A family of novel bio-based zwitterionic surfactants derived from oleic acid

Article abstract of DOI:10.1039/c4ra06851c

Bio-based zwitterionic surfactants have attracted increasing attention due to their renewable resources and excellent surface properties. A family of bio-based zwitterionic surfactants derived from oleic acid was prepared using a facile and high-yield route. All these bio-based zwitterionic surfactants exhibited outstanding surface properties. the Partner Organisations 2014.

Full text of DOI:10.1039/c4ra06851c

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A family of novel bio-based zwitterionic surfactants
derived from oleic acid†
Cite this: RSC Adv., 2014, 4, 38393
*
Qi-Qi Zhang, Bang-Xin Cai, Hong-Ze Gang, Shi-Zhong Yang and Bo-Zhong Mu
Received 9th July 2014
Accepted 31st July 2014
DOI: 10.1039/c4ra06851c
www.rsc.org/advances
Bio-based zwitterionic surfactants have attracted increasing attention
Zwitterionic surfactants, which are electrically neutral
due to their renewable resources and excellent surface properties. A compounds have small effective headgroup area due to the
family of bio-based zwitterionic surfactants derived from oleic acid proximity of their positive and negative charges.17 Bio-based
was prepared using a facile and high-yield route. All these bio-based zwitterionic surfactants have attracted more attention due to
zwitterionic surfactants exhibited outstanding surface properties.
their excellent surface and interfacial properties, low irritation,
good detergency, rich foaminess and ne stability;15,16 while
some improvement is still needed to produce zwitterionic
surfactants. Previously reported reaction conditions are harsh,
The current feedstock of the surfactant's hydrophobic part
mainly include two categories: (i) fossil resources with priority
to petroleum; and (ii) renewable biomass resources. Petroleum
products have been used as the main source of surfactant's
hydrophobic group, which account for nearly two thirds of the
organic carbon embodied in the nal surfactants.1 Since fossil
resources are nite and biomass is renewable, the share of
traditional petroleum-based surfactants, the resource of which
are totally from petroleum chemicals, in surfactant production
is gradually declining. Biomass is seen as one of the best
alternatives to replace fossil resources.2–7 Bio-based surfactants
as a kind of promising material are different from traditional
petroleum-based surfactants and biosurfactants.8 Although
biosurfactants are absolutely renewable and their surface
properties are outstanding, they have not been applied widely
due to their low production and high costs.9 The main resource
of bio-based surfactants is from abundant biomass like vege-
table oils,10,11 proteins,12,13 and carbohydrates.14
Many researchers have devoted themselves to the study of
bio-based surfactants derived from long-chain unsaturated fatty
acid, such as oleic acid, linoleic acid, and erucic acid. The
chemical synthesis of ultra long chain zwitterionic surfactants
and the surface activities of their solutions have been docu-
mented.10,11,15–17 These surfactants exhibit lower critical micelle
concentrations and lower surface tension, which are attributed
to their molecular structures.17–21
requiring high temperatures (>160 C)22,23 and expensive cata-
ꢀ
lysts,24 resulting in higher production costs. Looking for low-
cost and high-yield routes for the production of renewable
materials-derived zwitterionic surfactants with outstanding
surface/interfacial properties has become a major focus of
research interest.
In the present work, a family of bio-based zwitterionic
surfactants showing outstanding surface and interfacial prop-
erties was obtained through facile and high-yield chemical
modication and transformation of oleic acid molecules
(Scheme 1). To the best of our knowledge, none of the surfactant
molecules described here have been previously reported.
To obtain compound POAPMB, the chemical modication of
the instable double bond in oleic acid molecules was rst
carried out through a Friedel–Cras alkylation reaction using
benzene as an alkylation reagent and AlCl3 as a catalyst. The
generated phenyl octadecanoic acid (POA) underwent acyl
chlorination by sulfoxide chloride and was then amidated with
N,N-dimethyl-1,3- propylenediamine, generating N-phenyl-
octadecanoicpropyl-N,N-dimethylamine (POAPMA). Eventually,
POAPMA was reacted with sodium chloroacetate in methanol/
water (vmethanol : vwater ¼ 1 : 4); the product of this reaction was
then desalinated in alcohol and recrystallized in ethyl acetate to
obtain the nal bio-based zwitterionic surfactant, viz. POAPMB,
which has 58.1% bio-derived carbon in its molecule.
Following the chemical synthesis of compound POAPMB,
the structural diversity of bio-based zwitterionic surfactants was
also investigated using toluene and ethyl benzene as well as two
other diamines (N,N-dimethylethylenediamine and N,N-dieth-
ylethylenediamine) for the modication of the double bond and
State Key Laboratory of Bioreactor Engineering and Institute of Applied Chemistry,
East China University of Science and Technology, Shanghai 200237, P.R. China.
E-mail: bzmu@ecust.edu.cn; Fax: +86 21 64252485; Tel: +86 21 64252063
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c4ra06851c
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Scheme 1 Synthetic route of N-phenyloctadecanoicamidopropyl-N,N-dimethylcarboxylbetaine (POAPMB).
the carboxyl of oleic acid, respectively (Fig. 1). All the above gas/double distilled water/solid. Ultimate biodegradation (ulti-
compounds were analyzed and characterized by EI-MS/ESI- mate biodegra.) of the bio-based zwitterionic surfactants was
HRMS and 1H NMR (see ESI†). Surface tensions (SFT) were determined using the EPI Suite, BIOWIN3 biodegradation
measured using a surface tensiometer by the plate method and model, which is frequently used to estimate the degradation of
the interfacial tensions (IFT) were measured using an interface organic chemicals.25 Variation of the surface tension with the
tensiometer by the spinning drop method. The contact angle q concentration of the bio-based surfactants at 25 ꢀC is shown in
of the saturated surfactant solution was measured using the Fig. 2.
sessile drop technique on hydrophobic solid substrates, which
Dynamic interfacial tension between Daqing crude oil (the
has an average contact angle of 92ꢀ on the three phase contact composition and fundamental properties of the crude oil were
Fig. 1 Structural diversity of bio-based zwitterionic surfactants derived from oleic acid.
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In addition to the moderate synthetic condition, it is satis-
factory that the bio-based surfactants synthesized in the present
work exhibit excellent surface and interfacial properties. It is
noteworthy that these surfactants (modied both at the double
bond and the carboxyl group, Fig. 1 and Table 1) showed better
surface and interfacial properties than those without the
modication of the double bond by the addition of aromatic
hydrocarbon.21 This observation indicates the importance of the
addition of an aromatic hydrocarbon ring into the structure of
bio-based zwitterionic surfactants. It is important to mention
that surfactants with a benzene ring in the molecules have been
commonly used in oil recovery;26 thus, the bio-based zwitter-
ionic surfactants could be considered potent alternatives in oil
recovery.
Fig. 2 Variation of the surface tensions with the concentration of the
bio-based surfactants at 25 ꢀC. The error bars represent standard
deviations of the mean for triplicate measurements.
Presently, the surfactants used in oil recovery are mainly
petroleum sulfonates27–29 and alkyl benzene sulfonates,30,31
which are entirely derived from petroleum chemicals. Accom-
panying these surfactants, a strong alkali, which can cause well
bore scaling, stratum damage and permeability decline,32,33 is
added to reduce oil-water interfacial tension to ultralow values
and enhance oil recovery.34–37 Therefore, it will be of a great
signicance to nd a new kind of surfactant that can reduce the
oil–water interfacial tension to ultralow values with the aid of a
weak base or even in the absence of alkali. Bio-based zwitter-
ionic surfactants can reduce oil–water interfacial tension to
ultralow values in the absence of alkali; hence, they may have
important applications in enhanced oil recovery.
Ultimate biodegradation scores for bio-based zwitterionic
surfactants ranged from 2.4519 (POAEEB)–2.6727 (POAEMB),
indicating that the expected total degradation time was in the
order of “months” for these compounds. These results also
showed that bio-based zwitterionic surfactants are biodegrad-
able, and the degradation time is suitable for EOR, in which the
stability of surfactants for several months is needed.
Fig. 3 Dynamic interfacial tensions between Daqing crude oil and bio-
based surfactant solutions at 50 ꢀC.
listed in ESI,† section “Material”) and water at the concentra-
tion of 0.5 g Lꢁ1 bio-based zwitterionic surfactants in water
solutions at 50 ꢀC (the average temperature of the stratum in the
Daqing oil eld, China) are shown in Fig. 3.
Conclusion
The nal yield, surface/interfacial properties (calculation
method and formula are listed in ESI,† section “Surface
and interfacial properties”) and ultimate biodegradation of
bio-based zwitterionic surfactants are listed in Table 1. As
shown in Table 1, bio-based zwitterionic surfactants were
successfully prepared in high yields at relatively lower
temperatures (below 75 ꢀC) and atmospheric pressure.
Compared with other methods, which require at least
160 ꢀC,22,23 higher temperatures could be avoided in this
approach.
In summary, starting with oleic acid, a family of novel bio-based
zwitterionic surfactants, which have excellent interfacial prop-
erties was successfully synthesized via a facile and high-yield
chemical modication. More derivatives of these kinds of bio-
based zwitterionic surfactants could be obtained from other
unsaturated fatty acids through this facile and high-yield
chemical modication. Generally, waste cooking oils and non-
edible oils contain signicant amounts of long chain fatty acids.
Therefore, it is advantageous to consider these useless or
Table 1 Final yield, surface/interfacial properties and ultimate biodegradation of the bio-based zwitterionic surfactants
Final yield CMC
(%)
(mmol Lꢁ1
SFTCMC
SFTmin
Gmax
(mmol mꢁ2
Amin
IFTmin
Surfactant
)
(mN mꢁ1
)
(mN mꢁ1
)
)
(nm2 per molecule) Average q (mN mꢁ1
)
Ultimate biodeg.
4a POAPMB 85.4
4b TOAPMB 83.6
4c EOAPMB 84.2
4d POAEMB 88.5
5.58
4.32
3.31
4.08
3.13
28.1
30.6
32.7
28.4
33.6
27.9
26.4
27.8
25.8
28.9
7.71
5.56
5.29
7.08
5.38
0.22
0.30
0.31
0.23
0.31
47.83
50.32
51.40
46.70
54.04
0.0022
0.0081
0.0518
0.0019
0.0249
2.6417
2.5139
2.4829
2.6727
2.4519
4e POAEEB
84.3
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