Synthesis and Surface-Active Properties of a Homologous Series of Star-Like Triple-Chain Anionic Surfactants Derived from 1,1,1-Tris(hydroxymethyl)ethane

Article abstract of DOI:10.1007/s11743-015-1751-1

A novel homologous series of trimeric anionic surfactants, 3C _n TE3CNa (where n is a fatty acid chain length of 7, 10, or 12), with three hydrocarbon chains and three carboxylate heads connected via tri-etheric bonds were synthesized from long-chain α-bromo fatty acids and a triol, 1,1,1-tris(hydroxymethyl)ethane. The obtained trimeric carboxylic acids were esterified and purified by silica gel column chromatography, then hydrolyzed with dilute sodium hydroxide solution to form a series of trimeric carboxylate surfactant products. All prepared compounds were analyzed by IR, ¹H NMR, and ¹³C NMR spectroscopy to confirm their chemical structures. Their surface-active properties were investigated. The critical micelle concentrations (cmc) of 3C _n TE3CNa were in the range of 0.12-0.71 mmol/L, and the surface tensions at the cmc (γ _cmc) were 29.3-34.8 mN/m.

Full text of DOI:10.1007/s11743-015-1751-1

J Surfact Deterg (2016) 19:129–135
DOI 10.1007/s11743-015-1751-1
ORIGINAL ARTICLE
Synthesis and Surface-Active Properties of a Homologous Series
of Star-Like Triple-Chain Anionic Surfactants Derived
from 1,1,1-Tris(hydroxymethyl)ethane
Xu Li1 Fenglan Xing1 Qun Xu1 Xiaolong Sun1 Yuping Wang1
•
•
•
•
•
Liyan Wang1 Pinglang Wang1
•
Received: 21 January 2015 / Accepted: 5 October 2015 / Published online: 29 October 2015
Ó AOCS 2015
Abstract A novel homologous series of trimeric anionic
surfactants, 3CnTE3CNa (where n is a fatty acid chain
length of 7, 10, or 12), with three hydrocarbon chains and
three carboxylate heads connected via tri-etheric bonds
were synthesized from long-chain a-bromo fatty acids and
a triol, 1,1,1-tris(hydroxymethyl)ethane. The obtained tri-
meric carboxylic acids were esterified and purified by silica
gel column chromatography, then hydrolyzed with dilute
sodium hydroxide solution to form a series of trimeric
carboxylate surfactant products. All prepared compounds
were analyzed by IR, 1H NMR, and 13C NMR spectroscopy
to confirm their chemical structures. Their surface-active
properties were investigated. The critical micelle concen-
trations (cmc) of 3CnTE3CNa were in the range of
0.12–0.71 mmol/L, and the surface tensions at the cmc
(ccmc) were 29.3–34.8 mN/m.
by linker groups at the level of the head groups or very
close to the head groups of each monosurfactant. The
reported trimeric surfactants exhibit excellent physico-
chemical properties, such as low critical micelle concen-
tration (cmc), high efficiency in reducing the surface
tension of water, and good water solubility, superior to
those of the corresponding monomeric and dimeric (gem-
ini) surfactants.
By far the most investigated trimeric surfactants are
trisquaternary ammonium salts, i.e., three quaternary
ammonium species linked at the level of the head groups by
hydrocarbon spacer(s) [16, 17, 22–24]. For example, Zana
et al. [24] did the pioneering work and a synthesized tri-
meric surfactant of methyldodecylbis[3-(dimethyldodecy-
lammonio)propane]ammonium tribromide, 12–3–12–3–12,
which consists of three quaternary ammonium head groups
and three dodecyl chains connected by two propylene
spacer chains. Ikeda et al. prepared a series of quaternary
ammonium salts having a methyl- or a dodecylimino group
Keywords Trimeric surfactants Á Oligomeric surfactants Á
Carboxylate surfactants Á Anionic surfactants Á Critical
micelle concentration
or
a dimethyl- or a dodecylmethylimmonio group
(trisquaternary ammonium salt) between two dode-
cyldimethylammonio groups from dodecylamine and
epichlorohydrin [16]. Yoshimura et al. [18] synthesized
methylalkylbis[3-(dimethylammonio)ethyl]ammonium tri-
bromide. Gao et al. synthesized trimeric cationic surfactants
with ester groups in spacers [19].
Introduction
After the discovery of dimeric (gemini) surfactants and
their interesting and unexpected properties [1–10], trimeric
surfactants have appeared as a new class of surfactants in
the scientific literature in recent years [2, 11–21]. These
surfactants comprise three amphiphilic moieties connected
The reason most trimeric surfactants reported in the
literature are cationic is that amines are very strong
nucleophiles (even tertiary amines), making their synthesis
easier, and the quaternary salts are relatively easy to purify
by crystallization. On the other hand, without those
advantages, anionic trimeric surfactants are relatively dif-
ficult to synthesize and purify. That is why there are few
reports on the synthesis of trimeric anionic surfactants in
the literature. Also, although some star-like oligomeric
& Pinglang Wang
pinglangw@gmail.com
1
College of Chemistry and Chemical Engineering, Qiqihar
University, Qiqihar 161006, China
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Foaming Ability and Stability
surfactants have been reported in the literature [19, 25–28],
no anionic trimeric star-like surfactants were found. In this
study we report the synthesis of star-like trimeric anionic
surfactants using a relatively easy procedure and their
surface activities.
The foaming ability and stability were measured according
to the foam rising volume method. Thus, 20.0 mL of the
test trimeric anionic surfactant solution (0.1, 0.5, 1.0,
1.5 wt%) was placed in a 50-mL graduated cylinder. The
cylinder was plugged and continuously oscillated 25 times.
The foam volume (milliliters) above the solution level was
read and recorded as V0 immediately after shaking. Each
sample was allowed to stand undisturbed for 5 min and the
new foam volume above the solution level was recorded as
V5. The foaming ability was evaluated from the V0/20 ratio,
i.e., the foam volume generated from each milliliter of
surfactant aqueous solution. The foam stability was
reflected by the ratio of V5/V0, meaning the percentage of
the remaining foam volume over the original foam volume
after 5 min.
Experimental Procedures
Materials
The following chemicals were purchased from Aladdin
Industrial Corporation (Shanghai, China): thionyl chloride
(99.5 %), bromine (99.99 %), sodium hydride (60 % dis-
persion in mineral oil), and 1,1,1-tris(hydroxymethyl)ethane
(97 %). Heptanoic acid, decanoic acid, dodecanoic acid,
methanol, ethyl acetate, and dichloromethane were all of
analytical grade. All chemicals were used directly without
further purification. Tetrahydrofuran (THF) was dried by
distillation over sodium benzophenone ketyl radical. Doubly
distilled water was used in all experiments.
Synthesis of Novel Trimeric Carboxylate
Surfactants
Synthesis of a-Brominated Fatty Acids (I-a–c)
Characterization
Fatty acid (100 mmol) and thionyl chloride (9.3 mL,
130 mmol) were placed in a dry, 100-mL, three-necked,
round-bottom flask, equipped with a condenser (the top
of the condenser was connected to a drying tube and two
empty filter flasks in series with Tygon tubing to avoid
the risk of moisture suck-back into the reaction; the open
end of the tubing was inserted into a base solution,
NaOH, 30%, to absorb acid gas generated from the
reaction), under a nitrogen atmosphere and heated at
80 °C until no HCl gas evolution (bubbling through the
NaOH solution) was observed (took ca. 1.5 h). Bromine
(24.0 g, 150 mmol) was slowly added over 4 h, then held
at 65 °C overnight (16 h). The reaction mixture was
slowly poured into ice and mixed with ethyl acetate
(35 mL). The layers were separated and the organic
phase was washed with water (30 mL 9 3), dried over
MgSO4, and filtered. The filtrate was evaporated to
obtain the crude product which was distilled using an oil
pump (sand bath temperature 160 °C). The resulting
The synthesized surfactant molecules were characterized
1
by H and 13C nuclear magnetic resonance (NMR) spec-
troscopy using a Bruker Ascend 600 MHz spectrometer,
with chemical shifts recorded as ppm in CDCl3; TMS was
used as an internal standard. Fourier transform infrared
(FTIR) spectra were recorded on a Thermo Nicolet Avatar
370 (USA). Surface tension was measured at 25 °C using
an Auto Surface Tensionmeter JK99C (Zongchen Digital
Technical Equipment Co. Ltd, Shanghai, China).
Evaluation of Surface Activity
Aqueous surfactant solutions were freshly prepared with
different concentrations for the measurements. The aque-
ous solutions were placed in small crystallizing dishes and
allowed to equilibrate for at least 30 min at 25 °C in the
tensionmeter before the first measurement. The surface
tension was obtained by pulling the platinum ring from the
solution until the meniscus broke [29]. The platinum ring
was washed with ethanol, rinsed with distilled water, and
heated with a flame until red hot before each test. All
measurements were repeated at least three times until good
reproducibility was achieved. The cmc values were taken
at the intersection of the linear portions of the plots of the
surface tension against the logarithm of the surfactant
molar concentration.
product was
a pale orange liquid (the yield of
I-a = 91 %, I-b = 86.1 %, I-c = 95 %) (Scheme 1).
The structures were confirmed by 1H NMR. I-a d: 0.90 (t,
J = 7.0, 3 H), 1.35–1.51 (m, 6 H), 1.99–2.10 (m, 2 H),
4.25 (q, J = 6.6, 1 H); I-b: 0.86 (t, J = 7.0, 3H),
1.43–1.531 (m, 12 H), 1.97–2.13 (m, 2 H), 4.25 (t,
J = 7.4, 1H); I-c: 0.89 (t, J = 7.0, 3 H), 1.47–1.96 (m,
16 H), 1.97–2.12 (m, 2 H), 4.24 (q, J = 7.2, 1 H).
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J Surfact Deterg (2016) 19:129–135
131
Scheme 1 Syntheses of the
trimeric carboxylate surfactant
molecules
Br2
H2O
SOCl2
CH3(CH2)nCH2COOH
CH3(CH2)nCHBrCOOH
CH3(CH2)nCHBrCOCl
80oC/1.5h
80oC/12h
I-a (n=4)
I-b (n=7)
I-c (n=9)
O
O
65 oC/24h
THF
CH3(CH2)nCHBrCOOH
0 oC/1h
O
OH
(CH2)nCH3
(CH2)nCH3
O
HO
OH
NaH
O
HO
rt, 1h
HO
H3C(H2C)n
O
OH
O
O
CH3OH/H+
reflux 15h
O
OCH3
(CH2)nCH3
(CH2)nCH3
O
H3CO
H3C(H2C)n
O
II-a (n=4)
II-b (n=7)
II-c (n=9)
O
OCH3
O
O
O
O
O
O
O
O
NaOH
OCH3
(CH2)nCH3
(CH2)nCH3
OCH3
ONa
H3CO
NaO
H3C(H2C)n
O
O
O
reflux 6h
H3C(H2C)n
(CH2)nCH3
(CH2)nCH3
O
ONa
III-a (n=4) = 3C7TE3CNa
III-b (n=7) = 3C10TE3CNa
III-c (n=9) = 3C12TE3CNa
Preparation of Intermediates (II-a–c)
volatiles were evaporated under reduced pressure. The
residue was dissolved in 30 mL of ethyl acetate, washed
with water (15 mL 9 3), and then dried over Na2SO4 and
filtered. The filtrate was evaporated under reduced pres-
sure. The products II-a–c were pale yellow viscous oils,
which were purified by silica gel column chromatography
using a mixed solvent of 5 % of ethyl acetate in hexane as
an eluent. The obtained product was a colorless oil. The
yields of II-a, II-b, and II-c were 63.4 %, 55.1 %, and
49.7 %, respectively. The structures of the compounds II-
a–c were confirmed by 1H NMR, 13C NMR, and IR
spectra. II-a 1H NMR, d: 0.88 (t, J = 7.0, 3 H, CH3), 1.04
(s, 9 H), 1.28–1.54 (m, 18 H), 1.69 (q, J = 7.5, 6 H), 3.34
(d, 1 H), 3.42 (d, 1 H), 3.73 (s, 9 H), 3.79 (t, J = 6.3, 3 H);
13C NMR: 173.6, 79.7, 73.3, 51.6, 41.3, 33.0, 31.5, 25.1,
22.5, 17.0, 14.0; IR (film, cm-1): 2955.5 and 2862.1 (CH2,
CH3), 1751.6 (C=O), 1460.7 and 729.6 (CH2), 1346.8
Sodium hydride (0.528 g, 13.2 mmol) and 5 mL of dry
tetrahydrofuran were added to a flame-dried, 100-mL,
round-bottom flask. The mixture was stirred at room tem-
perature for 10 min. A solution of 1,1,1-tris(hydrox-
ymethyl)ethane (0.240 g, 2.0 mmol in 5 mL of THF) was
added dropwise, stirred at room temperature for 1 h, and
then placed in an ice bath. A solution of intermediate I
(6.6 mmol in 5 mL of dry THF) was added dropwise into
the reaction. The mixture was stirred in the ice bath for
30 min, heated to 65 °C, and stirred for 24 h at that tem-
perature. The reaction mixtures turned into milky solutions
which were cooled to room temperature. A small amount
of water was added and the THF was removed by evapo-
ration under reduced pressure. After cooling to room
temperature, the reaction mixture was acidified to pH 1 (pH
paper) with 5 % hydrochloric acid and extracted with ethyl
acetate (15 mL 9 3). The combined organic phases were
dried over MgSO4 and filtered. The filtrates were evapo-
ration under reduced pressure. The pale yellow liquid was
esterified in 15 mL of methanol using three drops of con-
centrated sulfuric acid (H2SO4). The mixture was heated to
reflux for 15 h, and then the round-bottom flask was placed
in an ice bath and a small amount of NaHCO3 was added to
neutralize the acid catalyst. The excess methanol and other
1
(CH), 1196.8–1300.2 (C–O–C). II-b H NMR, d: 0.89 (t,
J = 6.9, 3 H), 1.02 (s, 9 H), 1.22–1.41 (m, 36 H), 1.68 (q,
J = 7.2), 3.32 (d, 1 H), 3.72 (d, 1 H), 3.72 (s, 9 H), 3.78 (t,
J = 6.6, 3 H); 13C NMR: 173.6, 79.6, 73.3, 51.6, 41.2,
33.0, 31.8, 29.4, 29.3, 29.2, 25.4, 22.6, 17.0, 14.1; IR (film,
cm-1): 2953.0, 2925.8, 2856.4 (CH3, CH2), 1755.1 (C=O),
1465.1 and 722.5 (CH2), 1348.8 (CH), 1198.1–1131.8 (C–
O–C). II-c 1H NMR, d: 0.88 (t, J = 6.9, 3 H), 1.02 (s, 9 H),
1.26–1.43 (m, 48 H), 1.68 (q, J = 6.9, 6 H), 3.32 (d, 1 H),
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3.40 (d, 1 H), 3.72 (s, 9 H), 3.78 (t, J = 6.3, 3 H); 13C
NMR: 173.6, 79.7, 73.3, 51.6, 41.2, 33.0, 31.9, 29.6, 29.5,
29.4, 29.4, 25.5, 22.7, 17.1, 14.1; IR (film, cm-1): 2959.0,
2924.8, 2854.9 (CH3, CH2), 1755.5 (C=O), 1466.0 and
723.5 (CH2), 1345.6 (CH), 1197.9–1115.0 (C–O–C).
chromatography (the bands on the column tailed too long
and overlapped together). So they were esterified with
methanol using a catalytic amount of sulfuric acid. The
methyl esters were easily purified by silica gel chro-
matography with no tail phenomena on the column
observed. The pure ester was then easily hydrolyzed and
purified by crystallization. Overall, syntheses of the tri-
meric anionic surfactants, step by step, were smooth and
successful with high quality products and good yields.
Preparation of Final Products (III-a–c)
The intermediate II (1.0 mmol) and THF (10 mL) were
added to a three-necked, 50-mL round-bottom flask
equipped with a condenser. Sodium hydroxide aqueous
solution (5 %, 10 mL) was introduced and the mixture
heated to reflux for 6 h. The reaction mixture was cooled
and evaporated under reduced pressure to remove most of
the THF. Water was added and the mixture was washed
with dichloromethane (10 mL 9 3). The aqueous phase
was concentrated under reduced pressure, crystallized in a
refrigerator, and centrifuged. The resulting solid was dried
in a vacuum oven at 60 °C for 5 h to obtain a white solid.
The yields of III-a (3C7TE3CNa), III-b (3C10TE3CNa),
and III-c (3C12TE3CNa) were 83.1 %, 81.3 %, and
Equilibrium Surface Tensions
All three trimeric anionic surfactants, 3C7TE3CNa, 3C10-
TE3CNa, and 3C12TE3CNa, showed good water solubility
at room temperature. The surface tension isotherms as a
function of the logarithm of the concentration are shown in
Fig. 1. The surface tension decreased gradually with
increasing surfactant concentration and reached a clear
break point, which was taken as the cmc.
Of the three trimeric anionic surfactants, 3C10TE3CNa
was the most efficient at lowering the surface tension of
aqueous solutions. Its surface tension at the cmc (ccmc) was
29.3 mN/m, lower than those of the 3C7TECNa and
3C12TE3CNa, 34.7 and 31.5 mN/m, respectively. Also, the
cmc of 3C10TE3CNa, 0.12 mmol/L, was the lowest of the
three surfactants. The cmc of 3C7TECNa and 3C12TE3CNa
were 0.71 and 0.21 mmol/L, respectively.
1
79.5 %, respectively. III-a H NMR, d: 0.87 (t, J = 7.0, 3
H), 1.04 (s, 9 H), 1.31–1.46 (m, 18 H), 1.71–1,78 (m, 6 H),
3.25 (d, 1 H), 3.66 (d, 1 H), 3.82 (q, J = 4.8, 3 H); IR (film,
cm-1): 3426.6 (H2O), 2955.7, 2931.0 and 2858.4 (CH3,
CH2), 1577.6 and 1426.4 (COO-), 1324.9 (CH), 1096.3
1
(C–O–C), 731.8 cm-1 (CH2); III-b H NMR, d: 0.88 (t,
J = 6.9, 3H), 1.02 (s, 9 H), 1.26–1.31 (m, 36 H), 1.37–1.45
(m, 6 H), 3.26 (d, 1 H), 3.65 (d, 1 H), 3.82 (q, J = 4.8, 3H);
IR (film, cm-1): 3440.1 (H2O), 2956.7, 2923.8 and 2854.5
(CH3, CH2), 1581.4 and 1424.8 (COO-), 1324.9 (CH),
The results show that increasing the hydrocarbon chain
length from hexyl to nonyl caused a lowering of the cmc
and ccmc, whereas an increase from nonyl to undecyl
resulted in a little less surface activity. A possible reason
1
1109.2 (C–O–C), 731.8 (CH2); III-c H NMR, d: 0.89 (t,
J = 6.9, 3 H), 1.02 (s, 9 H), 1.26–1.44 (m, 48 H),
1.73–1.78 (m, 6 H), 2.17 (d, 1 H), 3.65 (d, 1 H), 3.82 (q,
J = 4.8, 3 H); IR (film, cm-1): 3432.5 (H2O), 2923.8,
2853.8 (CH3, CH2), 1593.7 and 1417.7 (COO-), 1467.7
(CH2), 1322.8 (CH), 1102.9 (C–O–C), 717.6 (CH2).
70
65
60
55
50
45
40
35
30
25
Results and Discussion
Synthesis and Purification
The first step in preparing the trimeric anionic surfactants is
to convert the long-chain fatty acids to a-bromo fatty acids.
Instead of the Hell–Volhard–Zelinsky reaction [30–32]
using phosphorus or phosphorus tribromide (PBr3), we
used thionyl chloride which is a more convenient and
easier to handle reagent. The reaction generates the acyl
chloride from carboxylic acids which react with bromine to
produce a-bromo fatty acids. However, we found that the
acids were not easy purified by either crystallization (too
many impurities co-exist) or silica gel column
-6.0
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
LogC (mol/L)
Fig. 1 Correlation of the surface tension and the logarithm of
concentration for aqueous solutions of the surfactants 3CnTE3CNa
(black square n = 7; black triangle n = 12; black circle n = 10) at
25 °C
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J Surfact Deterg (2016) 19:129–135
133
why 3C10TE3CNa shows the greatest surface activity is
that 3C7TE3CNa seems to show weak hydrophobicity for
intermolecular attraction owing to its short hydrocarbon
chain length, resulting in higher surface tension and cmc
values. On the other hand, 3C12TE3CNa seems to have
higher surface tension than that of 3C10TE3CNa owing to
strong intramolecular attraction between the three hydro-
carbon chains. In the case of 3C10TE3CNa, the intra- and
intermolecular interactions balance favorably and compact
micelles can form owing to strong hydrophobic
interactions.
the monomeric and the corresponding trimeric anionic
surfactants indicate that the trimeric anionic surfactants are
much more effective in adsorbing at the air–water inter-
face. Removing the hydrophobic parts of the surfactant
molecules from contact with water quickly lowers the free
energy of the interface (surface tension) as the concentra-
tion of the surfactants increases, and the surfactants start
aggregating into micelles when the surface becomes
saturated.
Foaming Ability and Stability of Trimeric Anionic
Surfactants
Interestingly, ccmc values of trimeric surfactants with C8,
C10, and C12 hydrocarbon chains reported in the literature
had a similar trend, i.e., C10 \ C12 \ C8 [15, 18]. In one
report, the trimeric surfactants were made using a triamine
linker reacted twice to generate surfactant molecules with a
hydrocarbon chain length of 8, 10, or 12; their ccmc values
were 39.9, 33.3, and C12 = 36.9 mN/m, respectively [14].
Another example was trimeric surfactants of quaternary
ammonium bromide with hydrocarbon chain lengths of 8,
10, or 12; their ccmc values were 35.1, 25.8, and 36.4 mN/
m, respectively, although the ccmc values of C8 and C12
were similar [17].
Foaming ability and foam stability for the three trimeric
anionic surfactants were studied as a function of concen-
tration in distilled water at room temperature. The ratios of
the initial foam volumes V0 (at time 0 min after oscillation)
and the surfactant solution volume (20 mL) are an indi-
cator of the surfactant foaming ability, and the ratio of
foam volume after standing for 5 min (V5) and the initial
foam volume (V0) reflect foam stability. The results of
foaming ability and foam stability of the three trimeric
surfactants are listed in Table 1.
Comparing with the cmc values of the monomeric
anionic surfactant sodium dodecanoate, 5.51–6.22 g/L
(2.5 9 10-2–2.8 9 10-2 mol/L), in water at 25 °C [33–
35], the cmc value of the corresponding trimeric surfactant
3C12TE3CNa is only 0.163 g/L (2.1 9 10-4 mol/L), about
two orders of magnitude lower than that of sodium dode-
canoate on a molar basis. Similarly, the cmc value of
3C10TE3CNa is only 0.087 g/L (1.3 9 10-5 mol/L), much
less than that of sodium decanoate, 5.548 g/L
(2.9 9 10-2 mol/L) [36]. The cmc values for the corre-
sponding dimeric anionic surfactants were not found in the
literature. The big differences in the cmc values between
As shown in Table 1, the foaming ability (V0/20) of
3C7TE3CNa increased from 54 to 74 % as its concentra-
tion increased from 0.1 to 0.5 wt%, and as the concentra-
tion continued increased to 1.0 and 1.5 wt%, it slightly
decreased to 61, and 57 %. For 3C10TE3CNa and 3C12-
TE3CNa as their concentration increased from 0.1 to
1.5 wt%, their foaming abilities increased from 58 to
108 % and 74 to 122 %, respectively. It is a common
feature for the three surfactants that the effect of concen-
tration on foaming ability is most notable when their
concentration increased from 0.1 to 0.5 wt%. The increases
of foaming ability were 37, 55, and 43 % for 3C7TE3CNa
Table 1 Foam properties of the
trimeric anionic surfactants
Surfactants
Concentration (wt%)
Foam volume (mL)
V0/20 (%)
V5/V0 (%)
V0 (0 min)
V5 (5 min)
3C7TE3CNa
0.1
0.5
1.0
1.5
0.1
0.5
1.0
1.5
0.1
0.5
1.0
1.5
10.8
14.7
12.1
11.3
11.6
18.0
19.0
21.5
14.8
21.2
25.8
24.3
10.5
14.0
11.8
11.0
10.7
18.0
17.3
19.7
14.5
19.4
24.8
23.0
54
74
97.2
95.2
97.5
97.3
92.2
100.0
91.1
91.6
98.0
91.5
91.6
94.7
61
57
3C10TE3CNa
3C12TE3CNa
58
90
95
108
74
106
129
122
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Conclusions
Trimeric anionic surfactants were successfully synthesized
by reacting a-bromo fatty acids (a-bromoheptanoic acid, a-
bromodecanoic acid, and a-bromododecanoic acid) with
1,1,1-tris(hydroxymethyl)ethane in the presence of sodium
hydride, followed by esterification with methanol, silica gel
column purification, and hydrolyzation in dilute base
solution to form the desired products .The syntheses, step
by step, were smooth with high quality products and good
yields.
The cmc values of the trimeric anionic surfactants
3CnTE3CNa (n = 7, 10, 12) are much lower than those of
the corresposting monomeric anionic surfactants, sodium
dodecanoate and sodium decanoate. Their cmc values are
only 1.5–3.0 wt% of those of the latter’s, or about two
orders of magnitude lower than those of the corresponding
monomeric surfactants on a molar basis, indicating that the
prepared trimeric anionic surfactants are much more
effective in lowering the free energy of the air–water
interface than the corresponding monomeric surfactants.
All three trimeric anionic surfactants showed high foaming
ability, which increases with increasing hydrocarbon chain
length at the same concentration level.
15. Yoshimuraa T, Kimurab N, Onitsukab E, Shosenjib H, Esumia K
(2004) Synthesis and surface-active properties of trimeric-type
anionic surfactants derived from tris(2-aminoethyl)amine. J Sur-
factants Deterg 7(1):67–74
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Acknowledgments The authors gratefully acknowledge the finan-
cial support from the fund for supporting the Specially Appointed
Professor from the Qiqihar University.
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