Journal of Saudi Chemical Society (2012) 16, 279285

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Evaluation of Schi bases of 2,5-dimercapto-1,3,4-

thiadiazole as photostabilizer for poly(methyl methacrylate)
a,*
Emad Yousif , Emaad Bakir a, Jumat Salimon b, Nadia Salih b

a
Department of Chemistry, College of Science, AL-Nahrain University, Baghdad, Iraq
b
School of Chemical Science and Food Technology, Faculty of Science and Technology, University Kebangsaan Malaysia,
43600 Bangi, Selangor, Malaysia

Received 24 December 2010; accepted 16 January 2011

Available online 21 January 2011

KEYWORDS Abstract The photostabilization of poly(methyl methacrylate) (PMMA) lms by Schiff bases of
Photochemistry; 2,5-dimercapto-1,3,4-thiadiazole compounds was investigated. The PMMA lms containing con-
PMMA; centration of complexes 0.5% by weight were produced by the casting method from chloroform sol-
UVVis spectroscopy; vent. The photostabilization activities of these compounds were determined by monitoring the
Photostabilizer; hydroxyl index with irradiation time. The changes in viscosity average molecular weight of PMMA
UV absorber; with irradiation time were also tracked (using benzene as a solvent). The quantum yield of the chain
2,5-Dimercapto-1,3,4-thiadi- scission (Ucs) of these complexes in PMMA lms was evaluated and found to range between
azole; 4.19 105 and 8.75 105. Results obtained showed that the rate of photostabilization of PMMA
Schiff base
in the presence of the additive followed the trend:
[1] > [2] > [3] > [4] > [5].
According to the experimental results obtained, several mechanisms were suggested depending on
the structure of the additive. Among them, UV absorption, peroxide decomposer, and radical scav-
enger for photostabilizer mechanisms were suggested.
2011 King Saud University. Production and hosting by Elsevier B.V.
Open access under CC BY-NC-ND license.

* Corresponding author. Tel.: +964 7901782816.
E-mail address: emad_yousif@hotmail.com (E. Yousif).
1319-6103 2011 King Saud University. Production and hosting by
Elsevier B.V. Open access under CC BY-NC-ND license.
Peer review under responsibility of King Saud University.
doi:10.1016/j.jscs.2011.01.009
Production and hosting by Elsevier
1. Introduction
Ultraviolet light stabilizers are used widely in plastics, cosmet-
ics, and lms. The main purpose of UV-stabilizer is to prevent
polymers from photodegradation or photocrosslinking caused
by ultraviolet light presented in sunlight and articial light
source. Ultraviolet light stabilizers are divided into inorganic
UV-stabilizers, organic UV-stabilizers, and otherkinds. Inor-
ganic UV-stabilizers, such as iron oxide, titanium oxide, chro-
mic oxide, and carbon black, usually cannot evenly distribute
in the plastic substrate so much as incompatible with the
polymer matrix. The nal effects depend on the particle size
and concentration (Zhao and Dan, 2006). These drawbacks
280
limit the application of inorganic UV-stabilizers. Organic
UV-stabilizers, generally with small molecular weight, include
uorescent compounds, phenyl-ester of benzoic acid, hydrox-
ylbenzophenone, benzotriazoles, etc. In the addition of these
stabilizers to plastic materials, problems such as migration,
incompatibility, volatility, and solvent extraction will inevita-
bly occur. It leads to a strong diminution of the materials
utilization. To resolve such problems, many approaches have
been developed, such as preparing reactive UV-stabilizer,
(Yousif et al., 2009; Grassie and Scott, 1985) introducing com-
patible side chains, or chemically anchoring of the additive to
the polymer backbone, etc (Andrady et al., 1988). Among
these methods, preparing high molecular weight UV-stabilizer
is a highlight because, for most of the polymer materials,
blending is the rst choice to enhance their UV-resistance.
Meanwhile, different high molecular weight UV-stabilizers
can be prepared by the copolymerization of a reactive UV-sta-
bilizer with other monomers. In this point, it is very convenient
to ameliorate the compatibility between UV-stabilizer and
plastic matrix by preparing suitable high molecular weight
UV-stabilizer (Harper et al., 1974). As part of our on-going
research on the photostabilization of polymers, the photostabi-
lization of PMMA was studied using Schiff bases of 2,5-dimer-
capto-1,3,4-thiadiazole compounds.
2. Experimental
2.1. Materials
The Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole com-
pounds were all prepared by the method previously described
by Salimon et al. (2010).
N N
C N N N N C
H H S H H
X X
where X = OOH, PNO2, PN(CH3)2, PCH3 or PCl. study. Actual absorbance, the difference between the absor-
3. Experimental techniques
3.1. Films preparation
Commercial PMMA was re-precipitated from chloroform
solution by alcohol several times and nally dried under vac-
uum at room temperature for 24 h. Fixed concentrations of
PMMA solution (5 g/100 ml) in chloroform were used to pre-
pare polymer lms with 40 lm thickness (measured by a
micrometer type 2610 A, Germany). The prepared complexes
(0.5% concentrations) were added to the lms starting at 0
concentrations (blank). It was necessary to control the
hygrometry and the rate of evaporation of solvent during cast-
ing to maintain good optical quality and very limited turbidity.
The lm transmission should be greater than 80% in the near-
UV range. The lms were prepared by evaporation technique
at room temperature for 24 h. To remove the possible residual
chloroform solvent, lm samples were further dried at room
E. Yousif et al.
temperature for 3 h under reduced pressure. The lms were
xed on stands especially used for irradiation. The stand is
provided with an aluminium plate (0.6 mm in thickness) sup-
plied by Q-panel company.
3.2. Irradiation experiments
3.2.1. Accelerated testing technique
Accelerated weather-meter Q UV tester (Q panel, Company,
USA), was used for irradiation of polymers lms. The acceler-
ated weathering tester contains stainless steel plate, which has
two holes in the front side and a third one behind. Each side
contains a lamp (type Fluorescent Ultraviolet Lights) 40 W
each. These lamps are of the type UV-B 313 giving spectrum
range between 290 and 360 nm with a maximum wavelength
313 nm. The polymer lm samples were vertically xed parallel
to the lamps to make sure that the UV incident radiation is
perpendicular on the samples. The irradiated samples were ro-
tated from time to time to ensure that the intensity of light inci-
dent on all samples is the same.
3.3. Photodegradation measuring methods
3.3.1. Measuring the photodegradation rate of polymer lms
using infrared spectrophotometery
The degree of photodegradation of polymer lm samples was
followed by monitoring FTIR spectra in the range 4000
400 cm1 using FTIR 8300 Shimadzu Spectrophotometer.
The position of hydroxyl absorption is specied at 3430 cm
1
(Rabek and Ranby, 1975).
The progress of photo-degradation during different irradia-
tion times was followed by observing the changes in hydroxyl
peak. Then hydroxyl index (IOH) was calculated by compari-
son of the FTIR absorption peak at 3430 cm1 with reference
peak at 1450 cm1, respectively. This method is called band in-
dex method which includes (Rabek and Ranby, 1975):
As
Is 1
Ar
where As is the absorbance of peak under study, Ar is absor-
bance of reference peak, and Is is the index of group under
bance of top peak and base line (A top peak A base line) is cal-
culated using the base line method (Rabek and Ranby, 1975).
3.3.2. Determination of average molecular weight Mv using
viscometry method
The viscosity property was used to determine the average
molecular weight of polymer, using the MarkHouwink rela-
tion (Mark, 2007)
g KMav 2
where [g] is the intrinsic viscosity, K and a are constants de-
pend upon the polymersolvent system at a particular temper-
ature. The intrinsic viscosity of a polymer solution was
measured with an Ostwald U-tube viscometer. Solutions were
made by dissolving the polymer in a solvent (g/100 ml) and the
ow times of polymer solution and pure solvent are t and t0,
respectively. Specic viscosity (gsp) was calculated as follows:
t
gre 3
t0
Evaluation of Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole as photostabilizer for poly(methyl methacrylate) 281

where gre is the relative viscosity 4. Results and discussion

gsp gre  1 4
The Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole com-
The single-point measurements were converted to intrinsic vis- pounds were used as additives for the photostabilization of
cosities by the relation (2) PMMA lms. In order to study the photochemical activity
p of these additives for the photostabilization of PMMA lms,
g 2=cgsp  lngre 1=2 5 the hydroxyl index was monitored with irradiation time using
where C is the concentration of polymer solution (g/100 ml). IR spectrophotometry. The irradiation of PMMA lms with
By applying Eq. (5), the molecular weight of degraded and UV light of wavelength, k 313 nm led to a clear change in
undergirded polymer can be calculated. Molecular weights of the FTIR spectrum. Appearance of bands in 3430 cm1 was
PMMA with and without additives were calculated from attributed to the formation of the hydroxyl group (Andrady
intrinsic viscosities measured in benzene solution using Eq. and Searle, 1989). The absorption of the hydroxyl group was
(2). The quantum yield of main chain scission (Ucs) (Nakajima used to follow the extent of polymer degradation during irra-
et al., 1990) was calculated from viscosity measurement using diation. This absorption was calculated as hydroxyl index. It
the following relation: is reasonable to assume that the growth of hydroxyl index is
a measure to the extent of degradation. However, in Fig. 1,
Ucs CA=Mv;0 g0 =g1=a  1=I0 t 6 the IOH of [5], [4], [3], [2], and [1] showed lower growth rate
with irradiation time with respect to the PMMA control lm
where C is the concentration, A is Avogadros number, Mv;o without additives. Since the growth of hydroxyl index with
is initial viscosity-average molecular weight, [g0] is intrinsic vis- irradiation time is lower than PMMA blank, as seen in
cosity of PMMA before irradiation, I0 is incident intensity, Fig. 1, it is suitable to conclude that these additives might be
and t is the irradiation time in second. considered as photostabilizers of PMMA polymer. Efcient

0.18

0.16
PMMA+[1]
PMMA+[2]
0.14 PMMA+[3]
PMMA+[4]
PMMA+[5]
0.12 PMMA

0.10
IOH

0.08

0.06

0.04

0.02

0.00
0 50 100 150 200 250 300
Irradation Time (hrs)

Figure 1 The relationship between the hydroxyl index and irradiation time for PMMA lms (40 lm thickness). Containing different
additives, concentration of additives are xed at 0.5% by weight.

250000

PMMA+[1]
PMMA+[2]
PMMA+[3]
200000 PMMA+[4]
PMMA+[5]
PMMA

150000
Mv

100000

50000

0
0 50 100 150 200 250 300

Irradiation Time (hrs.)

Figure 2 Changes in the viscosity average molecular weight Mv during irradiation of PMMA lms (40 lm) (control) and with 0.5 wt%
of additives.
282 E. Yousif et al.

3.50

PMMA+[1]
3.00
PMMA+[2]
PMMA+[3]

Main Chain Scission (S)

PMMA+[4]
2.50
PMMA+[5]
PMMA

2.00

1.50

1.00

0.50

0.00
0 50 100 150 200 250 300
Irradiation Time (hrs.)

Figure 3 Changes in the main chain scission (S) during irradiation of PMMA lms (40 lm) (control) and with 0.5 wt% of additives.

0.009

0.008
Degree of Deterioration (Alfa)

PMMA+[1]
0.007 PMMA+[2]
PMMA+[3]
0.006 PMMA+[4]
PMMA+[5]

0.005 PMMA

0.004

0.003

0.002

0.001

0.000
0 50 100 150 200 250 300
Irradiation Time (hrs.)

Figure 4 Changes in the degree of deterioration during irradiation of PMMA lms (40 lm) (control) and with 0.5 wt% of additives.

photostabilizer shows a longer induction period. Therefore,

the [1] is considered as the most active photostabilizer, fol- Table 1 Quantum yield (Ucs) for the chain scission for
lowed by [2], [3], [4], and [5] which are least active. PMMA lms (40 m) thickness with and without 0.5 (wt/wt)
additive after 250 h irradiation time.
4.1. Variation of PMMA molecular weight during photolysis in Additive (0.5 wt%) Quantum yield of main chain scission (Ucs)
the presence of by Schiff bases of 2,5-dimercapto-1,3,4- PMMA + [5] 4.19E05
thiadiazole compounds PMMA + [4] 4.39E05
PMMA + [3] 7.23E05
Analysis of the relative changes in viscosity average molecular PMMA + [2] 7.57E05
weight Mv has been shown to provide a versatile test for ran- PMMA + [1] 8.75E05
dom chain scission. Fig. 2 shows the plot of Mv versus irra- PMMA (blank) 4.53E04
diation time for PMMA lm with and without 0.5% (wt/wt) of
the selected additives, with absorbed light intensity of
1.052 108 ein dm3 s1. Mv is measured using Eq. (3) with
in the degree of branching such as that might arise from cross-
benzene as a solvent at 25 C. It is worth mentioning that
linking occurrence. It is observed that insoluble material was
traces of the lms with additives are not soluble in chloroform
formed during irradiation which provided an additional evi-
indicating that cross-linking or branching in the PMMA chain
dences to the idea that cross-linking does occur. For randomly
does occur during the course of photolysis (Mori et al., 1997).
distributed weak bond links (Gugumus, 1990) which break
For better support of this view, the number of average chain
rapidly in the initial stages of photodegradation, the degree
scission (average number cut per single chain) (S) (Shyichuk
of deterioration a is given as:
and White, 2000) was calculated using the relation:
ms
Mv;0 a 8
S 1 7 Mv
Mv;t
where m is the initial molecular weight. The plot of a as a func-
where Mv;0 and Mv;t are viscosity average molecular weight tion of irradiation time is shown in Fig. 4. The values of a of
at initial (0) and t irradiation time, respectively. The plot of S the irradiated samples are higher when additives are absent
versus time is shown in Fig. 3. The curve indicates an increase and lower in the presence of additives compared to the
Evaluation of Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole as photostabilizer for poly(methyl methacrylate) 283

OH HO OH HO *
N N N N
h
HC N HN NH N CH HC N HN NH N CH
S S
So S1

OH O * OH H O *
N N N N
H P.T.
HC N HN NH N C HC N HN NH N CH
S H S
S1 S1
IC
OH O * OH H O *
N N N N
H H
HC N HN NH N C HC N HN NH N C
S H S
So So
P.T.
OH HO OH HO *
N N N N
HC N HN NH N CH HC N HN NH N CH
S S
So So
+
heat

Scheme 1 The suggested mechanism of photostabilization of PMMA by Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds
through absorption of UV light and dissipation light energy as heat.

OH HO OH HO *
N N N N
h
HC N HN NH N CH HC N HN NH N CH
S S
So S1

OH O * OH H O *
N N N N
H P.T.
HC N HN NH N C HC N HN NH N CH
S H S
S1 S1
ICS
OH O * OH H O *
N N N N
H H
HC N HN NH N C HC N HN NH N C
S H S
T1 T1
P.T.
OH HO OH HO *
N N N N
ICS
HC N HN NH N CH HC N HN NH N CH
S S
So So
+
heat

Scheme 2 The suggested mechanism of photostabilization of PMMA by Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds
through absorption of UV light and dissipation light energy as heat.

corresponding values of the additive free PMMA. In the initial
stages of photodegradation of PMMA, the value of a increases
rapidly with time, these indicators indicates a random breaking
of bonds in the polymer chain. Another way of degradation
reaction characterization is the measurement of the quantum
yield of the chain scission (Ucs) (Yousif et al., 2010). The quan-
tum yield for chain scission was calculated for PMMA lms
with and without 0.5% (wt/wt) of additive mentioned above
using relation (6). The Ucs values for complexes are tabulated
in Table 1.
The Ucs values for PMMA lms in the presence of additive
are less than that of additive free PMMA (blank), which in-
crease in the order:
[1] > [2] > [3] > [4] > [5].
4.2. Suggested mechanisms of photostabilization of PMMA by
Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds
Through the overall results obtained, the efciency of thiadia-
zole derived Schiff base compounds as photostabilizers for
284 E. Yousif et al.

G G G G *
N N N N
h
HC N HN NH N CH HC N HN NH N CH
S S

G G G G *
N N N N _ +
HC N HN NH N CH HC N HN NH N CH
S S
+
heat

Scheme 3 The suggested mechanism of photostabilization of PMMA by Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds
through absorption of UV light and dissipation light energy as heat.

OH HO

N N

HC N HN NH+ N CH
S

PO / OH
OH O

N N

HC N HN NH+ N CH + POH / H2O

S

OH O

N N

HC N HN NH+ N CH
S

OH O

N N

HC N HN NH+ N C
S

etc

Scheme 4 The suggested mechanism of photostabilization of PMMA by Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds as
radical scavenger.

N N N N * N N

h + heat
S S S

Scheme 5 Suggested mechanism of photostabilization of 1,3,4-thiadiazole as UV absorber.

PMMA lms can be arranged according to the change in the
hydroxyl concentration as a reference for the comparison as
shown in Fig. 1 as follows:
[1] > [2] > [3] > [4] > [5].
Schiff base stabilize PMMA by different mechanisms such
as UV absorber, screener or by radical scavenger. These stabi-
lizers provide very good long-term stability and are usually
referred to these mechanisms. The most probable mechanisms
involved in a photostabilization is the change energy of
absorbed photon to the intramolecular proton transfer. This
reaction may occur by two proposed cycles Schemes 1 and 2,
the rst passes by intersystem crossing (ICS) process to the
excited triplet state, while the second is referred to internal
conversion (IC) process to the ground state.
Other mechanism explains the use of this compound as
photostabilizer is by charge separated species which could be
form of the excited state such a structure would allow dissipa-
tion of energy through rotation on increased vibration about
the central bond as shown in Scheme 3. The hydroxyl group
of the additive might acts as radical scavenger for photostabi-
lization process. Therefore this Schiff bases, besides acting as
UV absorber they may also act as radical scavenger additives
(Rasheed et al., 2009), Scheme 4.
Evaluation of Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole as photostabilizer for poly(methyl methacrylate)
The rings of 1,3,4-thiadiazole play a role in the mecha-
nism of the stabilizer process by acting as UV absorber.
The UV light absorption by these additives containing
1,3,4-thiadiazole dissipates the UV energy to harmless heat
energy Scheme 5.
Furthermore, this ring plays a role in resonating structures
conjugation of radical in peroxide decomposer Scheme 5,
which sport it function as a photostabilizer (Yousif et al.,
2007).
5. Conclusions
In the work described in this paper, the photostabilization of
PMMA lms using Schiff bases of 2,5-dimercapto-1,3,4-thiadi-
azole compounds were studied. These additives behave suc-
cessfully as photostabilizer for PMMA lms. The additives
take the following order in photostabilization activity accord-
ing to their decrease in hydroxyl index for PMMA lms.
[1] > [2] > [3] > [4] > [5].
These additives stabilize the PMMA lms through UV
absorption or screening, peroxide decomposer, and radical
scavenger mechanisms. The [1] compound was found to be
the more efcient in photostabilization process according to
the photostability and mechanisms mentioned above. These
mechanisms support the idea of using Schiff bases of 2,5-
dimercapto-1,3,4-thiadiazole compounds as commercial stabi-
lizer for PMMA.
Acknowledgments
The authors acknowledge the IIE, SRF, and to the supporting
staffs of School of Chemical Sciences and Food Technology,
Faculty of Science and Technology, University Kebangsaan
Malaysia and Department of Chemistry, College of Science,
Al-Nahrain University for their encouragement.
References
Andrady, A., Searle, N., 1989. Photodegradation of rigid PVC
formulations. II. Spectral sensitivity to light-induced yellowing by
polychromatic light. J. Appl. Poly. Sci. 37, 27892802.
Andrady, A., Hamid, S., Hu, X., Torikai, A., 1988. Effects of increased
solar ultraviolet radiation on materials. In environmental effects of
ozone depletion. J. Photochem. Photobiol. B Biol. 46, 96103.
285
Grassie, N., Scott, G., 1985. Polymer Degradation and Stabilization.
Cambridge University Press, London.
Gugumus, F., 1990. Mechanism of Polymer Degradation and
Stabilization. Elsevier, Amsterdam.
Harper, D., McKellar, N., Turner, P., 1974. Photostabilizing effect of
Ni(II) chelates in polymers. II. Effect of diamagnetic chelates on
polypropylene phosphorescence. J. Appl. Polym. Sci. 18 (311),
28022805.
Mark, J., 2007. Physical Properties of Polymers Handbook. Springer,
New York.
Mori, F., Koyama, M., Oki, Y., 1997. Studies on photodegradation of
poly(vinyl chloride) (Part I). Die Angewandte Mak-omolekulare
Chemie 64 (1), 8999.
Nakajima, N., Sadeghi, M., Kyu, T., 1990. Photodegradation of
poly(methyl methacrylate) by monochromatic light: Quantum
yield, effect of wavelengths, and light intensity. J. Appl. Poly. Sci.
41, 10231032.
Rabek, J., Ranby, B., 1975. Photodegradation, Photo-oxidation and
Photostabilization of Polymers. John Wiley, New York.
Rasheed, R., Mansoor, H., Yousif, E., Hameed, A., Farina, Y.,
Graisa, A., 2009. Photostabilizing of pvc lms by 2-(aryl)-5-
[4-(aryloxy)-phenyl]-1,3,4-oxadiazole compounds. Eur. J. Sci. Res.
30, 464477.
Salimon, J., Salih, N., Yousif, E., Hameed, A., Ibraheem, H., 2010.
Synthesis, characterization and biological activity of schiff bases of
2, 5-dimercapto-1,3,4-thiadiazole. Aust. J. Basic Appl. Sci. 4 (7),
20162021.
Shyichuk, A., White, J., 2000. Analysis of chain-scission and
crosslinking rates in the photo-oxidation of polystyrene. J. Appl.
Poly. Sci. 77 (13), 30153023.
Yousif, E., Hameed, A., Baker, T., 2007. Synthesis and photochemical
study of poly(vinyl chloride)-1,3,4-oxadiazole and 1,3,4-thiadia-
zole. J. Al-Nahrain Univ. 10, 712.
Yousif, E., Aliwi, M., Ameer, A., Ukal, J., 2009. Improved
photostability of PVC lms in the presence of 2-thioacetic acid-5-
phenyl-1,3,4-oxadiazole complexes. Turk. J. Chem. 33, 339
410.
Yousif, E., Hameed, A., Rashed, R., Mansoor, H., Farina, Y., Graisa,
A., Salih, N., Salimon, J., 2010. Synthesis and photostability study
of some modied poly(vinyl chloride) containing pendant ben-
zothiazole and benzimidozole ring. Inter. J. Chem. 2, 6580.
Zhao, Y., Dan, Y., 2006. Preparation and characterization of a high
molecular weight UV-stabilizer based on a derivative of 2,4-
dihydroxybenzophenone and its application in polymer materials.
J. Appl. Poly. Sci. 102, 22032211.