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e-Polymers 2008, no. 156
ISSN 1618-7229

Study on the effect of galbanic acid on photo-oxidative

degradation of linear low density polyethylene (LLDPE)
films

Reza Jahanmardi,1 Homa Assempour 1*

1*
Department of Polymer Engineering, Amir Kabir University of Technology, P.O.Box
15875-4413, Tehran, Iran; fax: +98 21 66469162; e-mail: asempour@aut.ac.ir.

(Received: 22 May, 2008; published: 30 November, 2008)

Abstract: Photo-oxidative degradation of LLDPE films (~ 250 μm thick) containing

varying amounts of galbanic acid (a type of coumarin derivatives) was investigated
by exposing the films to an artificial sunlight (emitted by 300 W OSRAM Ultra-
○
Vitalux lamps) at 40 C for extended time periods. Photo-oxidative degradation of
the neat polymer film and the LLDPE films containing benzophenone (an active
photo-initiator for PE) and coumarin alone were also studied under similar
conditions for comparison. The rate of photo-oxidation was assessed by measuring
tensile properties, gel content, carbonyl index, molecular weight and density. It was
shown that galbanic acid was highly effective in accelerating photo-oxidation of
LLDPE films and an outstanding acceleration of photo-oxidation was observed for
the film containing 0.2 wt % of galbanic acid in comparison with the film containing
the same amount of benzophenone. However, the film containing coumarin did not
exhibit considerable difference in behaviour in photo-oxidation relative to the neat
LLDPE film during the exposure time. On the basis of the obtained results, the pro-
oxidant activity of galbanic acid was described in terms of activity of the functional
groups existing in the substituted moiety of its molecules.

Introduction
With the steadily expanding use of polymers and ever increasing attention being paid
to environmental pollution, the use of degradable film forming polymers has become
a crucial need [1-2]. This is because of the fact that a great part of polymer wastes
derives from packaging films which resist to biodegradation and for most of them
recycling is neither practical nor economical. The problem of degradable polymers
can be partially solved by rendering conventional plastics photo-degradable [3].
Photo-degradation of the polymers in exposure to atmospheric oxygen and under
influence of UV rays of sunlight (photo-oxidative degradation or photo-oxidation) has
potential of facilitating biodegradation by reducing the molecular weight and
introducing oxygen-containing groups into the polymer chain which also facilitates
chemical degradation.
Polyethylene (PE) in various types (LDPE, LLDPE and HDPE) is extensively used as
packaging material due to its ideal physical properties, easy production and low cost
[4-5]. However, it is well documented that this polymer does not undergo
biodegradation within a realistic period of time (10 years), due to its chemical
inertness and its high molecular weight (>100000) [6-7]. Hence, this polyolefin has
received much attention for enhancement of photo-degradability [8]. The most
frequently adopted approaches to obtain PE with enhanced photo-degradability are

1
introducing the photosensitive carbonyl groups into the polymer chain by
copolymerization with small amounts of carbon monoxide or methyl vinyl ketone or by
simply mixing photo-initiator additives (photo-sensitizers or photo-activators) with the
polymer which accelerate oxidation process under influence of UV-rays of sunlight
through the generation of free radicals [9-14]. The most studied photoactive additives
for use in polyethylene are aromatic ketones such as benzophenone and organo-
soluble transition metal compounds such as acetyl acetonates and dithiocarbamates.
Galbanic acid (GA) is a type of coumarin derivative with the structure shown in
Scheme 1. It is the major component of the resins obtained from the exudates of the
roots of plants belongs to the genus Ferula such as Ferula galbaniflua which grows
wildly and widely in Iran and surrounding areas [16-20]. This substance with many
advantages (being colorless and odorless powder with melting temperature of 96 ○C
and decomposition temperature of 220 oC) easily admixes with polyethylene. Due to
the existence of various functional groups in its molecular structure GA is expected to
accelerate photo-oxidation of polyethylene.
In this work the influence of GA on overall photo-oxidation behavior of LLDPE films
has been examined and compared to the corresponding activities of benzophenone
(as a conventional aromatic ketone photo-initiator) and coumarin as a model
compound. Coumarin, as a model compound, was taken into investigation in order to
evaluate the role of aromatic unsaturated lactone moiety of GA molecule in the
photo-oxidative degradation of PE.
Photo-oxidation of the LLDPE films containing GA (0-0.2 wt %), benzophenone
(0.2 wt %) and coumarin (0.2 wt %) was performed and the physical and chemical
changes of the films upon UV exposure were monitored by measuring tensile
properties, gel content, carbonyl index, molecular weight and density.

Scheme 1. Structure of GA

Results and discussion

Mechanical properties
Elongation at break and also ultimate tensile strength are considered to be significant
tensile properties which are more sensitive to photo-oxidation process in
polyethylene films [25-29]. Fig.s 1 and 2 illustrate the variations in percentage of
retained ultimate tensile strength (Sr) and percentage of retained elongation at break
(εr) for the tested films as a function of UV exposure time, respectively. The initial
values of both tensile properties for the formulated films with GA, benzophenone and

2
coumarin were similar to that of the neat LLDPE film. This observation indicates that
the additives do not catalyze thermal degradation of the polymer under the
processing conditions.

160
F1
140 FG-05
Retained tensile strength (%)

FG-1
120
FG-2
100 FB-2
FC-2
80

60

40

20

0
0 50 100 150 200 250 300

UV exposure time (h)

Fig. 1. Variations of percentage of retained ultimate tensile strength of LLDPE films in

terms of UV exposure time.

150
F1
FG-05
125
FG-1
Retained elongation (%)

FG-2
100 FB-2
FC-2
75

50

25

0
0 50 100 150 200 250 300
UV exposure time (h)

Fig. 2. Variations of percentage of retained elongation at break of LLDPE films in

terms of UV exposure time.

Both of εr and Sr for all formulated films increase firstly in the early stages of photo-
oxidation and then decrease steadily until the samples become brittle. Comparing the
curves in Figs. 1 and 2 clearly reveals that GA has a profound effect on the rate of

3
photo-oxidation of LLDPE, as the film containing 0.2 wt % of GA looses 50% of its
initial elongation at break over about 62 h of UV exposure whereas the film
containing 0.2 wt % of benzophenone and the neat LLDPE film must be irradiated for
75 and 105 h, respectively.
The changes in both of εr and Sr in Figs. 1 and 2 also indicate that the efficiency of
GA on accelerating the rate of photo-oxidative degradation of the polymer is
dependent on its concentration.
The variation in the mechanical properties of the film upon UV-irradiation could be
attributed to the changes in cross-linking/chain-scission ratio occurring during UV
irradiation. Thus, the initial increase in εr could be attributed to the formation of cross-
links and decreasing of its value on extended exposure times can be correlated with
the increase in the rate of chain scission, hence decreasing the molecular weight of
the polymer. Also formation of surface defects in the samples caused by the UV
radiation that propagates along the specimen might be considered to be responsible
for a premature film rupture [15, 30-32]. This deduction could be assessed by
considering the results of extraction tests carried out on the unexposed and the
photo-oxidized samples given in Tab 2. The results indicate that gel content is
increased rapidly at the early stages of photo-oxidative degradation and disappears
by a slower rate after passing a maximum. However, formation of the maximum gel
content takes a longer time than that needed for εr and Sr to reach their maxima. This
behavior seems to be a general pattern in the photo-oxidation of PE [15]. The
phenomenon is also more pronounced in the case of the samples containing GA.

Tab. 2. Effect of UV exposure time on gel content of the samples.

Gel content (%)

UV exposure time (h) F1 FG-1 FG-2
0 0.2 0.0 0.0
48 1.6 4.3 5.0
72 2.2 5.3 4.9
120 2.9 4.5 3.0
260 2.7 1.4 0.5

FTIR studies
Fig. 3 represents the FTIR spectra of the neat LLDPE film before and after different
UV exposure time intervals. The significant changes of the spectra occurred in the
carbonyl (1840-1670 cm-1), hydroxyl (3500-3300 cm-1) and vinyl (909 and 1641 cm-1)
absorption bands [33-36]. The absorption band around 1712 cm -1, which can be
assigned to the C=O stretching of a ketone group grows in intensity with the UV
exposure time and at the same time a band broadening is observed indicating the
presence of more than one type of carbonyl group. The carbonyl band can be
assigned to C=O stretching vibrations in carboxylic acid groups (1700 cm -1), ketones
(1712 cm-1), aldehydes and/or esters (1733 cm-1) and γ lactones (1780 cm-1). Similar
behavior was observed in the spectra of all other tested films. The rate of photo-
oxidative degradation of the films was determined by evaluation of carbonyl index
(CI) in different exposure time intervals.

4
Fig. 3. FTIR spectra of neat LLDPE film before and after UV exposure at 40 ºC for
different times.

12
F1
10 FG-05
FG-1
8 FG-2
FB-2
6 FC-2
CI

0
0 100 200 300 400 500 600 700 800

UV exposure time (h)

Fig. 4. Variations of carbonyl index (CI) of LLDPE films in terms of UV exposure time.

Fig. 4 shows the variations of carbonyl index (CI) of LLDPE films in terms of UV
exposure time. As it is indicated in Fig. 4, samples containing GA shows higher
increase in CI in comparison with the neat LLDPE. Meanwhile, the increase in CI is
proportional to the concentration of GA in the films. It is reported that polyethylene
films enter into the decay stage at CI greater than 6 [10]. As it is seen in Fig. 4, the
neat LLDPE film does not reach the decay stage even after 600 h of UV irradiation,
whereas the sample containing 0.2 wt % of GA entered into the decay stage after
about 400 h of UV irradiation. Furthermore, increase in CI for the film containing 0.2%

5
wt of GA is much more than that of the film containing 0.2 wt % of benzophenone.
This observation implies that GA is much more effective than benzophenone in
enhancing the rate of LLDPE photo-oxidation. On the other hand, similar changes in
CI are observed for the neat LLDPE film and the film containing 0.2 wt % of coumarin
with UV exposure time. So, it might be concluded that coumarin structure has little
effect on enhancing the photo-oxidative degradation of LLDPE.

Molecular weight measurements

It has been reported that PE films containing pro-oxidants enter into the
embrittlement stage after their Mn decrease to less than 5000 g/mol [33]. Fig. 5
shows the effect of UV exposure time on the viscosity-average molecular weight (Mv)
of the samples. Fig. 5 reveals that while the neat LLDPE film and the film containing
0.2 wt % coumarin show relatively low changes in Mv upon UV exposure up to 600 h,
the LLDPE films containing 0.1 and 0.2 wt % of GA undergo significant changes in Mv
so that the Mv for the films containing 0.2 wt % of GA reaches to 5500 g/mol after 600
h of UV exposure. However, only the films containing 0.2 wt % of GA became fragile
upon UV exposure and its Mv decreased to a level that it approximately entered into
the embrittlement stage.

80
F1
70 FG-05
Molecular weight, Mv (kg/mole)

FG-1
FG-2
60 FB-2
FC-2
50

40

30

20

10

0
0 100 200 300 400 500 600 700

UV exposure time (h)

Fig. 5. Effect of UV exposure time on viscosity-average molecular weight (Mv) of

LLDPE films.

Density measurements
The effect of UV exposure time on density of LLDPE films is illustrated in Fig. 6. As it
is indicated, the density of the neat LLDPE film increases marginally from 0.920 to
0.941 g/cm3 after 600 h of UV exposure. At the same time, the film containing
0.2 wt % of GA shows a pronounced increase in density so that its density reaches
0.961 g/cm3. Increase in density is also proportional to the concentration of GA in the
films. The increase in density upon UV and/or heat exposure has been explained
considering the increase of crystallinity attributed to the decrease of the molecular
weight [30]. Moreover, the incorporation of oxygen into the amorphous regions of the

6
polymer via the formation of oxygen-containing groups can also be considered to be
responsible for the increase of the density [34].
As a whole, the results obtained from photo-oxidation experiments carried out on the
neat LLDPE film and the film containing 0.2 wt % of coumarin, it was proved that
aromatic unsaturated lactone moiety of GA does not play an important role in the
photo-oxidation of LLDPE. Thus, photo-activity of GA is supposed to arise from the
activity of the carboxylic acid group and/or the C=C bond existing in the substituted
moiety of its molecules. Although it is very difficult to find out the exact mechanism by
which GA promotes photo-oxidative degradation of the polymer, but it might be
assumed that this additive could act through the following reactions to induce photo-
oxidation process:
1. The probable reaction related to the C=C bond: The C=C bond can react with
singlet oxygen to give an allylic hydroperoxide via an "ene" reaction mechanism,
according to equation (1) [37-39].

(1)
Photo-decomposition of the formed hydroperoxide leads to formation of an alkoxy
and a hydroxyl radical. Hydrogen abstraction from the backbone of the polymer
chains by these radicals leads to formation of macromolecular alkyl radical. It is also
noteworthy that electronically excited O2 molecule, i.e., singlet oxygen, can itself be
produced by the electronic energy transfer from the n—π* triplet states of carbonyl
groups to the molecular oxygen, according to equation (2) [37-39].

(2)

0.97
F1
0.96 FG-05
FG-1
FG-2
0.95
Density (g/cc)

FB-2
FC-2
0.94

0.93

0.92

0.91
0 200 400 600 800

UV exposure time (h)

Fig. 6. Effect of UV exposure time on density of LLDPE films.

7
2. The probable reactions related to the carboxylic acid group: The pro-oxidant
activity of carboxylic acids can be attributed to the ease of hydrogen abstraction from
the acidic groups by peroxy radicals, according to equation (3) [35,40].

(3)
where, POOH is the macromolecular hydroperoxide. It is also reported that
bimolecular interaction between carboxylic acid and hydroperoxide leads to formation
of free radicals, according to equation (4) [41].

(4)

Conclusions
On the basis of the data gathered through examination of photo-oxidative degradation
of the LLDPE films, it is concluded that GA is a powerful photoactive reagent. The
efficiency of this new additive in enhancing photo-oxidative degradation of PE is much
more than that of even benzophenone, a conventional photo-initiator. Therefore, it
seems that GA is promising with regard to industrial use in PE films to combat
pollution caused by the discarded PE packaging films.

Experimental part

Materials
Additive free film grade LLDPE (LL-0209AA) was supplied as a powder by Arak
Petrochemical Co. Iran (MFI = 0.9 g/10 min and ρ = 0.920 g/cm3). GA was extracted
from galbanum resin (the resin obtained from the exudates of the roots of the plant
Ferula galbaniflua) available in Tehran market (Iran) with the aid of column
chromatography according to a procedure described by Iranshahi et al. [18]. All other
chemicals used in this study were purchased from Merck KGaA.
Film Preparation
LLDPE was incorporated with GA, coumarin and benzophenone alone at 160 oC in a
brabender internal mixer with a rotor rate of 60 rpm within 6 minutes and converted
into the films with a thickness of about 250 μm at 170 oC within 2 minutes with the aid
of a laboratory hot press. A film without additive was also prepared under the same
conditions as the formulated blank sample. The formulations of the prepared films are
given in Tab. 1.

Photo-oxidation procedure
LLDPE films were subjected to an accelerated photo-oxidation in a UV cabinet
equipped with four 300 W OSRAM Ultra-Vitalux sunlamps emitting artificial sunlight
with the same spectral radiation distribution of solar spectrum [21]. Samples were
mounted on the racks positioned at a distance of 25 cm from the lamps and the
temperature in the cabinet was maintained at 40 ± 1 ºC. The samples were collected

8
at different intervals to evaluate the effect of irradiation time on the photo-oxidation of
the films.

Tab. 1. Formulation of LLDPE films used for photo-oxidative degradation studies.

Sample
LLDPE (wt %) GA (wt %) Coumarin (wt %) Benzophenone (wt %)
designation
F1 100 - - -
FG-05 100 0.05 - -
FG-1 100 0.1 - -
FG-2 100 0.2 - -
FC-2 100 - 0.2 -
FB-2 100 - - 0.2

Evaluation of photo-oxidation
Mechanical properties of LLDPE films, i.e. tensile strength and elongation at break,
were measured, using a GALDABINI machine model Sun 2500 (Italy). The test
specimens with the length of 100 mm and width of 10 mm were cut from each of the
investigated films according to ASTM D 882-95a. The tests were carried out in an air
conditioned environment at 25 ○C and a relative humidity of 40%. The speed of
testing was 500 mm/min for samples with elongation at break greater than 100% and
25mm/min for those with elongation at break less than 100%. About five specimens
were tested for each experiment and average value was taken. The values of
elongation at break after an exposure time of t, in hours, (εt) and before exposure to
UV (εo) for a given sample were used for calculation of percentage of retained
elongation at break (εr) which is defined as:
εr = (εt /εo) 100. (5)
The percentage of retained ultimate tensile strength (Sr) was also calculated in the
same manner.
The structural changes of the polymer samples upon UV-irradiation were followed by
FTIR spectroscopy. FTIR spectra were recorded at different intervals using a Bomem
FTIR spectrophotometer. The spectra were taken as an average of 20 scans at a
resolution of 4 cm-1 in the range of 4000-400 cm-1.
The rates of photo-oxidative degradation of the polymer films were determined by
evaluation of carbonyl index (CI) in different exposure time intervals, based on the
following equation:
CI = A(1712) / A(2019) - CI0 (6)
where, A is the absorbance at the given wavenumber and CI0 is the original carbonyl
index. Absorption band at 2019 cm-1 was selected as an internal thickness band in
order to minimize the errors arising from the samples thickness [22]. CIo were
subtracted in order to remove the influence of the original carbonyl groups, so that,
the results only stand for the changes happened during the photo-oxidative
degradation process.
Gel content was determined according to ASTM D 2765-95. Approximately 0.3 g of
each sample was immersed in boiling p-xylene for 12 h using a specimen holder

9
made of 120-mesh stainless steel wire cloth and then dried under vacuum. The gel
fraction was determined from the insoluble residue.
The molecular weights of the samples were determined by dilute solution
viscometery. Films were dissolved in p-xylene and the intrinsic viscosity [η] was
measured using an Ubbelohde viscometer immersed in a silicon oil bath at 105 ○C.
The viscosity-average molecular weight (Mv) was calculated using the following
equation [23-24]:
[η]=16.5 × 10-3 Mv0.83 (7)
Density was measured on a density gradient column (DGC) according to ASTM
D1505-85. Two specimens were prepared from each sample. Density of a sample
was determined by submerging the specimens in a DGC of isopropanol and distilled
water containing calibrated density floats. Before insertion into the DGC, each
specimen was wetted with a 50/50 solution of isopropanol and water for 15 min. Each
sample was then gently placed into the column and allowed to reach equilibrium for
10 minutes before a reading was taken. All density measurements were performed at
25 ○C.

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