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256_CHEMICAL PROBLEMS 2021 no. 4 (19) ISSN 2221-8688_
UDC 661.185
OBTAINING AND STUDY OF OLIGOMERIC SURFACTANT BASED ON OCTADECYLAMINE AND OXYPROPYLENE
S.H. Zargarova
Yu. Mammadaliyev Institute of Petrochemical Processes, Khojaly Ave. 30, Az 1025, Baku e-mail: [email protected]
Received 23.09.2021
Accepted 09.12.2021
Abstract: Oligomeric surfactant based on octadecylamine and propylene oxide was synthesized. The degrees of oligomerization of octadecylamine was calculated as 6.2 Structure and composition of the surfactant was confirmed by using IR and UV-spectroscopy. Surface tension values with respect to concentration were examined and respective curve was plotted. Also, main surf activity parameters like CMC, ycMc, kcmc, C20, pC20, rmax, Amin were calculated. Critical micelle concentrations (CMC) and surface tensions at CMC were calculated as 1.58*10-4 mol/l and 31.92 mN/m respectively. Petrocollecting property and petrocollecting coefficients of the surfactant were studied for distilled, tap and sea water.
Keywords: octadecylamine, oligomer derivative, propoxylates, surfactant, petro-collecting coefficient DOI: 10.32737/2221-8688-2021-4-256-261
Introduction
Accidents may occur during drilling, which make it possible to clean surface of water refining or transportation of crude oil. As a from crude oil [7-14]. For this purpose, new result, million tons of crude oil and petro surfactant was synthesized based on products damage the soil and water. One of the octadecylamine and propylene oxide. Main well-known methods is to use surfactants in physical-chemical properties of the new order to clean surface of the water from thin surfactants, including colloidal-chemical ones, layers of crude oil [1-6]. were determined to apply them as
According to the literature, nitrogen base petrocollecting agents. components have ability to create surfactants
Experimental Part
Octadecyamine was a product of "Alfa stainless steel and equipped with a regulator of
Aesar GmbH & Co KG" firm (Germany) of temperature at close conditions and constant
purity > 98%. pressure. In the given reaction, potassium
Propylene oxide was a product of hydroxide was used as a catalyst. Amount of
"Organic Synthesis" factory (Sumgayit, catalyst was calculated as 3% of amount of
Azerbaijan) of 99.97-99.98% purity. alkylamine.
Potassium hydroxide was used as IR- spectrum was recorded by using an
"analytically pure" product of "Chemapol" firm ALPHA FT-IR spectrometer (Bruker, USA)
(Czech Republic). using KBr tablets.
Oligomer based on octodecylamine and Surface tension (y) values were
propylene oxide was synthesized at 140-150oC measured by Du Nouy ring method using KSV
for 13-14 hours in an autoclave made of Sigma 702 tensiometer (Finland).
CHEMICAL PROBLEMS 2021 no. 4 (19)
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Results and Discussion
The reaction between octadecyamine and propylene oxide is illustrated as follows:
(CH2-CH-0)mH
CH3
H37C18-NH2 + nCH^CH-CH3
H37C
37M8"
(CH2-CH-0)kH
CH,
where n=m+k.
The value of propoxylation degree-n is The IR spectrum of octadecyamine
equal 6.2. Gravitational method was used to propoxylate is given in Fig. 1. obtain values of n.
A f' "" ^ § 1 i i1' 1 111 1 s ^
1
j
—1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-
3800 3600 34OO 3200 3000 2800 2SOO 2400 2200 2000 1 BOO 1600 1400 1200 1000 SOO 600
wavenumber cm-1
Fig.1. IR spectrum of the surfactant based on octadecylamine and propylene oxide
200 400 600 800 IOOO
wavelenght (nm)
Fig.2. UV- spectrum of octadecylamine propoxylate (n = 6.2) in distilled water
According to IR- spectrum given in OH valent vibration bands. C-H valent vibration Fig.1, absorption bands at 3361 cm-1 represents bands of CH3, CH2 and CH groups are observed
at 2919-2850 cm-1 in the spectrum. The bands at 1464-1374 cm-1 corresponds C-H deformational vibrations, and bands 1275 cm-1 was attributed to valent vibration of C-N.
In the given spectrum band at 1059 cm-1 represent C-OH group. (CH2)x "pendulum"vibrations bands exist at 719 cm-1 in the spectrum.
UV-spectrum of octadecylamine
propoxylate in distilled water with a propoxylation degree of 6.2 is given in Fig.2. The transition n ^ g * in the nitrogen atom is represented at 213 nm.
In order to study the surface activity at 21oC of synthesized octadecylamine propoxylate, aqueous solutions in different concentrations was prepared and plot was given in Fig. 3.
10 V
o I—
0 0,0005 0,001 0,0015 0,002
c, mol/l
Fig.3. Surface tension at the water-air border versus concentration plot of the oligomer
Based on the plot given in Fig.3, the 10-4 mol/l and the values of nCMC, Tmax and Amin
surface activity parameters were calculated and were calculated by using followin equations [5-
given in Table 1. Critical micelle concentrations 6]: (CMC) of the oligomer were revealed as 1.58*
(1)
where R- is universal gas constant (R=8.3145 surfactant molecule at the water-air border
C/mol*K) and T is absolute temperature. (Amin) was determined by the given equation: The minimum value of the area for one
** (2)
"a XT.«
Table 1. Surface activity parameters of the synthesized surface-active oligomer
n CMCx104 (mol/l) yCMC (mN/m) nCMC (mN/m) Tmaxx1010 (mol/sm2) Amin x102 (nm2)
6.2 1.58 31.92 40.08 0.83 193.15
Petrocollecting and dispersing properties applied to distilled, drinking and seawater as a of octadecylamine propoxylate were studied and pure form, 5% aqueous and 5% ethyl alcohol
solution on Ramana crude oil. The in Table 2. petrocollecting result of the oligomer was given
Table 2. Petrocollecting coefficients of the synthesized oligomer
State of surfactant Duration, hours Maximum petrocollecting coefficient
Distilled water Tap water Sea water
Unthinned reagent 0.17-2 33.28 33.28 28.70
24-30 39.06 39.06 29.44
48-92 39.06 39.06 29.44
5% wt. aqueous solution 0.17-2 29.44 29.44 29.44
24-92 39.06 39.06 39.06
5% wt. ethanolic solution 0.17-2 33.28 36.80 36.80
24-92 36.80 36.80 36.80
As can be seen from Table 2, the petrocollecting coefficient during exposure in the range of 0.17-2 hours is less than the coefficient obtained after 24 hours. This is
explained as being due to the aggregation state of surfactant. Thus, the substance is solid and that is the reason for late effect of surfactant on thin oil layers.
Conclusion
Surfactant based on octacedylamine and propylene oxide was synthezided at 140-150oC. Surface activity property of the oligomer was studied by izoterm of surface tension versus concentration was plotted. According to the
curve, the parameters such as CMC, ycMc, tccmc, Tmax, and Amin were calculated. Maximum values of petrocollecing coefficient of the oligomer in all-distilled, tap and sea water were calculated as 39.06.
References
1. Asadov Z.H., Zarbaliyeva I.A., Abilova A.Z. New surfactants based on triglycerides, (ethanol) amines and orthophosphate acid, monograph, Baku: Muallim Publ., ISBN 978-9952-435-34-4, 2020 p. 313
2. Humbatov H., Dashdiyev R., Asadov A. Et al. Chemical Reagents and Petroleum Production, Baku:Elm Publ., 2001. 448 pp.
3. Asadov Z., Zarbaliyeva I., Zargarova S. Propoxylation of Aliphatic Amines by Propylene Oxide. Chemical Problems. 2017, no 1, pp.44-50.
4. Sun Y., Wang C., Wang W., Yang X., Di Serio M., Zhi L. Micellar Properties for Propoxylated Surfactants in Water/Alcohol Solvent Mixtures and Their Antibacterial and Polyester Fabric Antistatic Performances. Journal of Surfactants and Detergents. 2016, vol. 19, no 3, pp.543-552
5. Zarbaliyeva I.A. Synthesis and properties of non-ionic surface-active substances based on heptadecanoic acid and propylene oxide. Journal of Chemical Problems. 2018, no 3, pp. 350-361.
6. Wang W., Li J., Yang X., Li P., Guo C., Li Q. Synthesis and properties of a branched short-alkyl polyoxyethylene ether alcohol sulfate surfactant. Journa of Molecular Liquids. 2015, vol. 212, pp. 418-422.
7. Yada S., Suzuki T., Hashimoto S., Yoshimura T. Adsorption dynamics of domogeneous polyoxypropylene-polyethylene alkyl ether nonionic surfactants at the air/water interface. Journal of Molecular Liquids. 2018, vol. 255, pp. 208214.
8. Casandra A., Lin Y., Tsay R., Lin S. Adsorption kinetics of the partially
protonated cationic surfactant dodecylamine. Journal of Molecular Liquids. 2018, vol. 256, pp.312-319.
9. Mirgorodskaya A., Kushnazarova R., Lukashenko S., Voloshina A., Lenina O., Zakharova L., Sinyashin O. Carbamate-bearing surfactants: Micellization, solubilization and biological activity. Journal of Molecular Liquids. 2018, vol. 269, pp.203-210
10. Abo-Riya M., Tantawy A., El-Dougdoug Q. Synthesis and evaluation of novel cationic gemini surfactants based on Guava crude fat as petroleum-collecting and dispersing agents. Journal of Molecular Liquids. 2016, volume 221, pp.642-650.
11. Tantawy A., Mohamed H., Khalil A., Hebash K., Basyouni M. Novel bioactive imidazole-containing polymeric surfactants as petroleum-collecting and dispersing
agents: Synthesis and surface-active properties. Journal of Molecular Liquids. 2017, volume 236, pp.376-384
12. Zargarova S.H. Synthesis and Characterization of Surfactants based on Propoxy Derivatives of Amines and Ethylene Chlorohydrin. Processes of Petrochemistry and Oil Refining. 2021, vol. 22, no 1, pp. 5865.
13. Asadov Z.H., Rahimov R.A., Allahverdiyeva L.A., Ahmadova G.A., Zarbaliyeva I.A. Obtaining and study of new flocculant for treatment of industry wastewater contaminated by petroleum. Chemical Problems. 2017, no. 4, pp. 412417.
14. Zarbaliyeva I.A. Modifications of undecanoic acid with propylene oxide, orthophosphate acid and ethanolamines. Chemical Problems. 2017, no. 2, pp.192-200.
OKTADESiLAMiN УЭ PROPiLEN OKSiDi 9SASINDA OLiQOMER T9Bi9TLi SaTHi-AKTiV MADDÖNiN ALINMASI УЭ TÖDQiQi
S.H. Zargarova
AMEA, Y.Mammadaliyev adina Neft-Kimya Proseslari institutu, AZ 1025, Baki, Xocali prospekti, 30 e-mail: [email protected]
Oktadesilamin va propilen oksidi asasinda oliqomer tipli sathi aktiv madda sintez edilmi§dir. Oktadesilaminin oliqomerla§ma daracalari 6.2 olaraq hesablanmi§dir. Sathi-aktiv maddanin qurulu§u va tarkibi iQ- va UB- spektroskopiya üsulundan istifada etmakla tasdiq edilmi§dir. Qatiliqdan asili olaraq sathi garilma qiymatlari tadqiq edilmi§ va müvafiq izoterm ayrisi ?akilmi§dir. KMQ, Ykmq, tckmq, C20, PC20, rmaks, Amin kimi asas sathi aktivlik parametrlari hesablanmi§dir. Kritik misella amalagalma qatiligi (KMQ) va sathi garilma qiymatlari müvafiq olaraq 1,58*10-4 mol/l va 31,92 mN/m hesablanmi§dir. Sathi-aktiv maddanin distilla, i?mali va daniz suyu üzarinda neftyigma qabiliyyati tadqiq edilmi§dir. A^ar sözlar: oktadesilamin, oliqomer törama, propoksilat, sathi aktiv madda, neftyigma amsali
ПОЛУЧЕНИЕ И ИССЛЕДОВАНИЕ ОЛИГОМЕРНОГО ПОВЕРХНОСТНО-АКТИВНОГО ВЕЩЕСТВА НА ОСНОВЕ ОКТАДЕЦИЛАМИНА И
ОКСИПРОПИЛЕНА
С.Г.Заргарова
Институт нефтехимических процессов им акад.Ю Мамедалиева Национальной АН Азербайджана AZ 1025 Баку, пр.Ходжалы, 30; e-mail e-mail: [email protected]
Синтезировано олигомерное поверхностно-активное вещество (ПАВ) на основе октадециламина и оксипропилена. Степень олигомеризации октадециламина составила 6.2. Структура и состав поверхностно-активного вещества подтверждены методами ИК- и УФ-спектроскопии. Определены
значения поверхностного натяжения в зависимости от концентрации и построена соответствующая
кривая. Вычислены основные параметры поверхностной активности, такие как ККМ, уккм, пккм, C20,
PC20, Гтакс, Amin. Критическая концентрация мицеллообразования (ККМ) и поверхностное натяжение
при ККМ были вычеслены соответственно как 1.58 10-4 моль/л и 31.92 мН/м. Исследованы
нефтесобирающие свойства ПАВ на дистиллированной, пресной и морской воде.
Ключевые слова: октадециламин, олигомерное производное, оксипропилат, ПАВ, коэффициент
нефтесобирания.
