Journal of Radiation Industry 5 (2) : 107~112 (2011)

Electron Beam-induced Crosslinking and

Characterization of Polycaprolactone Films
in the Presence of Various Crosslinking Agents

Dong-Woo Kang, Chan-Hee Jung, In-Tae Hwang, Jae-Hak Choi* and Young-Chang Nho
Radiation Research Division for Industry and Environment, Advanced Radiation Technology Institute,
Korea Atomic Energy Research Institute, Jeongeup 580-185, Korea

Abstract - Electron beam-induced crosslinking of polycaprolactone (PCL) films containing various

crosslinking agents (CAs) was investigated in this study. PCL films containing various CAs prepared
by a solution casting method were irradiated by electron beams at various absorption doses and
the irradiated PCL films were investigated in terms of their crosslinking degree, thermal and
mechanical properties, and biodegradability. Based on the results of the crosslinking degree mea-
surement, triallyl isocyanurate was found to be most effective for the electron-beam induced cross-
linking of PCL films. The results of the UTM, DMA, and TMA revealed that the thermal and
mechanical properties of the crosslinked PCL films were greatly improved in comparison to those
of the pure PCL. The results of the enzymatic degradation test revealed that the biodegradability
of the crosslinked PCL films was reduced in comparison to that of the pure PCL.

Key words : Electron beam, Crosslinking agent, Crosslinking, Polycaprolactone, Thermal and
mechanical properties, Biodegradability

Among these biodegradable polymers, PCL has recently

INTRODUCTION
gained significant attention due to its diversity, biocompati-
biltiy, and good biodegradability. However, diverse applica-
The development of biodegradable polymers has attracted
tions of PCL have been restricted due to its low heat stabili-
significant attention due to the growing cognition of the need
ty, low processability, and poor mechanical properties (Darwis
to minimize the environmental pollution brought about by
1998). Thus, various techniques including crosslinking,
non-biodegradable polymer wastes (Gross and Kalar 2002;
composites with inorganic fillers, and blending with other
Vroman and Tighzert 2009). During the past decade, signifi-
polymers have been developed to make up for those draw-
cant advances have been made in the development of bio-
backs of PCL (Averous et al. 2000; Wu 2004; Wang et al.
degradable polymers with excellent properties comparable
2008). Among these techniques, crosslinking has been pre-
to those of petroleum-based polymers (Song et al. 2009). A
ferred since it is a facile and effective method to improve
variety of biodegradable polymers including polylactide,
thermal and mechanical stability (Huang et al. 2009).
poly(butylene succinate), poly(3-hydroxybutyrate), and
The crossinking of PCL has been carried out mainly by
polycaprolactone(PCL) have been developed as alternatives
radiation and peroxide techniques. The radiation-induced
for non-biodegradable polymers (Sodergard 2004).
crosslinking technique is quite fascinating in terms of the
crosslinking of PCL because it offers several advantages
* Corresponding author: Jae-Hak Choi, Tel. +82-63-570-3062,
Fax. +82-63-570-3090, E-mail. jaehakchoi@kaeri.re.kr such as an eco-friendly process, precise controllability, tem-

─ 107 ─
108 Dong-Woo Kang, Chan-Hee Jung, In-Tae Hwang, Jae-Hak Choi and Young-Chang Nho

perature-independence, and low energy consumption (Clen- (Daejeon, Korea). The energy and current density of the
land et al. 2003; Chmielewski et al. 2005). Thus, the cross- electron beams were 2 MeV and 1 mA cm-2, respectively.
linking of PCL by using high energy radiation in the pres- The total absorption dose ranged from 10 to 200 kGy.
ence or absence of crosslinking agents has been carried out
to improve its thermal and mechanical properties (Yoshii et 3. Characterization
al. 2000; Zhu et al. 2003; Abdel-Rehim et al. 2004). How-
The crosslinking degree of the irradiated PCL films with
ever, the electron beam-induced crosslinking of PCL films
or without CA was estimated by measuring their insoluble
in the presence of various kinds of crosslinking agents (CAs)
part in the dried sample after extraction in chloroform for
and the characterization of the crossinked PCL in multilater-
24 h. The crosslinking degree was calculated from the follow-
al aspects have been little studied.
ing equation:
In this article, the electron beam-induced crosslinking of
polycaprolactone (PCL) films in the presence of various CAs =W2/W1×100,
Crosslinking degree (%)=
was performed. The effects of the type and concentration of
where W1 and W2 are the weights of the dried sample before
CA on the electron beam-induced crosslinking of PCL films
and after extraction in chloroform, respectively.
was investigated. Moreover, the physical properties and
The tensile strength and elongation-at-break were measured
biodegradation of crosslinked PCL films were examined.
using a universal testing machine (Model 4210, Instron
Engineering Co., USA) according to the ASTM Standard
MATERIALS AND METHODS D638. The dynamic mechanical analysis was carried out by
using a dynamic mechanical analyzer (DMA, Q800 model,
1. Preparation of polycaprolactone films containing TA Instrument) under film-tension mode in a temperature
crosslinking agents range of -80 to 200� C min-1 and a
C at a heating rate of 5�

Polycaprolactone (PCL, MW: 80000) and chloroform were frequency of 1 Hz. The thermomechanical analysis (TMA)

purchased from Aldrich and Showa chemical companies, was performed on a TMA Q400 system (TA Instrument,
respectively. Triallyl isocyanurate (TAIC), trimethylolpropane USA) using an extension probe between 20 and 200�
C at a
triacrylate (TMPTA), and 1,6-hexanediol diacrylate (HDDA) C min-1 under a nitrogen atmosphere. The
heating rate of 5�
purchased from Aldrich were used as crosslinking agents enzymatic degradation test was carried out using lipase

(CAs). All the chemicals were utilized without further puri- enzymes that were extracted from Pseudomonas fluorescens

fication. PCL films containing various CAs were fabricated and their activity was about 300 units mg-1. The samples (2

using a solvent casting method. The content of CA in the ×2 cm square shaped films) were immersed in 2 ml of a

final composition was defined as the ratio of the CA mass phosphate buffer solution containing 100 μg ml-1 of lipase

to the total mass of the PCL films. Briefly, 10 wt% PCL enzymes at 37�
C. After incubation for a certain time, the

solutions with or without CA were prepared by dissolving resulting films were removed from the enzymatic solution,

PCL and CA in chloroform. The prepared solutions were washed with distilled water several times, and dried under a

cast on well-cleaned glasses and then placed in a fume hood vacuum at room temperature to a constant weight. The bio-

at room temperature for 4 h. Afterwards, to remove the degradation was estimated by measuring the ratio of weight

remaining solvent and moisture, the films were further dried loss to the initial weight of the films. The weight loss was
in a vacuum oven at 30�
C for 24 h. The thickness of the result- measured based on a decrease of the weight of the films
ing films was around 130 μm. before and after the enzymatic degradation. The experiment
was repeated three times to minimize the experimental error.
2. Electron beam irradiation

The prepared PCL films with or without CA were put into RESULTS AND DISCUSSION
aluminum pouches and thermally sealed after purging with
nitrogen gas. The samples were irradiated at room tempera- To investigate the electron beam-induced crosslinking
ture with an ELV-3 e-beam accelerator installed at EB-Tech behavior of PCL films in the presence of various CAs, the
 Electron Beam-induced Crosslinking of Polycaprolactone 109

crosslinking degrees of the pure PCL and PCL containing 100

different types of CAs irradiated at various doses were mea-

TAIC
sured and the results are shown in Fig. 1. The crosslinking 80

Crosslinking degree (%)

degree of the irradiated pure PCL was only 5.7% even at an
60
absorption dose of 100 kGy. On the other hand, the cross-
TMPTA
linking degree of PCL films containing various CAs exhibit-
40
ed a much higher crosslinking degree in comparison of that HDDA
of pure PCL. Among PCL films with various CAs, those 20
containing TAIC exhibited the highest crosslinking degree pure PCL
up to 80.9% at 100 kGy. Moreover, to find the optimal con- 0
tent of TAIC for the electron beam-induced crosslinking of
0 20 40 60 80 100
PCL films, the PCL films containing different contents of
Absorption dose (kGy)
TAIC were irradiated and their crosslinking degrees were
Fig. 1. Crosslinking degree of the pure PCL and PCL films contain-
measured. Fig. 2 shows the crosslinking degree of PCL films ing 1 wt% of various crosslinking agents as a function of
containing different contents of TAIC as a function of the the absorption dose.
absorption dose. At an absorption dose of less than 50 kGy,
the PCL films containing 1 wt% TAIC had a slightly higher
100
crosslinking degree than the other PCL films containing 3,
5, and 7 wt% TAIC. However, at an absorption dose of more 80
than 50 kGy, the crosslinking degrees of all the PCL films
Crosslinking degree (%)

containing different contents of TAIC were almost similar. 60 5 wt% TAIC

These results indicate that an increase in the TAIC contents 3 wt% TAIC
7 wt% TAIC
can not further enhance the electron beam-induced crosslink- 40 1 wt% TAIC
ing efficiency of PCL. Therefore, among crosslinking agents,
20
TAIC was found to be the most effective for the radiation- pure PCL
induced crosslinking of PCL, and the optimal concentration
0
of TAIC was considered as to be 3 wt% in this system. In
this study, the crosslinked PCL films containing 3 wt% TAIC 0 50 100 150 200

were further used to investigate their properties and biode- Absorption dose (kGy)

gradability . Fig. 2. Crosslinking degree of the pure PCL and PCL films contain-
ing various amounts of TAIC as a function of the absorption
The changes in the tensile strength and elongation-at-break
dose.
of the pure PCL and PCL films containing 3 wt% TAIC after
electron beam irradiation at various absorption doses were
investigated and the results are shown in Fig. 3. As shown pure PCL. These changes in properties could be due to the
in Fig. 3(a), the tensile strength of the irradiated pure PCL more effective formation of the crosslinked structure in the
film was slightly increased to 16.89 MPa with an increasing PCL film induced by electron beam irradiation in the pres-
absorption dose. On the other hand, the tensile strength of ence of TAIC (Jin et al. 2002).
the irradiated PCL containing 3 wt% TAIC was gradually The dynamic viscoelastic properties of the pure PCL and
increased up to 19.2 MPa with an increasing dose of up to PCL films containing 3 wt% TAIC irradiated at various
150 kGy, over which it seemed to level off. As shown in Fig. absorption doses was investigated by DMA. Fig. 4(a) shows
3(b), the elongation-at-break of the pure PCL film was sig- the storage modulus of the pure PCL films irradiated at vari-
nificantly reduced with an increasing absorption dose. Like- ous absorption doses. The non-irradiated pure PCL film
wise, in the case of the PCL film containing 3 wt% TAIC, exhibited a sharp drop in the storage modulus (E′) above its
the elongation-at-break was diminished, but the extent of melting temperature due to the melting of the crystalline
diminution was much smaller in comparison to that in the domains. In the case of the irradiated pure PCL films, the
110 Dong-Woo Kang, Chan-Hee Jung, In-Tae Hwang, Jae-Hak Choi and Young-Chang Nho

20
(a) 1000 (b)
19
800

Elongation at break (%)

Tensile strength (MPa)

18 3 wt% TAIC
600 3 wt% TAIC
17
400
16
200 pure PCL
15 pure PCL
0
14
0 50 100 150 200 0 50 100 150 200
Absorption dose (kGy) Absorption dose (kGy)

Fig. 3. Tensile strength (a), and elongation-at-break (b) of the pure PCL and PCL films containing 3 wt% TAIC as a function of the absorption
dose.

4 (a) 4 (b)
3 3

2 2
Log E′ (Pa)

Log E′ (Pa)

1 1

0 0
0 kGy

-1 10 kGy -1
200 kGy 20 kGy 200 kGy
20 kGy 10 kGy
-2 -2 50 kGy 150 kGy
50 kGy 150 kGy 0 kGy 100 kGy
-3 -3
100 kGy
40 50 60 70 80 90 100 40 80 120 160 200
Temperature (�
C) Temperature (�
C)

Fig. 4. Storage modulus of the pure PCL and PCL films containing 3 wt% TAIC at various absorption doses.

temperature for a sharp transition in E′ was slightly increas- in Fig. 5. The pure PCL film revealed a high deformation
ed with an increasing absorption dose. On the other hand, near its melting temperature. After irradiation, the deforma-
as shown in the Fig. 3(b), the irradiated PCL films containing tion temperature of the pure PCL film was slightly shifted
3 wt% TAIC exhibited a higher temperature for the sharp to a lower temperature. In the case of the non-irradiated
transition in E′ at the same dose in comparison to that of the PCL film containing 3 wt% TAIC, the deformation tempera-
pure PCL film, which was dependent on the absorption dose. ture was shifted to a lower temperature in comparison to that
This result can be ascribed to the greater formation of the of the pure PCL. On the other hand, the irradiated PCL film
crosslinked structure in the PCL films containing 3 wt% containing 3 wt% TAIC showed a much lower deformation
TAIC (Nugroho et al. 2001). at higher temperature. Thus, this improved heat stability of
To investigate the crosslinking effect on the thermal stabi- PCL films can be attributed to the formation of network
lity of PCL film that is generally required in polymer pro- structures in the PCL (Suhartini et al. 2003).
cessing at a high temperature, the pure PCL and PCL films To examine the crosslinking effect on the biodegradability
containing 3 wt% TAIC irradiated at an absorption dose of of PCL films, an enzymatic degradation test was performed
100 kGy were analyzed by TMA and the results are present and the results are shown in Fig. 6. The non-irradiated PCL
 Electron Beam-induced Crosslinking of Polycaprolactone 111

films in the presence of CAs was investigated in this study.

3500
Based on the results of the crosskining degree measurement,
3000
pure PCL at 0 kGy PCL was more effectively crosslinked in the presence of
Dimension change (μm)

2500 pure PCL at 100 kGy CA by electron beam irradiation than in the absence of CA.
2000 Among the CAs, triallyl isocyanurate (TAIC) was found to
1500 3 wt% TAIC at 0 kGy be most effective for the radiation-induced crosslinking of
1000 PCL, and the optimal concentration of TAIC was considered
3 wt% TAIC at 100 kGy
500
to 3 wt% in this system. The tensile strength of the irradiated
PCL films containing 3 wt% TAIC was increased with an
0
increasing absorption dose, whereas the elongation-at-break
-500
30 40 50 60 70 80 90 100 was relatively reduced in comparison of that of the pure
Temperature (�
C) PCL. The DMA results showed that the irradiated PCL films
Fig. 5. TMA heating curves of the pure PCL, irradiated pure PCL, containing 3 wt% TAIC had a much higher and wider rubbery
and irradiated PCL films containing 3 wt% TAIC at an
state plateau in comparison with the pure PCL. The TMA
absorption dose of 100 kGy.
results revealed that the irradiated PCL films containing 3
wt% TAIC had a much higher heat stability than that of the
pure PCL. The biodegradability of the irradiated PCL films
100
containing 3 wt% TAIC was much reduced with an increas-
80 0 kGy ing absorption dose. These changes in the physical properties
10 kGy
and biodegradability can be ascribed to the formation of
Weight loss (%)

60 crosslinked structures in the PCL films caused by electron

beam irradiation in the presence of TAIC.
100 kGy
40 20 kGy 50 kGy

20 ACKNOWLEDGMENTS
200 kGy
150 kGy
0
This research was supported by Nuclear R&D program
0 200 400 600 800 1000 1200 1400
through the National Research Foundation funded by the
Time (h)
Ministry of Education, Science and Technology, Korea.
Fig. 6. Weight loss of PCL films containing 3 wt% TAIC irradiated
at various absorption doses in enzymatic degradation test.

REFERENCES
film containing 3 wt% TAIC was degraded up to almost
more than 95% after an enzymatic degradation reaction for Abdel-Rehim HA, Yoshii F and Kume T. 2004. Modification
120 h. However, for the irradiated PCL films containing 3 of polycaprolactone in the presence of polyfunctional mono-
mers by radiation and its biodegradability. Polym. Degrad.
wt% TAIC, a degradation of less than 50% was achieved
Stab. 85:689-695.
even after a reaction for 1,320 h, which was dependant on
Averous L, Moro L, Dole P and Fringant C. 2000. Properties
the absorption dose. This result indicates that the formation of thermoplastic blends: starch-polycaprolactone. Polymer
of crosslinked structures in the PCL film caused by electron 41:4157-4167.
beam irradiation in the presence of TAIC diminished its Chmielewski AG, Haji-Saeid M and Ahmed S. 2005. Progress
biodegradability. in radiation processing of polymers. Nucl. Instrum. Meth.
B 236:44-54.
Cleland MR, Parks LA and Cheng S. 2003. Applications for
CONCLUSION radiation processing of materials. Nucl. Instrum. Meth. B
208:66-73.
The electron beam-induced crosslinking behavior of PCL Darwis D, Mitomo H, Enjoji T, Yoshii F and Makuuchi K. 1998.
112 Dong-Woo Kang, Chan-Hee Jung, In-Tae Hwang, Jae-Hak Choi and Young-Chang Nho

Heat resistance of radiation crosslinked poly(ε-caprolac- 2003. Raidition crosslinking of poly(butylene succinate) in
tone). J. Appl. Polym. Sci. 68:581-588. the presence of low concentrations of trimethallyl isocyanu-
Gross RA and Kalra B. 2002. Biodegradable polymers for the rate and its properties. J. Appl. Polym. Sci. 88:2238-2246.
envrionment. Science 297:803-807. Vroman I and Tighzert L. 2009. Biodegradable polymers. Ma-
Huang X, Li C, Zhu W, Zhang D, Guan G and Xiao Y. 2009. terials 2:307-344.
Ultraviolet-induced crosslinking of poly(butylene succinate) Wang S, Yaszemski MJ, Gruetzmacher JA and Lu L. 2008.
and its thermal property, dynamic mechnical property, and Photo-crosslinked poly(ε-caprolactone fumarate) networks:
biodegradability. Polym. Adv. Technol. in press. roles of crystallinity and crosslinking density in determining
Jin F, Hyon S-H, Iwata H and Tsutsumi S. 2002. Crosslinking mechanincal properties. Polymer 49:5692-5699.
of poly(Ｌ-lactic acid) by γ-irradiation. Macromol. Rapid Wu C-S. 2004. In situ polymerization of titanium isopropoxide
Commun. 23:909-912. in polycaprolactone: properties and characterization of the
Nugroho P, Mitomo H, Yoshii F, Kume T and Nishimura K. hybrid nanocomposites. J. Appl. Polym. Sci. 92:1749-1757.
2001. Improvement of processability of PCL and PBS blend. Yoshii F, Darwis D, Mitomo H and Makuuchi K. 2000. Cross-
Macromol. Mater. Eng. 286:316-323. linking of poly(ε-caprolactone) by radiation technique and
Sodergard A. 2004. Perspectives on modification of aliphatic its biodegradability. Rad. Phys. Chem. 57:417-420.
polyesters by radiation processing. J. Bioact. Compat. Zhu G, Liang G and Yu Q. 2003. Shape-memory effects of
Polym. 19:511-525. radiation crossliked poly(ε-caprolactone). J. Appl. Polym.
Song JH, Murphy RJ, Narayan R and Davies GBH. 2009. Bio- Sci. 90:1589-1595.
degradable and compostable alternatives to conventional
plastics. Phil. Trans. R. Soc. B 364:2127-2139. Manuscript Received: April 29, 2011
Suhartini M, Mitomo H, Nagasawa N, Yoshii F and Kume T. Revision Accepted: May 27, 2011