Products of the reaction of N-monochlorosufonamides with isobutylene-styrene oligomers as additives for lubricating oils

Article abstract of DOI:10.1134/S0965544110050142

The reaction between N-monochlorosufonamides and a low-molecular-mass isobutylene-styrene cooligomer in the presence of inorganic acids was studied. It was found that regardless of the substituent (hydrogen or alkyl radical) on the sulfonamide nitrogen, t

Full text of DOI:10.1134/S0965544110050142

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 5, pp. 402–405. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.A. Mamedov, M.F. Farzaliev, N.P. Ladokhina, F.A. Fatalizade, Z.R. Agaeva, 2010, published in Neftekhimiya, 2010, Vol. 50, No. 5, pp. 412–415.
Products of the Reaction of NꢀMonochlorosufonamides
with Isobutylene–Styrene Oligomers as Additives
for Lubricating Oils
S. A. Mamedov, M. F. Farzaliev, N. P. Ladokhina, F. A. Fatalizade, and Z. R. Agaeva
Institute of Chemistry of Additives, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
eꢀmail: nina_fuad@rambler.ru
Received February 24, 2010
Abstract—The reaction between
rene cooligomer in the presence of inorganic acids was studied. It was found that regardless of the substituent
(hydrogen or alkyl radical) on the sulfonamide nitrogen, the reactivity of ꢀmonochlorosulfonamides is very
high and results in the formation of ꢀchloropolyalkylarylsulfonamides in a reaction with a polymer. The
high yield of the product of the ꢀchlorosulfonamide reaction with the polymers is reached within 3–4 h at
50°C. It was revealed that the addition of ꢀethylꢀ ꢀchloroarylsulfonamide to unsaturated groups proceeds
easier as compared to other ꢀmonochloroamines, and the yield of the desired product reaches 90%. The
Nꢀmonochlorosufonamides and a lowꢀmolecularꢀmass isobutylene–styꢀ
N
N
ꢀ
β
N
N
N
N
products exhibit high anticorrosive and tribological behavior, and, when added in a 5% concentration to oil,
satisfactory detergent properties.
DOI: 10.1134/S0965544110050142
Nꢀchloroamides, as well as N,Nꢀdibromoamides of ties [5]. Such additives improve the viscosity index,
sulfonic acids, are widely used for the sulfamidation of decrease the pour temperature, and reduce the corroꢀ
aldehydes and ketones [1] and for the dipyranylation sive activity of oil. In this connection, the synthesis of
of alcohols and phenols [2]. ChloroamineꢀT is the best polymeric compounds containing both sulfonamide
reagent for the aminohydroxylation and aminohalcoꢀ and other functional groups is of great interest.
genation of alkenes [3].
In this work, we have studied the reaction between
ꢀmonochlorosulfonamides and an isobutylene–styꢀ
rene cooligomer. The choice of the latter reactant was
determined by the fact that isobutylene cooligomers
with vinylaromatic monomers superior in stability
against thermomechanical degradation to other comꢀ
mercial polymeric viscosity additives [6].
Earlier, we found [4] that the reaction between
ꢀchlorosulfonamides of sulfonic acids and
N
N
αꢀolefins
results in the formation of ꢀchloroalkylarylsulꢀ
Nꢀ
β
fonamides, and the product yield depends on the
nature of the medium and temperature. The direction
of the addition reaction and the conditions under
which a nucleophile is substituted for the chlorine
atom in
Nꢀ ꢀchloroalkylarylsulfonamides were studꢀ
β
EXPERIMENTAL
ied [4]. Some of the synthesized compounds showed
high anticorrosive and antioxidant activity as additives
for lubricating oils.
The reaction of
Nꢀmonochlorosulfonamides
(chloroamineꢀB, chloroamineꢀCB) with isobutyꢀ
It is known that increasing the length of alkyl radiꢀ lene–styrene cooligomers (MW = 600–650) was carꢀ
cal allows compounds to form protective stable films ried out in the presence of HCl as described elsewhere
on a metal surface, ensuring high lubricating properꢀ [4]:
Cl
R1
H
Cl
HCl
+ C1NNaSO2C6H4–R2
R1
A
H
NHSO2C6H4 R2
n
,
A
H
where R1 is the isobutylene–styrene coꢀoligomer
(MW = 600–650), A = –CH2– or –CH2CH2–, and
R2 = (1) H or (2) Cl.
The reactant chemicals were technicalꢀgrade chloꢀ
roamineꢀB, chloroamineꢀCB, and 2,5ꢀdibromobenꢀ
zenesulfoneꢀNꢀethylꢀNꢀchloroamide.
402

PRODUCTS OF THE REACTION OF
N
ꢀMONOCHLOROSUFONAMIDES
403
Nꢀ
β
ꢀchloropolyalkylarylsulfonamide (1). A mixture sulfonamide (3).The yield was 105.8 g (90%). Found,
of 65 g (0.1 mol) of coꢀoligomer, 35.23 (0.13 mol) %: halogen (Cl + Br) 20.4; N 1.41.
ꢀsodiumꢀ ꢀchlorobenzenesulfonamide (chloroamꢀ
The structure of compounds 1–3 was confirmed by
N
N
ine), and 100 ml of benzene was stirred for 20 min, and
then 18.2 ml of concentrated HCl was added dropwise
at a rate required for the temperature not to exceed
IR data. Comparison of the spectrum of the reactant
cooligomer with that of the products of its reaction
with chloroamines (compounds
ence of new functional groups. The spectra of
exhibit an absorption band at
= 3315–3370 cm–1
1–3) shows the presꢀ
50
°С
. The resultant mixture was stirred at 50 С for 3 h,
°
1–3
cooled, and diluted with 100 ml of hexane. The preꢀ
cipitate was filtered off, and the mother liquor was
washed with water and dried; the solvent was evapoꢀ
ν
corresponding to the transꢀassociated form of SO2N
and at a frequency of 3250 cm–1 referred to the NH
group. Both of these bands are absent from the specꢀ
trum of the reactant cooligomer. The absorption bands
at 1340–1350 and 1160–1170 cm–1, which likewise
are not displayed by the initial cooligomer, indicate the
presence of the SO2N group. The absorption bands at
640–650 and 560–580 cm–1 prove the presence of
rated. The residue, a viscous yellow product, was
Nꢀ
β
ꢀ
chloropolyalkylarylbenzenesulfonamide ). The
(
1
amount of unreacted sulfonamide (precipitate) was
4.1 g, and the product yield was 99 g (87.2%). Found,
%: Cl 6.81; S 3.01; N 1.67. The molecular weight
was 920.
2,5ꢀDibromobenzenesulfoneꢀ
N
ꢀethylꢀ
N
ꢀchloroaꢀ
halogen atoms in compounds 1–3.
mide (2) was synthesized via the reaction of 2,5ꢀdibroꢀ
The yields of the products were determined by two
methods: basing on the amount of chloroamine parꢀ
ticipating in the reaction and using a method of liquid
adsorption chromatography which is applied in studyꢀ
ing polymer additives and intermediate products [7].
The unreacted chloroamine was isolated as sulꢀ
mobenzenesulfoneꢀNꢀethylamide
with
sodium
hypochlorite.
2,5ꢀDibromobenzenesulfoneꢀNꢀethylamide (100 g)
was dissolved during heating in 500 ml of a 1 N soluꢀ
tion of NaOH; then, 400 ml of 1.4 M sodium
hypochlorite solution was added dropwise to the
resultant mixture and the latter was stirred for 2 h. The
product was filtered off and recrystallized from chloꢀ
fonamide insoluble in a benzene–nꢀhexane mixture
and was separated by filtration. The adsorbent used in
liquid chromatography was a mixture of SiO2/Al2O3 in
a ratio of 9 : 1. A specimen of the test substance was
roform. The yield of 2,5ꢀdibromobenzenesulfoneꢀ
Nꢀ
ethylꢀ ꢀchloroamide was 89.3 g (81.9%). bp 71–
N
dissolved in nꢀhexane and chromatographed on a colꢀ
72°C. Found, %: C 25.68; H 1.96; N 4.1. Calculated,
%: C 25.43; H 2.13; N 3.71.
Isobutylene–styrene coꢀpolymer (MW = 600–
650) was obtained as described elsewhere [6] by the
polymerization of isobutylene and styrene in the presꢀ
ence of AlCl3 as a catalyst.
umn with the adsorbent using hexane as an eluent and
washing the column until the substance is removed.
The solvent was removed and the product was
weighted. The residue in the column was washed with
a benzene–isopropanol blend taken in a 1 : 1 ratio.
The solvent was removed, and the residue was
weighted; its amount corresponded to the unreacted
product.
N
ꢀ
β
ꢀChloropolyalkylarylꢀ4ꢀchlorobenzenesulfoꢀ
2
namide ( ) was prepared in a similar way via the reacꢀ
tion of the cooligomer with chloroamineꢀCB. Taken:
65 g of cooligomer and 41.1 g of chloroamineꢀCB.
Obtained: 95 g (yield of 86.5%). Found, %: Cl 10.9
(11%); S 3.25; N 1.73.
RESULTS AND DISCUSSION
In the study of the influence of the temperature and
the time of the reaction between chloroamineꢀB and
the cooligomer taken in an equimolar ratio, it was
found that the product yield depends mainly on the
reaction temperature: increasing the temperature up
Nꢀ ꢀChloropolyalkylarylꢀNꢀethylꢀ2,5ꢀdibromoꢀ
β
benzenesulfonamide (3). The isobutylene–styrene
cooligomer (65.0 g (0.1 mol)) (MW = 650) was disꢀ
solved in 100 ml of benzene. A solution of 45.3 g
to 50 С increases the product yield. The further rise in
°
(0.12 mol) of
NꢀchloroꢀNꢀethylꢀ2,5ꢀdibromobenzeꢀ
the temperature increases the yield of chlorinated
byproducts, and the yield of the desired product
decreases. The optimal reaction time is 3 h.
nesulfonamide in 100 ml of benzene was added dropꢀ
wise to the resulting mixture at such a rate that the
temperature did not exceed 50°C. The resultant mixꢀ
ture was stirred at 50°C for 2–3 h, cooled, and diluted
with 100 ml of hexane. The precipitate was filtered off,
According to the obtained results, the addition of
N
ꢀalkylꢀ
than that of other chloroamines: the yield of the
ꢀethylꢀ2,5ꢀdibromobenzeneꢀ desired product reaches 90%:
Nꢀchloroarylsulfonamide proceeds easier
and the solvent was evaporated. The residue was
chloropolyalkylarylꢀ
Nꢀβꢀ
N
H
R
Br
Cl
Br
A
C2H5
Cl
R
H
+
N SO2
C2H5
SO2N
,
A
(3)
Br
Br
H
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010

404
MAMEDOV et al.
The results of tests of Nꢀβꢀchloropolyalkylarylsulfonamides
The anticorrosive, detergent, and tribological
properties of the products of the cooligomer reactions
Detergent properties
Concenꢀ
with chloroamines (compounds
As follows from the data presented in the table,
compounds admixed to Mꢀ8 lubricating oil
1–3) were examined.
Corrosion, according to the Paꢀ
Compound tration,
g/m2
pok–Zarubin–Vipꢀ
per method, points
wt %
1–3
exhibit high anticorrosive activity at a concentration of
2–3% and satisfactory detergent behavior at a 5% conꢀ
centration.
Mꢀ8 without
an additive
–
180–20
5.0–5.5
–
0.5
2
58.8
16.1
10.2
2.9
Studying the influence of the concentration of
compound 1 (Fig. 2) on the anticorrosive properties of
Iꢀ12A oil revealed that the optimal concentration for
lead and copper plates was 7 and 1%, respectively.
–
2.5–3
2.0–2.5
–
1
2
3
5
However, the addition of compound 1 makes it possiꢀ
2
5
5
62.1
16.3
6.4
ble to decrease the value of corrosion to 2 g/m2 in the
case of a copper plate (data obtained for a 7% concenꢀ
–
2.5–3
–
tration of compound
1). This finding indicates that
compound is a very strong copper passivator, despite
1
0.5
2
16.3
7.1
3.6
0.5
the presence of the chlorine atom.
–
–
An increase in the concentration of compound 1 in
Iꢀ12A oil leads to an increase in the general wear index
(Fig. 3) and a decrease in the wear spot diameter.
3
3
5
2.5–3
In summary, the products of the reaction between
the cooligomer and chloroamides of sulfonic acids in
addition to their anticorrosive and detergent properꢀ
ties considerably improve the antiwear properties of
where R is the isobutylene–styrene cooligomer and
A = –CH2– or –CH2CH2–
.
h
80
1
2
3
4
6
75
90
80
70
60
50
70
2
65
5
1
60
55
50
4
45
40
35
3
30
on the copper plate
25
2
20
2
15
on the lead plate
10
1
5
1
20
30
40
50
60
70
1
2 3 4 5 6 7 8 9 10
Concentration, %
T
,
°
C
Fig. 1. Influence of the reaction (
ture on the yield of the product in the reaction of
ꢀchloroꢀ ꢀsodiumbenzenesulfonamide with the isobuꢀ
tylene–styrene cooligomer.
1) time and (2) temperaꢀ
N
N
Fig. 2. Effect of the concentration of compound
1
on lead
2010
and copper plates.
PETROLEUM CHEMISTRY Vol. 50
No. 5

PRODUCTS OF THE REACTION OF
N
ꢀMONOCHLOROSUFONAMIDES
405
0.9
70
0.8
0.7
0.6
0.5
0.4
0.3
1
60
50
2
40
1
2
3
4
5
6
Concentration, %
7
8
9 10
Fig. 3. Effect of the concentration of compound 1 on the (1) wear spot diameter and (2) the load wear index (LWI) for Iꢀ12A oil.
3. M. P. Chatter, Synlett, No. 18 (2005).
4. S. A. Mamedov, A. M. Levshina, K. O. Kerimov, et al.,
oils and, hence, are effective multifunctional addiꢀ
tives.
Neftekhimiya 18, 396 (1988).
5. I. E. Vinogradova, Antiwear Additives for Lubricating
Oils (Khimiya, Moscow, 1971) [in Russian].
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37970 (2006).
2. A. Khanazaei, A. Postami, and M. Mahbonbifar, Cotol.
Commun. , 383 (2007).
8
,
6. A. M. Levshina, S. A. Mamedov, K. T. Kerimov, et al.,
Abstracts of Papers “Chemistry and Technology of Oil,
Fuel, and LubricantꢀCoolant Additives”, 1978, p. 53.
8
7. A. B. Caril, J. Inst. Petrol. 8, 34 (1972).
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010