using Fourier
transform infrared spectroscopy. Thermal properties of the bio-based coating materials and their copolymerization behaviors were
examined using differential scanning calorimetry and a thermogravimetric analyzer. Cross-link density and molecular weight between
cross-link were obtained from dynamic mechanical analysis. ECHM/DSO (1 : 1.43 weight ratio) films showed the highest elongation
at break (49.2%) with a tensile strength of 13.7 MPa. After 2 months of storage, the elongation at break and tensile strength of films
were 32% and 15.1 MPa, respectively. ESO/DSO films (w/w ratios of 1 : 0.1, 1 : 0.15, and 1 : 0.2) exhibited stable flexibility of 11–
13% of elongation at break without significant reductions in tensile strength (2.5–4.4 MPa) during a 2-month shelf life. Optical trans-
parencies of the films were comparable to commercial glass and polymers, and water uptake properties (0.72% and 2.83%) were sig-
nificantly low. V
C 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41773.

KEYWORDS: biopolymers and renewable polymers; cross-linking; films; mechanical properties; photopolymerization

Received 20 August 2014; accepted 12 November 2014

DOI: 10.1002/app.41773

INTRODUCTION Photopolymerization promotes quick curing and requires low

energy consumption. Photoinitiated cationic polymerization is
The most widely used coating materials in packaging applica-
commonly used methods for making coatings, adhesives, and
tions are polyethylene, polyvinyl alcohol, and fluorocarbon
printing inks in the polymer industry.10,11 It is also one of the-
which are synthesized from petroleum resources, and most of
common curing methods for epoxy resins such as epoxidized
the petrochemical coating materials are not biodegradable.1,2 soybean oil (ESO) and 3,4-epoxycyclohexylmethyl-3,4-epoxycy-
Environmental regulations have been designed to reduce chemi- clohexanecarboxylate (ECHM).3,12–15 Compared with free radi-
cal pollutants and conserve fossil fuels, and academia and cal photopolymerization, which is based mainly on acrylates,
industry are seeking sustainable alternatives to petroleum-based cationic photopolymerization of epoxy offers several advantages,
materials.3,4 Bio-based polymers such as proteins and polysac- including low shrinkage, uninhibitedness in oxygen, and post-
charides have been researched as raw materials for packaging polymerization after UV exposure stops.10,12,16 Compared with
applications,1 but their hydrophilic natures lead to poor water ESO, photopolymerized cycloaliphatic resins such as ECHM
resistance.5,6 Plant oils can be incorporated into coating materi- have shown excellent rigidity and adhesion to substrates, and
als without loss of water barrier properties1; moreover, plant high glass transition temperature,10,12 but the brittleness of the
oils also possess the advantages of intrinsic biodegradability and epoxy polymer has been a problem for making flexible packag-
low toxicity.7 Plant oils have become one of the most important ing coatings.17 Previous work in our lab identified that UV
sources of renewable materials in the chemical industry, making copolymerization of ESO, rosin ester, and soy polyols [i.e., dihy-
products such as surfactants, lubricants, paints, resins, adhesives, droxyl soy bean oil (DSO)] yields the flexibility, thermal stabil-
and coatings.4,7 Epoxidation of plant oil is commonly used to ity, and optical transmittance required to create flexible
produce functionalized olefin because of its economical process coatings.14 Soy polyols improved the softness and tackiness of
and significantly improved oil reactivity.8,9 ESO-based resin.18,19 Partially crystalline polymeric diols

C 2014 Wiley Periodicals, Inc.

V

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EXPERIMENTAL
Materials
ESO (Scientific Polymer Products, Ontario, NY), ECHM
(Sigma-Aldrich, St. Louis, MO), and PC-2506 (Polyset, Mechan-
icville, NY; [4-(2-hydroxyl-1-tetradecyloxy)-phenyl] phenyliodo-
nium hexafluoroantimonate) were kindly provided by the
respective companies.
Dihydroxyl Soybean Oil Synthesis
DSO was prepared according to our previous research with
modifications to reduce solvent and catalyst amounts and reac-
tion times. 14,18 Briefly, ESO (40 g, 40 mmol) was dissolved in
60 mL of tetrahydrofuran/water (40 mL : 20 mL) with 1.5%
(volume of ESO) of perchloric acid, and the mixture was mag-
netically stirred for 5 hours at room temperature. The aqueous
layer of the mixture was then separated from the organic layer
in a separatory funnel by adding 60 mL of ethyl acetate.
Perchloric acid in the aqueous layer was removed by water
washing, and saturated sodium bicarbonate (approximately 5–
6 mL) was added to neutralize the mixture. The solvent in the
Scheme 1. (a) Epoxidized soybean oil (ESO), (b) dihydroxyl soybean oil
organic layer was removed by a rotary evaporator with a tap
(DSO), and (c) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy- vacuum, then the organic layer was dried under high vacuum
late (ECHM). with a rotary evaporator to remove remaining water residues.
Preparation of UV-Cured Films
UV-curable copolymer films were prepared at various ratios of
[i.e., poly(e-caprolactone)] were researched to improve tensile
ESO and DSO and ECHM and DSO monomers. ESO and DSO
strength and elongation of ECHM polymers using cationic ther-
were mixed at weight ratios of 1 : 0.1, 1 : 0.15, and 1 : 0.2. The
mal polymerization.17
mixture was heated and mixed using a heat gun and a vortex
In this study, ESO and ECHM were used for examples of bio- mixer. Subsequently, 3 wt % (weight of ESO) cationic photoini-
based and non-bio-based epoxy resins, respectively. In addition, tiator PC-2506 was added to the mixture and mixed well using
DSO was formulated into the epoxy resins to improve polymer the vortex mixer and a sonicator.12,14 Approximately 8 g of the
flexibility. Chemical structures of ESO, ECHM, and DSO were mixture was spread over a glass plate (25.4 cm by 15.24 cm) as
shown in Scheme 1. Both ESO/DSO and ECHM/DSO resins a substrate using a wire wound rod (#90; ChemInstruments,
were UV-polymerized to form a copolymer which was cross- Fairfield, OH). The spread mixture was passed twice at a con-
linked by ether linkage because of homo-polymerization of veyor rate of 7 ft min21 (radiation dose of 1.7–1.8 J cm22)
epoxides or co-polymerization of an epoxide and an alcohol through a F300 UV system (1.8 kW, 6-in (300 W in21) lamps)
group (Scheme 2).11,12,15,20,21 Therefore, the objectives of this equipped with a LC6B benchtop conveyor (Fusion UV system,
study were to develop novel bio-based coating materials via Gaithersburg, MD). The UV lamp was 10 cm above the con-
photoinitiated cationic ring-opening co-polymerization of DSO veyor belt. To obtain free-standing films, appropriate thicknesses
with ESO and ECHM and to characterize the structural, ther- of the UV-cured films were from 0.13 to 0.15 mm. ECHM/DSO
mal, mechanical, shelf life, and optical properties of the poly- films were prepared similarly at ECHM/DSO weight ratios of
merized films. Various characterization techniques including 1 : 1, 1 : 1.18, and 1 : 1.43 with three UV passes. The UV-cured
Fourier transform infrared (FTIR) spectroscopy, differential films could not be detached from the glass substrate without
scanning calorimetry (DSC), thermogravimetric analysis (TGA), cohesion failure right after UV-curing. Based on our prelimi-
tensile testing, dynamic mechanical analysis (DMA), UV-visible nary test for making free-standing films, 3 hours is just enough
spectroscopy, and water uptake test were employed. to peel off the films from glass substrate without any cohesion

Scheme 2. UV-initiated cationic ring-opening polymerization of epoxides homopolymer (a) and epoxide-hydroxyl copolymer (b). E, E0 , and E00 are
epoxy monomers such as ESO and ECHM. D is DSO.

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failure. Therefore, all UV-cured films were peeled from the glass
plates 3 hours after the completion of UV curing, then films
were stored in the dark for 3 hours, 1 day, 5 days, 10 days, 1
month, and 2 months to obtain samples for shelf life and dark-
curing effect studies.
Fourier Transform Infrared Spectroscopy
Perkin-Elmer Spectrum 400 FTIR spectroscopy (Waltham, MA)
was used to verify cationic ring-opening photopolymerization
of the resins and the dark-curing effect by comparing functional
groups such as hydroxyl, epoxy, and ether groups. Data for non-
cured resin blends and UV-cured films at 3 hours and 10 days
after curing for both ESO/DSO (w/w ratio of 1 : 0.15) and
ECHM/DSO (w/w ratio of 1 : 1.18) films were collected.
Thermal Properties of UV-Cured Films
A DSC (TA DSC Q200, New Castle, DE) and a TGA (Perki-
nElmer Pyris 1 TGA, Norwalk, CT) were used to obtain thermal Figure 1. FTIR of ESO/DSO (weight ratio of 1 : 0.15) resin before UV
properties of the UV-cured films to determine thermal stability curing, 3 hours after UV curing, and 10 days after UV curing.
of the coating materials. All UV-cured samples for thermal anal-
ysis were measured within 30 min after UV curing to reduce Berlin, NJ). A strip of the film was applied on a tensile tester
dark-curing effect. UV-cured and noncured ESO/DSO (w/w (TT-1100, ChemInstruments, Fairfield, OH) with 12.7 cm of
ratio of 1 : 0.15) and ECHM/DSO (w/w ratio of 1 : 1.18) films initial grip separation and a rate of grip separation of 2.54 cm
and resins, as well as both monomers, were measured. Thermal min21. The mechanical test was conducted at various times (1,
transitions (glass transition temperature, Tg, and melting tem- 5, and 10 days, and 1 and 2 months) after UV curing to evalu-
perature, Tm) and heat of copolymerization (DH) were ate shelf life of the bio-based films.
obtained. All cured and noncured samples for DSC contained 3
Optical Transmittance
wt % (weight of ECHM or ESO) photoinitiator. Approximately
Optical transparency was measured with a UV-visible spectrom-
5–7 mg of the sample was heated from 250 C to 250 C at a
eter (Hewlett-Packard 8453) with a wavelength range of 200–
rate of 10 C min21 under a nitrogen environment in a hermetic
900 nm. The thickness of loading samples was 0.14 mm for
pan. Conventional Modulated Differential Scanning Calorimetry
ESO/DSO and ECHM/DSO films, and 0.91 mm for glass slides.
(MDSC) mode was used to determine accurate Tg of ESO/DSO
and ECHM/DSO cured films from 250 C to 200 C at a rate of Water Uptake Properties
3 C min21. Thermal decomposition characteristics of 1 : 0.15 Water absorption of the UV-cured films was estimated accord-
w/w ratio of ESO/DSO and a 1 : 1.18 w/w ratio of ECHM/DSO ing to 24 hours immersion test of ASTM D570-98. The loading
UV-cured samples were obtained using TGA and compared samples were 0.14–0.15 mm thick, and 2.54 cm long and wide.
with the decomposition characteristics of ESO and ECHM UV-
cured homopolymers, respectively, and 6–8 mg of each sample RESULTS AND DISCUSSION
was heated from 30 C to 650 C at a rate of 20 C min21 under UV-Polymerization
a nitrogen atmosphere. FTIR spectra were obtained to confirm functional groups of
ESO/DSO and ECHM/DSO UV-cured films before and after
Viscoelastic Behaviors of ESO/DSO and ECHM/DSO Films
photopolymerization (Figures 1 and 2). Epoxy peaks at
To obtain viscoelastic properties of the UV-cured films, dynamic
825 cm21, triglycerides at 1740 cm21, and alcohol bands
mechanical analysis (DMA) was performed with a TA DMA
around 3450 cm21 were detected in the noncured ESO/DSO
Q800 (New Castle, DE) with a tension/film clamp using rectan-
curve (Figure 1). After 3 hours of UV curing, the disappearance
gular specimens approximately 2 cm long, 1.27 cm wide, and
of the epoxy peak at 825 cm21 and the appearance of an ether
0.13–0.15 mm thick. The measurements were performed at a
peak at 1075 cm21 indicates that the reaction was completed
frequency of 1 Hz, a constant amplitude of 15 lm, and a heat-
for the polymerization of ESO and DSO (w/w ratio of 1 :
ing range of 250 C to 150 C with 10 C min21 increments. Tg
0.15)25 (Figure 1). For ECHM and DSO (w/w ratio of 1 : 1.18),
was determined at maximum tangent delta peak, and cross-link
the reaction was not fully complete in 3 hours, which was con-
density (me) and molecular weight between cross-link (Mc) were
firmed by the remaining small epoxy peak at 790 cm21 and the
calculated from an elastic modulus (E0 ) based on the rubbery
increment of the ether peak at 1070 cm21 after 10 days (Figure
plateau region at least 50 C above Tg.22–24
2). The cross-linking reaction of epoxy and alcohol leads the
Mechanical Properties of ESO/DSO and ECHM/DSO Films termination of chain propagation and the active center transfer-
Tensile strength and elongation at break were measured accord- ring from the polymer chain [Scheme 2(b)]. 11,21 In addition,
ing to ASTM D882-12. The UV-cured films were cropped to the cross-linking reaction with alcohol was dominant in
20.32 cm long, 1.27 cm wide, and 0.13–0.15 mm thick accord- ECHM/DSO copolymer because the ECHM/DSO resins con-
ing to ASTM D6287-09 using a dual-blade shear cutter (JDC tained more alcohol groups than the ESO/DSO systems. There-
Precision Cutter 1000 , Thwing-Albert Instrument Company, West fore, the longer time for the post-polymerization of ECHM/

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in epoxides mobility.12 Similarly, the ESO/DSO (w/w ratio of 1

: 0.15) after curing showed a curing peak at 136.13 C with DH
of 87.7 J g21, and both cured ECHM and cured ECHM/DSO
(w/w ratio of 1 : 1.18) also exhibited a peak of heat curing at
125.64 C with DH of 28.2 J g21 and 77.07 C with DH of 33.5 J
g21, respectively. The addition of DSO decreased the polymer-
ization temperature of ESO but not ECHM. ESO and DSO
have basically same backbone structures (i.e., triglyceride), and
the rate of epoxy-epoxy polymerization is lower than the rate of
epoxy-hydroxyl polymerization. The faster rate of epoxy-
hydroxyl polymerization is because of the less steric require-
ments for the nucleophilic attack by a hydroxyl in compared
with the attack by an epoxide. Therefore, the polymerization
temperature of ESO with DSO addition was reduced. However,
the polymerization temperature of ECHM was not reduced by
DSO addition, because ECHM is easily polymerized itself
Figure 2. FTIR of ECHM/DSO (weight ratio of 1 : 18) resin before UV because of its small steric hindrance of the less bulky structure
curing, 3hours after UV curing, and 10days after UV curing.
in compared with a triglyceride. Therefore, DSO did not signifi-
cantly affect a reduction of polymerization temperature of
DSO copolymer could be caused by the new protonated epoxide ECHM.
monomers during the active center transferring. The increased
alcohol bands around 3450 cm21 after curing of both ESO/DSO ESO and ESO/DSO showed larger DH than ECHM and ECHM/
and ECHM/DSO copolymers were because of the newly gener- DSO. Ring-opening photopolymerization of ESO tended to
ated hydroxyl groups from the epoxy ring-opening have a lower degree of polymerization. The lower degree of
polymerizations. cross-linking reaction of ESO could be because of epoxide steric
hindrance from the bulky structure of ESO. The steric hin-
Thermal Analysis drance of the ESO was also considered a reason for the low
ESO before UV curing had a small endothermic peak around degree of epoxy conversion in photoinitiated cationic polymer-
26 C showing crystalline structures of epoxide triglycerides ization.15 In compared with ESO/DSO, ECHM/DSO showed
[Figure 3(a)]. The peak disappeared after UV curing because higher degree of polymerization under UV-curing from the
crystallization was impeded by cross-linking of ESO epoxides13 DSC analysis although it had longer time of post-
[Figure 3(b)]. ESO before curing also showed a curing peak at polymerization completion using the FTIR results. Absences of
182 C with DH of 379.2 J g21. The ESO after UV curing melting peaks and presences of exothermic curing peaks in UV-
showed a shallow and broad exothermic peak at 134.81 C with cured films confirmed that soybean-derived coating materials
DH of 58.3 J g21, which was caused mainly by the cross-linking were thermosetting polymers. The photoinitiator (PC2506) had
reaction of residual epoxides because the heat from DSC con- melting and thermal decomposition peaks at 98.9 C and
tributed to the cross-linking reaction following an improvement 224.1 C, respectively. Tg was determined at various weight ratios

Figure 3. DSC thermograms of PC-2506, ESO, DSO, ESO/DSO (w/w ratio of 1 : 0.15), and ECHM/DSO (w/w ratio of 1 : 1.18) samples including the
photoinitiator before UV curing (a) and after UV-curing (b).

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Table I. Glass Transition Temperatures of Various Weight Ratios of ESO/ Dynamic Mechanical Properties
DSO and ECHM/DSO Based on MDSC and DMA Analysis The tensile and dynamic mechanical properties of the UV-cured
samples after 3 hours and 10 days of storage are summarized in
DMA Tg ( C) Table II. The cross-link densities (me) were calculated from the
MDSC Tg ( C)
storage modulus (E0 ) at 50 C greater than Tg in the rubbery
Monomer/ratio 0 hours 3 hours 10 days
plateau region [Figure 6(a,b)] following the below
ESO : DSO(1 : 0.1) 22.8 18.5 18.8 equation22–24:
ESO : DSO(1 : 0.15) 24.8 16.6 17.1 E 0 5 3me RT (1)
ESO : DSO(1 : 0.2) 25.4 14.0 14.9
where R is the gas constant and T is the absolute temperature.
ECHM : DSO(1 : 1) 51.0 66.7 67.1
The molecular weight between chain lengths (Mc) was estimated
ECHM : DSO(1 : 1.18) 36.2 60.8 58.5
following the below equation:
ECHM : DSO(1 : 1.43) 30.8 51.2 50.8
d
Mc 5 (2)
me
of both ESO/DSO and ECHM/DSO films through MDSC and
where d is the specific gravity of the polymer.
DMA analysis (Table I). The Tg from DMA was determined at
peak loss factor (Tan d) [Figure 5(a,b)], and that from DMA In Table II, the ESO/DSO films showed lower tensile strength
was approximately 20 C higher than that from DSC because than the ECHM/DSO films at both 3 hours and 10 days after
DMA and DSC determined Tg based on different mechanisms; UV curing. The apparently low mechanical strengths of the
however, both DMA and DSC showed the same tendency ESO/DSO films were also affected by their low Tg, which were
toward Tg of the films as affected by DSO. Tg decreased as DSO below room temperature, whereas the tensile tests were per-
increased because DSO acted as a plasticizer in the polymer formed at room temperature, during the samples’ rubbery
matrix. Compared with the ESO/DSO films, ECHM/DSO films states.26 The Tan d peaks of the ECHM/DSO films at 10 days
had much higher Tg, because of the rigid backbone structure of became narrower compared with those at 3 hours [Figure
ECHM and higher reactivity of the external epoxides. 5(a,b)]. This behavior could be attributed to the postpolymeri-
Thermal degradation of the films was measured using TGA zation of the ECHM/DSO films because the narrower width of
(Figure 4). All UV-cured ESO/DSO and ECHM/DSO films had Tan d peaks represented the increase in the homogeneity of
similar thermal stabilities and degraded in the temperature polymer networks23,24; however, the degrees of homogeneity of
range of 339 C to 428 C; however, the ECHM/DSO film the ESO/DSO polymer network did not change between 3 hours
became more thermally stable than ECHM alone. The degrada- and 10 days, as indicated by the Tan d peaks’ unchanged widths
tion temperatures of cured-ECHM were observed at 339 C for [Figure 5(a,b)]. These results were in accordance with the FTIR
5% weight loss and 408 C for 50% weight loss, and the decom- analysis as discussed in the previous section, so the change to
position temperatures of the ECHM/DSO (w/w ratio of 1 : the more uniform polymer network of the ECHM/DSO films
1.18) increased to 356 C for 5% weight loss and 428 C for 50% during postcuring could be a convincing reason for increases in
weight loss. their tensile strengths (Table II). Overall, less DSO led to higher
cross-link densities for both ESO/DSO and ECHM/DSO films
(Table II), which also could be concluded from the width and
height of the Tan d peaks in Figure 5(a,b). Broader Tan d peak
width and lower Tan d peak height indicated larger cross-link
density.27
E0 of the ESO/DSO and the ECHM/DSO films was estimated
from DMA measurements at 3 hours and 10 days after curing,
respectively [Figure 6(a,b)]. E0 at the glass transition region of
both ESO/DSO and ECHM/ DSO films at 3 hours decreased
as DSO contents increased [Figure 6(a)]. In addition, obvi-
ously lower E0 was obtained at both glass transition and rub-
bery plateau regions for the films after 10 days of storage with
more DSO additions [Figure 6(b)]. The reductions of E0 and
Tg with DSO additions indicated the plasticizing effects of
DSO. The increase in E0 at the rubbery plateau of the ESO/
DSO (w/w ratios of 1 : 0.15 and 1 : 0.2) and the ECHM/DSO
(w/w ratios of 1 : 1.18 and 1 : 1.43) at 3 hours after curing
[Figure 6(a)] were caused by heat curing of residual materials
during DMA heating.26 No significant increases in E0 of the
Figure 4. Thermal decomposition profiles of UV-cured samples of ESO, ESO/DSO (w/w ratios of 1 : 0.1) and the ECHM/DSO (w/w
ESO/DSO (w/w ratio of 1 : 0.15), ECHM, and ECHM/DSO (w/w ratio of ratios of 1 : 1) at 3 hours in their rubbery regions could be
1 : 1.18) from TGA. explained by a higher degree of polymerization during UV

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Figure 5. Loss factors of ESO/DSO and ECHM/DSO samples at 3hours (a) and 10days (b) after UV curing.

curing because of larger numbers of the epoxy sites under UV The tensile strength of the ECHM films of all ECHM/DSO
irradiation. The larger cross-link densities could effectively dis- ratios was much higher than that of ESO films and decreased
turb polymer chain mobility and curing during DMA heating. significantly as DSO increased. Films’ strength increased by 80–
E0 at the rubbery plateau regions of the ESO/DSO and ECHM/ 140% during the first month (Figure 8). Tensile strength
DSO films at 10 days after UV curing was higher than at the decreased during the 2-month storage time. Elongations at
rubbery region of the samples after 3 hours [Figure 6(b)]. The break of the ECHM-based films increased significantly as the
higher E0 in the rubbery region results in the increase of cross- DSO contents increased, but decreased as storage time increased
link densities and reductions of molecular weight between in the second month.
chain lengths (Table II).
Overall, both the ESO- and the ECHM-based films reached
Tensile Properties in Shelf Life Tests maximal tensile strength by one month of storage after comple-
The UV-cured ESO films at weight ratios of ESO : DSO (1 : tion of UV curing, and the ECHM/DSO films showed much
0.1, 1 : 0.15, and 1 : 0.2) showed a decrease in tensile strength higher tensile strength compared with the ESO/DSO films at all
as DSO contents increased (Figure 7). The tensile strengths of storage times. The excellent mechanical strength of the ECHM-
all samples increased by approximately 15–20% as storage time based films could be explained by the rigid structure of ECHM
approached 1 month. The tensile strengths of the films (w/w itself and the higher reactivity of the external oxiranes.15 In
ratios of 1 : 0.1 and 1 : 0.15) were slightly reduced at 2 months, addition, increased elongation at break of the ECHM-based
but the strength of the film (w/w ratio of 1 : 0.2) remained sim- films with larger amounts of DSO added was clearly related to
ilar. Elongation at break of the ESO-based films was not affected the decrement in Tg of the films. A similar result was also
by DSO additions or storage times. reported by L€ utzen.17 During our experiments, we found that

Table II. Summary of Cross-Link Density, Tensile Strength, Molecular Weight Between Chain Length, and Elongation of Various Weight Ratios of ESO/
DSO and ECHM/DSO at 3 Hours and 10 Days After UV Curing

Molecular weight
between
Cross-link density Tensile strength chain length Elongation
(mol m23) (MPa) (g mol21) (%)

Monomer/ratio 3 hours 10 days 3 hours 10 days 3 hours 10 days 3 hours 10 days

ESO : DSO(1 : 0.1) 1628.3 3376.9 3.9 4.0 655.2 306.7 11.2 11.5
ESO : DSO(1 : 0.15) 1145.6 1965.9 3.5 3.3 935.5 530.7 11.1 10.4
ESO : DSO(1 : 0.2) 1181.3 1598.5 3.0 2.7 884.2 658.6 10.4 11.6
ECHM : DSO(1 : 1) 459.9 584.7 26.8 34.5 2459.6 1833.0 13.4 3.7
ECHM : DSO(1 : 1.18) 339.1 425.3 19.7 29.5 3306.9 2512.4 21.1 10.3
ECHM : DSO(1 : 1.43) 332.3 372.1 11.6 15.7 3428.3 2878.1 42.2 44.1

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Figure 6. Storage modulus of ESO/DSO and ECHM/DSO samples at 3hours (a) and 10days (b) after UV curing.

pure ECHM film could not be peeled from the glass substrate The increases of the weights of the ESO/DSO (w/w ratios of of
after UV curing because of its highly brittle characteristic. DSO 1 : 0.2) and the ECHM/DSO (w/w ratios of 1 : 1.43) were
was an effective plasticizer of ECHM to increase the flexibility 0.66 6 0.06% and 2.83 6 0.2%, respectively, in the water uptake
of the UV-cured ECHM polymer for flexible coating test during 24 hours. Both ESO/DSO and ECHM/DSO poly-
applications. mers exhibited good water resistance. Additionally, the lower
water absorption of ESO/DSO could be related to its higher
Optical Transmittance and Water Uptake Properties
cross-link density.
The optical transmittances of the ESO/DSO (w/w ratios of 1 :
0.15) and the ECHM/DSO (w/w ratios of 1 : 1.18) were around CONCLUSIONS
90% in the visible light range, their transparency was similar to
microscope slide glass. In addition, 80% light transmittance of DSO was successfully copolymerized with ESO and ECHM,
polypropylene and 60% light transmittance of polyethylene in respectively, to produce bio-based coating materials through
visible ranges were confirmed from our previous research,18 UV-initiated cationic ring-opening polymerization. Photopoly-
making the transparencies of the ESO/DSO and the ECHM/ merization produced ether cross-linkage polymeric networks.
DSO UV-cured films comparable to glass and commercial plas- ECHM/DSO film was stronger than ESO/DSO film. Post-
tics. Accordingly, the bio-based polymers could be useful in polymerization effects were confirmed by spectral, thermal,
transparent coating applications. mechanical, and dynamic mechanical analyses. The ECHM/DSO
(w/w ratio of 1 : 1.43) film showed excellent flexibility during
the shelf life tested in this study. ESO/DSO (w/w ratio of 1 : 1)

Figure 7. Tensile strength and elongation at break of ESO/DSO (w/w Figure 8. Tensile strength and elongation at break of ECHM/DSO (w/w
ratios of 1 : 0.1, 1 : 0.15, and 1 : 0.2). ratios of 1 : 1, 1 : 1.18, and 1 : 1.43).

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and ECHM/DSO (w/w ratio of 1 : 1.18) films exhibited the 12. Voytekunas, V. Y.; Ng, F. L.; Abadie, M. J. M. Eur. Polym. J.
highest tensile strengths. Mechanical properties of these films 2008, 44, 3640.
remained stable during the 2-month shelf life. DSO was found 13. Shibata, M.; Teramoto, N.; Someya, Y.; Suzuki, S. J. Polym.
to be an effective plasticizer for both ESO and ECHM systems. Sci. B Polym. Phys. 2009, 47, 669.
The transparencies of soybean-based UV-cured films were simi- 14. Ahn, B. K.; Sung, J.; Kim, N.; Kraft, S.; Sun, X. S. Polym.
lar to that of microscope slide glass. Int. 2013, 62, 1293.
ACKNOWLEDGMENTS 15. Decker, C.; Viet, T. T. N.; Thi, H. P. Polym. Int. 2001, 50,
986.
This is contribution no. 15-014-J from the Kansas Agricultural
16. Sipani, V.; Scranton, A. B. J. Polym. Sci. A Polym. Chem.
Experimental Station. Financial support was provided by USDA- 2003, 41, 2064.
NIFA Biomass Research and Development Initiative program
17. Luetzen, H.; Bitomsky, P.; Rezwan, K.; Hartwig, A. Eur.
(Grant No. 2012-10006-20230).
Polym. J. 2013, 49, 167.
18. Ahn, B. K.; Kraft, S.; Wang, D.; Sun, X. S. Biomacromolecules
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