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ORIGINAL ARTICLE
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
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.
1. Introduction
* Corresponding author. Tel.: +964 7901782816.
Ultraviolet light stabilizers are used widely in plastics, cosmet-
E-mail address: emad_yousif@hotmail.com (E. Yousif). ics, and lms. The main purpose of UV-stabilizer is to prevent
polymers from photodegradation or photocrosslinking caused
1319-6103 2011 King Saud University. Production and hosting by
by ultraviolet light presented in sunlight and articial light
Elsevier B.V. Open access under CC BY-NC-ND license.
source. Ultraviolet light stabilizers are divided into inorganic
Peer review under responsibility of King Saud University. UV-stabilizers, organic UV-stabilizers, and otherkinds. Inor-
doi:10.1016/j.jscs.2011.01.009 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
Production and hosting by Elsevier
polymer matrix. The nal effects depend on the particle size
and concentration (Zhao and Dan, 2006). These drawbacks
280 E. Yousif et al.
limit the application of inorganic UV-stabilizers. Organic temperature for 3 h under reduced pressure. The lms were
UV-stabilizers, generally with small molecular weight, include xed on stands especially used for irradiation. The stand is
uorescent compounds, phenyl-ester of benzoic acid, hydrox- provided with an aluminium plate (0.6 mm in thickness) sup-
ylbenzophenone, benzotriazoles, etc. In the addition of these plied by Q-panel company.
stabilizers to plastic materials, problems such as migration,
incompatibility, volatility, and solvent extraction will inevita- 3.2. Irradiation experiments
bly occur. It leads to a strong diminution of the materials
utilization. To resolve such problems, many approaches have 3.2.1. Accelerated testing technique
been developed, such as preparing reactive UV-stabilizer, Accelerated weather-meter Q UV tester (Q panel, Company,
(Yousif et al., 2009; Grassie and Scott, 1985) introducing com- USA), was used for irradiation of polymers lms. The acceler-
patible side chains, or chemically anchoring of the additive to ated weathering tester contains stainless steel plate, which has
the polymer backbone, etc (Andrady et al., 1988). Among two holes in the front side and a third one behind. Each side
these methods, preparing high molecular weight UV-stabilizer contains a lamp (type Fluorescent Ultraviolet Lights) 40 W
is a highlight because, for most of the polymer materials, each. These lamps are of the type UV-B 313 giving spectrum
blending is the rst choice to enhance their UV-resistance. range between 290 and 360 nm with a maximum wavelength
Meanwhile, different high molecular weight UV-stabilizers 313 nm. The polymer lm samples were vertically xed parallel
can be prepared by the copolymerization of a reactive UV-sta- to the lamps to make sure that the UV incident radiation is
bilizer with other monomers. In this point, it is very convenient perpendicular on the samples. The irradiated samples were ro-
to ameliorate the compatibility between UV-stabilizer and tated from time to time to ensure that the intensity of light inci-
plastic matrix by preparing suitable high molecular weight dent on all samples is the same.
UV-stabilizer (Harper et al., 1974). As part of our on-going
research on the photostabilization of polymers, the photostabi- 3.3. Photodegradation measuring methods
lization of PMMA was studied using Schiff bases of 2,5-dimer-
capto-1,3,4-thiadiazole compounds. 3.3.1. Measuring the photodegradation rate of polymer lms
using infrared spectrophotometery
2. Experimental The degree of photodegradation of polymer lm samples was
followed by monitoring FTIR spectra in the range 4000
2.1. Materials 400 cm1 using FTIR 8300 Shimadzu Spectrophotometer.
The position of hydroxyl absorption is specied at 3430 cm
1
The Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole com- (Rabek and Ranby, 1975).
pounds were all prepared by the method previously described The progress of photo-degradation during different irradia-
by Salimon et al. (2010). 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):
N N
As
Is 1
Ar
C N N N N C
H H S H H
X X where As is the absorbance of peak under study, Ar is absor-
bance of reference peak, and Is is the index of group under
where X = OOH, PNO2, PN(CH3)2, PCH3 or PCl. study. Actual absorbance, the difference between the absor-
bance of top peak and base line (A top peak A base line) is cal-
3. Experimental techniques culated using the base line method (Rabek and Ranby, 1975).
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
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]
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.
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 The Ucs values for PMMA lms in the presence of additive
stages of photodegradation of PMMA, the value of a increases are less than that of additive free PMMA (blank), which in-
rapidly with time, these indicators indicates a random breaking crease in the order:
of bonds in the polymer chain. Another way of degradation [1] > [2] > [3] > [4] > [5].
reaction characterization is the measurement of the quantum
yield of the chain scission (Ucs) (Yousif et al., 2010). The quan- 4.2. Suggested mechanisms of photostabilization of PMMA by
tum yield for chain scission was calculated for PMMA lms Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole compounds
with and without 0.5% (wt/wt) of additive mentioned above
using relation (6). The Ucs values for complexes are tabulated Through the overall results obtained, the efciency of thiadia-
in Table 1. 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
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
PMMA lms can be arranged according to the change in the the rst passes by intersystem crossing (ICS) process to the
hydroxyl concentration as a reference for the comparison as excited triplet state, while the second is referred to internal
shown in Fig. 1 as follows: conversion (IC) process to the ground state.
Other mechanism explains the use of this compound as
[1] > [2] > [3] > [4] > [5].
photostabilizer is by charge separated species which could be
Schiff base stabilize PMMA by different mechanisms such form of the excited state such a structure would allow dissipa-
as UV absorber, screener or by radical scavenger. These stabi- tion of energy through rotation on increased vibration about
lizers provide very good long-term stability and are usually the central bond as shown in Scheme 3. The hydroxyl group
referred to these mechanisms. The most probable mechanisms of the additive might acts as radical scavenger for photostabi-
involved in a photostabilization is the change energy of lization process. Therefore this Schiff bases, besides acting as
absorbed photon to the intramolecular proton transfer. This UV absorber they may also act as radical scavenger additives
reaction may occur by two proposed cycles Schemes 1 and 2, (Rasheed et al., 2009), Scheme 4.
Evaluation of Schiff bases of 2,5-dimercapto-1,3,4-thiadiazole as photostabilizer for poly(methyl methacrylate) 285
The rings of 1,3,4-thiadiazole play a role in the mecha- Grassie, N., Scott, G., 1985. Polymer Degradation and Stabilization.
nism of the stabilizer process by acting as UV absorber. Cambridge University Press, London.
The UV light absorption by these additives containing Gugumus, F., 1990. Mechanism of Polymer Degradation and
1,3,4-thiadiazole dissipates the UV energy to harmless heat Stabilization. Elsevier, Amsterdam.
Harper, D., McKellar, N., Turner, P., 1974. Photostabilizing effect of
energy Scheme 5.
Ni(II) chelates in polymers. II. Effect of diamagnetic chelates on
Furthermore, this ring plays a role in resonating structures
polypropylene phosphorescence. J. Appl. Polym. Sci. 18 (311),
conjugation of radical in peroxide decomposer Scheme 5, 28022805.
which sport it function as a photostabilizer (Yousif et al., Mark, J., 2007. Physical Properties of Polymers Handbook. Springer,
2007). New York.
Mori, F., Koyama, M., Oki, Y., 1997. Studies on photodegradation of
5. Conclusions poly(vinyl chloride) (Part I). Die Angewandte Mak-omolekulare
Chemie 64 (1), 8999.
In the work described in this paper, the photostabilization of Nakajima, N., Sadeghi, M., Kyu, T., 1990. Photodegradation of
poly(methyl methacrylate) by monochromatic light: Quantum
PMMA lms using Schiff bases of 2,5-dimercapto-1,3,4-thiadi-
yield, effect of wavelengths, and light intensity. J. Appl. Poly. Sci.
azole compounds were studied. These additives behave suc-
41, 10231032.
cessfully as photostabilizer for PMMA lms. The additives Rabek, J., Ranby, B., 1975. Photodegradation, Photo-oxidation and
take the following order in photostabilization activity accord- Photostabilization of Polymers. John Wiley, New York.
ing to their decrease in hydroxyl index for PMMA lms. Rasheed, R., Mansoor, H., Yousif, E., Hameed, A., Farina, Y.,
[1] > [2] > [3] > [4] > [5]. Graisa, A., 2009. Photostabilizing of pvc lms by 2-(aryl)-5-
These additives stabilize the PMMA lms through UV [4-(aryloxy)-phenyl]-1,3,4-oxadiazole compounds. Eur. J. Sci. Res.
absorption or screening, peroxide decomposer, and radical 30, 464477.
scavenger mechanisms. The [1] compound was found to be Salimon, J., Salih, N., Yousif, E., Hameed, A., Ibraheem, H., 2010.
the more efcient in photostabilization process according to Synthesis, characterization and biological activity of schiff bases of
2, 5-dimercapto-1,3,4-thiadiazole. Aust. J. Basic Appl. Sci. 4 (7),
the photostability and mechanisms mentioned above. These
20162021.
mechanisms support the idea of using Schiff bases of 2,5-
Shyichuk, A., White, J., 2000. Analysis of chain-scission and
dimercapto-1,3,4-thiadiazole compounds as commercial stabi- crosslinking rates in the photo-oxidation of polystyrene. J. Appl.
lizer for PMMA. 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-
Acknowledgments zole. J. Al-Nahrain Univ. 10, 712.
Yousif, E., Aliwi, M., Ameer, A., Ukal, J., 2009. Improved
The authors acknowledge the IIE, SRF, and to the supporting photostability of PVC lms in the presence of 2-thioacetic acid-5-
staffs of School of Chemical Sciences and Food Technology, phenyl-1,3,4-oxadiazole complexes. Turk. J. Chem. 33, 339
Faculty of Science and Technology, University Kebangsaan 410.
Malaysia and Department of Chemistry, College of Science, Yousif, E., Hameed, A., Rashed, R., Mansoor, H., Farina, Y., Graisa,
A., Salih, N., Salimon, J., 2010. Synthesis and photostability study
Al-Nahrain University for their encouragement.
of some modied poly(vinyl chloride) containing pendant ben-
zothiazole and benzimidozole ring. Inter. J. Chem. 2, 6580.
References Zhao, Y., Dan, Y., 2006. Preparation and characterization of a high
molecular weight UV-stabilizer based on a derivative of 2,4-
Andrady, A., Searle, N., 1989. Photodegradation of rigid PVC dihydroxybenzophenone and its application in polymer materials.
formulations. II. Spectral sensitivity to light-induced yellowing by J. Appl. Poly. Sci. 102, 22032211.
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.