Synthesis and properties of lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt

Article abstract of DOI:10.14233/ajchem.2014.16950

The lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt was synthesized by using sodium bisulfite, epichlorohydrin, sodium phosphate and lauric acid. The influence factors on reaction temperature, reaction time, the amount of catalyst and reactant molar ratio to the yield were investigated. The favorable conditions of synthesizing were determined:epichlorohydrin was added into the solution of sodium bisulfite of 85 °C, stirring for 2 h and left for 1.5 h. 3-Chloro-2-hydroxy-propane sulfonic acid sodium was synthesized. 3-Chloro-2-hydroxy-propane sulfonic acid sodium was mixed into the solution of sodium phosphate at 55 °C and 4 h reaction time. The 2,3-oxiranemethane sulfonic acid sodium salt was formed. 2,3-Oxiranemethane sulfonic acid sodium salt solution was dropped into the solution of lauric acid at 90 °C, the dropping time 0.5 h and left for 2.5 h. Lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt was obtained. The yield was 85.2 % and was characterized by FTIR.

Full text of DOI:10.14233/ajchem.2014.16950

Asian Journal of Chemistry; Vol. 26, No. 14 (2014), 4449-4451
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.16950
Synthesis and Properties of Lauric Acid-2-hydroxy-3-propane Sulfonic Acid Sodium Salt
1,*
1
2
3
1
YULAN HAO , DANDAN YUAN , YAN WANG , YING QI and RONGMING ZHANG
1Provincial Key Laboratory of Oil and Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum
University, Daqing 163318, Heilongjiang Province, P.R. China
2PetroChina Daqing Petrochemical Company, Daqing 163711, Heilongjiang Province, P.R. China
3Oil Recovery Plant No. 6, Daqing Oilfield Corp. Ltd., Daqing 163514, Heilongjiang Province, P.R. China
*Corresponding author: E-mail: hyl4511@126.com
Received: 28 December 2013;
Accepted: 25 March 2014;
Published online: 5 July 2014;
AJC-15494
The lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt was synthesized by using sodium bisulfite, epichlorohydrin, sodium
phosphate and lauric acid. The influence factors on reaction temperature, reaction time, the amount of catalyst and reactant molar ratio to
the yield were investigated. The favorable conditions of synthesizing were determined:epichlorohydrin was added into the solution of
sodium bisulfite of 85 °C, stirring for 2 h and left for 1.5 h. 3-Chloro-2-hydroxy-propane sulfonic acid sodium was synthesized.
3-Chloro-2-hydroxy-propane sulfonic acid sodium was mixed into the solution of sodium phosphate at 55 °C and 4 h reaction time. The
2,3-oxiranemethane sulfonic acid sodium salt was formed. 2,3-Oxiranemethane sulfonic acid sodium salt solution was dropped into the
solution of lauric acid at 90 °C, the dropping time 0.5 h and left for 2.5 h. Lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt was
obtained. The yield was 85.2 % and was characterized by FTIR.
Keywords: Lauric acid, Epichlorohydrin, Synthesis, Lauric acid-2-hydroxy-3-propane sulfonic acid sodium salt.
INTRODUCTION
CH2 CH
O
CH2
Cl
CH2 CH CH2
Cl OH SO3Na
+NaHSO3
(1)
With the growing tension of oil energy situation, improving
oil recovery rate has became a major issue of oil exploitation.
Surfactant in terms of enhanced oil recovery has been increasingly
used1-6. Sulfonate surfactant is a kind of surfactant that has the
most yield and widest application. In this paper, Lauric acid-2-
hydroxy-3-propane sulfonic acid sodium salt was synthesized
by using fatty acid and epichlorohydrin. The product was
characterized by FTIR. The result shows that the surfactant has
a better surface activity. This new kind of surfactant has huge
potential based on the advantages of low cost and green.
The closed loop reaction of 3-chloro-2-hydroxy-propane
sulfonic acid sodium and sodium phosphate generates 2,3-
oxiranemethane sulfonic acid sodium salt.
CH2
CH2
CH2
CH
CH2 CH
+ Na2HPO4 NaCl
+
(2)
+ Na3 PO4
a
O
Cl
OH SO3N
SO3Na
The esterification reaction of epoxy propane sulfonate and
lauric acid generates stearic acid-2-hydroxy-3-propane sulfonic
acid sodium salt.
CH2 CH
EXPERIMENTAL
CH2
C11H23COOCH2CHCH2SO3Na
OH
+ C11H23COOH
(3)
O
SO3Na
Sodium bisulfite, sodium phosphate, epichlorohydrin,
octadecanoic acid, quaternary ammonium salts wereAR grade.
JC2000CI intravenous infusion of the contact angle of the inter-
facial tension measuring instrument, the Shanghai Morning
Digital Technology Equipment Co., Ltd. products; WRS-1B
digital melting point apparatus, Shanghai Fine Scientific
Instruments Co., Ltd. products; TENSOR27 infrared spectro-
meter, Bruker Spectrum Instrument Company products.
Synthetic principle: The sulfonation reaction of epichlo-
rohydrin and sodium bisulfite generates 3-chloro-2-hydroxy-
propane sulfonic acid sodium salt.
Synthetic procedure: A certain amount of water and sodium
bisulfite were placed in a four-necked flask equipped with a
reflux condenser, a thermometer and a stirring rod. The mixture
was then heated and stirred until all the sodium bisulfite was
dissolved. The epichlorohydrin was slowly added dropwise
to the solution when the temperature reached to 85 °C, left for
2 h and then stirring for 1.5 h. The solution was then cooled to
room temperature, and continued to cool in an ice bath, then
the solution was filtered to give a solid: 3-chloro-2 -hydroxy-
propane sulfonic acid sodium salt. The yield is 80.6 %.

4450 Hao et al.
Asian J. Chem.
82
80
78
76
74
72
70
68
The aqueous solution of sodium phosphate was heated to
55 °C, then the 3-chloro-2- hydroxy-propane sulfonic acid
sodium was added to the solution7. The product was cooled
after 4 h, and filtered. The filtrate was distilled under reduced
pressure to give a waxy 2,3-oxiranemethane sulfonic acid
sodium salt. The yield was 85.2 %.
The four-necked flask equipped with lauric acid, a moderate
amount of water and quaternary ammonium salt (catalyst) was
stirred and heated to 90 °C, then epoxy propanesul-fonate
solution was added dropwise to the four-necked flasks, droping
about 0.5 h, reaction 2.5 h maintained at 90 °C. The solution
was cooled and filtered to give crude product. The crude product
was recrystallized from ethanol to give the product as a white
powder in a yield of 85 %.
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
nn(sodium hydrogen sulfite):n(epichlorohydrin)
RESULTS AND DISCUSSION
Fig. 2. Effect of the molar ratio on the yield
Influence factors for synthesizing 3-chloro-2-hydroxy-
propanesulfonate
n (sodium hydrogen sulfite): n (epichlorohydrin) is 1.15:1,
the maximum yield of the product is 80.6 %. then yield tends
to be gentle.
Temperature:We explored the effects of reaction tempe-
rature on the yield of product on the condition that the reaction
time was 3.5 h, the molar ratio of the reactants was 1.15:1
(Fig. 1).
Effect of loading sequence on the yield and reaction
time: The experiment shows that adding dropwise epichloro-
hydrin to the aqueous solution of sodium bisulfite is beneficial
to the yield. As the sodium bisulfite is a good nucleophilic
reagent, the aqueous solution of sodium dithionite has a certain
concentration of H+, the acidic environment makes the epoxy
ring oxygen protonated, the C-O bond weaken, and ring carbon
atom with a positive charge. that increases the ability to bind
with a nucleophilic reagent, epichlorohydrin ring-opening
reaction is easily performed9. The yield is improved. Conver-
sely, if sodium bisulfate is added dropwise to epichlorohydrin.
the acidic environment in the initial stage of the reaction is
weak, the reaction does not proceed in a timely manner, and
thus reaction time is long, the yield is relatively low.
Fig. 1 showed that the reaction temperature increases, the
yield rises at first and then gradually reduces.When the reaction
temperature is below 75 °C, the sulfonating agent can not be
fully dissolved and affects the reaction proceeding8, and the
yield rises gently. When the temperature is higher than 85 °C,
with the reaction temperature increases, the yield slightly
decreases. Partial decomposition of sodium bisulfite at high
temperatures reduces the effective concentration of the sulfona-
ting agent. Epichlorohydrin, being also prone to self-polymeri-
zation reaction, results in the increasing of by products. These
factors make yield decreases. When temperature is 85 °C, the
maximum yield of the product is 80.6 %.
Influence factors for synthesizing the main product lauric
acid-2-hydroxy-3-propane sulfonic acid sodium salt
Catalyst screening: We explored the effects of different
catalysts (mass fraction 1.2 %) on the esterification reaction
on the condition that the reaction temperature was 90 °C,
reaction time was 3 h, n (epoxy propane sulfonate): n (lauric
acid) was 1:1.1, the data was shown in Table-1.
80
70
60
50
40
30
TABLE-1
EFFECT OF DIFFERENT CATALYSTS ON THE YIELD
Catalysts
Yield (%)
68.6
Sixteen alkyl trimethyl ammonium bromide
Benzyl trimethyl ammonium chloride
Benzyl triethyl ammonium chloride
78.3
85.2
Table-1 showed that when the other conditions are the
same, benzyl triethyl ammonium chloride is used as a catalyst,
the yield is higher than the previous two catalysts, so the
experiment used benzyl triethyl ammonium chloride.
65
70
75
80
Temperature (°C)
Fig. 1. Effect of the reaction temperature on the yield
85
90
95
Condition experiment: We have investigated the effect
of the amount of catalyst, reaction temperature, reaction time
and the molar ratio of on the product yield.As shown in Table-
2. When the w (catalyst) is 1.2 %, the T is 90 °C, the reaction
time is 3 h and the molar ratio of epoxy propane sulfonate and
lauric acid is 1:1, the yield is the highest, up to 85.2 %.
Reactant molar ratio: Effect of the molar ratio of sodium
bisulfite and epichlorohydrin on the yield is shown in Fig. 2.
Fig. 2 showed that when the reaction time is 3.5 h, the
reaction temperature is 85 °C and other conditions, the yield
rises with increasing the molar ratio of sodium bisulfite. when

Vol. 26, No. 14 (2014)
Synthesis and Properties of Lauric Acid-2-hydroxy-3-propane Sulfonic Acid Sodium Salt 4451
TABLE-2
EFFECT OF DIFFERENT CONDITIONS ON THE YIELD
S.No.
w(catalysts)
Yield (%)
t (°C) Yield (%)
h
Yield (%)
Molar ratio n(epoxy propane sulfonate):
Yield (%)
(%)
0.6
1.0
1.2
1.5
n(Lauric acid)
1:0.8
1
2
3
4
58.6
77.0
85.1
81.8
80
85
90
95
65.6
76.6
85.2
80.3
2.0
2.5
3.0
3.5
71.2
78.4
85.2
80.1
74.1
78.9
85.2
79.8
1:0.9
1:1.0
1:1.1
TABLE-3
CRITICAL MICELLE CONCENTRATIONS AND THEIR
SURFACE TENSIONS OF SURFACTANTS
Infrared spectrum: In Fig. 3, the absorption peak at 3362
and 1558 cm-1 may be due to hydroxyl special absorption peak.
The absorption peak at 1731, 1232 and 1180 cm-1 may be the
absorption peak of the ester group. The absorption peak in
2957 and 1422 cm-1 may be a methyl group absorption peak.
The absorption peak in 1052 cm-1 is due to sulfite group
stretching vibration absorption peak and in 2850 cm-1 is for
methylene group stretching vibration absorption peak, whereas
the absorption peak of the epoxy bond in 3050, 2150, 915 and
850 cm-1 are not present.
Samples
Surface tension (mN m-1)
CMC (mmol L-1)
SDS
40.0
8.0
Product
33.10
6.38
Table-3 suggested that the critical micelle concentration
of product is the lower compared with the conventional anionic
surfactant SDS. This showed the surfactant has a better surface
activity.
Conclusion
74
70
Lauric acid-2-hydroxy-3-propane sulfonic acid sodium
salt was synthesized by using fatty acid and epichlorohydrin.
The product was characterized by FTIR result shows this
surfactant has a better surface activity. The yield was 85.2 %.
The critical micelle concentration was 6.38 mmol × L-1. This
synthetic route has a lower reaction temperature, high yield,
readily available raw materials.
488.01
814.32
794.34
66
545.04
726.18
624.76
62
58
54
50
46
1629.59
1298.46
1461.15
3362.02
2957.36
1731.81
1422.47
1558.00
1052.30
1180.19
2921.28
1232.45
2850.37
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Fig. 3. FTIR absorption spectrum of the product
Measurement of critical micelle concentration: Critical
micelle concentration is the important parameter of surfactant
performance, surface tension of lauric acid -2-hydroxy-3-
propane sulfonic acid sodium salt of different concentration
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