A new cationic gemini surfmer: Synthesis and surface activities

Article abstract of DOI:10.1007/s11743-010-1211-x

A new cationic gemini surfmer (polymerizable surfactant or surface-active monomer) with an acrylic reactive group in its spacer group was synthesized and characterized, and its surface activity properties were examined in comparison with its intermediate surfactant 12-3OH-12?2Cl^-, a previously-reported gemini surfmer 12′-2-12′?2Br^-, as well as monomeric surfactant dodecyl trimethylammonium bromide. It was found that neither the incorporation of a double bond onto the gemini surfactant nor the change of location of the double bond will affect surface activities of the gemini surfactant.

Full text of DOI:10.1007/s11743-010-1211-x

J Surfact Deterg (2011) 14:73–76
DOI 10.1007/s11743-010-1211-x
LETTER TO THE EDITOR
A New Cationic Gemini Surfmer: Synthesis and Surface Activities
Xin Su
Limin Wei
•
Biqing Wang
•
•
Zhiyong Lu
•
Yujun Feng
Received: 27 March 2010 / Accepted: 21 April 2010 / Published online: 23 May 2010
Ó AOCS 2010
Abstract A new cationic gemini surfmer (polymerizable
surfactant or surface-active monomer) with an acrylic
reactive group in its spacer group was synthesized and
characterized, and its surface activity properties were
unique properties [2, 3], gemini surfactants find many
potential applications, such as catalysis and adsorption
applications [4], new synthetic vectors for gene transfec-
tion [5], analytical separations [6], solubilization processes
[7], biotechnology [8], enhanced oil recovery [9] and paint
additives [10], etc.
examined in comparison with its intermediate surfactant
-
1
2-3OH-12ꢀ2Cl , a previously-reported gemini surfmer
0
0
-
1
2 -2-12 ꢀ2Br , as well as monomeric surfactant dodecyl
Polymerizable surfactants or surface-active monomers
(surfmers) are a class of vinyl amphiphilic compounds,
which can function both as surfactants and monomers [11].
So surfmers could offer potential for developing hybrid
nanometer-sized reaction and templating media [11], and
have been used in a variety of applications including cap-
turing the structure of spherical micelles and as a stabilizer
in emulsion polymerization, miniemulsion polymerization,
and microemulsion polymerization [12–14].
trimethylammonium bromide. It was found that neither the
incorporation of a double bond onto the gemini surfactant
nor the change of location of the double bond will affect
surface activities of the gemini surfactant.
Keywords Gemini surfactant ꢀ Surfmer ꢀ
Cationic surfactant ꢀ Surface activity
Nevertheless, few reports have focused on surfactants
with both gemini architecture and a polymerizable group.
To the best of our knowledge, only Abe et al. [15] have
Introduction
0
0
-
Gemini surfactants are a novel family of amphiphilic
compounds made up of two amphiphilic moieties con-
nected at the level of, or very close to the head groups by a
reported a cationic gemini surfmer 12 -2-12 ꢀ2Br with the
?
molecular structure [CH = C(CH )COO(CH ) N (CH )
2
3
2 11
3 2
-
CH ] ꢀ2Br . It was found its surface activity is compara-
2
2
-
spacer group [1], normally referred to as m-s-mꢀ2X ,
ble to its corresponding conventional gemini surfactant
-
where m, s are the carbon numbers in each alkyl chain and
-
spacer, X represents the counterion. These surfactants
12-2-12ꢀ2Br which does not have a reactive double bond.
0
0
-
Unlike 12 -2-12 ꢀ2Br whose double bonds are located at
the terminal of the hydrophobic tails, a new cationic gemini
surfmer with a polymerizable group in the spacer is first
reported in this work.
usually have superior surface-active behavior over their
corresponding monomeric counterparts. Because of their
As shown in Scheme 1, the preparation of gemini
-
X. Su ꢀ B. Wang ꢀ Z. Lu ꢀ L. Wei ꢀ Y. Feng (&)
Chengdu Institute of Organic Chemistry,
Chinese Academy of Sciences,
surfmer 12-3AG-12ꢀ2Cl (AG denotes an acryloyl group)
was followed a two-step procedure: In a three-necked flask,
Chengdu 610041, People’s Republic of China
e-mail: yjfeng@cioc.ac.cn
41.2 g N,N-dimethyldodecan-1-amine was mixed with
10 ml hydrochloride (15%, v/v) for at least 0.5 h, and 5 g
epoxy chloropropane was then added dropwise. The
reaction solution was stirred continuously at 60 °C. After
12 h of reaction, the intermediate gemini surfactant
X. Su
Graduate School of the Chinese Academy of Sciences,
Beijing 100049, People’s Republic of China
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J Surfact Deterg (2011) 14:73–76
Scheme 1 The route towards
synthesis of the cationic gemini
surfmer
-
1
2-3OH-12ꢀ2Cl (OH denotes a hydroxyl group) was
(mol/l), and dc/dlnC is the slope below the CMC in the
surface-tension plots. The value of n (the number of species
at the interface whose concentration at the interface
changed with a change in surfactant concentration) was
1
obtained at an overall conversion of about 90%. H NMR
(
Bruker AMX300 300 MHz, CDCl , TMS) for 12-3OH-
3
-
1
2ꢀ2Cl : d 0.875 [t, 6H, 2CH CH ], 1.178–1.257 [m, 36H,
3
2
-
-
2
CH (CH ) CH ], 2.021 [1H, (CH ) CHOH], 3.224–3.321
3
taken as 3 for 12-3OH-12ꢀ2Cl and 12-3AG-12ꢀ2Cl
2 9
2
2 2
?
[
s, 12H, 4 N CH ], 3.541–3.622 [t, 4H, 2CH (CH )
2 9
because the gemini surfactants here are the divalent-
monovalent type [18]. The area occupied by a surfactant
molecule at the air/solution interface was obtained from the
saturated adsorption as follows:
3
3
?
CH CH N ], 3.754 [m, 4H, (CH N CH ) CHOH], 5.201
?
2
2
3
2 2
[
m, 1H, (CH ) CHOH]. The mixture of 8.3 g 12-3OH-
2 2
-
1
2ꢀ2Cl , 0.05 g hydroquinone and 30 g chloroform was
stirred at 45 °C for 2 h, and 1.5 g acryloyl chloride was
then added dropwise to the mixture quickly. After 5 h of
reaction, the solvent was evaporated off under reduced
pressure. The residue obtained was purified by column
chromatography on a silica gel column using chloroform/
acetone (2:1, v/v) as a mobile phase. The gemini surfmer
1
ACMC
¼
ð2Þ
NCCMC
where N is Avogadro’s number, and CCMC is the maximum
surface excess concentration at CMC.
Shown in Fig. 1 are the variations in surface tension of
-
-
-
12-3OH-12ꢀ2Cl , 12-3AG-12ꢀ2Cl and DTAB against
their concentrations in pure water. The surface tension of
all the three surfactants decreased with increasing surfac-
tant concentrations and then reached clear break points,
which were taken as their CMCs. The alteration in surface
1
8
1
2-3AG-12ꢀ2Cl , was obtained as a white solid (8.3 g,
1
5% yield, mp 125.7 °C) and H NMR (CDCl , TMS) for
3
-
2-3AG-12ꢀ2Cl : d 0.869 [t, 6H, 2CH CH ], 1.184–1.234
3
2
[
m, 36H, 2CH (CH ) CH ], 3.226–3.328 [s, 12H,
3 2 9 2
?
?
4
3
N CH ], 3.552-3.631 [t, 4H, 2CH (CH ) CH CH N ],
3 3 2 9 2 2
?
.774 [m, 4H, (CH N CH ) CHOCO], 5.011 [m, 1H,
-
tension with surfactant concentration of 12-3AG-12ꢀ2Cl
3
2 2
-
was similar to that of 12-3OH-12ꢀ2Cl , indicating that the
(
CH ) CHOCO], 6.102 [t, 1H, OCOCH = CH ], 6.203-
2 2 2
introduction of a double bond onto the skeleton of a gemini
surfactant will not affect the surface activity significantly.
This is in good agreement with the previous report on
6
.311 [t, 2H, OCOCH = CH2].
Surface tensions of the gemini intermediate 12-3OH-
-
-
1
2ꢀ2Cl andgeminisurfmer12-3AG-12ꢀ2Cl were measured
0
0
-
gemini surfmer 12 -2-12 ꢀ2Br
whose polymerizable
with the Wilhelmy plate technique using an automatic surface
tensiometer (BZY-1, Shanghai Hengping Instrument, China)
as described previously [16]. Measurements were taken at
2
5 ± 0.5 °C until a constant surface tension value was
reached. The critical micelle concentration (CMC) values
were taken at the intersection of the linear portions of the
surface tension plots against the logarithm of the surfactant
-
concentration. Stock solutions of 12-3OH-12ꢀ2Cl and
-
1
2-3AG-12ꢀ2Cl were diluted continuously with pure water,
respectively,andthesurfacetensionateachconcentrationwas
obtained by averaging three runs of measurement. For com-
parison, the surface activity of corresponding monomeric
surfactant, dodecyl trimethylammonium bromide (DTAB),
was measured under identical conditions. The amount of
adsorbedsurfactantCatthe air–waterinterfacewascalculated
using the Gibbs adsorption isotherm [17]
1
dc
nRT d ln C
C ¼ ꢁ
ꢂ
ð1Þ
Fig. 1 Variation in surface tension with surfactant concentration for
-
where R is the gas constant (8.31 J/molꢀK), T is the
gemini intermediate 12-3OH-12ꢀ2Cl , gemini surfmer 12-3AG-
-
absolute temperature (K), C is the surfactant concentration
12ꢀ2Cl and DTAB at 25 °C
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J Surfact Deterg (2011) 14:73–76
75
Table 1 Surface properties of
gemini surfactant investigated
6
Surfactant
CMC
(mol/l)
c
CMC
(mN/m)
A
CMC
2
(nm /molecule)
10 CCMC
(mol/m )
CMC/C20
2
-
1
2-3OH-12ꢀ2Cl and other
related surfactants at 25 °C
-
-
-4
-4
-4
-4
-2
1
2-3OH-12ꢀ2Cl
8.4 9 10
4.6 9 10
5.0 9 10
1.0 9 10
2.1 9 10
32.0
31.6
32.1
33.1
35.8
0.364
0.451
0.22
4.22
3.38
7.01
3.26
3.46
24
25
30
27
4.6
1
2-3AG-12ꢀ2Cl
-
*
Data reproduced from Ref.
12’-2-12’ꢀ2Br *
[
15]
-
1
2-3-12ꢀ2Cl **
DTAB
0.421
0.087
*
[
* Data reproduced from Ref.
19]
groups are located at the terminal of the hydrophobic tails,
-
Cu(II) and Ni(II) complexes of macrocyclic ligands in gemini
surfactant micelles. J Mol Catal 277:15–20
and corresponding gemini surfactant 12-2-12ꢀ2Br [15].
5
. Kirby AJ, Camilleri P, Engberts JBFN, Feiters MC, Nolte RJM,
S o¨ derman O, Bergsma M, Bell Paul C, Fielden ML,
Garc ´ı a Rodr ´ı guez CL, Gu e´ dat P, Kremer A, McGregor C, Perrin
C, Ronsin G, Eijk MCP (2003) Gemini surfactants: new syn-
thetic vectors for gene transfection. Angew Chem Int Ed
Table 1 compares surface activities in water for gem-
-
0
0
-
ini surfmers 12-3AG-12ꢀ2Cl , 12 -2-12 ꢀ2Br [15], gemini
-
-
surfactants 12-3OH-12ꢀ2Cl , 12-3-12ꢀ2Cl
[19] and
monomeric cationic surfactant DTAB. It is apparent that
gemini surfmer 12-3AG-12ꢀ2Cl- has a CMC value 2 orders
of magnitude smaller than that of DTAB. Moreover, the
4
2:1448–1457
6
. Veronovski N, Andreozzi P, Mesa C, Sfiligoj-Smole M, Ribitsch
V (2010) Use of gemini surfactants to stabilize TiO2 P25 col-
loidal dispersions. Colloid Polym Sci 288:387–394
. Lee HI, Pak C, Yi SH, Shon JK, Kim SS, So BG, Chang H, Yie
JE, Kwona YU, Kim JM (2005) Systematic phase control of
periodic mesoporous organosilicas using gemini surfactants.
J Mater Chem 15:4711–4717
-
cCMC value in water, 31.6 mN/m, of 12-3AG-12ꢀ2Cl is
7
smaller than that (33.8 mN/m) of DTAB. This is in line with
previous work showing that the presence of two hydropho-
bic groups in the gemini molecule leads to greater surface
activity [1, 20, 21]. On the other hand, the values of sur-
8. Piera E, Infante MR, Clape
thesis of arginine-based gemini surfactants. Biotechnol Bioeng
0:323–331
´
s P (2000) Chemo-enzymatic syn-
-
face activity for the gemini surfactants 12-3OH-12ꢀ2Cl ,
7
-
-
0
0
-
1
2-3AG-12ꢀ2Cl , 12-3-12ꢀ2Cl and 12 -2-12 ꢀ2Br are
9
. Chen H, Han L, Luo P, Ye Z (2005) The ultralow interfacial
tensions between crude oils and gemini surfactant solutions.
J Colloid Interface Sci 285:872–874
10. Galgoci EG, Chan SY, Yacoub K (2006) Innovative, gemini-type
molecular defoamer technology for improved coating aesthetics.
J Coat Technol 3:77–85
comparable and similar.
In summary, we successfully synthesized a cationic
-
gemini surfmer 12-3AG-12ꢀ2Cl using N,N-dimethyldod-
ecan-1-amine, epoxy chloropropane and acryloyl chloride.
Comparing with the monomeric surfactant, 12-3AG-
-
11. Summers M, Eastoe J (2003) Applications of polymerizable
surfactants. Adv Colloid Interface Sci 100–102:137–152
1
2ꢀ2Cl has the better efficiency and effectiveness in
1
2. Greence BW (1970) In situ polymerization of surface-active
agents on latex particles. J Colloid Interface Sci 32(1):90–95
3. Urquiola MB (1992) Emulsion polymerization of vinyl acetate
using a polymerizable surfactant. 1. Kinetic studies. J Poly Sci A
30:2619–2629
lowering the surface tension in water. Gemini surfmer
-
1
2-3AG-12ꢀ2Cl has a similar surface activity as other
1
gemini surfactants. Polymerization of the gemini surfmer is
under way.
1
1
1
1
4. Urquiola MB (1992) Emulsion polymerization of vinyl acetate
using a polymerizable surfactant. 2. Polymerization mechanism.
J Poly Sci A 30:2631–2644
Acknowledgments The financial supports from the Chinese Acad-
emy of Science, the open research fund program (200601) sponsored
by Key Laboratory for Colloid and Interface Chemistry of State
Education Ministry, Sichuan Provincial Bureau of Science and
Technology (2008GZ2004), as well as partial support from Chengdu
Base of the Graduate School of the Chinese of Sciences are greatly
acknowledged.
5. Abe M, Tsubone K, Koike T, Tsuchiya K, Ohkubo T, Sakai H
(
2006) Polymerizable cationic gemini surfactant. Langmuir
2:8293–8297
2
6. Sun Y, Feng Y, Dong H (2007) Adsorption of dissymmetric
cationic gemini surfactants at silica/water interface. Surf Sci
6
01:1988–1995
7. Rosen MJ, Cohen AW, Dahanayake M, Hua XY (1982) Rela-
tionship of structure to properties in surfactants. 10. Surface and
thermodynamic properties of 2-dodecyloxypoly (ethenoxyetha-
References
2 4 x
nol)s, C12H25(OC H ) OH, in aqueous solution. J Phys Chem
1
. Zana R (2002) Dimeric and oligomeric surfactants. Behavior at
interfaces and in aqueous solution: a review. Adv Colloid Inter-
face Sci 97:205–253
. Menger FM, Littau CA (1993) Gemini surfactants: a new class of
self-assembling molecules. J Am Chem Soc 115:10083–10090
. Menger FM, Keiper JS (2000) Gemini surfactants. Angew Chem
Int Ed 39:1906–1920
86:541–545
18. Zana R, Xia J (2003) Gemini surfactants: synthesis, interfacial
and solution-phase behavior, and applications. Dekker, New
York, pp 93
19. Zana R, L e´ vy H, Papoutsi D, Beinert G (1995) Micellization of
two triquaternary ammonium surfactants in aqueous solution.
Langmuir 11:3694–3698
2
3
4
. Qiu L, Jiang X, Gu L, Hu G (2007) Gemini metallomicellar
catalysis: hydrolysis of p-nitrophenyl picolinate catalyzed by
20. Rosen MJ (2005) Surfactants and interfacial phenomena, 3rd ed.
Wiley-Interscience, New York, pp 127–129
1
23

7
2
6
J Surfact Deterg (2011) 14:73–76
1. Zana R (2002) Dimeric (gemini) surfactants: effect of the spacer
group on the association behavior in aqueous solution. J Colloid
Interface Sci 248:203–220
Limin Wei was born in 1983, and is now a research assistant at
Chengdu Institute of Organic Chemistry (CIOC), Chinese Academy
of Sciences. She earned her bachelor degree in chemical engineering
from Sichuan University in 2005, and masters degree in polymer
chemistry and physics from CIOC in 2008. Then she joined in CIOC
focusing on new water-soluble polymers and functional monomers.
Author Biographies
Yujun Feng was born in 1971, and is now serving as professor and a
team leader at Chengdu Institute of Organic Chemistry (CIOC),
Chinese Academy of Sciences. After earning his Ph.D. in Applied
Chemistry from Southwest Petroleum University, China, in 1999, he
moved to France performing his two post-doctoral researches at a
joint laboratory of CNRS/Universit e´ de Pau and at Institut Fran c¸ ais du
P e´ trole (IFP). In 2004, he returned to CIOC and has been serving as a
team leader since then. Dr Feng’s research interest includes novel
water-soluble polymers and surfactants used for enhanced oil
recovery, and he has published more than 90 papers.
Xin Su was born in 1980, and received his B.Sc. from Jilin University
in 1999. He is now a 3rd-year Ph.D. student in polymer chemistry &
physics at Chengdu Institute of Organic Chemistry, Chinese Academy
of Sciences. His research interest is oligomeric surfactants and living/
controlled polymerization.
Biqing Wang was born in 1974, and is now a research assistant at
Chengdu Institute of Organic Chemistry (CIOC), Chinese Academy
of Sciences. After earning her bachelor degree in applied chemistry in
1
999 from Sichuan University, she joined the E’mei Semiconductor
Material Factory & Institute. In 2001 she moved to CIOC and is
currently interested in emulsion polymerization and novel surfactants.
Zhiyong Lu was born in 1977, and is now a research assistant at
Chengdu Institute of Organic Chemistry (CIOC), Chinese Academy
of Sciences. When receiving his masters degree in polymer materials
from Sichuan University in 2005, he joined the CIOC. His interest is
concentrating on water-soluble polymers.
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