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ISSN 1566-2543
Volume 18
Number 3
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J Polym Environ (2010) 18:291–297
DOI 10.1007/s10924-010-0174-3
ORIGINAL PAPER
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292 J Polym Environ (2010) 18:291–297
delivery devices by the US Food and Drug Administration. shown in Fig. 1. It has an average of three acrylates per tri-
Cellular compatibility of crosslinked PCL networks has also glyceride, which can be calculated from the peak intensities.
been reported [12]. By photopolymerization, biodegradable PEGDA (molecular weights 258, 575, and 700) and PEG
crosslinked polymer networks based on PEG-co-poly (molecular weight 20,000) were obtained from Fluka (Buchs,
(a-hydroxy acid) diacrylate macromers have been synthe- Switzerland). Lipase from Candida rugosa was obtained from
sized for biomedical applications [13, 14]. Sigma (St. Louis, MO, USA). PCL diol (molecular weight
In this study, we prepared novel soybean oil-based poly- 2,000) was obtained from Aldrich. Acryloyl chloride, trieth-
mer networks which can be potentially used as biodegrad- ylamine, the UV initiator 2,2-dimethoxy-2-phenylacetophe-
able and biocompatible materials for various biomedical none (DMPA), were all obtained from Aldrich. All other
and other applications. PEG diacrylate (PEGDA) and PCL chemicals used were of reagent grade and were used without
diacrylate (PCLDA) were synthesized and used as cross- further purification.
linking agent to prepare polymer networks by UV-initiated
free-radical polymerization with acrylated epoxidized soy-
bean oil (AESO). Photopolymerization reaction conditions Synthesis and Characterization of Diacrylated
were changed to obtain crosslinked polymer networks with Macromers
various mechanical properties. Lipase degradability was
studied by measuring weight loss in phosphate buffer solu- PEG (molecular weight 20,000) and PCL diol (molecular
tion (pH 7.2). 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
Experimental Part and soybean oil-based crosslinked polymer networks are
shown in Fig. 2. Typically, 4.0 g of diol was dissolved in
Materials 40 ml of benzene in a 100 ml of round-bottomed flask.
Then, triethylamine and acryloyl chloride were added to
AESO was obtained from Aldrich (Milwaukee, WI, USA). the flask at a ratio of 3 mol/mol diol. The reaction mixture
The chemical structure and 1H NMR spectrum of AESO is 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
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J Polym Environ (2010) 18:291–297 293
(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
Photopolymerization H2 C O
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
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
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
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
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
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296 J Polym Environ (2010) 18:291–297
elongation at breaks are comparable but tensile strengths are of AESO and MMA ranged from 20 to 30% of the initial
lower. More efforts to improve their mechanical properties weights after 4 months of soil burial depending on the dos-
should be devoted to not only ultimately replace petroleum- ages of initiator [17, 18]. Scanning electron microscopy
based polymers with more environmentally benign alterna- photographs of the AESO/MMA foams showed that pores of
tives, but also to benefit the agricultural community by the sample after soil burial was larger than those before soil
expanding the markets for soybean oil. burial [17]. Mildew spots appeared on the foams surface after
soil burial and the destructed cell structure was detected [18].
Polymer Degradation The biodegradability of the AESO/MMA foams was also
shown by the deterioration of compression behavior after
Lipase degradation characteristics of soybean oil-based soil burial [17].
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 Conclusion
weight in 24 days. For comparison, PCL-based polymer
networks degraded 8% of the initial weight during the same We have described novel soybean oil-based photo-cross-
period. The degradation of the polymer network is a linked polymer networks including biodegradable AESO/
function of the crosslinking density, as well as the hydro- PCL polymer materials. PEGDA and PCLDA macromers
lytic and enzymatic susceptibility [14, 16]. Kweon et al. were synthesized to use as crosslinking agents. Various
[12] reported that PCL networks formed from photopoly- soybean oil-based crosslinked polymer networks were
merization of PCL diol showed faster degradation behavior prepared by changing the composition of reaction mixture,
than PCL itself due to the incorporation of acrylate groups and the type and length of crosslinking agent. Tensile
into PCL and the lower crystallinity of the PCL networks strengths and elongation at breaks ranged from 0.5 to
compared to PCL itself. 11 MPa and 7 to 200%, respectively, depending on the
Weight losses were not observed with polymers prepared composition of reaction mixture. Weight losses were
from a 50:50 mixture of AESO and PEGDA (molecular observed with polymers prepared from AESO and PCLDA
weight 258) and PEG-based polymer networks in lipase in phosphate buffer solution containing lipase enzyme.
solution (Fig. 6), indicating that high crosslinking density of
the polymer network resulted from low molecular weight Acknowledgments This work was supported by grant No. R01-
2008-000-20067-0 from the Basic Research Program of the Korea
PEG might block the lipase attack sites, i.e., the ester bonds Science & Engineering Foundation and by the Ministry of Knowledge
present in AESO. It was reported, however, that AESO/ Economy (MKE) and Korea Institute for Advancement in Technology
methyl methacrylate (MMA) plastic foams were proved to (KIAT) through the Workforce Development Program in Strategic
be biodegradable during soil burial [17, 18]. According to the Technology.
data, weight losses of foams prepared from a 80:20 mixture
References
100
PEGDA 258
99 AESO and PEGDA 258
1. Shogren RL, Petrovic Z, Liu Z, Erhan SZ (2004) J Polym Environ
12:173–178
98 AESO and PCLDA 2000
2. Ashby RD, Solaiman DK (2008) J Polym Environ 16:221–229
PCLDA 2000
97 3. Swain SN, Biswal SM, Nanda PK, Nayak PL (2004) J Polym
Degradation (%)
96 Environ 12:35–42
4. Bonnaillie LM, Wool RP (2007) J Appl Polym Sci 105:1042–1052
95 5. Petrovic ZS (2008) Polym Rev 48:109–155
94 6. Andjelkovic DD, Valverde M, Henna P, Li F, Larock RC (2005)
Polymer 46:9674–9685
93
7. Henna PH, Andjelkovic DD, Kundu PP, Larock RC (2007)
92 J Appl Polym Sci 104:979–985
91 8. Li F, Hasjim J, Larock RC (2003) J Appl Polym Sci 90:1830–
1838
90 9. Merrill EW (1992) In: Harris JM (ed) Poly(ethylene glycol)
0 5 10 15 20 25 chemistry: biotechnical and biomedical applications. Plenum
Incubation time (day) Press, New York, pp 1–14
10. Kawai F (1994) In: Doi Y, Fukuda K (eds) Biodegradable plastics
Fig. 6 Degradation curves of polymers prepared from PEGDA and polymers. Elsevier, Amsterdam, pp 24–38
(molecular weight 258), a 50:50 mixture of AESO and PEGDA 11. Pitt CG (1990) In: Chasin M, Langer R (eds) Biodegradable
(molecular weight 258), PCLDA (molecular weight 2,000) and a polymers as drug delivery systems. Marcel Dekker, New York,
50:50 mixture of AESO and PCLDA (molecular weight 2,000) pp 71–120
123
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 16. Kim BS, Hrkach JS, Langer R (2000) J Polym Sci A 38:1277–
J-S, Akaike T, Cho C-S (2003) Biomaterials 24:801–808 1282
13. Sawhney AS, Pathak CP, Hubbell JA (1993) Macromolecules 17. Wu S, Rong M, Zhang M, Hu J (2007) Acta Polym Sin 10:993–
26:581–587 998
14. Kim BS, Hrkach JS, Langer R (2000) Biomaterials 21:259–265 18. Rong MZ, Zhang MQ, Wu SP, Wang HJ, Czigany T (2007)
15. Lee K-S, Kim DS, Kim BS (2007) Biotechnol Bioprocess Eng Mater Sci Forum 539–543:2311–2316
12:152–156
123