Synthesis of a novel branch fluorinated cationic surfactant and its surface activity

Article abstract of DOI:10.1016/j.jfluchem.2013.08.007

A novel branch fluorinated cationic surfactant trimethyl-(2-{4-[3,4,4,4- tetrafluoro-2-(1,2,2,2-tetra-fluoro-1-trifluoromethyl-ethyl)-1, 3-bis-trifluoromethyl-but-1-enyloxy]-benzenesulfonylamino}-ethyl)-ammonium iodide (BFCS) was synthesized successfully, and it's structure was characterized by FTIR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, MS. The surface activities of BFCS, the effect of temperature, electrolyte and combination with hydrocarbon surfactant were investigated. The results showed that BFCS exhibited excellent surface activity and combined properties.

Full text of DOI:10.1016/j.jfluchem.2013.08.007

Journal of Fluorine Chemistry 156 (2013) 5–8
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis of a novel branch fluorinated cationic surfactant and its
surface activity
*
Hong-Ke Wu, Jia-Qi Zhong, Hai-Min Shen, Hong-Xin Shi
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A novel branch fluorinated cationic surfactant trimethyl-(2-{4-[3,4,4,4-tetrafluoro-2-(1,2,2,2-tetra-
fluoro-1-trifluoromethyl-ethyl)-1,3-bis-trifluoromethyl-but-1-enyloxy]-benzenesulfonylamino}-eth-
yl)-ammonium iodide (BFCS) was synthesized successfully, and it’s structure was characterized by FTIR,
1H NMR, 13C NMR, 19F NMR, MS. The surface activities of BFCS, the effect of temperature, electrolyte and
combination with hydrocarbon surfactant were investigated. The results showed that BFCS exhibited
excellent surface activity and combined properties.
Received 24 April 2013
Received in revised form 18 August 2013
Accepted 19 August 2013
Available online 29 August 2013
Keywords:
ß 2013 Published by Elsevier B.V.
Fluorinated surfactant
Synthesis
Surface activities
1. Introduction
2. Result and discussion
It is well known that the fluorinated surfactants are widely used
in coatings [1–3], paints [4], inks [5], waxes, additives for etching,
leather, fire fighting foams [6,7], and so on [8–11]. It also displayed
diversity properties, such as thermal and chemical stability [12],
high surface activity and low critical micelle concentration.
Recently, n-perfluoroalkyl iodide (RFI) has become a research
focus in the synthesis of fluorinated surfactants. For example,
straight chain anionic, cationic, nonionic and amphoteric fluori-
nated surfactants were synthesized by introducing perfluoroalkyl
group into organic substances [13]. With the forbidden of
perfluorooctanote (PFOA) and perfluorooctane sulphonate (PFOS)
for persistent, toxic and bioaccumulable pollutants, it is necessary
to develop novel structural fluorinated surfactants. Hexafluor-
opropylene oligomer is an important starting material which can
be used to synthesize many fluorinated surfactants [14–16].
Introducing branch is one of effective strategies for synthesizing
non-bioaccumulable alternatives to PFOA [17].
2.1. Surface tension
Unlike many fluorinated surfactants, the branch fluorinated
cationic surfactant 6 (BFCS) exhibits excellent solubility in water at
room temperature, thus it could be employed to reduce the surface
tension of water. The curve of surface tension was obtained by
Wihemlmy (Fig. 1). The surface tension of BFCS was assessed by
means of tensiometry. It can be found that the cmc value of BFCS in
water is 6.0 Â 10À5 mol LÀ1 at 293 K and the surface tension of the
aqueous solution is 20.3 mN mÀ1 at the cmc. The value of surface
properties is lower than that of sodium perfluorooctanoate (about
24.7 mN mÀ1 at the cmc 3.1 Â 10À2 mol LÀ1 [18]). Its low surface
tension and cmc at room temperature make it a potential
surfactant, as a competitor when the C–F group was introduced.
2.2. Effect of temperature on the surface activity of BFCS
In view of these facts mentioned above, and also as a part of our
work on the synthesis of branch fluorinated cationic surfactant, the
title compound was designed and synthesized using hexafluor-
opropylene oligomer as starting material (Scheme 1). The surface
activities of BFCS were investigated in detail.
For the surface tension of ionic fluorinated surfactant,
temperature is a significant effect factor. At 1.2 Â 10À5 mol LÀ1
,
the surface tension of BFCS decreased from 68.1 mN mÀ1 to
55.0 mN mÀ1 when the temperature was increased from 293 K to
313 K (Fig. 2). When the concentration of BFCS is high
(ꢀ1.2 Â 10À4 mol LÀ1), the effect of temperature is small. This
phenomenon can be explained as following, the effect of
absorption from both sides of a vapor/liquid interface was
considered simultaneously. Furthermore the contribution from
the former is more important than from liquid [19–21].
*
Corresponding author. Tel.: +86 571 8832 0832; fax: +86 571 88320832.
E-mail address: shihxin@zjut.edu.cn (H.-X. Shi).
0022-1139/$ – see front matter ß 2013 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.jfluchem.2013.08.007

6
H.-K. Wu et al. / Journal of Fluorine Chemistry 156 (2013) 5–8
Scheme 1. Synthetic route to produce BFCS (6).
2.3. Effect of electrolyte on the surface activity of BFCS
under ions free. In double-layer terminology, they should be
classified as ‘‘indifferent’’. Rather, their hydration with more water
molecules keeps them out of the surface region. The observed ionic
specificities are relatively minor and do not exhibit a clear ionic
trend. According to general expectation, bigger ions would
dehydrate more easily than the smaller ones [22,23]. However,
the hardwater may vary dramatically with changes in the
solubility of BFCS, which can make the surface activity poor
(40.2 mN mÀ1).
The BFCS exhibited lower surface tension in different concen-
trations of electrolyte NaCl (1.0 g LÀ1 and 5.0 g LÀ1) aqueous
solution (Fig. 3). From Fig. 3, it indicated BFCS had good salt-
resistance. It has a strong attraction with just one water molecule
70
65
BFCS
2.4. Effect of combination with hydrocarbon surfactant on surface
tension of BFCS
60
55
50
45
40
35
30
25
20
15
The surface tension of PEG400 combined with BFCS (20%) was
decreased from 67.0 mN mÀ1 to 57.1 mN mÀ1 at 5 Â 10À3 g LÀ1
(Fig. 4). This decrease was observed by an increase of mass ratio of
BFCS in this surfactant combination. However, the change in the
surface tension is rather small, and further increasing of the total
concentration of the combined surfactants has no effect. That can
be explained by the following facts. At the critical micelle
concentration, the impurity becomes soluble in the micelles
because of its hydrophobic character, due to its low concentration
in bulk and surface concentration. Therefore, the interaction
between the combined surfactants is strengthened [24,25]. Thus
the surface activity was increased further. It can indicate that BFCS
exhibited excellent combination with hydrocarbon surfactants.
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
lg( C/mol.L-1)
Fig. 1. Surface tension measurements of BFCS.
70
65
60
55
50
45
40
35
30
25
20
15
70
65
313 K
303 K
293 K
0
g.L-1 NaCl
1.0 g.L-1 NaCl
5.0 g.L-1 NaCl
60
55
50
45
40
35
30
25
20
15
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0
-1
lg( C/mol.L-1)
lg(
C/mol.L )
Fig. 2. Effect of temperature on surface tension of BFCS.
Fig. 3. Effect of electrolyte on surface tension of BFCS.

H.-K. Wu et al. / Journal of Fluorine Chemistry 156 (2013) 5–8
7
70
65
60
55
50
45
40
35
30
25
20
15
4.2.2. Synthesis of [3,4,4,4-tetrafluoro-2-(1,2,2,2-tetrafluoro-1-
m(PEG400):m(BFCS)=1:0
m(PEG400):m(BFCS)=4:1
m(PEG400):m(BFCS)=1:1
m(PEG400):m(BFCS)=1:4
m(PEG400):m(BFCS)=0:1
trifluoromethyl-ethyl)-1,3-bis-trifluoro-methyl-but-1-enyloxy]-
benzene (3)
To a mixture of phenol (1.88 g, 0.02 mol) and sodium carbonate
(2.12 g, 0.02 mol) in dimethyl sulfoxide (DMSO, 10 mL), compound
2 (9.0 g, 0.02 mol) was dropwised at room temperature. The
mixture was stirred at 75 8C for 6.0 h. The resultant mixture was
washed with water (100 mL) and HCl solution (5%, 50 mL). The
organic phase was dried by Na2SO4. The colorless liquid 3 (9.45 g,
90%) was obtained by filtration. IR (cmÀ1):
y
(C55C) 1592.4,
(C–F) 1176.2, 1129.1, 1118.4, 975.3 cmÀ1 1H NMR
7.32(t, 2H, ArH), 7.20(t, 1H, ArH), 6.90 ppm (d,
y(C–O)
1228.3,
(CDCl3)
y
d
;
:
J = 10.14 Hz, 2H, ArH); 19F NMR (CDCl3): À56.29 (3F, CF3),
À71.53(6F, CF3), À72.62(6F, CF3), À167.62(1F, F), À169.74 ppm
(1F, F); MS(EI) m/z 524.0(M-1).
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
lg( C/mol.L-1)
4.2.3. Synthesis of 4-[3,4,4,4-tetrafluoro-2-(1,2,2,2-tetrafluoro-1-
trifluoromethyl-ethyl)-1,3-bis-tri-fluoromethyl-but-1-enyloxy]-
benzenesulfonyl chloride (4)
Fig. 4. Effect of combination with hydrocarbon surfactant on surface tension of
BFCS.
To a solution of compound 3 (10.5 g, 0.02 mol) in CH2Cl2
(50 mL), chlorosulfonic acid (4.66 g, 0.04 mol) was dropwised at
room temperature. After refluxing for 3 h, the solvent was
evaporated to give a white residue, and recrystallised in acetic
ether and petroleum ether to afford a white crystal 4 (10.9 g,
3. Conclusion
A novel branch fluorinated cationic surfactant trimethyl-(2-
{4-[3,4,4,4-tetrafluoro-2-(1,2,2,2-tetra-fluoro-1-trifluoro-
methyl-ethyl)-1,3-bis-trifluoromethyl-but-1-enyloxy]-benze-
88%). IR (cmÀ1):
1132.1, 1042.7,1010.3 cmÀ1
y
(C55C) 1594.1,
y
(C–O) 1241.8,
y
(C–F) 1184.6,
8.13(d,
;
1H NMR (CDCl3)
d:
J = 9.0 Hz, 2H, ArH), 7.15 ppm (d, J = 8.9 Hz, 2H, ArH); MS(EI)
m/z 621.9(M-1).
nesulfonylamino}-ethyl)-ammonium
iodide
(BFCS)
was
synthesized successfully. The structure of BFCS was character-
ized by FTIR, 1H NMR, 13C NMR, 19F NMR, MS. The surface
activities of BFCS, the effect of temperature, electrolyte and
combination with hydrocarbon surfactant were investigated.
The results showed that BFCS exhibited excellent surface activity
and combined properties.
4.2.4. Synthesis of N-(2-dimethylamino-ethyl)-4-[3,4,4,4-tetrafluoro-
2-(1,2,2,2-tetra-fluoro-1-trifluoro-methyl-ethyl)-1,3-bis-
trifluoromethyl-but-1-enyloxy]-benzenesulfonamide (5)
To a solution of compound 4 (6.22 g, 0.01 mol) in CH3CN
(40 mL), K2CO3 (1.38 g, 0.01 mol), N,N-dimethylethylenedi-amine
(0.88 g, 0.01 mol) was dropwised at room temperature [26–35].
After refluxing for 5 h, it was quenched with water (50 mL). Then
the resultant solution was extracted by ethyl acetate (3 Â 50 mL).
The combined organic phase was dried by Na2SO4. The solvent was
evaporated to give a white residue, which was recrystallised in
acetic ether and petroleum ether to afford a light yellow solid 5
4. Experimental
4.1. Materials and instruments
Hexafluoropropylene was purchased from Juhua Group
Corporation, Quzhou, China. Phenol, dimethyl sulfoxide,
chlorosulfonic acid, N,N-dimethylethylenediamine and iodo-
methane which were analytical grade, were purchased from
Shuanglin Chemical Reagent Company, Hangzhou, China.
Melting points were determined using an X-4 apparatus
and uncorrected. NMR spectra were measured on a Bruker
AV500 instrument using TMS as an internal standard and
(6.00 g, 89%). IR (cmÀ1):
(C–O) 1242.5, (S55O) 1014.1,
(DMSO-d6) : 7.94 (d, J = 9.80 Hz, 2H, ArH), 7.36 (d, J = 8.75 Hz, 2H,
y
(N–H) 3426.9,
y (C55C) 1590.9, 1300.9,
y
y
y
(C–F) 979.7, 734.5 cmÀ1; 1H NMR
d
ArH), 5.51 (s, 1H, NH), 2.88 (t, 2H, CH2), 2.19 (t, 2H,CH2), 2.03 ppm
(s, 6H, CH3); MS(EI) m/z 674.4(M-1).
4.2.5. Synthesis of trimethyl-(2-{4-[3,4,4,4-tetrafluoro-2-(1,2,2,2-
tetrafluoro-1-trifluoromethyl-ethyl)-1,3-bis-trifluoromethyl-but-1-
enyloxy]-benzenesulfonylamino}-ethyl)-ammonium iodide (6, BFCS)
Compound 5 (6.75 g, 0.01 mol) and iodomethane (2.97 g,
0.02 mol) were refluxed in MeCN (50 mL) for 5 h under the
atmosphere of N2, and then the resultant mixture was cooled to
room temperature. After the solution was evaporated under
reduced pressure, the residue was recrystallized in acetic ether and
petroleum ether. The resulting white solid 6 (7.12 g, 87%) was dried
CDCl3 as solvent. Mass spectra were performed on
a
Thermo Finnigan LCQ Advantage LC/mass detector instru-
ment. FTIR were recorded of Nicolet AVARAT 370 Fourier
transform infraed spectrometer from KBr pellets. The
characterization of the surface tension was carried out on
DCA-315 equipped with
platinum-iridium.
a Wihelmy plate, made of a
4.2. Synthesis of the branch fluorinated cationic surfactant (BFCS)
under reduced pressure. IR (cmÀ1):
1590.9, 1491.5; (C–O) 1242.5,
979.5, 742.0 cmÀ1. 1H NMR (CDCl3)
y
(N–H) 3446.3,
(S55O) 1014.2;
: 8.00 (d, J = 8.85 Hz, 2H, ArH),
y
(C55C) 1626.6,
y
y
y(C–F) 1240.8,
4.2.1. Synthesis of 1,1,1,2,4,5,5,5-octafluoro-3-(1,2,2,2-tetrafluoro-1-
trifluoromethyl-ethyl)-4-trifluoro-methyl-pent-2-ene (2)
d
7.28 (d, J = 8.70 Hz, 2H, ArH), 5.51 (s, 1H, NH), 3.82 (t, 2H, CH2), 3.25
(t, 2H, CH2), 1.97 ppm (s, 9H, CH3); 13C NMR (CDCl3): 40.10 (1C,
CH3), 44.92 (3C,CH2), 56.92 (1C,CH2), 116.70 (1C,benzene), 129.69
(2C, benzene), 137.09 (2C, benzene), 152.21(C, benzene),
123.20(1C, C55C), 120.87 (1C, C55C), 119.77 (1C, CF3), 118.55 (4C,
CF3), 117.59 (2C,CF); 19F NMR (CDCl3): À188.5 ppm (1F, F), À186.5
(1F, F), À91.3(6F, CF3), À90.2(6F, CF3), À75.0(3F, CF3); MS(EI) m/z
689.1(M-I).
To a solution of CsF (2.0 g) in MeCN (50 mL), hexafluoropro-
pylene (180.0 g, 1.20 mol) was added. The mixture was stirred at
50 8C for 1 h under 0.80 MPa. The resultant solution was washed by
distilled water (3 Â 100 mL), dried over anhydrous Na2SO4. Finally,
a colorless liquid 2 (160.2 g, 90%) was collected at 110 8C by
y
distillation. IR (cmÀ1): (C–F) 1397.9, 1300.7, 1272.6 cmÀ1; GC–MS
(70 eV) m/z: 450 (M+).

8
H.-K. Wu et al. / Journal of Fluorine Chemistry 156 (2013) 5–8
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