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KIMYA PROBLEMLORi № 1 2017
UDC 661.185
PROPOXYLATION OF ALIPHATIC AMINES BY PROPYLENE OXIDE Z.H.Asadov, I.A.Zarbaliyeva, S.H.Zargarova
Acad. Y.H.Mamedaliyev Institute of Petrochemical Processes Baku, 30 Khojaly avenue, e-mail: [email protected]
Nonyl amine, octadecyl amine and aminoamide of carboxylic acid fraction of linseed oil have been propoxylated using propylene oxide and the structure and composition of obtained propoxylates confirmed by IR-spectroscopy. Tensiometric measurements made it possible to reveal high surface activity of these propoxylates. As a result of laboratory tests through the use of thin films of Ramana crude oil on the surface of distilled, fresh and sea water, a good petroleum-collecting capacity of the synthesized reagents has been determined. Keywords: amines, propoxylation, surface activity, petroleum-collecting properties
INTRODUCTION
Surfactants are widely used in various spheres of mankind's activity [1]. Among these spheres, oil and gas industry must be mentioned first of all [2, 3]. In the world practice, mainly ethoxylates of higher alcohols and monocarboxylic acids are utilized [4]. However, over the past two decades, propoxylates of the mentioned alcohols and acids also drew great interest of specialists [2, 5, 6].
The present paper highlights propoxylation of higher aliphatic amines. An introduction of propoxy-groups into composition of alkyl amines promises obtaining of valuable surface-active compounds. A study into their physical-chemical properties is also of interest, especially for identifying new fields of application of these surfactants.
Nonyl amine and octadecyl amine were products of "Alfa Aesar" firm (Great Britain).
Linseed oil was the product of "Sultanbeyli" firm (Istanbul, Turkey).
Propylene oxide (PO) was the industrial product of "Organic Synthesis" plant (Sumgayit, Azerbaijan) of 99.8% purity.
Sodium hydroxide was used as a reagent of "analytically pure" grade ("Chemapol" firm, Czech Republic).
Potassium hydroxide was taken as a reagent of "analytically pure" grade ("Chemapol" firm, Czech Republic).
Nonyl amine and octadecyl amine were propoxylated by PO at 53°C and equimolar ratio of reactants for six hours in an autoclave made of stainless steel and equipped with a controlled heating system. The unreacted
amount of PO was evaporated from the final mixture at mild temperature until a constant mass obtained. By gravimetric measurements conversion of PO and average degree of propoxylation - n (the number of PO moles added to 1 mol of amine) were calculated. In both cases, the value of "n" was close to 1.0.
Propoxylated nonyl amine is a white paraffin-like soft solid. Propoxylated octadecyl amine is also a white paraffinic solid.
Diethylene triamine (DETA) was the reagent of Russia, molar mass-73.14 q.mol-1, density-0.707 qml-1, boiling point-55-56 °C, refractive index was 1.3850 (20 °C).
Surface activity of the synthesized products was studied at the air-water interface by means of "KSV Sigma 702" tensiometer (Israel) using Du Nouy ring [7]. The method
consists in measuring the maximum force necessary for detaching the ring off the liquid surface.
Specific electro-conductivity (k) of the aqueous solutions of the obtained compounds was measured by "Anion-4120" electro-conductometer (Russian Federation).
Petroleum-collecting capacity of the synthesized surfactants was evaluated according to the well-known method [3]. Distilled, fresh and sea waters were introduced into three Petri dishes (40 ml per each dish). 1 ml of petroleum was added to the surface of water in each dish (thickness of petroleum layer makes up ~0.165 mm). The surfactant (or its 5% wt. solution in water or ethanol) was added at the amount of 0.02 g. The petroleum-collecting capacity was estimated according to a change of surface area of the petroleum which becomes collected into a spot. This area was measured by a stencil plate with accuracy ~10%. The petrocollecting activity was characterized by collecting ratio - k, which indicates how many times the surface area of
the initial oil slick decreases under impact of the surfactant. Retention time of the collected oil - t is also registered and used for characteristics of the reagent.
Petrodispersing capacity of the reagents was estimated as the ratio of the cleaned water surface area and surface area of the initial oil slick (in %).
Characteristics of the used fresh water: density at 20°C 0.996 g*mL-1; pH 7.0-7.6; chemical composition (g-equiv / 100 g): Ca2+ 0.0052; Mg2+ 0.0023: Cl- 0.0007; SO^ 0.0044; HCO- 0.0273; CO32- 0.0009; total hardness 4.5 mg-equiv L-1; the sea (Caspian) water: density at 20°C 1.0098 g*mL-1; pH 7.7; chemical composition (mg / 1000 g): Na+ 2650; K+ 20: Ca2+ 250; Mg+2 900; NH+ 0.15; Cl- 500; SO4- 2800; NO- 0.1; PO34- 0.35; SiO2 0.5; total hardness 69.0 mg-equiv. L-1.
Ramana crude oil had the following characteristics: at 20°C the density - 0.86 g*mL-1; kinematic viscosity at 20°C - 0.16 cSt.
RESULTS AND THEIR DISCUSSION
The performed reactions of PO with nonyl amine and octadecyl amine may be described by the following scheme:
r-nh2 + ch2-ch-ch3
\/ o
r-nh-ch2-ch-ch3
o
h
where R is C9H19 or C18H37.
The structure and composition of the obtained alkyl aminoalcohols were identified by iR-spectroscopy method. For example, in the spectrum of octadecyl isopropylolamine there are the following absorption bands (cm-
1): 3329.9 v (OH), 3274.8 v (NH), 2957.0, 2914.3 and 2849.0 v (CH), 1643.6, 1568.1 and 848.9 ô (N-H), 1467.7, 1380.9 and 1342.3 Ô (CH), 1307.2 v (C-N), 1157.6 and 951.2 v (C-N), 1043.6, v (C-O), 718.4, ô (CH2)x.
Results of tensiometric measurements of interfacial tension (a) at the border of aqueous solutions of the obtained alkyl aminoalcohols with air as well as the determined values of specific electro-conductance of these solutions are given in Table 1.
Table 1. Results of measurements of interfacial tension at the border of aqueous solutions of the synthesized alkyl aminoalcohols with air and specific electro-conductance
Concentration of aqueous solution of alkyl aminoalcohol, % wt. Interfacial tension, mN/m Specific electrocon-ductance, |S/cm (20°C) Remarks
Nonyl isopropylolamine (19 °C) Amine number - 54.75 mg HCl/g
0.010 38.97 16.3
0.025 28.56 32.9
0.050 31.50 51.5
0.100 26.51 94.5
0.300 25.46 134.7
0.500 23.95 220.8
1.000 24.34 302.0
3.000 23.93 208.6
5.000 24.13 229.0
7.000 24.51 171.4
Octadecyl isopropylolamine (21 °C) At the lack of surfactant CT is 72.0 mN/m
0.01 34.69 11.6
0.03 33.90 8.5
0.05 33.16 8.1
0.10 32.87 24.7
0.30 32.54 18.7
0.50 32.98 23.1
1.00 33.16 11.3
3.00 33.88 50.8
5.00 34.51 19.7
As is seen from the obtained tensio-metric results, nonyl iso-propylolamine is more surface-active than octadecyl iso-propylolamine. The first alkyl aminoalcohol lowers O from 72.0 down to 24.1 mN/m (at concentration 5.0% wt.) whereas the second one decreases the interfacial tension down to only 32.5 mN/m (at concentration 0.3% wt.).
Electroconductometric analysis shows that aqueous solutions of nonyl
o
isopropylolamine have markedly higher values of specific electroconductivity than those of octadecyl isopropylolamine which may be explained by presence of significantly shorter alkyl group in the first one. Manifestation of conductivity by aqueous solutions of non-charged alkyl aminoalcohols is ensured by partial hydration of amino-fragments with the charged groups as follows:
r-nh-ch2-ch-ch3 + h2o—
h
r-nh2-ch2-ch-ch3 oh" Oh
In Tables 2 and 3, the results of laboratory studies of petrocollecting capacity of the synthesized surfactants are presented.
As is seen from Table 2, nonyl isopropylolamine in unthinned state is effective in all three waters (kmax is 44.25 in distilled and fresh waters, 22.25- in the sea water; t exceeds 3 days in all three cases). 5%
wt. aqueous solution of this reagent demonstrates a good petrocollecting capability in fresh water (kmax is 18.42, t is longer than ~ 4 days). 5% wt. ethanolic solution manifests marked petrocollecting properties in distilled (kmax=18.99, t>4 days) and sea (kmax=20.26, t>4 days) waters.
Table 2. Results of laboratory studies of petrocollecting capacity of nonyl isopropylolamine with regard to Ramana crude oil thin (thickness ~0.17 mm) film; room conditions
State of reagent Distilled water Fresh water Sea water
t, hour k t, hour K t, hour k
0.17 10.66 0.17 11.05 0.17 10.66
21.00 11.26 21.00 11.26 21.00 11.26
Unthinned reagent 25.50 14.92 25.50 14.92 25.50 11.26
44.50 22.25 44.50 22.25 44.50 14.92
68.00 44.25 68.00 44.25 68.00 22.25
72.00 44.25 72.00 44.25 72.00 22.25
Table 3. Results of laboratory studies of petrocollecting capacity of octadecyl isopropylolamine with respect to Ramana crude oil thin (thickness ~0.17 mm) film; room conditions
0.17 4.79 0.17 18.42 0.17 1. 45
20.00 1.58 20.00 14.47 20.00 1.31
23.50 1.58 23.50 14.83 23.50 1.24
5% wt. aqueous solution 43.50 1.46 43.50 14.83 43.50 1.24
67.00 16.89
71.00 17.88
94.50 15.18
0.17 18.99 0.17 6.39 0.17 17.37
20.00 14.14 20.00 1.67 20.00 13.51
23.50 14.47 23.50 1.73 23.50 16.43
5% wt. ethanolic solution 43.50 14.14 43.50 1.67 43.50 16.88
67.00 15.99 67.00 20.26
71.00 18.42 71.00 20.26
94.50 10.86 94.50 11.69
State of reagent Distilled water Fresh water Sea water
t, hour k t, hour K t, hour K
0.17 16.43 0.17 7.99 0.17 11.52
21.00 25.33 21.00 23.38 21.00 21.51
24.50 33.77 24.50 26.43 24.50 23.38
Unthinned reagent 44.50 35.76 44.50 26.43 44.50 21.51
68.00 24.32 68.00 22.51 68.00 18.42
72.00 24.32 72.00 22.51 72.00 18.42
95.50 5.06 95.50 11.05 95.50 9.35
0.17 3.25 0.17 8.35 0.17 12.25
1.50 14.47 1.50 12.52 1.50 16.25
5% wt. aqueous 21.00 27.83 21.00 30.14 21.00 16.25
solution 44.50 27.83 44.50 25.84 44.50 26.79
48.50 27.83 48.50 19.04 48.50 27.83
72.00 13.15 72.00 12.47 72.00 20.67
0.17 13.15 0.17 24.95 0.17 12.52
1.50 7.59 1.50 28.94 1.50 12.52
5% wt. ethanolic 21.00 12.39 21.00 36.17 21.00 16.52
solution 44.50 30.14 44.50 31.45 44.50 19.55
48.50 31.45 48.50 31.45 48.50 20.09
72.00 11.48 72.00 20.67 72.00 9.91
From Table 3 it follows that octadecyl isopropylol amine is an effective petroleum-collecting agent in all waters and in all forms of application. For example, in the sea water, when using 5% aqueous solution of this surfactant, kmax has the value 27.83, the retention time surpassing 3 days.
To compare results shown in Tables 2 and 3, it may be concluded that the second
synthesized surfactant with a longer hydrocarbon group (Ci8) has a higher petrocollecting capacity.
The use of PO propoxylation was also performed with DETA-based aminoamide of monocarboxylic acids fraction of linseed oil. The procedure of obtaining this amino amide is described in [8]. The scheme of the aminoamide propoxylation is as follows:
R-C(O)NH-(CH2)2 -NH-(CH2)2-NH2
PO
-►R - C(O) N-t-CH2
■ N
I
-N - CH2-CH(OH)-CH3
CH2CH(OH)CH3 CH2CH(OH)CH3 CH2CH(OH)CH3
Propoxylation degree was found to be 4. confirmed by IR-spectroscopy. The IR-The obtained product is a light-brown viscous spectrum is presented in Fig.1. liquid. Its structure and composition have been
Fig. 1. IR-spectrum propoxylate (n=4) of DETA - based aminoamide of linseed oil acid fraction
In the range 3200-3600 cm-1 O-H and N-H bonds valent, at 2966 cm-1 - C-H (of double bond) valent, 2925 and 2856 cm-1 - C-H (of CH3) and C-H (CH2) valent, 1645 cm-1 - C=O valent, 1550 cm-1 - NH deformational, 1456, 1416 and 1373 cm-1 - C-H (of CH3 and CH2 groups) deformational, 1279 and 1131 cm-1 -
C-N valent, 1050 cm-1 - C-O valent (of C-OH group) and 716 cm-1 -(CH2)n- "pendulum" vibrations bands are observed.
The results of surface tension measurements for the synthesized propoxylate at the border air-water are given in Table 4.
Table 4. Results of surface tension measurements for propoxylate (n=4) of DETA-based aminoamide of linseed oil acid fraction at the border air - water at 25°C
Concentration of the reagent, % wt
0.0010 0.0025 0.0075 0.0100 0.0250 0.0750 0.1000
Surface tension, mN/m
29.03 29.79 29.00 28.50 28.56 28.76 28.52
From these results it may be concluded that this propoxylate is surface-active because it lowers surface tension at the indicated border from ~ 72.0 down to 28.5 mN/m (at 0.01% wt).
The results of laboratory tests of the obtained propoxylate on petrocollecting and petrodispersing capacities are presented in Table 5.
Table 5. Results of laboratory tests of propoxylate (n=4) of aminoamide of linseed oil acid fraction on petrocollecting an petrodispersing capacities by the example of thin (thickness ~0.17 mm) films of Ramana crude oil; room conditions.
State of reagent Distilled water Fresh water Sea water
at application t, hour k t, hour k t, hour k
0-2.0 5.1 0-2.0 Disp. 0-2.0 3.7
Unthinned reagent 2.0-24.5 13.5 2.0-24.5 (98.7%) 29.7 2.0-24.5 24.3
25.0-169.0 30.4 25.0-169.0 30.4 25.0-169.0 30.4
169.0-280.0 -40.5 169.0-280.0 24.3 169.0-280.0 24.3
0-2.0 4.7 0-2.0 5.1 0-2.0 60.8
5% wt. aqueous solution 2.0-24.5 25.0-169.0 6.0 40.5 2.0-24.5 25.0-169.0 Disp. (99.7%) 30.4 2.0-24.5 25.0-169.0 40.5 20.3
169.0-280.0 61.0 169.0-280.0 40.5 169.0-280.0 30.4
According to the results above, the of the two alkyl amines as shown above. For
mentioned propoxylate manifests mainly example, in fresh and sea waters the value of
petrocollecting properties. The values of "k" reaches 40.5 and 60.9, respectively. collecting ratio exceed those for propoxylates
REFERENCES
1. Lange K.R. Surfactants Sanct-Petersburg: Professiya, 2005, 239 p. (In Russian).
2. Humbatov H.H., Dashdiyev R.A., Asadov Z.H. et al. Nonionic surfactants. Characteristics, obtaining, properties and application. Baku: Elm, 2000. 333 p. (In Azerbaijan).
3. Humbatov H.H., Dashdiyev R.A. Application of surfactants for liquidation of oil spills on the water surface. Baku: Elm, 1998. 210 p. (In Azerbaijan).
4. Schonfeldt N. Surfactants based on ethylene oxide. Moscow: Chemistry, 1982. 752 p. (In Russian).
5. Asadov Z.H. Azerbaijan oil industry. 2009, №2, p. 60-65.
6. Aga-zade A.D. Doctoral dissertation "Obtaining and application of surface-active propoxy-derivatives of aliphatic alcohols and higher monocarboxylic acids and compositions based on them". Azerbaijan, Baku: Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences, 2006. 399 p.
7. Trifonova M.Yu., Bondarenko S.V., Tarasevich Yu.I. Ukrainian Chemical Journal, 2009, 75, № 1, p. 28-32.
8. Asadov Z.H., Zarbaliyeva I.A., Eyyubova S.K. Materials of International Conference "Actual problems of modern chemistry and biology". 12-13 May 2016, Ganja State University. Ganja, 2016, p. 43-47 (In Azerbaijan).
ОКСИПРОПИЛИРОВАНИЕ АЛИФА ТИЧЕСКИХ АМИНОВ С ПОМОЩЬЮ ОКСИДА ПРОПИЛЕНА
З.Г.Асадов, И.А.Зарбалиева, С.Г.Заргарова
Институт Нефтехимических Процессов им. акад. Ю.Г.Мамедалиева Национальной АН Азербайджана AZ 1025 Баку, пр. Ходжалы, 30. e-mail: [email protected]
Осуществлено оксипропилирование нониламина, октадециламина и аминоамида фракции карбоновых кислот льняного масла с использованием оксида пропилена. Строение и состав полученных оксипропильных производных подтверждены методом ИК-спектроскопии. Тензиометрическими измерениями обнаружена высокая поверхностная активность этих соединений. Лабораторными испытаниями на примере тонких пленок раманинской нефти на поверхности дистиллированной, пресной и мордой вод установлена хорошая нефтесобирательная способность синтезированных реагентов. Ключевые слова: амины, оксипропилирование, поверхностная активность, нефтесобирательная способность
ALiFATiKAMiNLdRiNPROPiLEN OKSiDiiLd OKSiPROPiLLdgDiRiLMdSi
Z.H.ds9dov, i.A.Z9rb9liyeva, S.H.Zdrgdrova
AMEA Y.H.Mdmmdddliyev adina Neft-Kimya Proseslari institutu AZ 1025 Baki, Xocaliprospekti, 30. e-mail: [email protected]
Nonilamin, oktadesilamin va katan yaginin karbon tur§ulari fraksiyasmin aminoamidinin propilen oksidi ila oksipropilla§dirilmasi hayata kegirilmi§dir. Alinmi§ oksipropil toramalarinin qurulu§u va tarkibi iQ-spektroskopiya usulu ila tasdiq edilmi§dir. Tenziometrik olgmalarla bu birla§malarin yuksak sathi aktivliya malik olmasi a§kar olunmu§dur. Ramana neftinin distilla, igmali va daniz suyu sathindaki nazik neft tabaqalari uzarinda aparilmi§ laboratoriya sinaqlari naticasinda hamin reagentlarin yax§i neftyigiciliq qabiliyyati muayyan edilmi§dir. Agar sozlw. aminlar, oksipropilla§dirilma, sathi aktivlik, neftyigma xassalari.
Redaksiyaya daxil olub 05.01.2017.
