Synthesis and micellar behaviors of an anionic polymerizable surfactant

Article abstract of DOI:10.1002/jccs.201300372

A novel anionic polymerizable surfactant sodium (5-acryloyl-2-(dodecyloxy) phenyl) methane sulfonate has been synthesized from phenol, acrylic acid and bromododecane by esterification, Frise rearrangement, sulfomethylation reaction and Williamson etherification. The parameters of the micellar behaviors are as follows: The CMC was 150 ppm at 40 °C; The surface absorption amounts Γ_m was 3.208 × 10^-6 mol m^-2; The molecular areas A_m was 0.550 × 10^-18m² at the interface of air-water respectively; The aggregation number (N _agg) at C = CMC of this surfactant was 12. A novel anionic polymerizable surfactant sodium (5-acryloyl-2-(dodecyloxy)phenyl) methane sulfonate has been synthesized from phenol, acrylic acid and bromododecane by esterification, Frise rearrangement, sulfomethylation reaction and Williamson etherification. The surfactantsynthesized was phenyl ether, and wasn't hydrolyzed in acidicor alkalic condition.

Full text of DOI:10.1002/jccs.201300372

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Synthesis and Micellar Behaviors of an Anionic Polymerizable Surfactant
Lihua Ma,* Yongjun Guo, Rusheng Feng, Panpan Xiang and Chunhui Li
School of Chemistry and Chemical Engineering Department, Southwest Petroleum University, Chengdu, 610500, China
(Received: Jul. 24, 2013; Accepted: Jan. 8, 2014; Published Online: Feb. 17, 2014; DOI: 10.1002/jccs.201300372)
A novel anionic polymerizable surfactant sodium (5-acryloyl-2-(dodecyloxy)phenyl) methane sulfonate
has been synthesized from phenol, acrylic acid and bromododecane by esterification, Frise rearrange-
ment, sulfomethylation reaction and Williamson etherification. The parameters of the micellar behaviors
are as follows: The CMC was 150 ppm at 40 °C; The surface absorption amounts Gm was 3.208 ´ 10-6 mol
m-2; The molecular areas Am was 0.550 ´ 10-18m2 at the interface of air–water respectively; The aggrega-
tion number (Nagg) at C = CMC of this surfactant was 12.
Keywords: Synthesis; Polymerizable surfactant.
INTRODUCTION
Polymerizable surfactants have been widely used in
lyzed in acidic or alkalic condition. So the surface tension
increases sharply and the surfmers can not be used.10 Phen-
yl ether is a kind of useful surfactant and no hydrolyzation
is observed in acidic or alkalic condition. Based on this, a
novel anionic surface-active monomer sodium (5-acryloyl-
2-(dodecyloxy)phenyl) methane sulfonate has been syn-
thesized. The a,b-unsatuated group and sodium sulfo-
methyl group were introduced in to the phenyl ether seg-
ment by esterification, Fries rearrangement and sulfometh-
ylation reaction respectively. The surfmer, which was syn-
thesized by the above-mentioned methods was phenyl
ether, and wasn’t hydrolyzed in acidic or alkalic condi-
tion.
industry and daily life. The precursors of surfactants are
called surface-active monomer(abbreviated as surfmer),
which contain hydrophobic tail, hydrophilic head group
and polymerizable vinyl double bonds.1 Due to wide appli-
cations in scientific research and industry, surfmer has been
attracted more and more attention, such as in biological
simulation, functional polymer microspheres and novel
water-soluble hydrophobically associating polymers.2-7
Especially, surfmer plays a very important role in the syn-
thesis of hydrophobically associating polyacrylamide
(HPAM), which contains a small proportion of hydropho-
bic groups, usually in the form of pendant side chains or
terminal groups. Intermolecular hydrophobic interactions
cause the formation of a transitory three-dimensional net-
work of polymer chains in aqueous solution at certain poly-
mer concentration. Thereby, because of the reversible dis-
sociation process of the physical links occurring under
shear, these polymers exhibit particular rheological proper-
ties in solution. For instance, HPAM can show interesting
behavior as a function of shear rate or shear time, such as
shear thinning or thixotropy. The rheological behavior of
these compounds have led to great technological interest,
especially for tertiary oil recovery.8-9
RESULTS AND DISCUSSION
The character of the surfactant
Because of having one hydrophilic head group (sul-
fonic acid group) and two hydrophobic groups (phenol
ether chain and a,b unsaturated ketone), the molecule of
the surfactant (5a) in the Scheme 1 was obviously amphi-
philic. According to the molecular structure character of
the surfactant and previous works,1,3 it could be speculated
that the single hydrophilic head group extended into water,
the hydrophobic groups got close to each other under the
hydrophobic interaction, and finally the micelles were
formed. Because there were two hydrophobic groups, and
the long hydrophobic phenol ether chain would be bent, the
micelles of the surfactant would be looser than some com-
mon surfactants, such as sodium dodecyl sulfate (SDS) and
nonylphenol ether, which vertically arranged on the water-
air surface when forming micelles.
Surfmers were discovered by Freedman et al. in 1958
and much effort had been directed toward the synthesis and
application of them. Most of the studies focused on the
micellar behavior and the ability of polymerization of
surfmers. Many satisfactory results have been acquired,
but these surfmers are ester or amide, which were hydro-
* Corresponding author. Tel: +8602883037312; Fax: +8602883037312; Email: mary163com@163.com
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Determining critical micellar concentration and sur-
face activity
For the surfactant (5a), the aqueous solutions with a
Synthesis of sodium (5-acryloyl-2-(dode-
cyloxy)phenyl)methanesulfonate phenyl
acrylate
Scheme 1
series of concentrations were prepared. The surface ten-
sions of these solutions were measured at a given tempera-
ture, and the curves of surface tensions versus concentra-
tions (g~C) were plotted. Their CMC were determined
from the inflection points, and at the same time the surface
tensions corresponding to CMC, gCMC, was also obtained
on the curves of g~C. Fig. 2 displayed the measuring results
at 40 °C, and the CMC was 150 ppm for the surfactant. The
driving force of forming micelles of the surfactant was hy-
drophobic interaction of phenyl ether chain and a b unsatu-
rated ketone. The stronger the hydrophobic interaction
was, the smaller the CMC was. The CMC of the surfactant
(5a) was smaller, compared with the CMC of SDS, which
was 2700 ppm at 40 °C.1 This could be attributed to the
srtonger hydrophobic interaction between phenyl ether
chain and a b unsaturated ketone in the molecule 5a. It was
similar to those common surfactants in a homologous se-
ries.1 The longer hydrocarbon chain was, the smaller the
CMC was.
Measuring solubility in water and determining Krafft
temperature
The solubility of the surfactant (5a) at different tem-
peratures in water was measured by the UV absorptions
method.1 The UV absorbance of the surfactant (5a) solution
at 200-500 nm wavelength was showed in Fig. 1 (small fig-
ure). The absorption intensity of the surfactant (5a) in dif-
ferent concentration at different temperature at 215 nm
wavelength was also measured, and the curves of solubility
versus temperature (C~T) was shown in Fig. 1. It could be
clearly seen that there was an inflexion point on the curve.
The temperature corresponding to the inflexion point was
namely the Krafft temperature. For ionic surfactants, Krafft
temperatures were micellar critical temperatures, above
which the solubility increased rapidly due to the large num-
bers of micelles in the solution. Here the Krafft temperature
was about 35 °C.
Measuring surface excess and area occupied by a
surfactant molecule at water–air interface
The surface excess concentrations Gm (mol m-2) at
CMC were calculated from the Gibbs adsorption isotherm
equation,11
¶g
C
æ
ö
÷
Gm = -
(1)
ç
2.303RT ¶C
è
ømax,T
Fig. 1. UV-absorption spectra and solubility curves of
the surfactant (5a).
Fig. 2. Curve of surface tension vs. concentration of
three kinds of surfactants at 40 °C.
584
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Polymerizable Surfactant
where g (mN m-1) was the equilibrium surface tension at the
surfactant concentration, C (mol L-1), T was the absolute
temperature, and R = 8.314 J mol-1 K-1. In order to extract
the minimum surface area occupied by a surfactant mole-
cule, Am (m2), at water–air interfaced, at surface saturation,
the following equation was used,11 where NA was Avoga-
dro’s constant.
tration Cq were plotted, and the aggregation numbers (Nagg)
of the surfactant (5a) at a given concentration was ob-
tained. The curves of Nagg versus C were plotted, and the
Nagg at CMC were gained for the surfactant (5a) by extrapo-
lation.
The solution of the sufactant at 8CMC, the fluores-
cence spectra of pyrene at different concentrations of ben-
zophenone were shown in Fig. 3, and the line of ln(I0/I) ver-
sus Cq/(C-Ccmc) was plotted in Fig. 4, and the Nagg of the
surfactant at this concentration was gained. By the same
method, the Nagg of the surfactant at other concentrations
1014
Am =
(2)
N A Gm
The adsorption at water–air interface of the surfactant
(5a) was derived from the results in Fig. 2 and obtained by
using the Gibbs adsorption isotherm equation.
Gm = 3.028 ´ 10-6 mol m-2
Am = 0.55 ´ 10-18 m2
From the above data it could be seen that Gm of the
surfactant was smaller than that of SDS,1 whose Gm was 3.6
´ 10-6, whereas the Am (m2) was greater than that of SDS,
whose was 0.46 ´ 10-18 m2. The hydrophobic groups of the
surfactant was bigger than that of SDS, and this conforma-
tion would make the molecule area Am of surfactants at wa-
ter–air interface greater, so smaller Gm was resulted in.
Determining micellar aggregation number
Fig. 3. Emission spectrum of pyrene probe at diffent
Concentrations of quencher for sodium (5-ac-
ryloyl-2-(dodecyloxy)phenyl) methanesulfo-
nate system. The concentration was: 8 CMC;
concentration of quencher: C7 (0.045 mmol L-1)
> C1(0); temperature: 40 °C.
The micelle aggregation numbers of micelles, Nagg
,
for the surfactant (5a) was determined by the steady-state
fluorescence quenching technique (SSFQ).12 This method
was based on quenching of pyrene fluorescence by a hy-
drophobic quencher. Benzophenone was used as the
quencher. Excitation of the probe was at 340 nm and the
emission was monitored at 475 nm. By changing the
quencher concentration Cq (0–0.045 mmol L-1), a linear re-
I0
lationship between ln and Cq was obtained, the corre-
I
sponding equation is as follows:
N agg
I0
I
ln
=
´Cq
(3)
C -CCMC
where I0 was the fluorescence intensity of the probe in the
micellar solutions as in the absence of the quencher, and I
was the fluorescence intensity of the probe in the presence
of the quencher. CCMC and C were the critical micellar con-
centration and the total concentration of the surfactant, re-
spectively. According to the Eq. (3), the straight lines of
logarithm of the intensity ratio versus the quencher concen-
Fig. 4. Plot of ln(I0/I) vs. Cq/(C - CCMC). Concentra-
tion of sodium (5-acryloyl-2-(dodecyloxy)-
phenyl)methanesulfonate: 8CMC.
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were obtained, and the line of Nagg versus C was regressed.
Fig. 5 showed linear feature of Nagg versus C for the
surfactant. The Nagg at C = CMC were driven from extrapo-
lating the straight line, and the Nagg was 12.
determined by a 970CRT fluo-rescence spectrophotometer
(Shanghai Jingke).
Synthesis and characterizing of sodium (5-acryloyl-2-
(dodecyloxy)phenyl)methanesulfonate: Sodium (5-acryloyl-2-
(dodecyloxy)phenyl)methane sulfonate was synthesized from
phenol, thionyl chloride, acrylic acid, aluminum trichloride, car-
bon disulfide, formaldehyde, sodium sulfite, bromododecane and
dimethylformamide as Scheme 1 and IR spectrum of the sur-
factant (2a~5a) were shown in Fig. 6. Phenyl acrylate (2a): Phe-
nol (20.00 g, 0.21 mol) and (16.00 g, 0.22 mol) acrylic acid were
placed in a 100 mL three-necked flask, fitted with a reflux con-
denser and the condenser was connected to a gas absorption trap.
Thionyl chloride (24.00 g, 0.21 mol) were slowly added to the
above mixture. The mixture was heated on a water bath, cau-
tiously at first, until hydrogen chloride and sulphur dioxide
ceasesd to be evolved (about 1 hour). Then the apparatus was
placed on a ceramic-centred wire gauze and heated until the con-
tents were brought just to the reflux temperature in order to com-
plete the reaction (about 20 min). The reaction product was dis-
tilled and 24.00 g (80%) of colorless oil was obtained. 1H-NMR
has signals at (CDCl3, TMS) d = 5.96-6.17 (m, 2H, CH2=CH-
C(O)-O-Ph), 6.30-6.37 (m, 1H, CH2=CH-C(O)-O-Ph). 7.10-7.12
(m, 2H, aromatic), 7.14-7.25 (m, 3H, aromatic) ppm. HRMS
(ESI) calcd for C9H8O2 (M+1) 149.0524, found 149.0602. The
benzene C-H stretching vibrations were observed at 3056 cm-1,
the C-H stretch vibration of C=C-H group was found at 3407
cm-1, at 1741, 1602, 1494 and 1403 cm-1 were the C=C stretching
vibrations of the ring carbons, at 1717 cm-1 was the C=O stretch-
ing vibrations, at 1373 and 1066 cm-1 were the C-O stretching vi-
brations. 1-(4-hydroxyphenyl)prop-2-en-1-one (3a): 18.70 g
(0.14 mol) anhydrous aluminium chloride and 20 mL of carbon
From Fig. 4 it could be seen that the micellar aggrega-
tion number for the surfactant increased with concentration
enhancing, and there were fine linear relationship between
Nagg and concentration in the concentration range of 3–8
CMC. The Nagg of the surfactant was much smaller than
that of SDS, namely, 50.1 It was possible that the hydropho-
bic tail of the surfmer was bigger than that of SDS, and this
was disadvantageous to the association of the hydrocarbon
chains, which made the micelles looser, so very smaller
Nagg was resulted in.
EXPERIMENTAL
Material: Analytical grade solvents were used without pu-
rification. Phenol, thionyl chloride, acrylic acid, aluminum tri-
chloride, carbon disulfide, formaldehyde and sodium sulfite,
bromododecane and dimethylformamide were purchased from
Kelong Inc. (Chengdu, Sichuan, China).
Equipment: 1H NMR spectra was recorded by Bruker-400
MHz spectrometers, and the mass spectrometry was recorded by
Agilent 6224. UV-vis absorbance spectra was obtained by using a
SHIMADZU UV-1800 spectrometer and synthesized surfactant
were individually characterized by WQF-520 Infrared spectros-
copy (Beijing Beifen-Ruili Analytical Instrument Co). The solu-
tion surface tensions were measured by using a TX500C spinning
drop tensiometer (BOWING INDUSTRY CO.), and the fluores-
cence emission spectra of probe pyrene in different media were
Fig. 5. Relationship between Nagg and C for sodium (5-
acryloyl-2-(dodecyloxy)phenyl)methanesul-
fonate.
Fig. 6. IR spectrum of the surfactant (2a~5a).
586
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Polymerizable Surfactant
disulphide were placed in a 100 mL three-necked flask, which
was equipped with a dropping funnel, a sturdy mechanical stirrer
and a reflux condenser. The reflux condenser was attached a gas
absorption trap to the top of the condenser. 18.50 g (0.13 mol)
phenyl acrylate was slowly added in the flask, stirred. Much hy-
drogen chloride was evolved and absorbed by the trap. When all
the phenyl acrylate was introduced, the reaction mixture was
gently refluxed on a water bath for 2 hours. After the solvent was
distilled off, the result mixture was maintained at 80-100 oC by
heating for 3 hours. Then the reaction mixture was cooled and the
aluminium chloride complex was decomposed by slowly adding
100 mL 3N HCl. After cooling, the 1-(4-hydroxyphenyl)prop-2-
en-1-one was collected on the surface. Most of the product in the
upper layer had solidified by setting aside overnight and then was
filtered off by the pump. The product was rinsed thoroughly with
water, and dried at 70 °C. Final 12.00 g 65% dark solid was ac-
quired. 1H-NMR (CDCl3, TMS) has signals at d 4.57-4.60 (m, H,
CH2=CH-C(O)-Ph-O-H), 5.98 (d, J = 10.04 Hz, H, H-CH=CH-
C(O)-Ph-OH), 6.11-6.15 (m, H, H-CH=CH-C(O)-Ph-OH), 6.92-
6.94 (m, 2H, aromatic), 7.19 (d, J = 4.20 Hz, H, H-CH=CH-
C(O)-Ph-OH), 7.51-7.73 (m, 2H, aromatic) ppm. HRMS (ESI)
calcd for C9H8O2 (M+1) 149.0524, found 149.0602. A new ab-
sorption peak was the O-H stretching vibrations of phenol at 3444
cm-1. 735 cm-1 was the C-H stretching vibrations of ortho phenol.
Sodium (5-acryloyl-2-(dodecyloxy)phenyl)methanesulfonate
(4a): 5.00 g (0.07 mol) of 40% formaldehyde, 2 g NaOH, 13 g
(0.10 mol) sodium sulfite, 50 mL of water, 10.00 g (0.068 mol) of
1-(4-hydroxyphenyl)prop-2-en-1-one were added into a flask
equipped with a stirrer and a reflux condenser. The mixture was
heated with steam for 6 hours. After cooling, the supernatant liq-
uid was decanted from the undissolved sodium sulfite. This reac-
tion solution was neutralized with dilute sulfuric acid and evapo-
rated to dryness over steam. The residue was extracted with por-
tions of boiling 95% ethanol (200 mL), rotary evaporation to give
placed in a 100 mL round-bottomed flask fitted with a reflux con-
denser and sealed stirrer unit. The flask was boiled on a oil bath,
stirred for 8 hours. The solvent was removed with a rotary evapo-
rator and the result mixture was mixed into 100 mL of water. 5.80
g (68%) of sodium (5-acryloyl-2-(dodecyloxy)phenyl)methane
sulfonate was obtained by filtering the solid off by the pump.
1H-NMR (DMSO, TMS) has signals at d 0.79 (s, 2H, H-CH=CH-
-
C(O)-PhOCH2CH2(CH2)8CH2CH2-CH2-SO3 ), 1.12 (s, 16H, H-
-
CH=CH-C(O)-PhOCH2CH2(CH2)8CH2CH2-CH2-SO3 ), 2.71 (s,
-
2H, H-CH=CH-C(O)-PhOCH2CH2(CH2)8CH2CH2-CH2-SO3 ),
2.87 (s, 2H, H-CH=CH-C(O)-PhOCH2CH2CH2)8CH2CH2-CH2-
-
SO3 ), 4.05 (s, 2H, H-CH=CH-C(O)-PhOCH2CH2(CH2)8CH2CH2-
-
CH2-SO3 ), 4.12 (s, 2H, H-CH=CH-C(O)-PhOCH2CH2(CH2)8
-
CH2CH2-CH2-SO3 ), 4.17 (s, 1H, H-CH=CH-C(O)-PhOCH2CH2
-
(CH2)8CH2CH2-CH2-SO3 ), 4.70 (s, H, H-CH=CH-C(O)-
-
PhOCH2CH2(CH2)8CH2CH2-CH2-SO3 ), 7.19 (s, H, aromatic),
7.78 (s, H, H-CH=CH-C(O)-PhOCH2CH2(CH2)8CH2CH2-CH2-
-
SO3 ), 8.30 (s, 2H, aromatic) ppm. HRMS (ESI) calcd for
C22H33O5S (M+-1) 409.2049, found 409.2052. 2960 cm-1, 2854
cm-1 were C-H stretching vibrations of methyl group and 2923
cm-1 was C-H stretching vibrations of methylene.
CONCLUSIONS
A novel anionic surface-active monomer sodium (5-
acryloyl-2-(dodecyloxy)phenyl) methane sulfonate has
been synthesized, which was phenyl ether and wasn’t hy-
drolyzed in acidic or alkalic condition. The structure was
confirmed by 1H NMR spectra, mass spectrometry and IR
spectrum. The micellar behaviors showed that the CMC
was 150 ppm at 40 °C, the surface absorption amounts Gm
was 3.208 ´ 10-6mol m-2 and the molecular areas Am was
0.550 ´ 10-18m2 at the interface of air–water respectively.
The aggregation number (Nagg) at C = CMC of this sur-
factant was 12 by steady-state fluorescence probe method.
This study was aimed at supplying basic theory references
for synthesis hydrophobically associating polyacrylamide
(HPAM), which could be used in both acidic and alkalic
condition for tertiary oil recovery.
1
9.80 g (61%) brownish yellow solid. H-NMR (D2O, TMS) has
-
signals at d 4.70 (s, 2H, H-CH=CH-C(O)-PhONa-CH2-SO3 ),
-
6.48-6.50 (m, H, H-CH=CH-C(O)-PhONa-CH2-SO3 ), 6.51 (d, J
-
= 2.00 Hz, H, H-CH=CH-C(O)-PhONa-CH2-SO3 ), 6.59 (s, H, ar-
-
omatic), 7.18-7.74 (m, H, H-CH=CH-C(O)-PhONa-CH2-SO3 ),
ACKNOWLEDGEMENTS
7.77-7.79 (m, H, aromatic), 7.93-7.95 (m, H, aromatic) ppm.
HRMS (ESI) calcd for C10H8O5S (M-1) 240.2325, found
240.0092. 1186, 1049 cm-1 were stretch vibrations for sulfonic
acid group, and 626 cm-1, 522 cm-1 were in-plane bending vibra-
tion. Sodium (5-acryloyl-2-(dodecyloxy)phenyl)methane sul-
fonate (5a): 5.00 g of the product of the previous step, 4.25 g
(0.017 mol) of biomedicine and 20 mL dimethyl sulfoxide were
This work was carried out as a part of the National
Science and Technology Major Project, China
(2011ZX05010-004). The authors are grateful for the fi-
nancial support.
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