Preparation and surface activity of phosphated alkyl oligoglucosides

Article abstract of DOI:10.1007/s11743-010-1190-y

A family of phosphated alkyl oligoglucoside surfactants was prepared by reacting alkyl oligoglucosides with phosphorus oxychloride. The alkyl oligoglucosides were obtained by an usual method in which the glucose is reacted with a fatty alcohol containing 10-18 carbon atoms. These novel phosphated surfactants have been found to exhibit good surface tension, foaming and wetting power. The critical micelle concentration was found to increase with the length of hydrocarbon chain of the surfactant. The surface excess concentration and the interfacial area per surfactant molecule are reported. These phosphated surfactants also exhibit a good performance to improve the whiteness and wetting of cotton fabrics in a hydrogen oxide bleaching system, and they are also found to be more biodegradable than conventional surfactants. AOCS 2010.

Full text of DOI:10.1007/s11743-010-1190-y

J Surfact Deterg (2010) 13:417–422
DOI 10.1007/s11743-010-1190-y
ORIGINAL ARTICLE
Preparation and Surface Activity of Phosphated Alkyl
Oligoglucosides
Keng-Ming Chen
Chien Fu Wang
•
Li-Huei Lin
Mou-Chuan Hwang
•
Min-Yan Dong
•
•
Received: 27 July 2009 / Accepted: 25 February 2010 / Published online: 3 April 2010
Ó AOCS 2010
Abstract A family of phosphated alkyl oligoglucoside
surfactants was prepared by reacting alkyl oligogluco-
sides with phosphorus oxychloride. The alkyl oligogluco-
sides were obtained by an usual method in which the
glucose is reacted with a fatty alcohol containing 10–18
carbon atoms. These novel phosphated surfactants have
been found to exhibit good surface tension, foaming and
wetting power. The critical micelle concentration was
found to increase with the length of hydrocarbon chain of
the surfactant. The surface excess concentration and the
interfacial area per surfactant molecule are reported. These
phosphated surfactants also exhibit a good performance to
improve the whiteness and wetting of cotton fabrics in a
hydrogen oxide bleaching system, and they are also found
to be more biodegradable than conventional surfactants.
Introduction
During the past few years, many natural waters have been
polluted by chemicals from various sources. Some of them
are surfactants which originate mainly from household
detergents, personal care products, washing agents, and
processing supplies used in industry. A great deal of work
has been done in trying to take into account biodegrad-
ability in the use of surfactants [1–3].
Alkyl polyglucosides, derivatives of carbohydrates like
glucose (hydrophilic moiety) and long chain fatty alcohols
(hydrophobic moiety), exhibit an amphiphilic structure
similar to the traditional surfactants, with more biode-
gradability and toxicologically safety [3]. Strictly speaking,
alkyl polyglucosides are not new surfactants, but they have
been again reconsidered recently, because of increasing
environmental concerns. Some studies investigating the
properties of these derivatives and their application in
detergents, personal care and industrial processes have
been reported recently [4–9]. In general, the alkyl poly-
glucosides are classified as nonionic surfactants and only
limited information [10] is available with regard to anionic
derivatives of alkyl polyglucoside as detergents or as
auxiliaries in industrial uses, such as fabric dyeing
processes.
Keywords Synthesis ꢀ Phosphated glucoside ꢀ
Surfactant ꢀ Biodegradable
K.-M. Chen (&) ꢀ M.-Y. Dong ꢀ C. F. Wang
Department of Polymer Engineering,
National Taiwan University of Science and Technology,
In our previously study, we reported the preparation and
surface active properties of a series of biodegradable dex-
trin derivatives [7–9]. In this paper we present the prepa-
ration and surface properties of a series phosphated alkyl
oligoglucosides. These surfactants are prepared by the
anionic modification of alkyl oligoglucosides with phos-
phorus oxychloride [11]. The alkyl oligoglucosides were
obtained by an usual method in which glucose is reacted
with fatty alcohol containing 10–18 carbon atoms in the
presence of a catalyst. The properties studied in this paper
43, Keelung Road, Section 4, Taipei, Taiwan, ROC
e-mail: kchen@mail.ntust.edu.tw
L.-H. Lin
Department of Chemical and Material Engineering,
Vanung University, 1, Van Nung Road, Shuei-Wei Li,
Chung-Li 320, Taiwan, ROC
M.-C. Hwang
Department of Materials and Textiles,
Oriental Institute of Technology, Pan-Chiao,
Taipei 22061, Taiwan, ROC
1
23

4
18
J Surfact Deterg (2010) 13:417–422
include surface tension, contact angle, foaming properties,
and the influence of surfactants on the bleaching process of
cotton fabrics. The biodegradability of these surfactants
was evaluated by the determination of the ratio of BOD/
COD [2].
Fig. 1. In the initial step, the alkyl oligoglucosides were
obtained by the reaction of 1 mol glucose with 1 mol fatty
alcohol with 1 g of acid catalysis (p-toluene sulfonic acid)
according to a usual method reported elsewhere [3–5]. The
fatty alcohols used in this study had 10–18 carbon atoms. In
the second step, 1 mol alkyl oligoglucoside obtained from
step 1, was reacted with 1 mol phosphorus oxychloride and
1 mol of solvent (chloroform) to obtain an anionic derivative.
The phosphorus oxychloride was used in the present study
because it was the proper agent to attain a pure anionic
product. Then, in step 3, the modified glucosides were reacted
with 1 mol sodium hydroxide aqueous solution to form the
sodium salt. The products were purified by using ethanol to
remove the impurities; the analyses of the final products are
shown in Table 1.
Experimental
Materials
Glucose,p-toluenesulfonicacid, fattyalcoholandphosphorus
oxychloride, solvents, and other chemicals purchased from
Hayash Pure Chemical Co. were reagent grade. Sodium
dodecylbenzene sulfonate (SDBS) was supplied by Sigma–
Aldrich Co. and used to compare the biodegradability of
phosphated alkyl oligoglucosides surfactants. The BOD and
COD test reagents were purchased by Merk Co. and used
without further purification. A commercial grey cotton fabric
was used for the scouring and bleaching experiments.
The structure of the final products was confirmed by
infrared (IR), proton nuclear magnetic resonance (NMR)
spectral analysis and elemental analysis. IR spectra were
obtained with a Japan Spectroscopic FT/IR-3 spectropho-
tometer and NMR spectra were acquired with a Varian 360
L NMR spectrometer.
Preparation and Analyses
Surface Activity Measurements
Although the actual reaction mechanisms are much more
complicated [3], the preparation of phosphated alkyl gluco-
side derivatives may be split into three steps as represented in
The surface tension was determined at room temperature
with a Japan Kaimenkaguka CBVP-A3 surface tensiometer.
Fig. 1 Preparation of anionic
modified alkyl oligoglucosides
Step 1
CH OH
2
CH2OH
catalyst
O
H
H
O
H
H
H
H
H
+
H O
+
C H2n+1OH
2
OH
H
n
OH
°
O-C H
OH
OH
100 C 8hr
OH
n
2n+1
H
OH
H
OH
Cl
Cl
P
Step 2
CH O
O
H
CH OH
2
2
solvent
O
H
O
H
H
O
H
H
H
+
POCl3
OH
+
HCl
OH
H
°
O-CnH2n+1
OH
O-CnH2n+1
0~2 C 4hr
O
H
O
H
OH
Cl
P
P
Cl
Cl
Cl
O
Step 3
Cl
NaO
Cl
P
ONa
P
CH O
O
CH O
O
H
2
2
O
H
O
H
H
O
H
H
+
NaOH
OH
H
O
OH
H
O
+
HCl
°
O
O-CnH2n+1
25 C
O-CnH2n+1
O
O
H
H
Cl
P
ONa
P
P
P
Cl
ONa
Cl
NaO
Cl
O
ONa
O
No.I
n=10
No.II n=12
No.III n=14
No.IV n=16
No.V
n=18
1
23

J Surfact Deterg (2010) 13:417–422
419
Table 1 Analyses of anionic modified alkyl oligoglucosides
The bleaching recipe included: H O (20%) 10 g/L, NaOH
2 2
5
g/L, NaSiO 3 g/L, auxiliaries 2 g/L, liquor ratio 30:1,
3
Compound Anionic Molecular Elemental analysis
group
temperature 80 °C, time 40 min. After the bleaching, the
reflectance of the cotton fabric was measured using an ACS
spectrophotometer and the results were used to calculate
whiteness [16]. The bleached fabrics was also used to
evaluate the wetting ability by the measured height of
water penetrating into fabric [17].
weight
C (%)
H (%)
Found Calc. Found Calc.
I
3.300
3.421
3.538
3.652
3.824
729.2
772.3
814.7
856.9
906.2
26.33 23.53 3.81
27.97 25.59 4.17
29.46 27.52 4.42
30.81 29.33 4.81
31.78 31.03 4.98
3.43
3.79
4.13
4.44
4.74
II
III
IV
V
Results and Discussion
Preparation
The critical micelle concentration (CMC) and the sur-
face tension at the CMC were determined from the
breakpoint of the plot of surface tension versus the loga-
rithm of the concentration. The surfactant surface excess
The alkyl oligoglucosides used in the present study are
prepared by reacting fatty alcohol with glucose. It is known
that the reaction products are present as a mixture of mono-
-
2
concentration at the air/solution interface (C) in mol m
was calculated using the following Gibbs adsorption iso-
,
di- and higher glucosidized compounds (which are known
as alkyl oligoglucosides). Next, these alkyl oligoglucoses
were reacted with phosphorus oxychloride and neutralized
by sodium hydroxide to obtain the anionic surfactant spe-
cies. It is known that the chemistry of alkyl oligoglucose
phosphates derivatives is much more complicated, because
the reaction between an alkyl oligoglucoside and phos-
phorus oxychloride readily forms two ester bonds of the
mono- or the diester. Nevertheless, an idealized and sim-
plified preparation process of phosphated alkyl oligoglu-
coside may be represented as in Fig. 1. A typical IR
spectrum of the phosphated alkyl glucoside derivatives
therm equation [12, 13]:
C ¼ ꢁð1=iRTÞðdc=d ln CÞ
in which c represents the surface tension in m Nm , R is
the gas constant (8.314 J mol
-
1
-
1
-1
K ), T is the absolute
temperature, C is the surfactant concentration, and (dc/d
lnC) is the slope below the CMC in the surface tension
plots. The area occupied by the surfactant molecule at the
air/solution interface, Acmc, was obtained from the
saturated adsorption as follows:
Acmc ¼ 1=NCcmc
-
1
-1
displays bands at 3,365 cm (O–H), 2,851–2,940 cm
-1
-1
(C–H), 1,040–1,110 cm (C–O), 957–1,150 cm (P–O–C)
in which N is Avogadro’s number, and Ccmc represents the
surface excess concentration at the CMC. The value of i
represent the number of species at the interface for which
the concentration changes with the surfactant concentra-
tion. The alkyl polyglucosides are classified as nonionic
surfactant, for mixtures of ionic and nonionic surfactants in
aqueous solution in the absence of added electrolyte, so the
which are characteristic of the desired compound.
1
Compound structure was further supported by the H-NMR
spectrum, which exhibits signals at d 0.8–1.0 ppm
(R–CH ), 1.2–1.4 ppm (–CH ), 3.3–4.0 ppm (–CH –OH).
2 2 2
Surface Tension
-
2
coefficient i = 1 for the dilute solution (10 M or less) of
phosphated alkyl oligoglucosides surfactants [14, 15].
The phosphated derivatives of alkyl oligoglucosides pre-
pared in this study exhibit an amphiphilic structure similar
to conventional surfactants. The glucose, hydroxyl and
phosphated groups compose the hydrophilic moieties,
whereas the aliphatic chain containing 10–18 carbon atoms
is the hydrophobic tail. The surface-active molecules is
concentrated at the surface and reduces the surface tension,
as shown in Fig. 2. The results indicate that an increase in
the chain length of the alcohol tends to decrease the surface
activity. These results are opposite to the reported results of
the influence of alkyl groups for almost all conventional
surfactants. It may be due to the increase of the average
number of D-glucose unit per alkyl chain (degree of poly-
merization of alkyl polyglucosides) as the length of long-
chain alcohol increases and the hydrophilicity of the
Application Measurements
Foaming properties were determined by the Ross-Miles
method. Foam production was measured by the height of
the foam initially produced, and foam stability was mea-
sured by the height after 3 min. The contact angle was
measured by a FACE CA-5 contact angle meter. A 0.2%
(
by weight) surfactant solution was prepared. The ageing
time of the drop is 1 min. The biodegradability of these
surfactants was evaluated by the determination of the ratio
of BOD/COD as previously reported [2].
A rapid laboratory dyeing machine was used to study the
bleaching of a grey cotton fabric by hydrogen peroxide.
1
23

4
20
J Surfact Deterg (2010) 13:417–422
8
7
6
5
4
3
2
0
0
0
0
0
0
The occupied area per molecule for the surfactants gives
some information on the packing degree of adsorbed
molecules. In the present case, this value increases with
increasing chain length. This may indicate that the inter-
action between hydrocarbon chains might not be attractive
but sterically repulsive. It is worth noting that the area
occupied by the phosphated alkyl oligoglucoside is larger
than that of the sugar-based surfactants with the same
hydrocarbon chain length [10], which could be attributed to
the electrostatic repulsion between neighboring anionic
head groups.
No.I
No.II
No.III
No.IV
No.V
Wetting Power
0
1
E-4
1E-3
0.01
0.1
1
The wetting power of a surfactant is one of its most
important properties. For example, in laundry cleaning or
textile processing use, the wetting power of surfactants
may accelerate the diffusion or penetration of alkali
chemicals and dyes into the fibers and improve the deter-
gency or dyeing effects.
-
3
Concentration (m mol dm )
Fig. 2 Plots of surface tension against concentration of anionic
modified alkyl oligoglucosides
surfactant rises. As would be expected, the increase in the
hydrophobicity of surfactants result in an increased surface
activity. The present results indicate that the increased
hydrophilicity of the surfactants provided by the anionic
and nonionic hydrophilic moieties more than compensate
for the increased hydrophobicity produced by longer alkyl
groups [18].
The contact angles formed between solutions of alkyl
glucoside derivatives and an acrylic plastic plane and
cotton fabric are shown in Table 3. The angles are found to
be smaller than those found with water, indicating that all
the solutions of all products possessed the power to wet the
acrylic plastic and the fabric.
Surface Excess Concentration and Occupied Area
Foaming Properties
The CMC of conventional ionic surfactants is known to
decrease with an increasing number of carbon atoms in the
hydrophobic groups. In this study, the CMC increases with
a longer hydrocarbon chain. These phosphated surfactants
have a higher CMC than the anionic surfactants with amide
groups, as reported by Yoshimura et al. [18]. The surface
excess concentration and area occupied by the surfactant
molecule at CMC were calculated from the surface data
according to the Gibbs adsorption equation, and the results
are summarized in Table 2. It is shown that the excess
concentration of surfactant decreases as the length of the
alkyl chain increases. These results indicate that the
decreasing of the length of the alkyl chain produces a
higher surface activity.
Foaming is a complex matter and by no means well
understood, although foam is of great practical importance,
for instance in cosmetics, or because it must be suppressed
owing to its unfavorable effects. However, the low-foam-
ing tendency of surfactants is an important property in
some applications, such as in the use of mechanical dish-
washing agents and dyeing auxiliaries in modern textile-
dyeing processes.
Table 4 shows the foaming properties, as the initial
height of produced foam and the foam height after 3 min.
In comparison to other alkyl polyglucosides, for example a
higher alcohol reacting directly with polyglucoses, the
Table 3 Contact angles of anionic modified alkyl oligoglucosides
Compounds
Contact angle (°)
Acrylic plastic
Cotton fabric
Table 2 Surface active properties of anionic modified alkyl
oligoglucosides
H
2
O
74
50
54
61
64
70
124
72
Compound CMC
(
c
mmol dm ) (mN (910 mol m ) (nm molecule )
cmc
C
cmc
A
cmc
I
-3
-6
-2
2
-1
II
81
-1
m
)
III
IV
V
91
I
13.65
16.56
27.78 3.77
34.60 3.39
0.441
0.490
96
II
108
1
23

J Surfact Deterg (2010) 13:417–422
421
Table 4 Foaming properties of anionic modified alkyl
oligoglucosides
Table 6 Ability of surfactants to improve the wetting power and
whiteness
Compounds
Foam height (cm)
Initial
Compounds
Height of water
adsorption
Whiteness of bleached
fabrics (E313)
After 3 min
I
6.6
4.9
1.7
1.1
0.7
0
55.42
55.02
54.66
54.25
54.03
53.21
I
2.7
2.3
4.2
2.0
1.0
1.8
0.9
3.7
1.6
0.7
II
II
III
IV
V
III
IV
V
Blank
derivatives prepared in this paper exhibit a lower foama-
bility. This lower foaming is probably due to the presence
bleaching system are shown in Table 6. The presence of
surfactants increases the effects of oxidation in bleaching
baths and prepare the more purified fabrics for the next
processes of dyeing or printing.
of multi-hydrophilic groups causing
a considerable
increase in area per molecule and thus reducing the surface
cohesive force [19, 20].
Acknowledgments The authors would like to thank Mr. C. C.
Cheng for his assistance with the experiments. This work was sup-
ported in part by the National Science Council of the R.O.C. under
contract number NSC 91-2216-E011-011.
Biodegradability
After use, the surfactants contained in household deter-
gents, personal care products, washing agents and pro-
cessing materials used in industry, end up in wastewaters.
Consequently ecological issues are of first concern for this
class of compounds. The results of the total biodegradation
of the derivatives prepared in this study are shown in
Table 5. After 10 days their biodegradation is greater than
References
1. Piorr R (1987) Surfactants in consumer products. Sevak Publi-
cation, Bombay, p 22
2
. Swisher RD (1987) Surfactant biodegradation. Marcel Dekker,
New York, p 513
6
0% and consequently, they should be regarded as readily
biodegradable. Apparently, they are considerably more
biodegradable because they would be natural foods of
bacteria present in sewage or river water.
3
. Balzer D, L u¨ der H (2000) Nonionic surfactants: alkylpolyglu-
cosides. Marcel Dekker, New York, p 365
4. Mansfield RC (1974) Process for preparation of alkyl glucosides
and alkyl oligosaccharides. US Patent 3,839,318
5
6
. Langdon WK (1977) Glycoside polyethers. US Patent 4,011,389
. Akira F, Akira Y, Yukinaga Y (1992) Phosphorylated glycoside
and production thereof. Japan Patent 04-009394
Influence on Bleaching of Cotton Fabrics
In the processes of textile industry, scouring and bleaching
are carried out to prepare cloths for dyeing. The scouring
and bleaching treatments do not rely primarily on the use of
surfactants. Nevertheless, rapid and even wetting of the
cloths is of major importance, and to assist this, some
auxiliaries may be added. The ability of phosphated alkyl
glucoside surfactants to improve the whiteness and the
wetting power of cotton fabrics in a hydrogen peroxide
7. Wang HJ, Chen KM (2005) Preparation and surface activity of
biodegradable polymeric surfactants. I. Preparation and surface
activity of dextrin derivatives. J Appl Polym Sci 98:711–717
8
. Wang HR, Chen KM (2006) Preparation and surface active
properties of biodegradable dextrin derivative surfactants. Col-
loids Surf A 281:190–193
9
. Wang CF, Chen KM (2008) Preparation and surface activities of
novel multiply hydrophilic dextrin-derived surfactants. Colloids
Surf A 320:1–5
10. Yoshimura T, Ishihara K, Esumi K (2005) Sugar-based Gemini
surfactants with peptide bonds-synthesis, adsorption, micelliza-
tion, and biodegradability. Langmuir 21:10409–10415
1
1
1
1. Osanai S, Yamada G, Hidano R (2010) Preparation and properties
of phosphate surfactants containing ether and hydroxy groups. J
Surf Deterg 13:41–49
2. Yoshimura T, Ichinokawa T, Kaji M, Esumi K (2006) Synthesis
and surface-active properties of sulfobetaine-type zwitterionic
Gemini surfactants. Colloids Surf A 273:208–212
3. Nyuta K, Yoshimura T, Esumi K (2006) Surface tension and
micellization properties of heterogemini surfactants containing
quaternary ammonium salt and sulfobetaine moiety. J Colloid
Interface Sci 301:267–273
4. Rosen M (1987) Surfactants and interfacial phenomena. Wiley-
Interscience, New York, p. 61 and 174
Table 5 Biodegradability of anionic modified alkyl oligoglucosides
Compound
COD
BOD
5
BOD10
BOD/COD (%)
5
days
10 days
I
1,107
944
520
550
585
114
708
634
685
249
47.0
58.3
61.6
10.9
63.9
67.2
72.2
23.9
III
V
949
a
SDBS
1,040
1
a
Sodium dodecylbenzenesulfonate
1
23

4
1
22
J Surfact Deterg (2010) 13:417–422
5. Han F, Zhang G (2004) Synthesis and characterization of glu-
cosamide-based trisiloxane Gemini surfactants. J Surf Deterg
Li-Huei Lin is an Associate Professor in the Department of Chemical
and Material Engineering, Vanung University. She received her Ph.D.
degree in 2006 from the National Taiwan University of Science and
Technology.
7
:175–180
1
1
6. AATCC Test Method 110-2000, Whiteness of Textiles
7. Japanese Industrial standard-L-1096 (1999) Water absorption
speed test method B. Byreck Method
8. Yoshimura T, Esumi K (2004) Synthesis and surface properties of
anionic Gemini surfactants with amide groups. J Colloid Interface
Sci 276:231–238
9. Lin LH, Chiang CY, Liu HJ, Chen KM (2002) Preparation and
properties of water-soluble polyester surfactants. I Preparation
and surface activity of poly(ethylene glycol)-dimethyl 5-sulfo-
isophthalate sodium salt polyester surfactants. J Applied Polym
Sci 86:2727–2731
0. Chen KM, Tsai CC (1988) Synthesis and surface activity of
maleic anhydride-polyethylene glycol-phthalic anhydride poly-
meric surfactants. J Am Oil Chem Soc 65:1346
Min-Yan Dong is a Ph.D. student in the Department of Polymer
Engineering, National Taiwan University of Science and Technology.
1
1
Chien Fu Wang obtained his Ph.D. degree form the National Taiwan
University of Science and Technology in 2010. He is now working at
the Intellectual Property Office, Ministry of Economic Affairs.
Mou-Chuan Hwang is an Associate Professor in the Department of
Materials and Textiles, Oriental Institute of Technology. He received
his Ph.D. degree in 1993 from the National Taiwan University of
Science and Technology. His research field is surfactant applications
and dyeing.
2
Author Biographies
Keng-Ming Chen is a Professor in the Department of Polymer
Engineering, National Taiwan University of Science and Technology.
His main research interests are functional surfactants, polymer
chemistry and dyeing agents.
1
23