Pigment & Resin Technology

Synthesis and evaluation of new antioxidants for styrene butadiene rubber

Galal Nawwar Sayed Yakout M.S.A El-Sadiek Salwa El-Sabbagh
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To cite this document:
Galal Nawwar Sayed Yakout M.S.A El-Sadiek Salwa El-Sabbagh, (2011),"Synthesis and evaluation of new antioxidants for
styrene butadiene rubber", Pigment & Resin Technology, Vol. 40 Iss 6 pp. 399 - 409
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 Synthesis and evaluation of new antioxidants
for styrene butadiene rubber
Galal Nawwar, Sayed Yakout and M.S.A El-Sadiek
Green Chemistry Department, National Research Centre, Cairo, Egypt, and
Salwa El-Sabbagh
Polymers and Pigments Department, National Research Centre, Cairo, Egypt

Abstract
Purpose – The purpose of this paper is to study the effect of new heterocyclic compounds on styrene butadiene rubber (SBR) mixes.
Design/methodology/approach – It has been found that the starting material 1 could react with cyromazine (2) and/or 4-aminoantipyriene (4)
as amino compounds in the presence of triethylorthoformate and in the boiling dioxane to yield triazine-3 and/or pyrazolo 5 derivatives, respectively.
The chemical structures of the new products 3 and 5 have been established by their elemental analyses spectroscopic data IR, Ms and 1H, 13C NMR.
These two compounds were evaluated as antioxidants in SBR, and this evaluation was confirmed by physico-mechanical properties of vulcanizates,
IR spectra and scanning electron microscope.
Findings – The difference between maximum torque MH and minimum torque ML (DM), tensile strength, modulus and elongation at break increases
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in the presence of prepared antioxidants while the equilibrium swelling decreased. The rubber vulcanizates were subjected to thermal oxidative aging
at 908C for up to seven days. It has been found that new compounds 3 and 5 can protect SBR vulcanizates against oxidative deterioration.
Research limitations/implications – The solubility of the prepared compounds 3 and 5 is very poor and they are only soluble in dimethyl formamide
(DMF) or dimethyl sulphoxide (DMSO) which have high boiling points. Also, new compounds 3 and 5 have melting points (above 3008C).
Practical implications – Triazine and antipyrine derivatives have many medical and industrial applications.
Originality/value – The new synthesized compounds revealed excellent antioxidant behaviour in comparison with the commercial antioxidant phenyl-
b-naphthyl amine (PbN) which is used in industry.

Keywords Plastics and rubber technology, Vulcanization, Styrene butadiene rubber, SBR, Antioxidant, Cyromazine, 4-aminoantipyriene,
Oxidation resistance

Paper type Research paper

Introduction inflammatory activities (Yakout and El-Sabbagh, 2007; Isobe

One of the widely used synthetic rubbers is the copolymer
styrene butadiene rubber (SBR) due to its high fracture
elongation. However, it has low elastic modulus and durability.
Also, it is employed in the tire industry and for other rubber
items.
Raw rubber (SBR) is not smooth or homogeneous and has
poor physical properties, so other materials are mixed with it such
as: antioxidants, accelerators, softeners and fillers to improve its
properties. The ingredients of mixes, present in small quantities,
influence the physical properties to a small extent.
Also, nitrogen heterocyclic compounds have many
applications in the rubber industry and the synthesis of
organic compounds and the evaluation of their efficiency in
rubber mixes as accelerators or antioxidants still create
increasing interest. On the other hand, the uracil antioxidants
are environmentally safe, since they do not form hazard
compounds during vulcanization. Moreover, many uracil
derivatives have been reported to have antioxidative and anti-
The current issue and full text archive of this journal is available at
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Pigment & Resin Technology
40/6 (2011) 399– 409
q Emerald Group Publishing Limited [ISSN 0369-9420]
[DOI 10.1108/03699421111180554]
et al., 2003). They are also known to be associated with coronary
anticoagulant (South et al., 2006), antiviral (Gazivoda et al.,
2005) and herbicides activities (Kamireddy and Murray, 1996).
In addition, some uracils are also known as efficient corrosion
inhibitors (Dafali et al., 2003). There are many factors affects
the efficiency of the antioxidants such as rubber type, the nature
of other rubber ingredients in the mixes, time of aging and also
on their chemical structures (Morton, 1973; Pitrofskir and
Tarasova, 1980).
In spite of the fact that such organic compounds which can be
used as accelerators, antioxidants and anti-fatigue agents are
added in very small amount, they play a very important role in
determining the service characteristics of the obtained rubber
vulcanizates, consequently, the elaboration of heat resistant
national task (Ismail et al., 2002; Klein et al., 2005; Rapta et al.,
2009; Wazzan et al., 2005; Youssef et al., 2003). Recently, uracil
and/or benzothiazole derivatives have been reported as good
antioxidants in natural rubber mixes (Yakout and El-Sabbagh,
2007). Also, we have found that lignin, which could be extracted
from rice straw waste, acts as antioxidant and thermal stability
agent for SBR (Nawwar et al., 2009).
To continue our work, the reaction of the cheap starting
material, cyano acetyl urea 1 with cyromazine 2 and/or
The authors are thankful to STDF for providing the financial support for
the project ID 133.

399
 Evaluation of new antioxidants for styrene butadiene rubber
Galal Nawwar et al.
4-amino antipyrene 4 and triethylorthoformate have been
investigated in one pot reaction to produce the uracil
derivatives 3 and/or 5, in a fairly good yield, respectively.
These two new compounds 3 and 5 have been evaluated as
antioxidant agents in SBR.
Experimental
Melting points are uncorrected and were taken on electro
thermal 9100 apparatus. IR spectra were recorded on Carl
Zeise spectrophotometer model “UR 10” using KBr.
1
H-NMR spectra were determined on Jeol 270 MHz using
tetramethylsilane as an internal standard. Mass spectra were
recorded on Finigan SSQ 7000 mass spectrometer.
Microanalysis was performed by the Central Service
Laboratory at Cairo University and the Microanalytical
Laboratory at National Research Center. Found: C, 60.28;
H, 2.94; N, 12.10; S, 9.22 percent.
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1-(4-amino-6-[cyclopropylamino] 2 1, 3, 5triazin-2-yl)
1, 2, 3, 4-tetrahydro 2 2, 4-dioxopyrimidine-5-
carbonitrile (3)
Compound 1 (0.01 mole, 1.27 gm), triethylorthoformate (0.03
mole, 4.4 ml) and N-cyclopropyl 2 1,3,5-triazine 2 2,4,6-
triamine (cyromazine) 2 (0.01 mole, 1.7 gm) were refluxed in
dioxane for 8 h (until the evolution of NH3 ceased). The
precipitate was formed on hot, then it was filtered off, dried and
recrystallised from dimethyl formamide (DMF)/H2O:
. M.P. above 3008C, yield 85 percent.
1 .
.
H-NMR (DMSO-d6, TMS [DMSO, dimethyl
sulphoxide]), d ¼ 0.4 2 0.8 (m, 4 H, cyclopropane
protons); 1.2 (m, 1H, cyclopropane protons); 6.1 (brs, 2H,
NH2); 6.6, 8.0 (2brs, 2H, 2NH); 8.8(s, 1H, pyrimidine H).
. IR (KBr), y cm2 1, 1,622, 1,704, (2CO), 22,238 (CN),
3,185, 3,332 (NH2), 3,426(NH).
.
Mass: m/z (Mþ ¼ 286, 20 percent).
.
Anal. calcd for C11H10N8O2 (286) C, 46.15; H, 3.49; N,
39.16 percent.
.
Found: C, 46.0; H, 3.1; N, 38.8 percent.
1,2,3,4-tetrahydro-1-(2,5-dihydro 2 2,3-dimethyl-5-
oxo-1-phenyl-1H-pyrazol-4-yl) 2 2,4-dioxopyrimidine-
5-carbonitrile (5)
Compound 1 (0.01 mole, 1.27 gm), triethylorthoformate
(0.03 mole, 4.4 ml) and 4-amino 2 2, 3-dimethyl-1-phenyl-3-
pyrazolin-5-one (4-amino antipyrene) 4 (0.01 mole, 2.03 gm)
were refluxed in dioxane for 8 h (until the evolution of NH3
ceased). The precipitate was formed on hot, then it was filtered
off, dried and recrystallised from butanol:
.
M.P. above 3008C, yield 80 percent.
1
.
H-NMR (DMSO-d6, TMS), 2.2 (s, 3H, CH3); 3.1 (s,
3H, N-CH3); 3.7 (s, 1H, NH); 7.3-7.6 (m, 5H,
Aromatics); 8.6(s, 1H, pyrimidine H-6).
.
IR (KBr), y cm2 1, 1,644, 1,695 and 1,745 (3CO), 2,229
(CN), 3,000 (NH).
.
Mass: m/z (Mþ ¼ 323, 100 percent).
.
Anal. Calcd for C16H13N5O3 (323) C, 59.4; H, 4.2; N,
21.6 percent.
.
Found: C, 59.1; H, 4.0; N, 21.3 percent.
400
Pigment & Resin Technology
Volume 40 · Number 6 · 2011 · 399 –409
Materials
Rubber
SBR, butadiene styrene copolymer, styrene content 23.5
percent, specific gravity 0.945 ^ 0.005, moony viscosity
ML(1 þ 4) at 1008C ¼ 52 ^ 3, average molecular weight
140,326 (calculated in the previous work (Yehia et al., 1993)
using the Mark-Houwink equation), glass transition
Tg ¼ 2608C from Bayer AG, Germany.
Solvent and chemicals
All solvent and chemical reagents were of pure grade and were
further purified, if necessary, by distillation. Other rubber
ingredients were those customarily used in rubber industries.
Techniques for reparation and characterisation
All rubber mixes were prepared on a laboratory two-roll mill
of 470 mm diameter and 300 mm working distance. The
speed of the slow roller was 24 rpm, with a 1:1.4 gear ratio.
The rubber was mixed with other ingredients according to
ASTM (D15-72; 2007) and careful control of temperature,
nip gap and sequenced addition of ingredients.
Vulcanization was carried out in a single-daylight
electrically heated auto controlled hydraulic press at
142 ^ 18C and pressure 4 MPa. The compounded rubber
and vulcanizates were tested according to standard methods,
namely:
.
ASTM D 2084-07 (2007) for determination of
rheometric characteristic using a Monsanto Rheometer
(model 100).
.
ASTM D 412-06 (2006); DASTMD624-07(2007) for
determination of physico mechanical properties using
Zwick tensile testing machine (model 1425).
Thermal oxidative aging was carried out according to
ASTM D 3629 (2007).
.
Hardness was determined according to ASTM D 2240-07
(2007).
.
Swelling was determined according to ASTM D 471-07
(2007).
It was possible to make use of the swelling data to calculate
the molecular weight between two successive crosslinks (MC)
by the application of the well-known Flory Rehner equation
(Zhang et al., 2003).
Crosslinking density:
     
1 1 21
u¼ Mc Mc ¼ rV0 Þ
2 2 2
 
  1=3 VR
£ Lnð1 2 VR Þ þ VR þ mV2R = VR 2
2
where r is the density of rubber; Vo the molar volume of solvent
absorbed (for toluene Vo ¼ 106.3 cm3/mole); VR is the volume
fraction of the rubber in the swollen material (Calculated as VR
¼ 1/(1 þ Qm)); where Qm (equilibrium swelling):
V
Qm ¼
ðWd =r1 Þ
V is the volume of solvent absorbed by rubber and r1 the density
of solvent and (m), the interaction parameter for SBR is 0.446.
Electron microscopy
Phase morphology was studied using a JEOL JXA-840A
electron probe micro analyser supplied by JEOL, Japan.
 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

The fracture surfaces were gold coated to avoid electrostatic
changing during examination.
Results and discussion
Cyanoacetylurea 1 could be easily prepared (Enomoto et al.,
2001) in good yield by the reaction of urea and cyanocetic
acid, which are commercially available chemicals. Compound
1 has been used as starting material for the synthesis of
variety of heterocycles (Allam et al., 2001, 2002). Thus,
Cyanoacetylurea 1 was allowed to react with quantitave
amount of cyromazine (2) and/or 4-amino antipyrene (4) and
triethylorthoformate in boiling dioxane to give 1-(4-amino-
6-[cyclopropylamino] 2 1, 3, 5triazin-2-yl) 1, 2, 3, 4-
tetrahydro 2 2, 4-dioxopyrimidine-5-carbonitrile (3) and
1,2,3,4-tetrahydro-1-(2,5-dihydro 2 2,3-dimethyl-5-oxo-1-
phenyl-1H-pyrazol-4-yl) 2 2,4-dioxopyrimidine-5-carbonitrile
(5), respectively. In the proton NMR, the new uracil derivatives 3
and 5 revealed H-6 pyrimidine proton as a singlet signal at
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antioxidants where DM may be taken as the extent of
crosslinking in the rubber phase (Manna et al., 1999).
It is evident that DM is higher in the case of M2 than M3,
i.e. the crosslink density increase for M2. Also, it is clear that
the increased tensile strength, modulus at 100 percent strain
and hardness while decreased equilibrium swelling and
elongation at break.
Effect of the different concentrations of the investigated
antioxidants on SBR
The prepared antioxidants were incorporated in SBR
formulation at different concentrations as shown in Tables
III and IV. Also, the rheometric characteristics of the mixes, as
well as the physico-mechanical properties of the vulcanizates
are presented in these tables and Figures 1-3. From the data
shown in Table III, the maximum torque, which is a measure
of the stiffness of the compound, is found to be increased with
the increase in concentration of antioxidant which contain
pyrazol ring (compound 5). It is directly related to the
modulus of the compound. On the other hand, the stress 100

d ¼ 8.5 ppm (see “experimental” section).

Effect of the compounds prepared on the vulcanization
of SBR mixes
Uracil derivatives were incorporated into SBR mixes in
equimolar quantities to phenyl-b-naphthyl amine (PbN)
which is antioxidant used widely in the rubber industry, this
is due to their similar chemical structure. The rheometric
characteristics, as well as the physico-mechanical properties of
the vulcanizates are given in Tables I and II.
From these data, it is clearly seen that the value of scorch
time, cure rate index (CRI) minimum torque of the prepared
antioxidant M2 decreased while scorch time for M3
approximately is the same level with PbN. This behaviour
may be due to the presence of pyrazol ring in M2 while in M3
presence cyclopropylamins. Also, it is noticed that the
difference between maximum torque MH and minimum
torque ML, (DM), increases in the presence of prepared
percent strain, tensile strength, Young’s modulus, hardness
and crosslink density ( y ) increased with increasing
concentration of antioxidant up to the ratio 2 phr and then
the improvement decreases. While equilibrium swelling and
MC decreased with increasing concentration of antioxidant.
It is also evident that DM has its highest value at concentration
1.47 phr (mix. no. M2). Also, we can see that all SBR mixes with
and without compounds under investigation have almost the
same level of optimum cure time (tc90). It is worthy to notice that
compound 5 increases the crosslink density of the vulcanization
more than compound 3. This can be explained by its antioxidant
effect, which is attributed to the presence of the pyrazol moiety.
Also, from data in Table IV, it is clear that SBR vulcanizates
containing 1.3 phr of the prepared compound 3 (mix. no. M3)
have the highest value of the physical properties in comparison
with the other mixes containing different concentrations of
antioxidant 3. Furthermore, these formulations have the lowest
value of equilibrium swelling and the highest value of hardness,

Table I Rubber formulations and rheometric characteristics of SBR mixes

Ingredient in phr M0 M1 M2 M3
SBR 100 100 100 100
Stearic acid 2 2 2 2
Zinc oxide 5 5 5 5
Hisil 40 40 40 40
Processing oil 3 3 3 3
Sulphur 2.5 2.5 2.5 2.5
CBS 1 1 1 1
PbN – 1 – –
S21 (prepared antioxidant) compound 5 – – 1.47 –
S22 (prepared antioxidant) compound 3 – – – 1.30
Rheometric characteristics at 152 6 18C
Minimum torque (ML) (dN.m) 13 13.25 9.75 11.5
Maximum torque (MH) (dN.m) 61 69 71 67.5
Optimum cure time (min) 26.25 25 25 25.75
Scorch time (min) 10.25 8.75 7.75 10.25
CRI (min 2 1) 6.25 6.15 5.8 6.45
DM (Mmax 2 Mmin) (dN.m) 48 55.75 61.25 56
Notes: CBS – N-cyclohexyl-2-benzothiazole sulphenamide; PbN – phenyl-b-naphthyl amine

401
 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Table II Physico-mechanical properties of SBR mixes containing the prepared antioxidants

Ingredient in phr M0 M1 M2 M3
s 100 (MPa) 1.49 1.74 1.96 1.54
Tensile strength (MPa) 8.48 9.33 11.49 10.93
Elongation at break (%) 796 898 743 785
Young’s modulus (N/mm2) 1.4 1.68 1.71 1.48
Equilibrium swelling (%) 339 312 263 283
Soluble fraction (%) 6.04 4.88 4.39 4.6
Molecular weight between crosslinks (Mc) (g/mole) 6,562 5,556 3,968 4,587
Crosslink density, y 3 104 (mole/cm3) 0.762 0.9 1.26 1.09
Hardness, shore A 55 57 61 63

Table III Effects of the different concentrations of compound 5 (S21) on the rheometric characteristics and physico-mechanical properties of SBR mixes
Formulation no. M4 M5 M2 M6 M7 M8
Concentration in phr 0.5 1 1.47 2 2.5 3
Rheometric characteristics at 152 6 18C of compound 5
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Minimum torque (dN.m) 11 11 9.75 12 12.75 13

Maximum torque (dN.m) 65 66 71 72 72 72
Optimum cure time (min) 24.5 24.75 25 24.75 25 24.38
Scorch time (min) 9.25 9.5 7.75 9.75 9.75 9.25
CRI (min2 1) 6.56 6.56 5.8 6.67 6.56 6.61
DM (Mmax 2 Mmin) (dN.m) 54 55 61.25 60 59.25 59
Physico-mechanical properties of compound 5
Equilibrium swelling (%) 289 267 263 257 282 282
Soluble fraction (%) 4.92 4.87 4.39 3.89 4.07 4.17
Molecular weight between crosslinks (Mc) (g/mole) 4,780 4,088 3,968 3,791 4,554 4,554
Crosslink density, y 3 104 (mole/cm3) 1.05 1.22 1.26 1.32 1.098 1.098
Hardness, shore A 58 60.25 61 64 61 62

Table IV Effects of the different concentrations of compound 3 (S22) on the rheometric characteristics and physico-mechanical properties of SBR mixes
Formulation no. M9 M10 M3 M11 M12 M13
Concentration in phr 0.5 1 1.3 2 2.5 3
Rheometric characteristics at 152 6 18C of compound 3
Minimum torque (dN.m) 11.25 11 11.5 11.25 11 10.75
Maximum torque (dN.m) 66 67 67.5 65 66.5 66.5
Optimum cure time (min) 26.25 26.5 25.75 26 25.75 25
Scorch time (min) 9.25 9.75 10.25 9.5 9.25 9.25
CRI (min2 1) 5.88 5.97 6.45 6.06 6.06 6.34
DM (Mmax 2 Mmin) (dN.m) 54.75 55.75 56 53.75 55.5 55.75
Physico-mechanical properties of compound 3
Equilibrium swelling (%) 320 299 283 297 304 305
Soluble fraction (%) 5.05 4.8 4.6 4.8 4.47 4.52
Molecular weight between crosslinks (Mc) (g/mole) 5,854 5,112 4,587 5,045 5,285 5,319
Crosslink density, y 3 104 (mole/cm3) 0.854 0.978 1.09 0.991 0.946 0.94
Hardness, shore A 57 59 63 58 60 59

besides the CRI. This means that the physical properties have
been improved by using investigated antioxidants. The stress,
strain curves for the vulcanizates are given in Figure 4 which
shows that addition of antioxidants 5 or 3 increases the strain
(Scheme 1), as well as the increasing in the stress. This may be
due to the increase in crosslink density. The elongations at break
values show a decrease in the presence of antioxidant 3 than in the
presence of antioxidant 5. This may be due to the decrease in
flexibility, resulting from the increase in crosslink density.
Effect of the compound prepared on the thermal
oxidative aging of SBR vulcanizates
The SBR mixes containing compounds 5 and 3 were
subjected to thermal oxidative aging in an aerated oven at

402
 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 1 The relation between modulus at 100 percent elongation, tensile strength and elongation at break of SBR vulcanizates without and with
different type of antioxidants

14 1,000

900
12
800

Modulus at b100% elongatlon and 10 700

Elongatlon at break.%
Tenslle strength. MPa
600
8
500
6
400

4 300

200
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2
100

0 0
Mo M1 M2 M3
Type of antloxldants

M T.S E,%

Figure 2 The relation between modulus at 100 percent elongation, Figure 3 The relation between modulus at 100 percent elongation,
tensile strength and elongation at break of SBR vulcanizates with tensile strength and elongation at break of SBR vulcanizates with
different concentration of antioxidants (S21) different concentration of antioxidants (S22)

16 1,200 12 1,200
Modulus at 100% elongation,

14
1,000 10 1,000
100% elongation, Tensile

Elongation at break, %
Elongation at break,%

Tensile strength ,MPa

12
strength, MPa

800 8 800
Modulus at

10

8 600 6 600
6
400 4 400
4
200 2 200
2

0 0 0 0
M2 M4 M5 M6 M7 M8 M3 M9 M10 M11 M12 M13
Concentrations of antioxidant, Phr Different concentrations of antioxidant, Phr
M T.S E%
M T.S E,%

908C ^ 18C for different time periods up to seven days.

The modulus at 100 percent strain values registers a slight
increase after thermal aging for all samples (Figures 5 and 6). On the other hand, we can see that the prepared compounds
The increase in modulus values may be due to the formation 5 or 3 are more efficient as antioxidants than the reference
of additional crosslinking (Figures 7-9). The retained values compound PbN. The efficiency of these prepared compounds
of tensile strength and strain at break were calculated and are greatly depends on the type of substitution groups in the
shown in Figures 6 and 7 and Figures 10 and 11. From these uracil ring. These results are in good agreement with
figures, it is clearly seen that the retained values of stress at the retained values of equilibrium swelling and are shown in
rupture and strain at rupture decrease with the increase of the Figures 8 and 12 which confirm that the prepared compounds
ageing time. protect the sample against oxidative degradation.

403
 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 4 Stress-strain curves of SBR vulcanizates without and with different types of antioxidants
12

10

Stress, MPa
6

0
0 200 400 600 800 1,000
strain, %

Mo M1
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M2 M3

Scheme 1 Reaction mechanism for prepared antioxidants 3 and 5

NH2
H3C NH2
N N
N O H
H3C N N
N NH2 H2N N
4 NC H
Ph 2

+ O O +
1
CH(OC2H3)3 CH(OC2H5)3

O
O
NC
NH NC
NH

N O N O
H3C

N N N
H3C N O
H2N N N
Ph
H
5 3

The study of all curves of the relative changes in Differentiation of this equation with respect to time
physico-mechanical properties against time showed that they gives the rate of change of the retained values of the
obey the exponential relationship shown in equation: physico-mechanical with respect to aging time:

Y ¼ aebt ð2 # t # 7 daysÞ dY=dt ¼ abebt

It can be seen from these figures that the prepared
where Y is the tensile strength, t is the aging time and a and b compounds 5 or 3 have higher antioxidants efficiency than
are material constants. reference compound (PbN).

404
 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 5 The relation between aging time and retained values of stress Figure 7 The relation between aging time and retained values of strain
at 100 percent strain of compound 5 (S21) at break of compound 5 (S21)
270 120
Retained values of stress at 100% strain, %

Retained values of strain at break,%

245
100

220
80
195
60
170

40
145

120 20

95 0
0 2 4 6 8
70 Aging time, days
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0 2 4 6 8
Aging time, days M0 M1 M2 M4
M5 M6 M7 M8
M0 M1 M2

M4 M5 M6

M7 M8
Figure 8 Retained equilibrium swelling in toluene vs aging time for
Figure 6 The relation between aging time and retained values of SBR vulcanizates containing different concentrations of prepared
tensile strength of compound 5 (S21) compound 5 (S21)

110 130
Retained values of tensile strength,%

100 115
R.V. of equilibrium swelling, %

90
100
80
85
70

60 70

50
55
40
0 1 2 3 4 5 6 7
40
Aging time, days 0 1 2 3 4 5 6 7
Aging time, days
M0 M1 M2
M4 M5 M6 M0 M1 M2 M4
M7 M8 M5 M6 M7 M8

IR spectra SBR matrix and the band at 1,611 cm2 1 due to polybutadiene
Infrared spectrometry is used to study the chemical and unsaturated components. In Figure 13(b) where IR
interaction between the prepared antioxidants 5 or 3 (M2 or spectra of SBR vulcanizates containing antioxidants PbN
M3), PbN (M1) and SBR rubber (Mo). Figure 13 shows a (M1) shows the small absorption bands at 1,543, 1,495 and
typical IR spectrum for SBR. From the spectrum it is clear 1,415 cm2 1 for N-H bending vibrations implies the presence
that the bands that appeared between 753 and 922 cm2 1 are of amines in the sample (due to PbN). While the band that
indicative of the presence of CH bending frequency of appeared at 3,433 cm2 1 is indicative of the presence of N-H
styrene. On the other hand, the band at 753 cm2 1 for all the stretching which proves that PbN was incorporated on the
vulcanizates due to the styrene moiety present in SBR. The SBR chain. The IR spectrum of the M2 is shown in
bands at 2,921 and 2,851 cm2 1 for CH2 stretching due to Figure 13(c). It exhibits characteristic imide group absorption

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Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 9 The relation between aging time and retained values of stress Figure 11 Retained values of strain at rupture vs aging time for SBR
at 100 percent strain of compound 3 (S22) vulcanizates containing compound 3 (S22)
260 120
Retained values of stress at 100% strain, %

100
220

R.V. of strain at rupture,%

80
180
60

140
40

100 20

0
60 0 2 4 6 8
0 2 4 6 8 Aging time, days
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Aging time, days

M0 M1 M3
M0 M1 M3 M9 M9 M10 M11
M12 M13
M10 M11 M12 M13

Figure 10 Retained tensile strength vs aging time for SBR vulcanizates Figure 12 Retained equilibrium swelling in toluene vs aging time for
containing compound 3 (S22) SBR vulcanizates containing different concentrations of prepared
compound 3 (S22)
115
115

100
R.V. of equilibrium swelling, %
R.V. of tensile strength, %

100

85
85

70 70

55 55

40 40
0 2 4 6 8 0 2 4 6 8
Aging time, days Aging time, days

M0 M1 M3
M0 M1 M3
M9 M10 M11
M9 M10 M11 M12 M13
M12 M13

at 1,739 cm2 1 (typical of imide carbonyl asymmetrical and spectra of SBR vulcanizates containing antioxidant 3 (M3).
symmetrical stretch). The most important features of the spectra are the carbonyle
The broad band at 3,429 cm2 1 is due to the N-H stretching absorption occurring at 1,735 cm2 1 (which is due to the uracil
vibration while the bands around 1,561 and 1,542 cm2 1 are derivative 3). The band at 3,439 cm2 1 can be attributed to the
attributed to the N-H bending (which is due to the uracil N-H stretching confirming the presence of uracil and also
derivative 5). The presence of bands at around 2,851 cm2 1 suggests the presence of secondary amino group (-NH-) while
(symmetrical CH3 stretching vibration), these bands the small absorption band at 1,540 cm2 1 for N-H bending
overlapped with the N-C-H stretching bands. These results vibration implies the presence of unreacted amines in the
further indicate that the prepared antioxidant 5 (M2) has been sample. The appearance of a band at 1,458 cm2 1 supported
incorporated within the SBR chain. In Figure 13(d) where IR the presence of amine hydrocarbon chain in the uracil derivative

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 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 13 The infrared spectrum

100

100
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100

100

95

90

87
4,000 3,000 2,000 1,000 400
–1)
Wavenumber (cm
Notes: (a) SBR without antioxidant; (b) SBR with Pb N; (c) SBR with M2;
(d) SBR with M3

3 (N-H deformation bending band). The band at 1,394 cm2 1
can be assigned to stretching C-N. The characteristic bands
confirm that the addition of prepared antioxidant compound 3
(M3) to SBR induces some specific interaction between phases.
Electron microscope investigations
Scanning electron microscopy offers the simplest investigative
procedure, since it reveals surface features. The internal
structure of the SBR vulcanizate was investigated by viewing
the future surfaces created at ambient temperature.
Figure 14(a) shows the morphology of SBR vulcanizate
without antioxidant. Lamellae were obtained resembling
cavities homogeneously distributed all over the surface. In
the case of SBR vulcanizates loaded with PbN, it reveals an
increase in the number of cavities and cracks, i.e. a smoother
surface with a reduction in matrix deformation as shown in
Figure 14(b). While for antioxidant S21 (compound 5) for
different concentration the separate particles are distributed
on their surface (Figure 14(c) and (e)). It was seen that the
size of the dispersed phase (SBR) domains decrease with the

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 Evaluation of new antioxidants for styrene butadiene rubber Pigment & Resin Technology
Galal Nawwar et al. Volume 40 · Number 6 · 2011 · 399 –409

Figure 14 Scanning electron micrograph with magnification 1000

× 1,000 50 µm × 1,000
50 µm (b)
(a)
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50 µm × 1,000
(c)
50 µm × 1,000
(d)

50 µm × 1,000 50 µm × 1,000
(e) (f)

50 µm × 1,000 50 µm × 1,000
(g) (h)
Notes: (a) Without antioxidant; (b) contain PbN; (c) 0.5 phr of compound 5; (d) 1.47 phr of
compound 5; (e) 3 phr of compound 5; (f) 0.5 phr of compound 3; (g) 1.3 phr of compound 3;
(h) 3 phr of compound 3

408
 Evaluation of new antioxidants for styrene butadiene rubber
Galal Nawwar et al.
addition of antioxidant S22 (compound 3) and no gross phase
separation is present in the surface (Figure 14(f) and (h)).
Conclusion
From the results shown above, it has been found that:
. The prepared antioxidants have good thermal stability.
.
As the aging time increase, the rubber contained prepared
antioxidants or PbN have better aging resistance than
without (Mo).
.
The crosslink density increases by adding antioxidant to
rubber while the equilibrium swelling decrease.
.
The mechanical properties have been more improved after
adding the prepared antioxidant than without antioxidant
or with PbN.
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Corresponding author
Salwa El-Sabbagh can be contacted at: salwa_elsabbagh@
yahoo.com
 This article has been cited by:

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Centre, Cairo, Egypt Fathy M. Abdelrazek Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt Salwa
H. El-Sabbagh Polymer and Pigments Department, National Research Centre, Cairo, Egypt . 2014. Proper use of rice straw
black liquor: lignin/silica derivatives as efficient green antioxidants for SBR rubber. Pigment & Resin Technology 43:3, 159-174.
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