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Soybean Oil-Based Photo-Crosslinked Polymer Networks

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DOI: 10.1007/s10924-010-0174-3

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Soybean Oil-Based Photo-Crosslinked
Polymer Networks

Journal of Polymers and the

Environment
formerly: `Journal of
Environmental Polymer
Degradation'

ISSN 1566-2543
Volume 18
Number 3

J Polym Environ (2010)

18:291-297
DOI 10.1007/
s10924-010-0174-3

1 23
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1 23
 Author's personal copy
J Polym Environ (2010) 18:291–297
DOI 10.1007/s10924-010-0174-3
ORIGINAL PAPER
Soybean Oil-Based Photo-Crosslinked Polymer Networks
Han-Min Kim • Hak-Ryul Kim • Beom Soo Kim
Published online: 21 April 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Novel soybean oil-based crosslinked polymer
networks were prepared by UV photopolymerization and
their mechanical properties were evaluated. Poly(ethylene
glycol) diacrylate (PEGDA) and biodegradable poly(e-cap-
rolactone) diacrylate (PCLDA) were synthesized and used as
crosslinking agent to form crosslinked polymer networks by
UV-initiated free-radical polymerization with acrylated
epoxidized soybean oil (AESO). The synthesis of acrylate
end-capped macromers was confirmed using FT-IR and 1H
NMR spectroscopic techniques. Photopolymerization time,
the composition of reaction mixture, and the type and length
of crosslinking agent were changed to obtain crosslinked
polymer networks with various mechanical properties.
Polymers prepared from AESO and PCL degraded 6% of the
initial weight in 24 days in phosphate buffer solution (pH
7.2) containing lipase enzyme. These potentially biode-
gradable and biocompatible polymers can be used as eco-
friendly materials for biomedical and other applications to
replace the existing petroleum-based polymers currently
used.
Keywords Acrylated epoxidized soybean oil

Poly(ethylene glycol) diacrylate
Poly(e-caprolactone)
diacrylate
Photo-crosslinked polymer network

Ecofriendly
Biodegradable
H.-M. Kim
B. S. Kim (&)
Department of Chemical Engineering, Chungbuk National
University, Cheongju, Chungbuk 361-763, Republic of Korea
e-mail: bskim@chungbuk.ac.kr
H.-R. Kim
Department of Animal Science and Biotechnology, Kyungpook
National University, Daegu 702-701, Republic of Korea
Introduction
The widespread use of nonbiodegradable, petroleum-based
polymers has raised many concerns in terms of both eco-
nomical and environmental aspects. There is a growing
interest in biomaterials derived from renewable resources
such as vegetable oils [1–3]. These biopolymers offer the
advantages of low cost, ready availability of starting mate-
rials, and possible biodegradability. Thermosetting foams
were prepared with a high bio-based content from acrylated
epoxidized soybean oil and carbon dioxide [4]. Polyols
and polyurethanes were prepared from vegetable oils [5].
Thermosetting resins from nonfunctionalized natural oils
have been developed via cationic, free-radical, and thermal
polymerizations [6, 7]. Various different polymeric materials
ranging from soft rubbers to tough and rigid plastics were
prepared by the copolymerization of vegetable oils with sty-
rene and divinylbenzene [8]. Even though these thermosets
can be considered biobased, their applications as biodegrad-
able and biocompatible materials would be limited because
the comonomers used (styrene and divinylbenzene) are toxic
and the biodegradability of resulting polymers is unknown.
Poly(ethylene glycol) (PEG) is a biocompatible, non-
toxic, and nonimmunogenic water soluble polyether. It has
been used as biomedical materials in blood-contacting
devices due to its unique protein or cell-resistant properties
[9]. Besides biomedical applications, PEG has a long history
as specialty polymers to be used as raw materials for syn-
thesizing detergents or polyurethanes [10]. Biodegradability
of PEG and its derivatives by activated sludges was also
reported [10]. Poly(e-caprolactone) (PCL) is a biocompati-
ble and biodegradable polymer that belongs to the aliphatic
polyester family [11]. Extensive in vitro and in vivo bio-
compatibility and efficacy studies have been performed,
resulting in approval of a number of medical and drug
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292 J Polym Environ (2010) 18:291–297

delivery devices by the US Food and Drug Administration.
Cellular compatibility of crosslinked PCL networks has also
been reported [12]. By photopolymerization, biodegradable
crosslinked polymer networks based on PEG-co-poly
(a-hydroxy acid) diacrylate macromers have been synthe-
sized for biomedical applications [13, 14].
In this study, we prepared novel soybean oil-based poly-
mer networks which can be potentially used as biodegrad-
able and biocompatible materials for various biomedical
and other applications. PEG diacrylate (PEGDA) and PCL
diacrylate (PCLDA) were synthesized and used as cross-
linking agent to prepare polymer networks by UV-initiated
free-radical polymerization with acrylated epoxidized soy-
bean oil (AESO). Photopolymerization reaction conditions
were changed to obtain crosslinked polymer networks with
various mechanical properties. Lipase degradability was
studied by measuring weight loss in phosphate buffer solu-
tion (pH 7.2).
Experimental Part
Materials
AESO was obtained from Aldrich (Milwaukee, WI, USA).
The chemical structure and 1H NMR spectrum of AESO is
shown in Fig. 1. It has an average of three acrylates per tri-
glyceride, which can be calculated from the peak intensities.
PEGDA (molecular weights 258, 575, and 700) and PEG
(molecular weight 20,000) were obtained from Fluka (Buchs,
Switzerland). Lipase from Candida rugosa was obtained from
Sigma (St. Louis, MO, USA). PCL diol (molecular weight
2,000) was obtained from Aldrich. Acryloyl chloride, trieth-
ylamine, the UV initiator 2,2-dimethoxy-2-phenylacetophe-
none (DMPA), were all obtained from Aldrich. All other
chemicals used were of reagent grade and were used without
further purification.
Synthesis and Characterization of Diacrylated
Macromers
PEG (molecular weight 20,000) and PCL diol (molecular
weight 2,000) were end-capped with acrylate groups to
form a polymerizable macromer [14, 15]. The overall
reaction schemes for the synthesis of diacrylated macromer
and soybean oil-based crosslinked polymer networks are
shown in Fig. 2. Typically, 4.0 g of diol was dissolved in
40 ml of benzene in a 100 ml of round-bottomed flask.
Then, triethylamine and acryloyl chloride were added to
the flask at a ratio of 3 mol/mol diol. The reaction mixture
was stirred for 3 h at 75 °C. After the reaction, it was
O

O O C CH2
H2 O C
C CH2 O H
C C CH3
H2 O H2 O C H2 O C C CH C
H H2C H2 H H2
C C C C
H3C C C C CH C O CH4 OH
H H H H2 HO 3
H2C H2 H2
5 OH 9 O H
6 C CH C C
7 C C
H
CH3
H2
C O
O 8 H2C C 1
2
O

8
9

2
5 7
4 6

Fig. 1 1H-NMR spectrum of AESO

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(a) O O
in 1 ml of 1-vinylpyrrolidinone) were added to the reaction
O
H2
C
H2
C C
H2
C O
H2
C C
H2
C
H2
C O
mixture at 2% (w DMPA/w macromer) and polymerized
H C C C O C C O C C C H
H2 H2 H2
n
H2 H2 H2 H2 H2
n
for 20–50 min using a low-intensity UV lamp at 366 nm
Poly(ε-caprolactone) diol (PCL diol) under air at room temperature. Polymer samples were
Acryloyl chloride prepared as thin films with a thickness of 170 lm by
Triethylamine simple solution casting.
- HCl
CH2 O O CH2

HC O
H2
C
H2
C C
H2
C O
H2
C C
H2
C
H2
C O CH
Characterization of Crosslinked Polymer Networks
C C C C O C C O C C C C
H2 H2 H2 H2 H2 H2 H2 H2
n n
O O
Poly(ε-caprolactone) diacrylate (PCLDA) After polymerization, samples were dried under vacuum
H2 H2 O
C
O
CH2
H2
O
O
C
H2
C
O
O
C
C
H
CH2

CH3
for 24 h. The films were weighed (W1), and were then
O C O C C CH C
H C C H2C H2 H H2

extracted with chloroform for 24 h. The films were dried

C C
H3C C C C CH C O CH HO OH
H H H H2 H2 H2
H2C O H
OH C CH C C
C C H CH3

Photopolymerization H2 C O

again and weighed (W2). The gel content was calculated as

O H2C C
O

Acrylated epoxidized soybean oil (AESO)

W2/W1.
Crosslinked polymer network based on soybean oil and PCL To measure the tensile properties of the soybean oil-
based crosslinked polymer networks, the tensile tests
(b) H
H2
C O
H2
C
H2
C O
specimens with the dimension of 45 mm 9 5 mm were
O C
H2
C
H2
O
n-2
C
H2
H
prepared by cutting the sheets. Tensile tests were per-
Poly(ethylene glycol) (PEG) formed using a universal testing machine (LR-30K,
Lloyd Instruments, Hampshire, UK) at room temperature
Acryloyl chloride
Triethylamine
according to ASTM D638. The gauge length was 15 mm,
O
-HCl
CH2
and each test was performed at a constant crosshead speed
H2 H2 H2 of 20 mm/min. At least six sample specimens were tested
C C O C C O CH
HC O C
H2
C
H2
O C
H2
C for each sample to obtain an average tensile test data to
n-2
CH2 O report.
Poly(ethylene glycol) diacrylate (PEGDA)

O O C
O
CH2
Lipase Degradation
H2 O C
C CH2 O C C H CH3
H2 O H2 O C H2 O C C CH C
C C H C C H2C H2 H H2
H3C C C C CH C O CH HO OH
H H H H2 H2 H2
H2C O H
OH C CH C C

Photopolymerization
C
O
C
H2
H2C
H
C
C
O
O
CH3
Crosslinked polymer network films (initial weight: 0.18 g,
Acrylated epoxidized soybean oil (AESO) film dimensions: 30 mm 9 30 mm, and thickness: 0.17 mm)
was immersed in 100 ml of 0.1 M phosphate buffer solution
Crosslinked polymer network based on soybean oil and PEG (pH 7.2) which contains lipase enzyme (0.1 g) in sterilized
Fig. 2 Reaction schemes for the synthesis of polymerizable diacry-
conical flask. The reaction mixture was incubated at 37 °C
late and crosslinked polymer network. a AESO/PCL polymer and with shaking at 200 rpm. The films were periodically
b AESO/PEG polymer removed, rinsed with water and dried to constant weight
before analyses. Weight loss was monitored gravimetrically
filtered to remove triethylamine hydrochloride. The diac- at various intervals of time. The degradation tests were set up
rylated macromer was obtained by pouring the filtrate in a as a single film in a single flask and at different times the film
large excess of hexane. The solid precipitate was dried was withdrawn, weight loss measured, and reintroduced into
under vacuum for 24 h. the same flask.
FT-IR spectra were measured using a Bomem MB100
spectrophotometer. The 1H NMR spectra were measured
with a Bruker Avance-500 MHz spectrometer in CDCl3. Results and Discussion

Preparation of Soybean Oil-Based Crosslinked Polymer Synthesis and Characterization of Polymerizable

Networks Crosslinkers

PEGDA (molecular weights 258, 575, 700, and 20,000) or Figure 2a and b show the overall reaction schemes for the
PCLDA (molecular weight 2,000) were dissolved in chlo- synthesis of polymerizable PCLDA and PEGDA macro-
roform at 50% (w/v) concentration and mixed with AESO mers and the crosslinked polymer networks. The FT-IR
at various weight ratios. Crosslinked polymer networks spectra of PEG (molecular weight 20,000) and PEGDA are
were formed by UV photopolymerization of the mixture shown in Fig. 3a. An absorption band at 3,503 cm-1
solution. The initiator solution (0.1 g of DMPA dissolved shown in PEG is attributable to the terminal hydroxyl

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294 J Polym Environ (2010) 18:291–297

(a) 120 120

100 100

Transmittance (%)

Transmittance (%)
80 80

60 60

40 40

20 20

0 0

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumbers (cm )
-1 Wavenumbers (cm )

(b) O CH2
1
H2 H2 H2
C C O C C O CH
HC O C C O C C
H2 H2 H2
n-2
CH2 O
2

2 1

Fig. 3 a FT-IR spectra of PEG (molecular weight 20,000; left panel) and PEGDA (right panel) and b 1H-NMR spectrum of PEGDA

group, which was almost undetectable in the PEGDA due of 88%. The FT-IR and 1H NMR spectra of PCLDA were
to acrylation. The peaks at 1,722 cm-1 in the PEGDA are reported in our previous paper [15].
ascribed to the ester stretch due to the acrylate function-
alities. The formation of PEGDA was also confirmed Gel Contents and Mechanical Properties of Soybean
through the 1H NMR spectrum as shown in Fig. 3b. The Oil-Based Crosslinked Polymer Networks
vinyl groups of the PEGDA appeared within the range of
5.79–6.43 ppm. The conversion of PEG diol to PEGDA Various soybean oil-based crosslinked polymer networks
was calculated to be 98% using the integral intensities of were synthesized by altering the weight ratio of AESO to
peaks 1 (acrylate protons) and 2 (protons adjacent to the crosslinking agent, the molecular weight of PEG (258, 575,
terminal acrylate groups). PCLDA was also synthesized 700 and 20,000), and the type of crosslinking agent
from PCL diol (molecular weight 2,000) with a conversion (PEGDA and PCLDA). Crosslinked three dimensional

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J Polym Environ (2010) 18:291–297 295

100 (a) 24
elongation
98 22 tensile strength
20
96
18

Elongation at break (%)

Tensile strength (MPa)
94 16
Gel content (%)

92 14
90 12
10
88
8
86 6
84 4
82 2
0
80 95:5 80:20 60:40
20 30 40 50 Weight ratio of AESO to PEGDA258
Photopolymerization time (min)
(b) 350 12
elongation
Fig. 4 Effect of photopolymerization time on gel contents of tensile strength
polymer networks prepared from a 50:50 mixture of AESO and 300 10

Elongation at break (%)

Tensile strength (MPa)

PEGDA (molecular weight 258)
250
8
200
6
networks were formed upon free-radical polymerization 150
under UV irradiation. The extents of conversion of a 50:50 4
mixture of AESO and PEGDA (molecular weight 258) to 100
the crosslinked networks (gel content) with exposure time 50 2
to UV light are shown in Fig. 4. High gel contents over
95% were obtained with UV exposure times more than 0 0
90:10 50:50 0:100
30 min, suggesting that soybean oil-based crosslinked
Weight ratio of AESO to PEGDA20,000
polymer networks were successfully formed. The highest
gel content was 98% when the photopolymerization time (c) 45 2.0
elongation
was 40 min. 40 tensile strength

Tensile strength (MPa)

The tensile properties of various photopolymerized
Elongation at break (%)

35 1.6
networks are shown in Fig. 5. Tensile strengths of polymer
30
networks prepared from AESO and low molecular weight 1.2
25
(258, 575 and 875) PEGs ranged from 1 to 4 MPa, while
20
high molecular weight (20,000) PEG-based polymer net- 0.8
works showed higher tensile strengths (5–11 MPa). The 15

tensile strengths of PCL-based networks were lower (less 10 0.4

than 1 MPa). Elongation at breaks of polymer networks
prepared from AESO and low molecular weight PEGs
decreased with increasing PEG fraction, ranging from 10 to
20%, due to the low flexibility of low molecular weight
PEG compared with AESO. Higher elongations as 40–
200% were obtained from the networks prepared with
AESO and high molecular weight PEG because PEG
20,000 is more flexible. With PCLDA as crosslinking
agent, elongations of 28–35% were obtained. Without
crosslinking agent, polymer networks were not formed in
photopolymerization conditions used in this study. In view
of synthesizing polymers from renewable resources, it
would be desirable to use crosslinking agent as little as
possible because PEGDA and PCLDA are petroleum-
based. However, small addition of crosslinking agent (5%)
to AESO resulted in a soybean oil-based polymer network
5
0 0.0
90:10 50:50 0:100
Weight ratio of AESO to PCLDA2,000
Fig. 5 Tensile properties of polymer networks prepared from AESO
and a PEGDA (molecular weight 258), b PEGDA (molecular weight
20,000), and c PCLDA (molecular weight 2,000)
formation by UV photopolymerization. By changing the
fraction and type of crosslinking agent, tensile strengths
and elongation at breaks of the soybean oil-based polymer
networks could be controlled.
In summary, the ranges of tensile strengths and elongation
at breaks obtained were 0.5–11 MPa and 7–200%, respec-
tively. Compared with current petrochemical polymers,

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296
elongation at breaks are comparable but tensile strengths are
lower. More efforts to improve their mechanical properties
should be devoted to not only ultimately replace petroleum-
based polymers with more environmentally benign alterna-
tives, but also to benefit the agricultural community by
expanding the markets for soybean oil.
Polymer Degradation
Lipase degradation characteristics of soybean oil-based
polymer networks were investigated in phosphate buffer
solution at 37 °C (Fig. 6). Polymers prepared from a 50:50
mixture of AESO and PCLDA degraded 6% of the initial
weight in 24 days. For comparison, PCL-based polymer
networks degraded 8% of the initial weight during the same
period. The degradation of the polymer network is a
function of the crosslinking density, as well as the hydro-
lytic and enzymatic susceptibility [14, 16]. Kweon et al.
[12] reported that PCL networks formed from photopoly-
merization of PCL diol showed faster degradation behavior
than PCL itself due to the incorporation of acrylate groups
into PCL and the lower crystallinity of the PCL networks
compared to PCL itself.
Weight losses were not observed with polymers prepared
from a 50:50 mixture of AESO and PEGDA (molecular
weight 258) and PEG-based polymer networks in lipase
solution (Fig. 6), indicating that high crosslinking density of
the polymer network resulted from low molecular weight
PEG might block the lipase attack sites, i.e., the ester bonds
present in AESO. It was reported, however, that AESO/
methyl methacrylate (MMA) plastic foams were proved to
be biodegradable during soil burial [17, 18]. According to the
data, weight losses of foams prepared from a 80:20 mixture
100
PEGDA 258
99 AESO and PEGDA 258
98 AESO and PCLDA 2000
PCLDA 2000
97
Degradation (%)
96
95
94
93
92
91
90
0 5 10 15 20
Incubation time (day)
Fig. 6 Degradation curves of polymers prepared from PEGDA
(molecular weight 258), a 50:50 mixture of AESO and PEGDA
(molecular weight 258), PCLDA (molecular weight 2,000) and a
50:50 mixture of AESO and PCLDA (molecular weight 2,000)
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J Polym Environ (2010) 18:291–297
of AESO and MMA ranged from 20 to 30% of the initial
weights after 4 months of soil burial depending on the dos-
ages of initiator [17, 18]. Scanning electron microscopy
photographs of the AESO/MMA foams showed that pores of
the sample after soil burial was larger than those before soil
burial [17]. Mildew spots appeared on the foams surface after
soil burial and the destructed cell structure was detected [18].
The biodegradability of the AESO/MMA foams was also
shown by the deterioration of compression behavior after
soil burial [17].
Conclusion
We have described novel soybean oil-based photo-cross-
linked polymer networks including biodegradable AESO/
PCL polymer materials. PEGDA and PCLDA macromers
were synthesized to use as crosslinking agents. Various
soybean oil-based crosslinked polymer networks were
prepared by changing the composition of reaction mixture,
and the type and length of crosslinking agent. Tensile
strengths and elongation at breaks ranged from 0.5 to
11 MPa and 7 to 200%, respectively, depending on the
composition of reaction mixture. Weight losses were
observed with polymers prepared from AESO and PCLDA
in phosphate buffer solution containing lipase enzyme.
Acknowledgments This work was supported by grant No. R01-
2008-000-20067-0 from the Basic Research Program of the Korea
Science & Engineering Foundation and by the Ministry of Knowledge
Economy (MKE) and Korea Institute for Advancement in Technology
(KIAT) through the Workforce Development Program in Strategic
Technology.
References
1. Shogren RL, Petrovic Z, Liu Z, Erhan SZ (2004) J Polym Environ
12:173–178
2. Ashby RD, Solaiman DK (2008) J Polym Environ 16:221–229
3. Swain SN, Biswal SM, Nanda PK, Nayak PL (2004) J Polym
Environ 12:35–42
4. Bonnaillie LM, Wool RP (2007) J Appl Polym Sci 105:1042–1052
5. Petrovic ZS (2008) Polym Rev 48:109–155
6. Andjelkovic DD, Valverde M, Henna P, Li F, Larock RC (2005)
Polymer 46:9674–9685
7. Henna PH, Andjelkovic DD, Kundu PP, Larock RC (2007)
J Appl Polym Sci 104:979–985
8. Li F, Hasjim J, Larock RC (2003) J Appl Polym Sci 90:1830–
1838
9. Merrill EW (1992) In: Harris JM (ed) Poly(ethylene glycol)
25 chemistry: biotechnical and biomedical applications. Plenum
Press, New York, pp 1–14
10. Kawai F (1994) In: Doi Y, Fukuda K (eds) Biodegradable plastics
and polymers. Elsevier, Amsterdam, pp 24–38
11. Pitt CG (1990) In: Chasin M, Langer R (eds) Biodegradable
polymers as drug delivery systems. Marcel Dekker, New York,
pp 71–120
 Author's personal copy
J Polym Environ (2010) 18:291–297 297

12. Kweon HY, Yoo MK, Park IK, Kim TH, Lee HC, Lee H-S, Oh
J-S, Akaike T, Cho C-S (2003) Biomaterials 24:801–808
13. Sawhney AS, Pathak CP, Hubbell JA (1993) Macromolecules
26:581–587
14. Kim BS, Hrkach JS, Langer R (2000) Biomaterials 21:259–265
15. Lee K-S, Kim DS, Kim BS (2007) Biotechnol Bioprocess Eng
12:152–156
16. Kim BS, Hrkach JS, Langer R (2000) J Polym Sci A 38:1277–
1282
17. Wu S, Rong M, Zhang M, Hu J (2007) Acta Polym Sin 10:993–
998
18. Rong MZ, Zhang MQ, Wu SP, Wang HJ, Czigany T (2007)
Mater Sci Forum 539–543:2311–2316

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