Synthesis and Characteristics of Dodecyl Isopropylolamine and Derived Surfactants

Article abstract of DOI:10.1007/s11743-015-1762-y

Dodecyl isopropylolamine has been synthesized on the basis of dodecylamine and propylene oxide. The structure of dodecyl isopropanolamine has been determined by X-ray diffraction, elemental analysis, IR- and NMR-spectroscopic methods. Ionic surfactants have been synthesized by interaction of dodecyl isopropylolamine with various acids (HCl, HBr, acetic and propionic) and alkyl halides (methyl iodide, ethyl bromide and n-propyl bromide). Colloidal-chemical parameters, petroleum-collecting and petroleum dispersing capacities of the synthesized cationic surfactants have been studied.

Full text of DOI:10.1007/s11743-015-1762-y

J Surfact Deterg
DOI 10.1007/s11743-015-1762-y
ORIGINAL ARTICLE
Synthesis and Characteristics of Dodecyl Isopropylolamine
and Derived Surfactants
Ziyafaddin H. Asadov1 Ravan A. Rahimov1 Khuraman A. Mammadova1
•
•
•
Atash V. Gurbanov2 Gulnara A. Ahmadova1
•
Received: 21 January 2015 / Accepted: 16 November 2015
Ó AOCS 2015
Abstract Dodecyl isopropylolamine has been synthe-
sized on the basis of dodecylamine and propylene oxide.
The structure of dodecyl isopropanolamine has been
determined by X-ray diffraction, elemental analysis, IR-
and NMR-spectroscopic methods. Ionic surfactants have
been synthesized by interaction of dodecyl isopropylo-
lamine with various acids (HCl, HBr, acetic and propionic)
and alkyl halides (methyl iodide, ethyl bromide and n-
propyl bromide). Colloidal-chemical parameters, petro-
leum-collecting and petroleum dispersing capacities of the
synthesized cationic surfactants have been studied.
formulations, thickeners for acidic reagents, and antistatic
agents, improvers of detergency, lubricity and wear resis-
tance [1, 2]. However, it should be mentioned that ionic
derivatives of such alkoxy-derivatives have not been
studied extensively. It is known that a rise in concentration
results in formation of micelles which causes a change in
surfactants properties [3, 4]. For instance, some authors [5]
observed various types of self-organization and formation
of different structures that are dependent on geometrical
packing parameters.
Study of the solid-state structure of surfactants may be
informative for clarifying hydrogen bond interactions and
understanding local forces responsible for association of
surfactant molecules. The intrinsic structure of solids may
be studied by X-ray diffraction of single crystals. How-
ever, as obtaining single crystals is difficult, this method
enables revelation of only some crystalline structure [6–
10]. It is known that head-group substantially impacts
properties of surfactants [11, 12]; thus, by variation of
head-group structure it is possible to change the properties
of surfactants. From this standpoint, the synthesis of
surfactants with different head-groups based on dodecyl
isopropylolamine (DIPA) is of scientific and practical
interest. As the synthesized surfactant has petrocollecting
and petrodispersing properties, it is possible to obtain
more effective petrocollecting and petrodispersing
reagents by changing a polar group structure. Creation of
effective petrocollecting and petrodispersing surfactants is
one of the most impactful applications for surfactants now
[4, 13, 14].
Keywords Amine Á Surfactant Á Surface tension Á
Micellization Á Adsorption Á Counterion Á Petroleum-
collecting
Introduction
Introduction of alkoxy-groups into alkylamines leads to
valuable products that are important for various applica-
tions. For example, they may be used as auxiliary agents in
the textile industry and activators for pesticide
Electronic supplementary material The online version of this
article (doi:10.1007/s11743-015-1762-y) contains supplementary
material, which is available to authorized users.
& Ravan A. Rahimov
revan_chem@mail.ru
In this work, single crystals of DIPA were obtained for
the first time by employing a solvent-evaporation method.
DIPA was then reacted with various acids and alkyl
halides. The properties of the cationic surfactants were
studied.
1
Institute of Petrochemical Processes of Azerbaijan National
Academy of Sciences, Hojaly ave. 30, 1025 Baku, Azerbaijan
2
Baku State University, Z. Khalilov st. 23, 1148 Baku,
Azerbaijan
123

J Surfact Deterg
of alkyl amines the reaction was carried out in a nitrogen
atmosphere. The reaction was performed with mixing at a
temperature of 23–25 °C over a 120–150 h duration.
During the reaction viscosity increases, color darkens and
crystal formation is observed. The amine concentration
becomes stabilized at the end part of the reaction, when no
weight decrease is observed upon heating of the mixture.
Recrystallization of the formed DIPA was performed in
cold acetone. DIPA yield equaled 74 %.
Experimental Procedures
Reagents and Instruments
A
Bruker TOP SPIN spectrometer (300.13 and
75.46 MHz) was used for recording 1H-NMR and 13C-
NMR spectra. Chemical shift values (d) in ppm are given
downfield with regard to TMS. Ethanol-d6 was used as a
solvent. For recording IR spectra (in KBr disks), an
ALPHA FT-IR (Bruker) spectrometer was used.
IR, results were, in cm-1: 3333.9 m (OH), 3280.8 m
(NH), 2957.0, 2915.1 and 2848.2 m (CH), 1464.6, 1371.5
and 1298.0 d (CH), 1157.4, 954.7 and 915.3 m (C–N), 720.0
Propylene oxide (PO) was of 99.8 % purity, manufac-
tured by the ‘‘Organic Synthesis’’ factory in Sumgayit City,
Azerbaijan. Acetic acid and propionic acid had purity
higher than 95 % (Sigma–AldrichÒ, Germany).
Hydrochloric and hydrobromic acids were used as aqueous
solutions of concentration 37 and 48 %, respectively
(Merck, Germany). 1-Dodecylamine of purity [98 % was
provided by Alfa Aesar GmbH and Co KG (Germany).
Alkyl halides were of ‘‘Chemical line’’ (Russian Federa-
tion) production. The purity was higher than 98 %.
1
d (CH2)x (Fig. S1). H NMR (300.18 MHz, ethanol-d6), d
(ppm): 0.92 (CH3), 1.29 (CH–CH3), 1.30–1.32 (CH2
chain), 1.5 (CH2–CH2–NH), 2.36–2.52 (CH2–NH)
3.79–3.87 (CH2–CH) (Fig. S 2). 13C NMR (75.49 MHz,
ethanol-d6), d (ppm): 13.7 (CH3), 21.7 (CH3–CH),
22.6–31.9 (alkyl group), 49.5 (NH–CH2–CH2), 62.7–63.7
(NH–CH2–CH), 64.2–65.3 (NH–CH2–CH) (Fig. S 3).
Elemental analysis results for C15H33NO in mass %: N,
5.75; C, 74.02; H, 13.60. Calculated: N, 5.75; C, 74.01; H,
13.66.
Water Types Used
X-Ray Structure Determination
Three types of water were used: distilled, fresh (hardness
4.2 mg equiv/L), and sea water. Water of the Caspian sea
had the following characteristics: q20 = 1.0098 g/mL,
pH = 7.7. Its composition is as following (mg/L): Na?
The crystal of DIPA (C15H33NO, Mr = 243.42) is colorless,
with Tm = 44 °C, 0.03 9 0.03 9 0.30 mm, triclinic, space
group P 1, at T = 100 K: a = 4.2071(16), b = 13.246(5),
2650; K? 90; Ca2? 250; Mg2? 900; NH4 0.15; Cl- 500;
?
2-
-
3-
-
˚
c = 14.621(6) A, a = 77.326(5), b = 87.102(5), c =
SO4 2800; NO3 0.1; PO4 0.35; NO2 0.007; SiO2
0.5; oil products -0.005 %; dissolved oxygen 8 mg/L.
Total hardness is 69.0 mg eq/L.
3
81.809(5), V = 786.7(5) A , Z = 2, dcalc = 1.028 g/cm3,
˚
F(000) = 276, l = 0.062 mm-1. 12162 total reflections
(4532 unique reflections, Rint = 0.0336) were measured on a
Bruker SMART APEX II CCD automated diffractometer
Surface Tension Measurements
˚
(MoKa radiation, k = 0.71073, A graphite monochromator,
u- and x-scan modes, 2hmax = 60°). Determination of the
structure was made using direct methods. Refining was
performed by full-matrix least squares method using aniso-
tropic displacement parameters for all types of atoms except
hydrogen. Identification of hydrogen atoms in the amino
fragments was made in Fourier difference syntheses. They
were included into the refinement at fixed positions. Isotropic
thermal positions were taken as [Uiso(H) = 1.5Ueq(O) and
Measurements of surface tension were performed on a
DuNou¨y ring KSV Sigma 702 tensiometer (Israel). The
measured sample was placed in a glass cell (with a double
jacket) using a water bath for thermostatting. A Pt wire ring
was placed inside the sample solution and gradually pulled
through the liquid–air surface. Surface tension values were
reported as an average over three readings with 3 min
interval between measurements. The Pt wire ring was
washed with water and flamed with a Bunsen burner
between measurements. The surface tension of distilled
water did not deviate from 72.1 (20 °C) by more
than 0.2 mN/m.
U
iso(H) = 1.2Ueq(N)]. For the other hydrogen atoms, the
coordinates were computed on the basis of geometrical
considerations, then they were refined using the Riding
model using thermal parameters Uiso(H) = 1.5Ueq(C) for
the methyl groups and Uiso(H) = 1.2Ueq(C) for all the
remaining groups. The final divergence factors were
R1 = 0.042 for 3561 independent reflections with
I [ 2r(I) and wR2 = 0.123 for all independent reflections,
S = 1.057. All calculations were carried out using the
SHELXTL (PC version 6.12) program [15], (Table S1, S2).
Synthesis of DIPA
A 50-mL flat-bottom flask equipped with a magnetic stir-
rer, thermometer, and reflux condenser was charged with
0.1 mol dodecylamine and 0.1 mol PO. To avoid oxidation
123

J Surfact Deterg
Crystallographic data for DIPA have been deposited in the
Cambridge Crystallographic Data Center, CCDC 874945.
Copies of this information may be obtained free of charge
from the Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: ?44 1223 336033; e-mail: deposit@ccdc.
cam.ac.uk or http://www.ccdc.cam.ac.uk).
Results and Discussion
Synthesis of DIPA
The reaction between dodecylamine and PO can be illus-
trated by the following reaction Scheme 1.
The obtained DIPA is a transparent solid which melts at
44 °C. It has a goad solubility in ethanol, isopropyl alcohol,
acetone, benzene, hexane, and CCl4. DIPA only partially
dissolves in water (when 5 g of DIPA and 95 g of water are
mixed, 10–12 % of DIPA are dissolved). The reaction
between DIPA and carboxylic acids proceeds according to
Scheme 2.
Synthesis of Ionic Surfactants Based on DIPA
DIPA (0.3 mol) and hexane (10 mL) were placed in a
3-neck round-bottomed flask. This mixture was agitated till
the DIPA was fully dissolved. The corresponding quantity
(0.3 mol) of organic acid or alkyl halides was added to the
mixture to form the respective anion and new head
hydrophilic groups of DIPA. During the reaction a weak
evolution of heat is observed. The final mixture underwent
vacuum distillation to remove the solvent. The ammonium
salts obtained dissolve in water well and their aqueous
solutions possess electroconductivity. The carboxylate salts
and the salt derived from methyl iodide are liquids but the
rest of the salts are paste-like substances. The yield of the
salts based on alkyl halides was 92–93 %. The yield of
carboxylate-type salts was 97–98 %. Observation of the
absorption band at 2066 cm-1 of IR-spectra of the syn-
thesized salts characteristic for N?H2 group as well as
disappearance of the bond at 1705 cm-1 intrinsic for
COOH–group in the carboxylate-type salts and appearance,
instead of it, of bonds at 1407 and 1568 cm-1 belonging to
COO--group evidence formation of ionic surfactants.
The obtained salts have good solubility in water, ethyl
and isopropyl alcohols, acetone, hexane, benzene and CCl4.
Dodecylisopropanolammonium carboxylate salts are
transparent viscous liquids.
The reaction between DIPA and alkyl halides proceeds
according to Scheme 3.
The resulting salts dissolve in such solvents as water,
ethyl and isopropyl alcohols, benzene, acetone, hexane and
CCl4. Dodecylmethylisopropylolammonium iodide salt is a
transparent viscous liquid whereas dodecylethylisopropy-
lolammonium bromide and dodecylpropylisopropylolam-
monium bromide salts are solid substances.
Crystal Structure of DIPA
The perspective view of the structure is depicted in Fig. 1.
As a result of intermolecular O–H…N and N–H…O
hydrogen bonds, molecules are connected in the form of a
unidimensional chain extended along the a axis with par-
allel arrangement of the alkyl chain. The geometric
parameters of the hydrogen bonds are summarized in
Table 1. The structure shows intermolecularly directed
four-membered O–H…OH…OH… interactions which are
illustrated in the packing diagram (Fig. 2).
Determination of Petroleum-Collecting
and Petroleum-Dispersing Capacities
Studies of petroleum-collecting and petroleum-dispersing
capacities of the obtained surfactants have been conducted
in parallel for pure-state reagents and their 5 % wt. alco-
holic solutions. As an example of crude oil, Ramana pet-
roleum (from an oil field in Absheron peninsula,
Azerbaijan) was taken (at 20 °C its density was 0.86 g
cm-3 and kinematic viscosity was 0.16 cm2 s-1). To a thin
film (0.15–0.16 mm thickness) of the petroleum on the
water surface (in petri dishes) 0.02 g of the surfactant (or
its solution) was added. Petrocollecting factor-K was
computed using the relationship K = So/S, where So is the
initial area of the petroleum slick surface at the start of the
test, and S is an area of the petroleum surface accumulated
in the form of thickened spot. During the observations, the
spot surface area was periodically measured and for these
certain time intervals (s) the values of K were calculated.
Petroleum-dispersing capacity was estimated by the degree
of cleaning of contaminated water surface from petroleum
-KD which was computed as a ratio of surface areas of the
cleaned water and the initial area of the petroleum film.
Colloidal-Chemical Parameters of the Synthesized
Ionic Surfactants
The plots of the surface tension (c) vs the molar concen-
tration on the natural logarithmic scale (lnC) for the salts at
25 °C are shown in Figs. 3, 4 and 5. Critical micelle con-
centration (CMC) which is defined by a sharp break and the
surface tension at CMC obtained from Figs. 3, 4 and 5 are
summarized in Table 2. As is seen from this table, when
chloride counterion of the surfactant is replaced by
Scheme 1 Synthesis of DIPA
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J Surfact Deterg
Scheme 2 Synthesis of
dodecylisopropylolammonium
carboxylate salts
Scheme 3 Synthesis of dodecylalkylisopropylolammonium halide salts
Fig. 1 X-ray structure of DIPA
Table 1 Parameters of H–
˚
bonds (A and deg) in the
structure of DIPA
D-H…A
d(D*-H)
d(H…A*)
d(D…A)
\(DH…A)
O(1)–H(1O)…N(1) [-x ? 1,-y ? 1,-z]
N(1)–H(1 N)…O(1) [-x ? 2,-y ? 1,-z]
0.851
0.863
1.94
2.24
2.779(1)
3.059(1)
170
159
* D is the proton donor; A is the proton acceptor
Fig. 2 Intermolecular hydrogen
bonds in DIPA
bromide-anion and acetate-ion by propionate-ion, the value
of CMC decreases. CMC also diminishes when passing
from methyl iodide-based salt to ethyl bromide- and propyl
bromide-based salts. Similar trends are observed for gemini
where (–dc/dlnC) indicates the surface activity, T is the
absolute temperature and R is the universal gas constant. It
is evident that C is dependent on the concentration of
surfactant and Cmax is attained at CMC. The pre-factor-‘‘n’’
shows the number of ions formed by a surfactant molecule.
In the case of our salt, the value of ‘‘n’’ may be taken as 2.
The value Cmax is necessary for computing the minimal
area (symbolized by Amin, nm2) of a molecule at the solu-
tion-air surface according to the equation [21, 23]:
[ethanediylbis(dimethyltetradecylammonium)]
[16],
alkylpyridinium [17], cetyltrimethylammonium [18],
1-dodecylammonium [19], decyltrimethylammonium [20]
and other type surfactants [21–23].
Table 2 indicates that the counterions are important for
maximum values of surface excess concentration–Cmax, as
well as the minimal surface area per molecule of surfac-
tant—Amin at the border of aqueous solution with air.
The values of surface excess concentrations–C (mol/
cm2) were computed by the formula [21, 23]:
Amin ¼ 1016=NCmax
ð2Þ
where N represents Avogadro’s number. The values of
Cmax and Amin depend on the molecular structure. As is
seen from the table, upon replacing of chloride counterion
by bromide or acetate anion by propionate anion the value
C ¼ ð1=nRTÞðÀdc=dlnCÞ
ð1Þ
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Fig. 3 Surface tension vs the concentration of dodecylisopropylo-
lammonium carboxylate salts in aqueous solution (25 °C). 1-Dode-
cylisopropylolammonium acetate, 2-dodecylisopropylolammonium
propionate
Fig. 4 Surface tension vs the concentration of dodecylisopropylo-
lammonium halide salts in aqueous solution (25 °C). 1-Dodecyliso-
propylolammonium
bromide
chloride,
2-dodecylisopropylolammonium
Fig. 5 Surface tension vs the concentration of dodecylalkylisopropy-
lnolammonium halide salts in aqueous solution (25 °C). 1-Dodecyl-
methylisopropylolammonium iodide, 2-dodecylethylisopropylolam-
monium bromide, 3-dodecylpropylisopropylolammonium bromide
123

J Surfact Deterg
of Cmax decreases, whereas Amin increases. In the salts
based on methyl-, ethyl- and propyl halides with an elon-
gation of alkyl chain Cmax rises, while Amin diminishes,
despite the fact that in the case of methyl group the
counterion of the surfactant is iodine.
a ¼ S2=S1
ð4Þ
where S1 and S2 are slopes of the conductivity dependence
at the concentrations lower and higher than CMC. The
degree of counterion binding (b) was computed as [24]:
The effectiveness of surface tension reduction (pCMC) is
estimated from the equation [21, 23].
b ¼ 1 À a
ð5Þ
The values of b are shown in Table 2. The values of
CMC determined by intersection point of two straight lines
differ little from those found on the base of surface tension
measurements.
pCMC ¼ c0 À cCMC
ð3Þ
where c0 is the surface tension of water and cCMC is the
surface tension of surfactant solution at CMC. The values
of pCMC for the obtained salts at 298 K temperature fall
into the range 41.9–45.9 mN m-1. When Cl- is replaced
by Br-, pCMC increases, but with replacement of the
acetate anion as a counterion by a propionate anion pCMC
decreases. In the case of the salts derived from methyl-,
ethyl- and propyl halides pCMC rises with an increase in the
alkyl chain length.
If Cl--counterion in the surfactant becomes replaced by
Br-, b increases. Similar trends were shown by J Keiper
and LS Romsted [25] for tetramethylammonium halides, S
Manet and coauthors for ethanediylbis(dimethyltetradecy-
lammonium) halides [16], and HN Patreck et al. for
cetyltrialkylammonium halides [26]. But when acetate-
anion is substituted by propionate-anion, the value of b
diminishes. Similar results were obtained in [16] for
ethanediylbis(dimethyltetradecylammonium) carboxylate
surfactants in the range of carboxylate chain C1–C4. In the
case of the salts based on ethyl- and propyl bromide
elongation of the alkyl chain makes b lower. In cetyltri-
alkylammonium bromide salts [26] with elongation of
alkyl group the value of b decreases too.
Further, the values of adsorption efficiency (pC20), are
useful in comparing the efficiency of adsorption of sur-
factant at the air/water interface [4]. The larger the pC20
value, the higher is the efficiency of surface adsorption of
the surfactant and the bigger is the decrease of surface
tension. pC20 rises when Cl- counterion is substituted by
Br- and acetate-ion by propionate-anion and, also, if alkyl
chain is elongated in the salts based on alkyl halides.
Thermodynamic Properties of the Synthesized Salts
Conductimetric Measurements
In the case of these salts the change in the standard Gibbs
free energy of micelle formation (DGmic) may be computed
according to Eq. 6 [27].
Graphs showing dependence of specific electroconductivity
on the surfactant concentration at 25 °C were drawn
(Figs. 6, 7, 8). As can be seen, specific conductivity rises
with an increase in concentration. On the basis of slopes of
conductivity/concentration plots both above and below the
CMC of the curve the ionization degree (a) was found [24]:
DGmic ¼ ð2 À aÞRTlnCMC
where R is universal gas constant, and T is the absolute
ð6Þ
temperature (298.15 K).
Fig. 6 The plots of electrical conductivity against concentration of
dodecylisopropylolammonium carboxylate. 1-Dodecylisopropylolam-
monium acetate, 2-dodecylisopropylolammonium propionate. The
error of electrical conductivity value is 0.3 lS/cm
Fig. 7 The plots of electrical conductivity against concentration of
dodecylisopropylolammonium halide. 1-Dodecylisopropylolammo-
nium chloride, 2-dodecylisopropylolammonium bromide. The error
of electrical conductivity value is 0.3 lS/cm
123

J Surfact Deterg
´
2
˚
here ACMC has the unit A per molecule, and pCMC shows
the surface pressure (in mN/m) at CMC.
The values of DGmic and DGad are given in Table 2. It is
evident that both micelle formation and adsorption are
spontaneous processes as the values of DGmic and DGad are
negative. At the same time, DGad is more negative from
which it may be concluded that adsorption precedes
micellization.
Cationic Surfactants as Oil Slicks Collection Agents
It has been established that dodecylisopropylolammonium
chloride as a 5 % aqueous solution has a higher petroleum-
collecting capacity (Kmax = 34.4, s = 144 h) than the
other compounds in distilled water (Table 3). However, as
the mineralization degree of water rises, the petrocollecting
effect of the compound decreases (in the sea water
Kmax = 20.3, s = 192 h). This compound in undiluted
form, in all three types of water, shows a petro-dispersing
capability (KD = 86.8–91.1 % s = 192 h). Dodecyliso-
propylolammonium bromide as 5 % aqueous solution is a
more effective collector than the other compounds in fresh
and sea waters (Kmax = 30.4, s = 100 h). In distilled water
‘‘K’’ equals 20.3. In undiluted form the compound has a
Fig. 8 The plots of electrical conductivity against concentration of
dodecylalkylisopropylolammonium halide. 1-Dodecylmethyliso-
propylolammonium iodide, 2-dodecylethylisopropylolammonium
bromide, 3-dodecylpropylisopropylolammonium bromide. The error
of electrical conductivity value is 0.3 lS/cm
The changes of the standard value of Gibbs free energy
for adsorption process (DGad) for the synthesized salts were
calculated by Eq. (7) [27].
DGad ¼ ð2 À aÞRTlnCMC À 0:6023pCMCACMC
ð7Þ
Table 3 Petroleum-collecting and petroleum dispersing properties of ionic surfactants
State of surfactant added to petroleum film
Distilled water
Fresh water
Sea water
s (h)
R (KD)a
s (h)
R (KD)
s (h)
R (KD)
Dodecylisopropylolammonium acetate
Undiluted product
0–100
95.5 %
0-100
0–100
95.5 %
30.4
0-100
0–100
95.5 %
91.3 %
5 % wt aqueous solution
Dodecylisopropylolammonium propionate
Undiluted product
0–25, 30–100
20.3, 86.8 %
0–100
0–100
86.8 %
12.2
0–100
0–100
91.1 %
30.4
0–100
0–100
95.7 %
20.3
5 % wt aqueous solution
Dodecylisopropylolammonium chloride
Undiluted product
0–192
0–144
86.8 %
34.4
0–192
0–192
86.8 %
91.1 %
0–192
0–192
91.1 %
20.3
5 % wt aqueous solution
Dodecylisopropylolammonium bromide
Undiluted product
0, 1–100
0–100
20.3, 91.1 %
20.3
0, 1–100
0–100
30.4, 93.4 %
30.4
0, 1–100
0–100
30.4, 86.8 %
30.4
5 % wt aqueous solution
Dodecylmethylisopropylolammonium iodide
Undiluted product
0–100
0–100
91.1 %
91.1 %
0–100
0–100
30.4
0–100
0–100
91.1 %
95.5 %
5 % wt aqueous solution
Dodecylethylisopropylolammonium bromide
Undiluted product
95.5 %
0, 1–100
0–100
15.2, 86.8 %
15.2
0, 1–100
0–100
15.2, 95.5 %
20.3
0–100
0–100
98.9 %
20.3
5 % wt aqueous solution
Dodecylpropylisopropylolammonium bromide
Undiluted product
0–100
0–100
12.3
14.5
0–100
0–100
15.2
16.2
0–100
0–100
95.5 %
91.1 %
5 % wt aqueous solution
a
K petrocollecting factor, KD degree of cleaning of water surface from petroleum
123

J Surfact Deterg
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between a dye and cationic surfactants: effects of alkyl chain,
head group, and counterion. Colloids Surf A Physicochem Eng
Asp 380:119–127
petrocollecting effect during the initial time but at the end
petrocollecting becomes replaced by petrodispersing.
Dodecylisopropylolammonium acetate and dodecyliso-
propylolammonium propionate as 5 % aqueous solutions
possess a high petrocollecting capacity in fresh water
(Kmax = 30.4, s = 100 h). In the sea water dodecyliso-
propylolammonium acetate 5 % aqueous solution of
demonstrates petrodispersing (KD = 91.3 % s = 100 h),
while 5 % aqueous solution of dodecylisopropylolammo-
nium propionate shows petrocollecting properties
(Kmax = 20.3, s = 100 h). Dodecylisopropylolammonium
acetate and dodecylisopropylolammonium propionate in
undiluted form mainly manifest petrodispersing capability.
Among the obtained salts dodecylmethylisopropylolam-
monium iodide, dodecylethylisopropylolammonium bro-
mide, dodecylpropylisopropylolammonium bromide salts
and their 5 % aqueous solutions have a higher petrocol-
lecting and petrodispersing effectiveness in distilled and
fresh waters. The other reagents have a relatively low
petroleum-collecting activity. As among the synthesized
salts dodecylisopropylolammonium bromide in the form of
5 % wt. aqueous solution has the highest effectiveness in
petrocollecting in the sea water, it may be used for
removing thin petroleum films off the water surface.
12. Borse M, Sharma V, Aswal VK, Goyal PS, Devi S (2005) Effect
of head group polarity and spacer chain length on the aggregation
properties of gemini surfactants in an aquatic environment.
J Colloid Interface Sci 284:282–288
Conclusion
DIPA in the form of a single crystal has been synthesized
on the basis of dodecylamine and PO and has been char-
acterized by IR- and NMR-spectroscopy. The crystal
structure DIPA has been determined by X-ray diffraction
techniques. Novel surfactant salts were synthesized by the
interaction of DIPA with different electrophilic agents
(carboxylic acids, hydrogen halides and alkyl halides). In
the ammonium salts obtained, the nature of the head group
and counterion largely influences colloidal-chemical
parameters and their surface-active properties. In sea water,
the highest petroleum-collecting capacity is exhibited by
5 % aqueous solution of dodecylisopropylolammonium
bromide.
13. Asadov ZH, Rahimov RA, Salamova NV (2012) Synthesis of
animal fats ethylolamides, ethylolamide phosphates and their
petroleum-collecting and dispersing properties. JAOCS
89:505–511
14. Tamanura K, Morrow NR, Loahardjo N, Winoto W (2013)
Retraction of oil slicks using surfactants. U.S. Patent
2013/0168324 A1
15. Sheldrick GM (2001) SHELXTL, V6.12, Bruker AXS Inc.,
Madison, WI
16. Manet S, Karpichev Y, Bassani D, Kiagus-Ahmad R, Oda R
(2010) Counteranion effect on micellization of cationic gemini
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Acknowledgments This work was supported by the Science
Development Foundation under the auspices of the President of the
˙
Republic of Azerbaijan—Grant No. EIF-Mob-4-2014-1(16)-11/05/4.
19. Dantas TNC, Wanderley Neto AO, Moura EF, Scatena H, Fon-
seca JLC (2009) Counterion nature and alkylammonium halide
adsorption thermodynamics.
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Ravan A. Rahimov received his B.Sc. in Chemistry from Baku
State University (Azerbaijan) in 2001, his M.Sc. in Polymer
Chemistry from Baku State University in 2003 and his Ph.D. in
Petrochemistry from IPCP in 2009. He is currently a leading scientific
researcher in the laboratory of surfactants of IPCP. His research
includes studies of oligomeric surfactants and modification of
synthetic rubbers.
Khuraman A. Mammadova received her B.Sc. in Chemistry from
Baku State University (Azerbaijan) in 2005, her M.Sc. in Physical
Chemistry from Sumgait State University (Azerbaijan) in 2012. She is
currently a senior scientific researcher in the laboratory of surfactants
of IPCP. Her research includes studies of oligomeric surfactants and
polymer-surfactant complexes.
27. Rosen MJ (2004) Surfactants and interfacial phenomena, 3rd edn.
John Wiley, New York
Atash V. Gurbanov is an assistant professor in the Baku State
University in Azerbaijan with a research field in X-ray analysis.
Ziyafaddin H. Asadov received his M.Sc. in Chemical Engineering
from the Azerbaijan State Oil Academy (Baku) in 1972, his Ph.D. in
Polymer Chemistry from the Institute of Petrochemical Synthesis of
the USSR Academy of Sciences (Moscow) in 1979 and his D.Sc. in
Petrochemistry from the Institute of Petrochemical Processes (IPCP)
of the Azerbaijan Academy of Sciences (Baku) in 1992. In 2003, Z.
H. Asadov was awarded the title of professor in Polymer Chemistry
from the Higher Attestation Commission under the President of
Gulnara A. Ahmadova received her M.Sc. in Chemical Engineer-
ing from the Azerbaijan State Oil Academy in 1981 and her Ph.D. in
Polymer Chemistry from IPCP in 1991. She is currently a chief
scientific researcher in laboratory of surfactants in IPCP. Her research
includes studies of polymeric and oligomeric surfactants.
123