Novel azophenols derivatives as antioxidant for

Egyptian base oil

Ashraf.M.Ashmawy*, Ahmed. M. El-Sawy
Chemistry Department, Faculty of Science, AL-zhar
University, 11884, Egyp.
*Corresponding author: ashraf_ashmawy2002@yahoo.com
Abstract
The oxidation stability of base oil ,delivered from co-operative
petroleum company, in the present azo phenol derivatives, 2-sec-
butyl-4-((3-chlorophenyl)diazenyl)phenol(I) and 2-sec-butyl-4-((3-
nitrophenyl)diazenyl)phenol(II) were synthesized and studied as
antioxidant for base oil. The synthesized compound was elucidated
via Elemental analysis, proton nuclear magnetic resonance 1H-NMR,
and electron ionization mass spectroscopy (EI-MS). The inhibition
performance of the synthesized compound was determination via
change in total acid number (TAN). The information show that
compound II is greater efficiency than compound I.

Key words: Azo-phenol, base oil, oxidation stability, total acid

number (TAN), and lubricating oil.

Introduction:
Lubricating oils are products formulated with using base oils and
additive compounds suitable to provide the preferred lubricant
characteristics for a specific application and performance degree for
which they are intended[1]. A lubricant may additionally serve the
function of dissolving or transporting foreign debris, and dissipating
heat [2]. Base oils are the major components of lubricants,
representing typically 85% or extra of the formulation.

The base oil is made from petroleum crude oil via various
processing steps [3]. Oxidation is a big problem inherent in the use of
lubricating engine oils in internal combustion engines [4, 5].
Oxidation produces harmful species, which ultimately compromises
the unique functionalities of a lubricant, shortens its service life, and
to a more extreme extent , damages the machinery it lubricates [6].
This oxidation is the primary reason of growth in viscosity, pour

1
point, sludge, and enhanced engine corrosion and conventional liquid
lubricants show poor oxidative and thermal stability at higher
temperature ranges [7, 8]. Antioxidants are the key additive that
protects the lubricant from oxidative degradation, permitting the fluid
to meet the demanding requirements for use in engines and industrial
packages [9, 10]. The presence of antioxidant components delays the
oxidation of base oil both by reaction with oxygen or with primary
oxidation products, such as organic radicals. The strong products of
this reaction do not react further and thereby prevent the radical chain
reaction [11]. Antioxidants can usually be considered as free radical
inhibitors of peroxide decomposers, and might range in chemical
structures. Three types of components had been proved to achieve
success in controlling the degradation of lubricating oils; radical
scavengers, and hydro peroxide decomposers in addition to
synergistic combinations of each of them[6, 12] .Various classes of
compounds had been used as antioxidant-additives too, which include
phenols, amines and heterocyclic compounds as well as synergistic
mixtures of them and additionally azo compounds. A small
percentage, sufficient to deactivate said catalyst of metal. Deactivator
having formula

HO ‫ــــ‬A‫ـــــ‬N N‫ـــــ‬B‫ـــ‬OH

Where in A and B are divalent organic radicals, aromatic in nature

such as benzene, naphthalene and pyrazolone series[13].The aim of
this work prepared of new azo phenol compounds and study the
effect of this compounds as antioxidant.

Experimental
All reagents (purchased from Aldrich, Merk Co., and Fluka Chemical
Co.) were of analytical grade and used without further Purification.
The tested base oil was delivered from co-operative petroleum
Company. The physicochemical characteristics of the base oil are
tabulated in Table 1.

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1- Preparation of additives (I and II) [14]
(i) Diazotization

A mixture of aniline derivatives (3-chloroaniline, 3-nitroaniline)

(0.05 mol) was dissolved in distilled water and (0.05 mol) of dilute
hydrochloric acid. The mixture was cooled in ice bath to zero.
Sodium nitrite (0.05 mol) was added drop wise while stirring.
Maintaining the temperature from 0 the resulting mixture was stirred
for 1h.

(ii)Coupling

A solution of (0.05 mol phenol was dissolved in (0.05 mol) NaOH in

15 ml of water, was cooled to 0-5°C in an ice bath. This solution was
then gradually added to the prepared diazonium solution. The mixture
was stirred for further 20 min. The product was acidified by acetic
acid. The product was filtered, washed with distilled water and
recrystallized from acetic acid. The yield and melting point for the
prepared I and II (95 %, 98%) and (110°C, 170°C) respectively.

The main scheme of preparation is shown as follows:

Schematic (1) Diagram for Preparation of Compound І and ІІ:

3
2- Characterization of two additives structure:
The two prepared compounds are elucidated by using
different tools:

2.1 Elemental Analysis

The composition of the prepared compounds has been determined
quantitatively in weight percentages. It was carried out in the Micro
analytical Center, the center publication for research, Cairo, Egypt.
By CHNS-932 (LECO) Vario Elemental Analyzers.

2.2 FT-IR Spectroscopy:

IR spectra of the synthesized compounds were determined by using
FTIR spectrometer Model 960M000g, ATI Mattson Infinity Series,
USA. The spectra of the studied samples were measured in the range
of 4000 – 400 cm-1 with a suitable scan resolution 4cm and scan rate
32 cm/min.

2.3 protons Nuclear Magnetic Resonance (1H NMR)

Spectroscopy:
1
HNMR spectra recorded on a Varian 300 MHz (Germany 1999)
using TMS as internal standard (Cairo University).

2.4 Mass spectroscopy:

Mass spectroscopy was one using direct inlet unit (D1-50) of
SHIMADZU GC/MS-QP5050A. At the regional center for
mycology; AL-Azhar University.

3- Oxidation stability study

The oxidation test was carried out according to ASTM D standard
method. The operating temperature was changed to 120ο C instead of
90οC. The oxidation cell in the static mode contained 200 ml. base
oil, and activated copper and iron wires Catalysts. The base stock
sample was subjected to oxidation with pure oxygen (99.95%) at a
flow rate of 0.1 liter/hour for maximum 96 hours. The
characterized azo derivatives compounds (I-II) were concentrations

4
(250, 500,750 and 1000 ppm). The oil sample after, 24, 48, 72 and 96
hours of oxidation time were analyzed for total acid number .

3.1Total Acid Number (TAN)

Total acid number was carried out according to ASTM standard test
methods (D-664).

Result and discussion

The physic- chemical properties of the base oil are in this study are
represented in Table (1):

Table (1): The Physicochemical properties of the Base Stock

Test Result Test method

Density @ 15.5 °C, 0.884 ASTM D – 1298
g/L
Pour Point, °C Zero ASTM D – 97
Viscosity @ 40 °C 52.06 ASTM D – 445
@ 100 °C 7.23 ASTM D – 445
Viscosity Index 96.7 ASTM D – 2270
(VI)
Total Acid Number 0.067 ASTM D – 664
(TAN)
Sulfur Content, wt 0.34 ASTM D – 4294
%
Color 2.5 ASTM D – 1500
Ash Content, wt % 0.003 ASTM D – 482
Copper Corrosion Ia ASTM D – 130
Flash point, °C 162 ASTM D – 92
Aniline point 100.5 ASTM D – 611
Molecular Weight 468.9
1. Confirmation of the structures for I and II
The structure of I and II is elucidated via the following tools of
analysis:

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1.2. Elemental Analysis:
Elemental analysis was performed for the synthesized azophenols and
the obtained results are shown in Table2.

Table (2): Elemental analysis of (I-II)

C% H% N%
element
Cpd
Calc. Obs. Calc. Obs. Calc. Obs.
I 66.55 65.55 5.93 4.49 9.70 9.80
II 64.20 63.88 5.72 5.91 14.04 14.85
The data obtained from Table 2 show that the calculated values of the
elements were in good compatibility with that measured.

1.3. Infra-Red spectra of I and II

Infrared absorption bands for compounds (I-II) are given in table 2.

Table (2): Infrared absorption band for compounds (I-II)

Cpd. Streaching of,(Ѵ , cm-1 )

OH CHaromatic CHaliphatic N=N Cl NO2

I 3383 2992 2735 1459 687
II 3428 2956 2727 1468 - 1587-
1342
1
1.4. H-NMRspectroscopy
Chemical shift of the prepared compounds are given in Table 3.

6
 Table (3): Chemical Shifts of compound (I, II)

I II

b-
Type of a b b- c d e f g h i j k l
proton
Chemical I 11.54 8.28 7.83 7.64 8.08 8.11 6.57 7.53 3.25 1.76 1.05 0.82
-
Shift ppm II 11.34 10.4 - 8.29 7.86 7.00 6.96 7.14 6.74 3.42 1.54 3.07 1.05
Spin I s s m d t t d d m m d t -
multiplicity II s s - t t m d d d m m d t
Where (s) singlet, (d) doublet, (t) triplet and (m) multiplet.

Fig. (3): 1HNMR of the prepared compound (I).

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 Fig. (4): 1HNMR of the prepared compound (II).
Table 4-4 illustrates the following:

 The great chemical shift (𝛿) for the hydroxyl proton (a)
(11.43-11.54 ppm) is due to the attachment of the –OH to the
withdrawing aromatic ring which makes the hydroxyl proton
more deshielded (because of the high electronegativity of the
aromatic ring through conjugation).

 In case of the aromatic protons (b,b-, c, d, e,f and g), they have
different chemical shift values (𝛿), because they are
unsymmetrical.

 The aliphatic protons (h,i,j and k) have different (𝛿) values

according to their position to the aromatic ring. So, i have
highest value chemical.

1.5 Mass spectroscopy:

Molecular ion peak of the prepared compounds are given in Tables
(4) and Figures (5,6).

Tables .4. Molecular ion peak of the prepared compounds.

Cpd. Molecular formal m/z obs. m/z cal.

I C16H17Cl N2O 289 288

II C16H17N3O3 300 299

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Fig. (5): Mass spectroscopy of the prepared compound (I).

Fig. (6): Mass spectroscopy of the prepared compound (II).

From the previous table and figures we noted that the molecular ion
peaks were in accordance with the calculated molecular weight for
the prepared compounds.

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 1.6. Oxidation Stability Measurement:
The original base oil fraction has good properties as shown in table
(1) low pour point (zero), low total acid number (0.06) and moderate
viscosity index value (96.7) which mean that the oxidation stability
decrease and become more sensitive for oxidation.

Oxidation Stability Decrease

Base oil must have good oxidation stability. Oxygen which is present
in the oil and can also ingress from the environment and constituents
of the oil is one of the more influential factors on oxidation process
[15, 16].

Table (7): Change of Total Acid Number (TAN) for base oil without
and with addition of two prepared Azo Phenols compounds (Ι and ΙΙ).

Conc. ppm Total Acid Numbers, mg KOH / g Sample x 10 2

Base Base oil + I Base oil + II

oil
Time (Hrs) 250 500 750 1000 250 500 750 1000

24 94 53 49 47 45 42 27 25 19
48 102 56 51 49 46 44 30 27 22
72 120 58 53 50 48 45 31 28 23
96 201 60 55 52 49 47 32 29 24

In table (7) the TAN for base oil after oxidation increased rapidly
(0.06-0.94- 1.0-1.2-2.01) at oxidation time (0, 24, 48, 72 and 96hrs.)
respectively so at time 96hrs.the base oil damaged and must use
additives to prevent the autoxidation reaction and make study for the
efficient for each one on TAN at different conc. 250, 500,750 and
1000ppm and interval 24, 48, 72 and 96hrs.

Temperatures act as a catalyst as well as some metals such as copper.

The oxidation stability of base oil at high temperature is known to be
autocatalytic process involving a four- step initiation of free radical

10
chain reaction, chain propagation, chain branching and termination of
radical chain, which lead to the formation of a complex mixture of
oxygenated products, such as hydro peroxides, alcohols, ketenes and
carboxylic acid.

The parameters for estimating the stability of the base oil sample
without and with the two prepared azo phenols compounds (I, II) are
the total acid number TAN.

Fig.7. Variation of Total Acid Number (TAN) of base oil without and
with 250 ppm I and II

11
Fig.8. Variation of Total Acid Number (TAN) of base oil without and
with 500 ppm I and II

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Fig.9. Variation of Total Acid Number (TAN) of base oil without and
with 750 ppm I and II

Fig.10. Variation of Total Acid Number (TAN) of base oil without

and with 1000 ppm I and II

1.6.1 Effect of The Oxidation Time on Total Acid

Number (TAN):
TAN analysis can be used for indirect measurement of the
degree of oil oxidation. The data of the total acid number are given in
table (7) and graphically represented by figures (7,8,9,10). The
figures shows change in TAN values with time for the base oil at
120OC at different intervals 24, 48, 72 and 96hrs. also from figure the
TAN increased with oxidation time. This increment due to the
formation of peroxides during the oxidation process and when oil
subjected to heat and oxygen air.

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1.6.2 Effect of two prepared Azo phenols compounds (Ι
and ΙΙ):
First of all, the total acid numbers decrease by increasing the
additive conc. from 250 ppm to 1000 ppm. Among the two azo
phenols I, and II, the efficiency order of these compounds towards
decreasing TAN is ranked as follows II > I. This because the
compound II can prevent the free radical to for rapidly than
compound I so the oxidation process not completed and also the
formation of acids is almost stopped.

IV. Conclusion:
The results obtained in this work, indicate the following:
Increasing the oxidation time, always increase the total acid
number. The prepared antioxidant additives proved to be
successful in controlling the oxidation stability of the base stock.
We noticed for compound (II), has more efficiency than
compound (II).

Reference

1. Alves, J.C.L. and R.J. Poppi, Determining the presence of

naphthenic and vegetable oils in paraffin-based lubricant oils
using near infrared spectroscopy and support vector
machines. Analytical Methods, 2013. 5(22): p. 6457-6464.
2. Doaa .I.Osman, M.I.N., Ali A M El-Bassoussi and Ashraf. M.
Ashmawy, Oxidation Stability Control of Egyptian Base
Stock
Using Some Newly Azophenols II. IOSR Journal of Applied
Chemistry (IOSR-JAC) 2016. 9(9): p. 86-99.
3. Haus, F., O. Boissel, and G.-A. Junter, Multiple regression
modelling of mineral base oil biodegradability based on their
physical properties and overall chemical composition.
Chemosphere, 2003. 50(7): p. 939-948.
4. Ofunne, G., A. Maduako, and C. Ojinnaka, Studies on the
effects of temperature on the chemical characteristics of
automotive crankcase oils and their base oils. Tribology
international, 1991. 24(3): p. 173-178.

14
5. Colclough, T., Role of additives and transition metals in
lubricating oil oxidation. Industrial & engineering chemistry
research, 1987. 26(9): p. 1888-1895.
6. Dong, J., et al., Lubricant additives chemistry and
applications. 2003.
7. Adhvaryu, A., Y.K. Sharma, and I.D. Singh, Studies on the
oxidative behavior of base oils and their chromatographic
fractions. Fuel, 1999. 78(11): p. 1293-1302.
8. Kamal, R.S., N.S. Ahmed, and A.M. Nasser, Study the
efficiency of some compounds as lubricating oil additives.
Applied Petrochemical Research, 2013. 3(1-2): p. 1-8.
9. Wu, Y., et al., Improvement of oxidative stability of
trimethylolpropane trioleate lubricant. Thermochimica Acta,
2013. 569: p. 112-118.
10. Zhang, L., G. Cai, and W. Eli, Synthesis and characterization
of novel liquid ester‐phenolic antioxidant based on
dipentaerythritol. Lubrication Science, 2013. 25(3): p. 209-
216.
11. Omrani, H., et al., Assessment of the oxidative stability of
lubricant oil using fiber-coupled fluorescence excitation–
emission matrix spectroscopy. Analytica chimica acta, 2014.
811: p. 1-12.
12. El Sayed, H., et al., Antioxidant Additives for Lubricating
Oils. Synthesis and Evaluation of some Polyfunctionalized
Phenols Linked to Heterocycles. 1980.
13. Clarkson, R.G., Stabilization of organic substances. 1946,
Google Patents.
14. Ashmawy, A.M., et al., Preparation and evaluation of some
novel liquid crystals as antioxidants. Molecular Crystals and
Liquid Crystals, 2017. 643(1): p. 188-198.
15. Cerny, J., Z. Strnad, and G. Sebor, Composition and oxidation
stability of SAE 15W-40 engine oils. Tribology international,
2001. 34(2): p. 127-134.
16. I. Osman, D., A. R. Taman, and A. I. Hashem. Production
and Properties of Different Types of Lubricating Oils
Lubricating Oil Industry. 2013; Available from: http://nbn-
resolving.de/urn:nbn:de:101:1-201312108550.

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