Novel bioactive imidazole-containing polymeric surfactants as petroleum-collecting and dispersing agents: Synthesis and surface-active properties

Article abstract of DOI:10.1016/j.molliq.2017.04.040

Novel series of imidazole-containing polymers and polymeric surfactants have been synthesized via an efficient procedure. It included copolymerization of 1-vinyl-imidazole (VIM) with lauryl methacrylate (LMA) initiated by benzoyl peroxide and the ¹H NMR spectroscopic data was utilized to estimate the monomer reactivity ratio. Conversion of polymers to surfactants was achieved through quaternization of the imidazole nitrogen with dimethyl sulphate. Spectroscopic techniques were used to elucidate the chemical structures of all synthesized compounds. The surface-active properties of polymeric surfactants beside their activities against various microbes were investigated. In addition, petroleum-collecting and dispersing properties of surfactants in diluted and undiluted form in varying waters were evaluated.

Full text of DOI:10.1016/j.molliq.2017.04.040

Accepted Manuscript
Novel bioactive imidazole-containing polymeric surfactants as
petroleum-collecting and dispersing agents: Synthesis and
surface-active properties
Ahmed H. Tantawy, Hany I. Mohamed, Ahmed A. Khalil,
Kaouser A. Hebash, Mahmoud Z. Basyouni
PII:
DOI:
Reference:
S0167-7322(16)33787-4
doi: 10.1016/j.molliq.2017.04.040
MOLLIQ 7193
To appear in:
Journal of Molecular Liquids
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Revised date:
Accepted date:
6 December 2016
8 March 2017
11 April 2017
Please cite this article as: Ahmed H. Tantawy, Hany I. Mohamed, Ahmed A. Khalil,
Kaouser A. Hebash, Mahmoud Z. Basyouni , Novel bioactive imidazole-containing
polymeric surfactants as petroleum-collecting and dispersing agents: Synthesis and
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ACCEPTED MANUSCRIPT
Novel bioactive imidazole-containing polymeric surfactants as
petroleum-collecting and dispersing agents: Synthesis and surface-
active properties
Ahmed H. Tantawy1,2, Hany I. Mohamed1,*, Ahmed A. Khalil1, Kaouser A. Hebash1,
Mahmoud Z. Basyouni1
1Chemistry Department, Faculty of Science, Benha University, Benha-13518, Egypt
2Hubei Insect Resources Utilization and Sustainable Management Key Laboratory,
College of Plant Science and Technology, Huazhong Agricultural University, Wuhan
430070, People's Republic of China
*Email: hany.ibrahim@fsc.bu.edu.eg
Abstract
Novel series of imidazole-containing polymers and polymeric surfactants have
been synthesized via an efficient procedure. It included copolymerization of 1-vinyl-
imidazole (VIM) with lauryl methacrylate (LMA) initiated by benzoyl peroxide and
the 1H NMR spectroscopic data was utilized to estimate the monomer reactivity ratio.
Conversion of polymers to surfactants was achieved through quaternization of the
imidazole nitrogen with dimethyl sulphate. Spectroscopic techniques were used to
elucidate the chemical structures of all synthesized compounds. The surface-active
properties of polymeric surfactants beside their activities against various microbes
were investigated. In addition, petroleum-collecting and dispersing properties of
surfactants in diluted and undiluted form in varying waters were evaluated.
Keywords: 1-Vinylimidazole; Lauryl methacrylate; Reactivity ratios; Polymeric
surfactants; Petroleum-dispersing agents.
1. Introduction
Macromolecules, which include diazole moiety, have been proposed as
carrying an active part of various electrolyte-containing enzymes [l-3]. A great
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number of proteins, such as histamine and histidine, comprise of imidazole ring,
which is partly attributable to their catalytic activity. Consequently, comprehensive
research on the catalytic activity of imidazole monomers [4] and polymers [5] as well
has been reported. Furthermore, homopolymers of 1-vinylimidazole and poly(N-
vinylpyrrolidone)-co-poly(1-vinylimidazole) blocks have been used as new coating
technology for separation of proteins [6].
The remarkable ability of polymeric surfactants to alter the indices of surfaces
and interfaces make them so popular. Such synthesized compounds have become vital
components in many formulations beside some industrial processes [7-13]. The
properties of polymeric surfactants such as detergency, emulsification, and foaming
may exhibit a great variation with the precise chemical characteristics. The
characteristic and position of the water-loving groups together with the arrangement
and number of the hydrophobic groups determined the surface-active properties of the
molecule [14-16].
Fatty amphiphilic surfactants are commonly used for controlling the growth of
bacterial strains in various media. These salts, with their quaternary nitrogen, exhibit a
variety of pharmacological properties, which include germicidal, antibacterial and
antifungal activities [17-19]. A series of cationic surfactants in which their nitrogen
atoms were the heteroatoms in aromatic bases may be expected to improve the
biological action [20-23]. Cationic surfactants, and more particularly the quaternary
ammonium compounds, have the strongest effect against all round microorganisms.
They have been used to diminish the growth of different bacterial strains [24, 25].
The main objective of the present work was to prepare and evaluate some
novel polymeric compounds based surfactants as petroleum-collecting and petroleum-
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dispersing chemicals in varying waters in various forms. In addition, their surface and
antimicrobial properties were studied.
2. Materials and experimental techniques
2.1. Materials
1-Vinylimidazole (VIM), methacrylic acid and N,N'-dicyclohexyl-
carbodiimide (DCC) were obtained from Sigma-Aldrich. Lauryl alcohol and
benzoylperoxide (BP) were used as received from Sigma–Aldrich. Dimethyl sulphate
(DMS), dichloromethane (DCM), dimethylformamide (DMF), tetrahydrofuran (THF),
diethyl ether and methanol were purchased from Al-Nasr chemical company. FT-IR
(ATR) spectra were recorded on Thermo-Scientific, Nicolet iS10 FT-IR
1
13
spectrophotometer. H and C NMR spectra were measured in CDCl3 as solvent and
tetramethylsilane (TMS) as internal standard on Varian Mercury operating at 300
MHz in Chemistry Department, Faculty of Science, Cairo University.
2.2. Experimental techniques
2.2.1. Synthesis of lauryl methacrylate (LMA)
In an ice bath system, a solution of lauryl alcohol (10 mmol) in DCM was
added drop wisely to a solution of DCC, (11 mmol) and methacrylic acid (10 mmol)
in DCM (20 mL) within 10 minutes with continuous stirring. Stirring was continued
for another 4 h at room temperature followed by filtration. The filtrate was
concentrated under vacuum then the crude product was purified by column
chromatography via silica gel as adsorbent (eluent: DCM) to afford lauryl
methacrylate. Yield (86%); FT-IR (, cm−1): 2854–2925 (C-H aliphatic fatty chain),
1721 (C=O of ester group), and 1146 (C-O), (Figure 1).
<<Figure 1>>
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2.2.2.Copolymerization of 1-vinylimidazole (VIM) and lauryl methacrylate (LMA)
Copolymerization of 1-vinylimidazole and lauryl methacrylate with different
molar ratios was carried out in a four-necked kettle equipped with stirrer, reflux
condenser, inlet system of inert gas and dropping funnel. In a water bath at 70-80C,
the polymerization kettle was placed. At first, dimethylformamide (DMF) and LMA
were added to the kettle and heated to 70C then, the initiator BP and VIM were
charged drop by drop. The reaction mixture was stirred at 80C. Copolymers were
recovered by precipitation in methanol, filtered, refined and dried under vacuum. The
yield of products P2-P6 ranges from 80 to 90%.
Figures 2a and 3a represent the FT-IR spectra of P2 and P4 copolymers,
respectively. They reveal absorption bands at 2852–2952 for υC-H fatty aliphatic
chain, 1721 for υC=O of ester, 1672 for υC=N, 1651 for υC=C, and 664 cm−1 for υC-
1
N. H NMR gave signals at δ (ppm): 0.87(t, 3H, CH3 of aliphatic chain), 1.25(m,
20H, 10CH2 of aliphatic fatty chain), 1.57(s, 3H, CH3 of acrylate group), 1.92(t, 1H,
N-CH), 2.14(d, 4H, 2CH2-CH), 3.90(t, 2H, CH2-O), and 7.21-7.52(m, 3H, CH
aromatic of imidazole ring) as shown in Figures 2b and 3b. 13C NMR spectra for
copolymer P4 exhibited signals at δ (ppm): 14.07(CH3 of fatty chain), 22.60(CH3-
CH2), 25.98(CH3-C-C=O), 29.17-29.60(9C, 9CH2 of fatty chain), 31.80(CH2-C-
C=O), 36.45(CH2-CH), 44.32(C-C=O), 49.94(CH-N), 65.60(CH2-O), 118.28,
125.39, 137.81 (3C, 3CH aromatic), and 173.37 (C=O), (Figure 3c).
<<Figure 2 & Figure 3>>
2.2.3. Quaternization of [VIM-co-LMA] copolymers
In a closed system, the polymeric surfactants were obtained by reacting the
synthesized [VIM-co-LMA] copolymers with excess amount of DMS in the absence
o
of solvent. The mixture was maintained at 80 C for 72 h with stirring. The products
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[PS2, PS3 & PS4] were afforded by recrystallization from diethyl ether several times
to remove all unreacted substrates. The isolated yields of the products were 80-85%.
The structure of prepared polymeric surfactants were elucidated by FT-IR that
showed strong absorption bands of the 1,3-dialkylimidazoliumcation [26] at 1465,
1253 and 1162 cm−1. The broad peak at 3443 cm−1 is due to the absorbed water in the
sample, showing the highly hygroscopic nature of target molecules as shown in
Figures 4a and 4b.
<<Figure 4>>
2.3. Measurements
2.3.1. Surface Tension and electrical conductivity
Values of surface tension of aqueous solutions of polymeric surfactants were
recorded by Tensiometer-K6 processor (krüss company, Germany) using the ring
method. Each sample was determined from the average of three times measurements
and all measurements were recorded at 298K. Before measurements, the surface
tension value of the pure water was demonstrated in the range of 72.0±0.3 mN/m.
Also, the electrical conductivity of the obtained polymeric surfactant solutions was
measured by conductivity meter (model Type AD3000; EC/TDS and Temperature
meter) at 298 K. The measurement values were done in triplicates for each solution
at the same temperature.
2.3.2.Krafft point
The Krafft temperatures for the synthesized polymeric surfactants were
measured by visual observations. The concentrations of surfactant solution were at
least twice the CMC (critical micelle concentration) of the studied surfactants [27].
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2.3.3.Foaming power
After shaking 100 mL of 0.1% (wt/v) of the polymeric surfactant solution
vigorously in a stopperd graduated 250 mL cylinder at room temperature, foam power
of polymeric surfactants was measured [28]. Initially, the foam height (in cm)
represent the foaming power, and the stability of foam was determined by the falling
of height after 3 min.
2.3.4. Emulsifying stability
A mixture of 10 mL (0.5%) of the surfactant solutions with 10 mL of paraffin
oil at 303K (room temperature) was shaked vigorously to measure the emulsion
stability [29]. The strength of the polymeric surfactants to form a stable emulsion
(emulsion stability) was expressed as the time needed to separate 9 mL of pure
surfactant solution away from oil.
2.3.5. Petroleum-collecting and petroleum-dispersing capacities
The study of collecting and dispersing activities towards petroleum thin films
of the polymeric surfactants (in the pure state and in the form of 5 wt% aq. solution)
has been carried out. The Red sea crude oil (density and kinematic viscosity at 20oC
are 0.84 g/cm3 and 0.13 cm2/s, respectively) from the oil fields in the South Sinai
(Egypt) was used. The method in literature [30-32] was used for calculation.
2.3.6. Antimicrobial activity
Evaluation of antimicrobial activities (in vitro) of prepared polymeric
compounds was carried out against a range of microorganisms comprising bacteria
and fungi.
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2.3.6.1 Test organisms
The following microbial strains for testing purposes were obtained from the
Botany Department, Faculty of Science, Benha University, Egypt: Staphylococcus
aureus (Gram-positive), Bacillus cereus (Gram-negative), Aspergillus niger, and
Rhizopus oryzae.
2.3.6.2 Hole-plate diffusion method
A hole-plate diffusion method [33] was used to estimate the ability of a drug
to kill or inhibit the growth of living microorganisms. A suspension with 0.5
McFarland standard turbidity. Holes of 6 mm diameter were made on the Mueller-
Hinton agar plate (8 mm thick) inoculated by flooding and filled with 200 µL of
compound aqueous solution (1 mg/mL). The plates containing the bacteria were
incubated at 35-37°C for 24 h while those of fungi were incubated at 25-27 °C for 48
h. The inhibition zone around each hole was used to evaluate the activity against
microbes. Standard antibacterial drug (Tetracycline) and antifungal one
(Amphotericin B) were tested.
3. Results and discussion
3.1. Synthesis
The synthesis process of the polymeric surfactants is shown in Figure 5. The
first step is an esterification reaction between lauryl alcohol and methacrylic acid to
form lauryl methacrylate. The second one includes copolymerization of 1-vinyl-
imidazole (VIM) with lauryl methacrylate (LMA) with different molar ratios to form
polymeric compounds P2-P6. A simplified mechanism for the copolymerization
involves initiation through phenyl radicals (generated form thermal decomposition of
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benzoyl peroxide) followed by the chain propagation with the two monomers (VIM &
LMA) and then termination of the formed chains (Figure 6).
<<Figure 5 & Figure 6>>
The copolymer composition was calculated via utilizing 1H NMR
spectroscopic data. The method described in our previous work [34-36] was used in
1
the present work for the quantitative analysis of these copolymers by H NMR
spectroscopy. This method includes determining the resonance area that efficiently
represents monomer component, subtracting any interferences and dividing that area
by the number of protons per/monomer component giving that resonance, to obtain
the relative moles of each component. The results are shown in (Table 1) and we
found that monomer reactivity ratio for VIM-LMA copolymers are r1 = 0.502, r2 =
5.084 by Fineman–Ross (Figure 7a) and r1 = 0.488, r2 = 4.992 by Kelen–Tüdös
(Figure 7b). The r1r2 value for VIM-LMA equals 2.436, which indicates that the
copolymer should have a random distribution of the monomer units. In addition,
composition curve for copolymerization of VIM with LMA is shown in Figure 8.
<<Figure 7, Figure 8 & Table 1>>
The third step is a quaternization process of some synthesized polymeric
compounds using DMS to form novel polymeric surfactants. In a word, these
polymeric surfactants could be readily accessed in good yields under mild conditions,
and the preparation/purification procedures were simplified in comparison to other
polymeric surfactants reported previously. In addition, all synthesized compounds
were confirmed from different spectroscopic techniques.
3.2. Surface tension and micellization
Surface tension is the most vital characteristic among the surface-active
properties of a surfactant solution. The surface tension (γ) values versus the
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concentration of the obtained surfactant at 298 K are shown in Figure 9. Such figure
showed that the initial raise in the concentration leads to a sudden drop in the values
of the surface tension of the surfactant solutions. However, a slow decrease in the
surface tension took place at the break point, indicating the accumulation of surfactant
molecules to form aggregates. The value of prepared polymeric surfactants
concentration at the break point is shown as the CMC of the synthesized surfactants.
The values of CMC recorded in Table 2 for the synthesized compounds PS2, PS3 and
PS4 are 0.015, 0.057 and 0.025%, respectively.
<<Figure 9 & Table 2>>
Figure 10a-c showed the relation between electrical conductivity of
synthesized surfactants solution (k) and concentration. In each plot, intersection at the
point CMC has been obtained from two lines with different slopes. The CMC values
calculated from electrical conductivity plots were recorded in Table 2. Finally, it was
found that the values of CMC obtained from surface tension measurements are near to
those obtained from electrical conductivity measurements.
<<Figure 10>>
3.3. Krafft point
The Krafft points of surfactants can be used to evaluate their solubility. The
lower the Krafft point of a surfactant, the better its solubility. From Table 2, it is
noted that the obtained polymeric surfactant gave Krafft point values below 0 oC, this
reveals the good solubility of these surfactants.
3.4. Emulsifying power
The tendency of emulsification of the surfactants solution reflects its ability to
locate at the boundaries between opposite phases. The increase in the elapsed time
until separation of the desired quantity of aqueous layer, from the emulsified system,
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refers to the stability of the formed emulsion and vice versa. The results in Table 2
indicate that PS3 needs long time to separate a desired amount of water than the other
synthesized compounds, so PS3 has high emulsion power than PS2 and PS4. Emulsion
formation technology is very important in different applications, especially drug
formulations, cosmetics and paints.
3.5. Foaming properties
The prepared polymeric surfactants exhibited relatively low foaming heights.
As expected, the synthesized compounds solutions showed moderate foaming
volumes ranging from 80 to 160 mL for PS2, PS3 and PS4 as shown in Table 2. The
low-foaming tendency of surfactants is important in some applications such as dyeing
auxiliaries in the modern textile industry and mechanical dishwashing agents.
3.6. Petroleum-collecting and petroleum-dispersing properties
Experiments were preformed to investigate the effect of surfactants on the
accumulation or dispersion of petroleum thin films. All results were recorded in
Table 3, and it was noted that different forms (diluted/undiluted) of all furnished
polymeric surfactants gave good petroleum-collecting and petroleum-dispersing
action. PS2 exhibits very high petroleum-dispersing in both diluted and undiluted
form, whereas Kd ranges from 91.30 to 97.50%, τ= 55-166 h (in distilled, fresh and
sea waters).
<<Table 3>>
Interestingly, PS3 in undiluted form gave a good petroleum-collecting effect
in all used waters and the values range from 30.11 to 33.50, τ = 30-166 h.
Additionally, in distilled and fresh waters, diluted form of PS3 exhibited high
petroleum-collecting properties, whereas K= 32.22, τ= 30-166 h and K= 33.11, τ= 30-
166 h, respectively. However, in sea water, PS3 in diluted form gave high petroleum-
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dispersing effect (Kd= 95.60%, τ= 40-166 h). By contrast, undiluted form of PS4
exhibited very good petroleum-collecting capacity in distilled water (K= 33.60, τ =
30-166 h), but in fresh and sea waters gave very high petroleum-dispersing action,
whereas Kd is 97.60%, τ = 30-166 h. Also, in sea water, diluted form of PS4 exhibits
very high petroleum-dispersing effect (Kd =97.60%, τ = 20-166 h).
By summarizing, all of the prepared polymeric surfactants gave good
petroleum-dispersing and petroleum-collecting effects and it can be used as petroleum-
dispersing and collecting agents. As well as we can see that the synthesized polymeric
surfactants have better petroleum-dispersing and collecting properties comparing with
the corresponding conventional surfactants studied before [37, 38].
3.7. Antimicrobial activity
The effectiveness of the synthesized polymeric surfactants against number of
microorganisms was tested with the aim of obtaining specific derivatives that could be
potent in chemistry, medicine or agriculture. Such compounds were screened for
evaluation their potency against bacteria (Staphylococcus aureus and Bacillus cereus),
and fungi (Aspergillus niger and Rhizopus oryzae). The obtained results, as diameter
of inhibition zone (mm), were given in Table 4.
<<Table 4>>
Concerning the activity against Gram-positive bacteria (Staphylococcus
aureus), all tested compounds showed excellent activities. On the other hand,
compounds PS2 and PS3 showed good activities against Gram-negative bacteria
(Bacillus cereus), while compound PS4 has no effect on this microbe. Concerning the
data of antifungal activity, the three polymeric surfactants exhibited strong inhibition
against Aspergillus niger, but they give negative results against the fungus Rhizopus
oryzae.
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4. Conclusions
In this study, novel polymeric surfactants have been synthesized and
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characterized by FT-IR, H NMR and C NMR spectra. The results of CMC values
of synthesized surfactants were investigated via surface tension and electrical
conductivity methods and the values are near to identical. In addition, the Krafft
points of the synthesized polymeric surfactants are below 0oC, which indicate a good
solubility of such compounds in aqueous media. The petroleum-collecting and
petroleum-dispersing capacities of synthesized polymeric surfactants showed that all
of them gave good petroleum-dispersing and petroleum-collecting effects and they
can efficiently be used for this purpose. Compounds PS2 and PS3 exhibited good
activities against Gram-negative bacteria (Bacillus cereus). Also, the data showed that
the three polymeric surfactants exhibited strong inhibition against Aspergillus niger,
but they gave negative results against the fungus Rhizopus oryzae.
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LIST OF FIGURES
No.
Caption
Figure 1
Figure 2
Figure 3
FT-IR spectrum of lauryl methacrylate (LMA).
FT-IR (a) and 1H NMR (b) spectra of VIM-co-LMA (P2).
FT-IR (a), 1H NMR (b) and 13C NMR (c) spectra of VIM-co-LMA (P4).
Figure 4
Figure 5
Figure 6
FT-IR spectra of (a) PS2 and (b) PS4.
General scheme for synthetic procedure of polymeric surfactants.
A simplified mechanism for the copolymerization step.
Finemen-Ross plot (a) and Kelen-Tüdös plot (b) for copolymerization where a and b
are the molar ratios (M1/M2) of the comonomers in the feed and copolymer,
Figure 7
respectively.
Composition curves for copolymerization of VIM with LMA, f1 = mole fraction of M1 in
feed and F1 = mole fraction of M1 in copolymer
Figure 8
Figure 9
Figure 10
Variation of the surface tension with the concentration of the prepared polymeric
surfactants (wt/v) in water at 298 K.
Variation of concentration of synthesized polymeric surfactants (wt/v) with electrical
conductivity (μS.cm-1) at 298 K.
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Figure 1:
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Figure 2:
(a)
(b)
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Figure 3:
(a)
(b)
(c)
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Figure 4:
(a)
(b)
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Figure 5:
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Figure 6:
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Figure 7:
(a)
(b)
VIM-LMA
r1=0.488
r2=4.992
0.6
0.4
0.2
0
0
0.2
0.4
0.6
0.8
1
1.2
-0.2
ɳ
-0.4
-0.6
-0.8
-1
ξ
amin . amax
where: ɳ = a(b-1)/(αb+a2) , ξ = a2/(αb+a2) and α =
b
. b
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Figure 8:
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Figure 9:
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Figure 10:
(a)
(b)
(c)
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LIST OF TABLES
No.
Caption
1
Analytical data for copolymerization of VIM with LMA with different ratios by using H
NMR.
Table 1
Table 2
Table 3
Table 4
Surface-active properties of synthesized polymeric surfactants.
Petroleum-collecting and petroleum-dispersing properties of some novel polymeric
surfactants.
Antimicrobial activity (in vitro) of the synthesized polymeric surfactants.
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Table 1:
Feed composition Conversion weight Copolymer composition
Compd. no.
a
(%)
b
P2
P3
P4
P5
P6
4.00
2.33
1.50
1.00
0.67
1.33
0.75
0.35
0.25
0.16
9.5
8.8
9.1
7.11
9.4
a M1/M2 in the feed composition
b M1/M2 in the copolymer composition
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