Polymer Degradation and Stability 61 (1998) 329-342

0 1998 Elsevier Science Limited. All rights reserved

Printed in Great Britain
PII: SOl41-3910(97)00217-6 0141-3910/98/$--see front matter

Trapping of volatile low molecular weight

photoproducts in inert and enhanced degradable
LDPE

Farideh Khabbaz, Ann-Christine Albertsson & Sigbritt Karlsson*

Department of Polymer Technology, The Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden

(Received 17 July 1997; accepted 7 September 1997)

Degradation of enhanced degradable low-density polyethylene (LDPE) (with

photosensitizers and biodegradable filler) was carried out under accelerated UV
exposure in sealed vials in order to capture the shortest and most volatile low
molecular weight products. The photoproducts were identified by gas chromato-
graphy-mass spectrometry (GGMS) and polymer-matrix degradation mon-
itored by high temperature size exclusion chromatography (HTSEC), Fourier
transform infrared spectroscopy (FTIR) and differential scanning calorimetry
(DSC). The components identified were series of ketones, linear and branched
alkanes, alkenes, carboxylic acids, lactones, alcohols and esters. The identifica-
tion of 2,5_hexanedione has not been reported before. Degradation products
from the additives which were used to increase the degradation were found.
Benzoic acid and benzaldehyde were formed in LDPE containing SBS pro-oxi-
dant in master batch (MB) samples. 1,2,Ctrimethyl benzene and acetophenone
were identified only in samples containing carbon black. The degradation rate of
the enhanced degradable LDPE differ and samples containing iron dimethyl-
dithiocarbamate (FeDMC) degraded faster than other materials, while LDPE
modified with both FeDMC and nickel dibutyldithiocarbamate (NiDBC) showed
the lowest degradation rate. The next most degradable material is LDPE con-
taining starch and SBS pro-oxidant in MB. The high rate susceptibility of MB
samples to photodegradation is due to presence of both pro-oxidant system and
corn starch. 0 1998 Elsevier Science Limited. All rights reserved

1 INTRODUCTION with metal salts, starch and other additives.2-5

The excellent physical properties of polyolefins
make them suitable as packaging and film materi-
als. Photodegradable polyolefins have been pro-
posed as one solution to decrease their long
degradation time and general low or even complete
resistance to biodegradation.
Degradation in natural environments is influenced
by a variety of factors such as heat, oxygen, moist-
ure, stress, macro-organisms, ultraviolet light and
micro-organisms in the soil.’ To enhance the envir-
onmental degradation of PE a number of different
approaches are used, such as copolymerization
with ketone containing materials or compounding
*To whom correspondence should be addressed.
329
These additives are designed to accelerate chemical,
biological and/or photodegradation. An efficient
way to increase photodegradability of PE is to
incorporate additives, e.g. transition metal dithio-
carbamates which work as photoinitiators. Ultra-
violet (UV) energy absorbed by the metal
complexes release the metal ions, which act as cat-
alysts to break the polymer chains. Nickel, zinc,
and cobalt complexes act as stabilizers, while iron
and copper complexes act as sensitizers.6 In the
case of a combination of nickel dithiocarbamate
(photo-antioxidant) and iron dithiocarbamate
(photo pro-oxidant) a wide range of embrittlement
times is obtained in which the induction period is
controlled by the nickel complex and the post-
induction period rate by the iron complex.7 Iron
dithiocarbamate at low concentrations causes very
330 F. Khabbaz
fast photodegradation of the polymer, but it shows
a well-characterized induction period which increa-
ses with higher concentrations in the polymer.*
Another important characteristic of this metal
dithiocarbamate is that it also increases the stabi-
lity of the polyolefin to thermal oxidation during
processing.
Incorporation of a biopolymer such as starch
produces a plastic film with a porous structure,
which enhances the accessibility of the plastic
material to oxygen and micro-organisms.9 Photo-
degradation and thermal degradation are
enhanced if pro-oxidant containing transition
metal ions are used together with starch. The
amount of low molecular weight compounds, sur-
face area and hydrophilicity are increased by
photo-oxidation which in turn promote further
degradation of polymers. As a consequence it is
easier for micro-organisms to attack the chain,
which then degrades first to shorter fragments of
PE chains and finally to the end products, carbon
dioxide and water.iO
Photo-oxidation of polyethylene may lead to
significant formation of low molecular weight
photoproducts. Because of their low molecular
weight, most of these photoproducts migrate out of
the polymer. As a consequence, analysis of the
oxidative evolution of the solid polymer alone does
not permit monitoring of the formation of these
photoproducts. l1 Photooxidation in a weathero-
meter results in loses of the most rapidly migrating
compounds which decrease the possibility to resolve
the photo-oxidative mechanisms.
The aim of the present work was to trap, identify
and discuss the role of the most rapidly migrating
photodegradation products of enhanced degrad-
able polyethylene. Two classes of commercial
degradable polyethylene based materials were
investigated; polyethylene containing metal com-
pounds as photosensitizers (Scott-Gilead process)
and starch with or without pro-oxidant (Griffin
process). The mechanisms of formation of volatile
compounds in degradable PE are proposed. A
new solid phase micro-extraction (SPME) method
was developed to extract photoproducts from the
gas phase above the polymer samples. The
identification of photodegradation products was
performed by gas chromatography-mass spectro-
metry (GC-MS). The changes in polymer matrices
were analysed by size exclusion chromatography
(SEC), Fourier transform infrared (FTIR) spec-
troscopy and differential scanning Calorimetry
(DSC).
et al.
2 EXPERIMENTAL
2.1 Materials
Two classes of degradable low density polyethylene
were investigated in this study: Materials made by
(a) the Scott-Gilead process and (b) the Griffin
process.
2.1 .l The additives used in the Scott-Gilead process
GS 1: LDPE containing iron dimethyldithiocarba-
mate (FeDRC); GS2: LDPE containing iron
dimethyldithiocarbamate FeDRC and 0.8% carbon
black; GS3: LDPE containing FeDRC and nickel
dibutyldithiocarbamate (NiDRC). The film thick-
nesses were 27.5 pm (GSl), 26 pm (GS2) and
21 pm (GS3) and the films were a gift from the late
Professor D. Gilead, Plastopil-Hazorea.
2.1.2 Starch-filled materials based on the Grifin
process
30~m films were made by a conventional blown
film process of a LDPE grade of MFI 2 acquired
from AT0 (France). The samples contained 20%
pro-degradant additives (LDPE-MB) which in
different ways promote degradation, 7.7% starch
(LDPE-Starch) and 20% pro-oxidant (LDPE-
PO). The pro-degradant additives were introduced
into the LDPE matrix in the form of masterbatch
(MB). The MB consisted of corn starch, LLDPE,
styrene-butadiene copolymer (SBS) and manga-
nese stearate. The pro-oxidant system consisted of
styrene-butadiene copolymer (SBS) and manga-
nese stearate.
2.1.3 Control material
Commercial polyethylene without additives pro-
moting degradation was used as a control material
(denoted as Pure LDPE). All measurements were
performed with triple samples.
2.2 UV exposure (degradation procedure)
Photoaging of polymer samples was performed in
an Atlas UVCON screening device equipped with
eight fluorescent sunlamps (FS-40) giving radiation
between 280-350 nm. About 1.9 g of each sample
(7 x 4cm) was placed in the sealed glass vials (pur-
chased from Perkin-Elmer). The sealed vials were
used to enable collecting the volatile degradation
products during the photodegradation for identifi-
cation with GC-MS. These vials were mounted on
racks positioned 5cm from the lamps. The UV
 Trapping of volatile low molecular weight photoproducts
absorption range of the vials was between 200 and
290nm and the samples were exposed to UV
radiation between 290 and 350nm. During the
irradiation the temperature increased to about
47”C, and exposure time was 50 and 300 h.
2.3 Solid phase microextraction (SPME) procedure
The SPME assembly and fibers were purchased
from Supelco Inc. The SPME method developed
involves a few steps. Two microextraction fibers
were selected for extraction of the degradation
products. These were coated with poly-
dimethylsiloxane (100 pm) and carbowax/divi-
nylbenzene (65 pm) and useful for nonpolar and
polar compounds respectively. During headspace
SPME extraction, the 1 cm fiber contained in a
syringe needle was inserted into the sealed sample
vials for 30min at 60°C. The fiber was exposed to
the headspace above the polymer. The fiber was then
retracted back into the SPME needle and immedi-
ately inserted into the GC injector for desorption.
The fiber assembly was cleaned between injections
by allowing the fiber to remain in the heated injec-
tor of the GC for approximately 8 min.
2.4 Gas chromatography-mass spectrometry
(GC-MS)
Analysis was performed with a Varian 3400 gas
chromatograph coupled to a Finnigan SSQ7000
mass spectrometer. The analysis columns were a
DB-5MS (30 x 0.25mm I.D., film thickness
0.25 pm) and a DB-Wax (30 x 0.25 mmI.D., film
thickness 0.25pm) capillary columns from J&W
Scientific.
Analysis with DB-5 MS column started by cool-
ing the column to -178°C using liquid nitrogen in
order to trap the volatile components. Oven tem-
perature was programmed from 30°C for 3 min to
240°C at 6°C min-’ then held for 5 min at 240°C.
When using DB-Wax column, the oven tem-
perature was programmed from 40°C for 3 min to
220°C at 6”Cmin’ then held for 1Omin at 220°C.
Helium was used as carrier gas. A split-splitless
injector was used in the splitless mode. Injector
temperature was 250°C (DB-SMS) and 230°C (DB-
Wax).
The identification of some of the degradation
products was established by comparison of their
mass spectra with spectra recorded in the NST
mass spectra data base and checked by comparison
of retention times with that of a known sample.
331
Others were identified only by comparison with the
NST data base.
2.5 Molecular weight determination
Changes in the molecular weights were measured
using a Waters model 150-C high temperature SEC
apparatus equipped with two PLgel 10 p mixed-B
columns (30cm length, 7.8mm diameter) from
Polymer Laboratories. 1,2,3-trichlorobenzene con-
taining Santonox R (a phenolic anti-oxidant) was
used as a mobile phase at 135°C and the flow rate
was 1.Oml min-‘. Polystyrene standards were used
for calibration.
2.6 Fourier transform infrared spectroscopy (FAIR)
The FTIR spectra of the films were obtained in a
Perkin-Elmer Model 1760 FTIR spectrometer,
equipped with a micro holder and a KRS-5 prism
having a incident angle of 45”, in the range of 800-
4000cm-‘. Special interest was focused on the
carbonyl region. Carbonyl absorbance at
1718 cm-’ was measured relative to the CH2 scis-
soring peak at 1463 cm-‘.
2.7 Differential scanning calorimetry (DSC)
A Mettler-Toledo 820 DSC differential scanning
calorimeter was used. The heating rate was 10°C
min-’ and the sample size, was 5-6mg. The runs
were performed in a nitrogen atmosphere. The
DSC method for determining the percent crystal-
linity of polyethylene samples is based on a heat of
fusion of 293.1 Jg-’ for 100% crystalline PE. All
measurements were performed with triple samples.
3 RESULTS AND DISCUSSION
Photo-oxidation of polyethylene leads to a sig-
nificant formation of low molecular weight photo-
products. As a consequence of their low molecular
weight most of these products migrate very rapidly
from the polymeric matrix. In order to capture
these volatile components, a method to trap these
compounds was developed. The samples were
placed in sealed glass vials and exposed to UV
radiation between 290 and 350nm in the weather-
ometer. This is near the solar UV radiation that
reach the earth (from 295 nm in the summer to
about 3 10 nm in the winter). l2 The glass vials are
those which are used in direct head-space gas
332
chromatographic analysis of volatile compounds in
liquids and solid materials.
3.1 Degradation products and pattern
The low molecular weight degradation products in
polyethylene films after 0, 50 and 300 h of UV
radiation were extracted with SPME fiber from the
gas phase above the samples. SPME is a fast, sim-
ple, solvent free, and sensitive technique and has
been successfully applied to the analysis of both
polar and non-polar analytes from solid, liquid, or
gas phase.13 We have recently developed SPME
methods for polymers and compared them with
traditional head-space GC technique.14 Several
volatile and semi-volatile compounds from oxida-
tion of the PE samples have been identified.
Figures 1 and 2 show the GC-MS chromato-
grams of the volatile and semi-volatile products
extracted by dimethylsiloxane and carbowax fibers
40
42
80 -
62
60 - 36
Fig. 1. GC-MS chromatogram of the degradation products formed in GSl materials after 300 h of UV radiation, extracted with
SPME and polydimethylsiloxane fiber and analyzed with a DB-5 column (nonpolar compounds).
F. Khabbaz et al.
from the GS-1 material. The largest number and
intensity of products were found in GSl materials.
A wide variety of oxidation products were
observed in the experiments, including oxygen-
containing compounds and unoxidized hydro-
carbons. Table 1 presents the identified products
from the different materials. Similar degradation
products at different concentrations were found in
the gas chromatogram of all the materials. The
main components found were ketones, linear and
branched alkanes, alkenes, carboxylic acids, lac-
tones, alcohols and esters. The predominant prod-
ucts were 2,5-hexanedione, carboxylic acids (C2,
C4, C5), 4-oxopentanoic acid and a homologous
series of ketones (C2-C17). The concentration of
these ketones in the gas phase decreased with
increasing molecular weight.
In GS-1 samples, alcohols such as ethanol, l-
propanol, 1-butanol and 1-pentanol were identified
in low quantities only. Traces of tetradecanol and
36
\ P2 /
40
!
6!
 Trapping of volatile low molecular weight photoproducts
100 1
I40 1
62
43
40 -
20 -
i,i-,,~_
I
L _______________
____ 1000
__________________-------
Fig. 2. GC-MS chromatogram of the degradation products formed in GSl materials after 300 h UV radiation,
SPME and carbowax fiber and analyzed with a DB-Wax column (polar compounds).
hexadecanol were found only in the LDPE-starch
samples. The styrene part of the pro-oxidant
(SBS) resulted in the formation of benzoic acid
and benzaldehyde in the LDPE samples contain-
ing MB. ls17 Degradation products of carbon
black were identified in GS2 samples only. These
were 1,2,4-trimethyl benzene and acetophenone.
Phthalates, identified, are either additives from
the polymers or external contaminants from sam-
ple preparation. Butylated hydroxy toluene (BHT),
was identified only in GS3 samples, and is a pro-
cess antioxidant. This is added to polymers to
protect them during processing, where heat expo-
sure can occur during drying, compounding,
extruding and molding. The lack of BHT in the
other materials may be why their induction period
is much shorter which means that BHT has already
disappeared as a result of degradation. Evidence of
epoxides were found in the mass spectra. It was,
however, not possible to establish the exact struc-
tures. Further studies on the formation of epoxides
will be undertaken in future.
333
64
77
66
63
67
I
68
extracted with
Acetic acid, but no formic acid, and low
amounts of other carboxylic acids were extracted,
separated and identified by SPME with dimethyl-
siloxane fiber and a DB-5 GC column. Extraction
performed by SPME with carbowax fiber and
analyzed with DB-Wax GC column gave instead
carboxylic acids (Cl-C14), 4-oxopentanoic acid
and 5oxohexanoic acid as the predominant com-
pounds. The nonpolar dimethylsiloxane fiber
absorbs very low amount of highly polar com-
pounds.
3.2 Molecular weight changes
Figure 3(a)-(d) shows the changes in the weight
average molecular weight (Mw), number average
molecular weight (Mn), Mz-average molecular
weight and polydispersity of LDPE containing the
additives compared to a control sample of pure
LDPE.
All materials demonstrate a decrease in Mw.
GSl films, which contained a photosensitizer,
334 F. Khabbaz et al.

Table 1. Volatile and semi-volatile products identified in the materials after 300 h of radiation

Compounds Gilead- Gilead- Gilead- Pure LDPE LDPE LDPE

Scott 1 Scott 2 Scott 3 LDPE + 20% MB t 2O%PO + 7.7% Starch

Hydrocarbons
1 2-methyl, propaneb + + + +
2 butanea + + + +
3 pentanea + + + +
4 hexanea + + + + + +
5 1,2-dimethylcyclopet~tane~ + + +
6 heptanen + + + + + + +
7 3-methyl, heptaneb + + +
8 2-methyl, heptaneb + + +
9 octand + + + + + + +
10 3-methyl, octaneb +
11 nonane” + + + + + + +
12 decane” + + + + + + +
13 2,2-dimethyl, nonaneb +
14 undecane” + + + + + + +
15 dodecanen + + + + + + +
16 tridecanea + + + + + + +
17 2,2,7-trimethyl, undecaneb +
18 branched alkane +
19 I-tetradecenea + +
20 tetradecane” + + + + + + +
21 I-pentadecene” + + + + +
22 pentadecane + + + + + + +
23 3-methyl, pentadecaneb +
24 I-hexadecene” + + + + + + +
25 hexadecane” + + + + + + +
26 3-methyl, hexadecaneb + +
27 I-heptadecene” + + + + +
28 heptadecane“ •k + + + + + +
29 3-methyl, heptadecaneb + +
30 I-octadecenea + + + + +
31 octadecanen + + + + + +
32 1-nonadeceneb + +
33 nonadecane” + + -t + +
34 2-methyl, nonadecaneb +
35 eicosanea + + + + + +
Ketones
36 Acetone“ + + + + + + +
37 2-butanone” + + + + + + +
38 2-pentanonea + + + + + + +
39 4-methyl, 2-pentanonea +
40 2-hexanone” + + + + + + +
41 3-heptanone” + +
42 2-heptanone’ + + + + + + +
43 2,5-hexanedione” + + + + + + +
44 2-methyl, 4-heptanoneb + +
45 3-octanonea + + + + + +
46 2-octanone” + + + + + + +
47 6-methyl, 2-octanoneb +
48 2-methyl, 4-octanoneb + +
49 3-nonanoneb +
50 2-nonanonea + + + + + + +
51 5-decanoneb + +
52 2-decanone” + + + + + + +
53 2-methyl, 4-decanoneb + +
54 2-undecanone” + + + + + + +
55 2-dodecanone” + + + + + +
56 2-tridecanone” + + + + + +
57 2-tetradecanonen -t + + + + +
58 2-pentadecanonea + + + -c + -e +
59 2-hexadecanoneb +
60 2-heptadecanoneb +

(continued)
 Trapping of volatile low molecular weight photoproducts

Tabk l-contd
Compounds Gilead- Gilead- Gilead- Pure LDPE LDPE LDPE
Scott 1 Scott 2 Scott 3 LDPE + 20% MB + 2O%PO + 7.7% Starch
- -
Carboxylic acid
61 formic acid*,’ +
62 acetic acid” + +
63 propanoic acid” + + +
64 butanoic acid= + + +
65 pentanoic acid” + + +
66 hexanoic acida + +
67 heptanoic acid” + +
68 octanoic acida + + +
69 nonanoic acid” + + +
70 decanoic acid“ + + +
71 undecanoic acid” + + +
72 dodecanoic acid” + + + +
73 tridecanoic acid” + + + +
74 tetradecanoic acid” +
75 hexadecanoic acid” +
76 benzoic acid” +
Ketoacids
77 Coxopentanoic acidb*c + +
78 5-oxohexanoic acidb,c + +
Lactones
79 5-methyldihydro, 2(3H)-furanone” +
80 5-ethyldihydro, 2(3H)-furanoneb +
81 5-propyldihydro, 2(3H)-furanoneb +
82 5-butyldihydro, 2(3H)-furanoneb +
83 5pentyldihydro, 2(3H)-furanoneb +
84 5-hexyldihydro, 2(3H)furanoneb +
85 5-heptyldihydrom, 2(3H)-furanoneb +
86 5octyldihydro, 2(3H)-furanoneb +
87 5-nonyldihydro, 2(3H)furanoneb
Alcohols
88 ethanol” +
89 I-propanol” +
90 I-butanol” +
91 I-pentanol” +
92 tetradecanoP +
93 hexadecanol” +
Esters
94 acetic acid, methylestefl
95 acetic acid, ethylestef
96 acetic acid, propylestefi
97 butanoic acid, methylestefl
98 acetic acid, butylestep +
99 propanoic acid, butylesteP
Miscellaneous
100 Carbondioxide” + + + + + + +
101 diethylphthalate” +
102 bis(Zmethoxy ethyl) phthalateb + + + + +
103 acetophenone” +
104 1,2,4-trimethyl benzeneb +
105 2-methyl, hexanalb + +
106 benzaldehyde” +
107 2-propyl-5-oxohexanalb +
108 butylated hydroxy toluene (BHT) +
Epoxides
109 *
110 *
111 *

u Identified by mass spectrometry through comparison with the NST data base and standard retention indices.
b Identified by mass spectrometry through comparison with the NST data bas.
c Detected only when extraction was performed by carbowax/divinylbenzene fiber and DB-Wax was used as analysis column.
* Some epoxides, that was not possible to establish the exact structures.
336 F. Khabbaz et al.

(4 (b)

i-l
n 50hUV
q 3OUhUV

T
60W0

50000

(c)

EOOWO

Fig. 3. (a) The weight average molecular weight (Mw), (b) number-average molecular weight (Mn), (c) Mz average molecular
weight and (d) polydispersity of different materials after 0, 50, 300 h of UV irradiation.

demonstrated a significant decrease of the Mw.
After 300 h radiation the reduction in molecular
weight were accompanied by the formation of a
large amount of low molecular weight degradation
products.
GS2, LDPE-MB, LDPE-PO, LDPE-Starch and
Pure LDPE show also a decrease in Mw. The
molecular weight decrease was not monotonous
for all the materials. After 50 h of radiation there
was a slight increase in the Mw in the GSl and GS2
materials as opposed to the other materials which
showed a slight decrease in Mw after the same time
of radiation. The initial increase in weight may be
caused by the incorporation of oxygen into the
system through the photo-oxidative mechanism. It
can also be because hydroperoxides formed during
the irradiation are very sensitive to UV light and
decompose quickly to radicals.18 When the amount
of radicals increase some of them probably react
with each other and chain elongating reactions will
 Trapping of volatile low molecular weight photoproducts
take place. 19,20 GS3 samples containing photo-
stabiliser (GS3) demonstrated no significant chan-
ges in Mw during the aging.
Changes in the Mn paralleled changes in Mw.
GSl, GS2, LDPE-PO, LDPE-Starch demon-
strated a slight increase in Mn after 50 h radiation
after which Mn decreased. Reduction in Mn was
very fast for GSl material. LDPE-MB and Pure
LDPE also showed a decrease in Mn. Mn for GS3
increased slightly after 50 h radiation and remained
almost unchanged after 300 h of UV exposure. Mn
is influenced by the lower molecular weight frac-
tions, while Mw is influenced by the higher molec-
ular weight fractions. Reduction in both Mn and
Mw indicates that chain breaking reactions take
place.
The Mz of GSl and GS2 increased slightly dur-
ing the first 50 h after which it started decreasing.
Mz of GSl reduced dramatically after 300 h of
treatment. LDPE-MB, LDPE-PO and LDPE-
Starch also showed a decrease in Mz, but the
changes in Mz for LDPE-PO and LDPE-Starch
was small. GS3 showed no significant changes in
Mz. Opposite to the other materials Pure LDPE
showed a continuous increase in Mz. The reduction
of Mz implies chain cleavage reaction for all sam-
ples while the increase of Mz value for the Pure
LDPE indicates chain elongation.
The polydispersity index (Mw/Mn) which repre-
sents the width of the Mw distribution, decreased
significantly for the GSl material from the initial
value of 5.3 to 3.3. This indicates a narrowing in
the overall molecular weight distribution (MWD).
GS2 and GS3 also showed a decrease in MWD but
the reductions are smaller than for GS 1. The poly-
dispersity of LDPE-MB, LDPE-PO and LDPE-
starch demonstrated a slight reduction after 50 h of
radiation, thereafter it increased again. For Pure
LDPE, polydispersity increased from 5.8-7.7 dur-
ing the experiment which implies a broad MWD.
The results from SEC analysis show that the GSl
material with the highest reduction in molecular
weight is more photodegradable than the other
materials. The next more degradable material is
LDPE-MB followed by LDPE-PO, GS2, LDPE-
starch and pure LDPE samples. GS3 show the
lowest reduction in molecular weight and thereby
the lowest degradability. Main chain scission is the
dominate degradation reaction in GSl, GS2, MB,
PO and Starch materials, because both Mn and
Mw decrease. This process will result pre-
dominantly from the decomposition of polymeric
hydroperoxides, but also from peroxy and alkoxy
337
free radicals that lead to decrease in the average
molecular weight of the polymer. Mn and Mw for
pure LDPE become smaller while a broadening of
distribution is observed. These indicate that main
chain scission in Pure LDPE is the dominant pro-
cess but some cross-linking also occurs.
3.3 Functional group change
The extent of oxygen uptake was followed by
measuring the carbonyl absorption at 1710-
1740 cm-* after 0, 50 and 300 h of UV radiation.
Figure 4 shows the changes in the carbonyl absor-
bance as a function of irradiation time (h) for the
different materials. The carbonyl index is almost
constant during the first 50 h. After 50 h exposure it
increases dramatically for the GSl samples (to
almost 66%). MB and PO show the second most
rapid increase in carbonyl index (to almost 29%).
For GS2 carbonyl index increases to 23%. Changes
in carbonyl index of LDPE-starch and Pure-
LDPE are small, while GS3 samples containing
nickel-iron dithiocarbamate show the longest
induction period and almost no changes in carbo-
nyl index are detected.
Figure 5 shows the FTIR-spectra of all samples
after 300 h irradiation. During the accelerated
exposure the apparent differences noted are the
carbonyl regions: 1780, 1740, 1718 and 1710 cm-’
which are assigned, respectively, to y-lactone, ester,
ketone and carboxylic acid species.
3.4 Variability in crystalliuity change
Polyethylene is a semicrystalline polymer. It can be
considered to behave like a two phase system:
alternating a well-ordered crystalline phase and a
less rigid amorphous phase. Neighboring crystal-
line lamellae are connected by tie molecules, pas-
sing through the amorphous interlamellar regions.
The crystalline phase of PE does not absorb gas
molecules to any detectable extent and oxygen is
not consumed for oxidative degradation reac-
tions.21 As a consequence it is assumed that oxida-
tion of polyethylene is restricted to the amorphous
regions.
Figure 6 shows changes in crystallinity for dif-
ferent materials. It was observed that the crystal-
linity of all samples increased with the time of
exposure to photo-oxidation. GSl materials show
the largest increase in crystallinity. The increase in
crystallinity is due to oxidative crystallization and
scission of constrained chains in the amorphous
338 F. Khabbaz et al.

0 50 300
Time (hours)
Fig. 4. Carbonyl index as a function of irradiation time for different materials.

C,
b

woo 1wo 5zw nw 24000 2000 1wo 1200 MO

Wave Number (cm-‘)

Fig. 5. FTIR spectrum of the materials after 300 h irradiation: (a) GSl; (b) MB; (c) GS2; (d) PO; (e) starch; (f) control; (g) GS3.
 Trapping of volatile low molecular weight photoproducts 339

25 J I
0 50 100 IS0 200 250 300

Time (hours)

Fig. 6. Changes in the crystallinity as a function of photo-oxidation time for LDPE modified with different additives.

region that lead to relaxation of local stresses volatile degradation products is due to the photo
which allows the resulting free segments to crystal- sensibilizing role of iron. Reduction of the trivalent
lize.** iron complex by UV-radiation with the subsequent
While the crystallinity of all samples increased formation of initiating radicals leads to oxidative
during the UV radiation the melting temperature breakdown of the polymer.24 LDPE containing
remained almost constant. Figure 7 shows the
thermogram of unexposed, 50 and 300 h exposed
for GSl films. The melting peak becomes larger
with increasing time of exposure but the melting
temperature remains almost steady. The broad-
ening of the melting peak may occur due to cre-
ation of new intermolecular polar bonds (carbonyl
groups) which lead to secondary crystallization.23

3.5 Correlation between molecular weight,

degradation products and carbonyl index

There is a good correlation between the molecular

weight, carbonyl index and formation of degrada-
tion products. GSl samples show the highest
reduction in molecular weight (88%), have the
highest carbonyl index (66%) and have also shown
50 70 90 110 130
the largest number and highest concentration of
degradation products. The increase in carbonyl Temperature (“C)
index during UV irradiation that is paralleled by Fig. 7. DSC termogram of GSl samples after 0, 50 and 300 h
reduction in molecular weight and forming of the of UV irradiation.
340 F. Khabbaz et al.

iron dithiodimethylcarbamate and carbon black
(GS2) shows moderate degradation. This behavior
is expected since carbon black is a UV absorbing
additive and it prevents the photo excitation of
iron-dithiocarbamate. At the same time the energy
absorbed from UV by carbon black causes an
increase in the temperature in the material and
thereby increases the possibility of degradation.
Samples containing nickel-iron dithiocarbamate
(GS3) show a negligible decrease in the molecular
weight which is correlated to almost no changes in
carbonyl index and the lowest concentration in
degradation products.
LDPE containing masterbatch demonstrated the
next highest degradation after GSl. This was due
to the effect of both pro-oxidant system and starch.
Samples consisting of LDPE and only pro-oxidant
or starch showed lower rate of molecular weight
decrease than LDPE-MB. Both carbonyl index
and concentration of degradation products were
however, almost similar in LDPE-MB and LDPE-
PO, whereas they were lower for LDPE-starch.
Even LDPE-starch is more photo degradable
than Pure LDPE which is due to the rapid change
in the degree of polymerization when poly-
saccharides are exposed to UV light.25 Starch is
composed of amylose and amylopectine which in
turn consist of glucose units linked by glycosidic
bonds. The &C-O bond on the glucose units acts
as a weak chromophore and absorbs UV light and
causes chain scission that affects also the LDPE-
matrix. It is evident that the pro-oxidant is the
main responsible part for the photodegradation of
LDPE-MB, but the starch may also contribute.
3.6 Mechanism for the formation of degradation
products
The identified photodegradation products show
that the degradation follows the generally accepted
oxidation reaction scheme. The formation of free
radicals is followed by attack of free radicals on the
polymer chain, reaction of these with oxygen pro-
ducing peroxy radicals, abstraction of hydrogen

-CH2-CH-(cH2)2-CH,-CH,- _+ -CH>-CH-(CH&- CHi-CH2- -

B

-cH,-CH-(cH,)*--CH,-CH, - % -CH,-CH-WH,),-CH -cH,- -

.
b-0. I:

-CHZ-YH-(CH& -CH-CH2- % - CHI-CH-(CH2)z~~-~~7- &

OOH ' AOH 0-O.

Cw)
R'+ -CH,-YH-(CHJ,-_FH-CH, m
OOH OOH

-CH,-I- '
(CH,),-&CH,- + 2H,O

-
R
CH2-CH2-C-(CH,)2-C-CH,-CH,
9 - N=-CH,-CH,-C-(CH,),-c'
FI CH,-CH2 \
,CH-
a
0, H

-
FI
-CH,-CH,-C-(CH,),-C;\
/C&-C& \
*CH-
O-H
0
W
- -CH,-CH,-&(CH,)+? + CH,=CH -CH,-
'OH
I
+0 0 0
- CH,--CH,-c
P-_(CH,), -ii --CH, e CH;+CH,-CH&CH, + 2CH,=CH-CH,-

Scheme 1. A mechanism for the formation of 2,Shexanedione by intramolecular attack of the peroxy radical on the hydrogen atom
in y-position.
 Trapping of volatile low molecular weight photoproducts
producing hydroperoxides and more free radicals,
cleavage of the O-O bond of the hydroperoxides
and formation of alcohols and carbonyl containing
groups such as acids, ketones, lactones, esters,
etc.26
The formation of ketones results from the Nor-
rish type I and type II mechanisms. The latter will
generate vinyl unsaturation. Vinyl groups can not
absorb UV radiation above 300nm but they may
react with the singlet oxygen generated photo-
chemically in PE which makes them susceptible to
free radical attack.27
Rust2* has shown that compounds containing
suitably located tertiary carbon atoms may oxi-
dized to give high yields of products of multiple
attack. The most favored pattern of reaction
involves attack of the peroxy radical in the B-posi-
tion. The next most favored is intramolecular
attack by peroxy radical which is found when two
atoms intervene (y-attack). The formation of 2,5-
hexanedione is due to intramolecular attack of the
initially formed secondary peroxy radical on the
hydrogen atom in y-position, followed by forma-
tion of a second peroxy group that abstracts a
hydrogen from another polymer molecule to form
the second hydroperoxide. The decomposition of
2,5-dihydroperoxides during UV-irradiation pro-
duce the highly reactive hydroxyl radicals which
under certain conditions abstract the labile tertiary
hydrogen at the carbon atom. An intermediate
biradical is formed which subsequently gives two
carbonyl groups according to Scheme 1.
Ketoacids are formed by intramolecular hydro-
gen abstraction via a cyclic transition state.29 The
formation of carboxylic acid is due to the Norrish
type I reaction. UV irradiation of carbonyl com-
pounds yields carbonyl-bearing free radicals which
can further oxidize to carboxylic acids. Carboxylic
acid might also result from aldehydic inter-
mediates.30 Carboxylic acids are not photosensitive;
they do not undergo further reactions and aceumu-
late in the system during photo-oxidation.31
The aliphatic hydrocarbons identified are formed
as a result of chain scission while y-lactones are
formed when reactions occur between carboxylic
acid and hydroxyl group in the 1,4 position3’ or
when 1,4 dihydroperoxide32 decomposes.
4 CONCLUSION
A method to trap the most volatile of the photo-
products of enhanced degradable polyethylene has
341
been developed. Similar degradation products but
at different concentrations were found in all the
materials. The main components identified were
ketones, linear and branched alkanes, alkenes, car-
boxylic acids, lactones, alcohols and esters. The
2,5-hexanedione identified in all samples has to our
knowledge not previously been reported as a
photodegradation product. Its formation is
explained by the intramolecular attack of the initi-
ally formed secondary peroxy radical on the
hydrogen atom in the y-position. Benzoic acid and
benzaldehyde were formed in LDPE containing
SBS pro-oxidant while 1,2,4-trimethyl benzene and
acetophenone were identified only in the samples
containing carbon black.
Samples containing FeDMC demonstrated a
larger degradation rate than all other samples.
LDPE-MB showed the next highest degradation
after GSl while LDPE with FeDMC and carbon
black showed moderate rate of degradation. The
iron dithiocarbamate is more prone to absorb
UV light early in the aging period while carbon
black which is also a UV absorbing additive also
prevents the photo excitation of iron-dithio-
carbamate. The energy absorbed from UV radia-
tion by carbon black also causes an increase in
the temperature of the material which further
promotes the thermolysis. In the LDPE-MB
samples, the pro-oxidant system is the main part
responsible for degradation of that material.
Samples containing FeDMC and NiDBC demon-
strate negligible degradation during the investiga-
tion period due to longer induction times at the
present concentrations. Our results demonstrate
that starch also has an influence on the photo-
degradation of the LDPE-MB by the weak UV
absorption of the CO-C groups in the starch
molecule.
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