Documente Academic
Documente Profesional
Documente Cultură
ABSTRACT: Mono- and di-esterified glycerols were synthesized by the base catalyzed reaction of glycerol with aliphatic dicarboxylic acid esters (C2C9): 2,3-dihydroxy-propyl oxalate (2),
1,3 dioxalyloxy propan-2-ol (3), 1,3-dimethoxyoxalyloxy propan2-ol (5), 2,3-dihydroxy-propyl malonate (6), 2,3-dihydroxy-propyl
methyl malonate (7), 2,3-dihydroxy-propyl methyl succinate (8),
1,3-dimethoxysuccinyloxy propan-2-ol (9), 2,3-dihydroxy-propyl
methyl glutarate (10), 1,3-dimethoxyglutaryloxy propan-2-ol
(11), 2,3-dihydroxy-propyl methyl azelate (14), and 1,3dimethoxyazelyloxy propan-2-ol (15). Their structures were elucidated by spectrometric methods. Compounds 8, 10, 2,3-dihydroxy-propl methyl adipate (12) and 14 were found to possess
surface active properties and the ability to reduce the interfacial
tension between paraffin and water.
Paper no. S1511 in JSD 9, 147152 (Qtr 2, 2006).
KEY WORDS: Diglycerol ester, dimethyl ester, glycerol,
monoglycerol ester.
metabolism of fats. In addition, this synthetic ester [bis-(glycerol 1,3-distearate) succinate] possesses lubrication properties
(5). Mono- and di-esterified glycerol esters which are useful for
the synthesis of biodegradable polymers and surfactants were
synthesized from the enzymatic esterification of glycerol with
adipic, sebacic acids, and their dimethyl ester derivatives (6).
The synthesis of oligoesters from oxalic acid and glycerol
was reported by Alksnis and colleagues (7). Polyester films,
which are useful in surface coatings industries, were synthesized from glycerol with different chain lengths of aliphatic
and aromatic dicarboxylic acids (8,9).
As there are only limited reports on the synthesis of glycerol with short carbon chain dicarboxylic acid esters, the
present study on synthesis of glycerol ester by the transesterification of glycerol with dicarboxylic acid esters (C2C9)
represents a contribution to this subject.
Parameters that affect the transesterification were examined in order to optimize the yield of products. In this study,
the reaction of glycerol with dimethyl succinate was used as
a model, as the formation of monoester can be conveniently
used to monitor the progress of reaction.
EXPERIMENTAL PROCEDURES
Materials. Glycerol (99.2%) was purchased from Fisher
Chemicals (Leicestershire, United Kingdom). The dicarboxylic acid esters (dimethyl oxalate, dimethyl malonate,
dimethyl succinate, dimethyl glutarate, dimethyl adipate,
and dimethyl azelate) and molecular sieves (4 ) were purchased from Fluka (Buchs, Switzerland), and potassium hydroxide was purchased from Merck (Darmstadt, Germany).
The solvents used were high-performance liquid chromatography (HPLC) grade.
Methods. The alcoholysis was performed in a 250-mL
three-necked flask equipped with a reflux condenser, thermometer, and a sampling port. The flask was heated to
80C in a water bath, and its contents were stirred magnetically. The reagents used were in a molar ratio, 4 mol of glycerol to 1 mol of acid ester; the reaction was catalyzed by 0.2
wt% of potassium hydroxide and 2 wt% of molecular sieves.
On completion of the reaction, the reaction mixture was
JOURNAL OF SURFACTANTS AND DETERGENTS, VOL. 9, NO. 2 (QTR 2, 2006)
148
G.H.P. CHO ET AL.
149
GLYCEROL ESTERS
OH
OH
OH
C
H
(C H 2 ) n C
OH
2 n=0
6 n=1
O C
OH
C OH
OH
O C (C H 2 )n
OH
OH
H
O C H3 H
O C
OH
O
O C
(C H 2 ) n
O CH 3
O
(C H 2 ) n
C O CH 3
4 n=0
5 n=0
7 n=1
9 n=2
8 n=2
11 n = 3
10 n = 3
13 n = 4
12 n = 4
15 n = 7
14 n = 7
FIG. 1. Structure of synthesized compounds.
TABLE 1
Composition of Base-Catalyzed Reaction Based on GC Chromatogram
Reaction of
glycerol with
Dimethyl oxalate
Dimethyl malonate
Dimethyl succinate
Dimethyl glutarate
Dimethyl adipate
Dimethyl azelate
Glycerol (%)
Dicarboxylic
acid ester (%)
Monoester (%)
Diester (%)
1.74
1.14
1.01
1.06
1.61
1.57
90.99
71.60
37.09
22.75
7.60
3.55
5.16
27.26
54.03
65.34
75.57
78.75
2.11
nda
7.87
10.85
15.79
16.13
150
G.H.P. CHO ET AL.
OH
OH
OH
H
+ MeOC(CH2)n COMe
OC(CH2)n COMe
OC(CH2)n COMe
OH
OH
OH
OC(CH2)n COMe
KOH
60
50
40
30
20
10
0
0
10
15
Reaction time (hours)
20
151
GLYCEROL ESTERS
70
60
50
40
30
20
10
0
0
10
15
20
60
80
concentrations (00.6 wt%) showed an increase of reaction rate (Fig. 3), but the optimal value was about 0.2
wt%.
The reaction temperature also influences the rate of
reaction and the yield of glycerol esters. Therefore different reaction temperatures were studied to determine the
optimum temperature. Reaction temperatures studied
were 80C, 100C, and 120C. At higher temperatures, the
amount of monoester in the reaction mixture increased
and it reached a maximum level after 6 h when the reaction was carried out at 100 to 120C, whereas it took 8 h
at a lower temperature (Fig. 4). Furthermore, the formation of diester from monoester was faster when the temperature was higher. However, the overall yield at the end
of the reaction was not affected by temperature. In this
case, the formation of both monoester and diester were
produced in an overall yield of 80% after 15 h of reaction
time.
Esterification is a reversible reaction. Water is the byproduct formed during the process and it would cause the
ester to hydrolyze. The equilibrium will shift to the formation of ester if water is removed during the reaction. This
can be done with the assistance of molecular sieves (13). In
this case, molecular sieves were deliberately added to has-
50
40
Monoester
30
20
Diester
10
0
0
10
15
20
70
Monoester
60
50
40
30
Diester
20
10
0
0
10
15
20
152
G.H.P. CHO ET AL.
TABLE 2
Physical Data of 10% (vol/vol) Monoglycerol Esters
Properties
Temperature
(C)
Compound
8
Compound
10
Compound
12
Compound
14
Appearance
25
Surface tension
(mN/m)
25
30.72
30.53
30.72
30.01
Interfacial tension
(mN/m)
25
16.80
14.50
10.35
9.87
>100
>100
>100
>100
glycerides (8) could be used in conjunction with harsh detergents like sodium lauryl sulfate to reduce the irritation
of the sulfate ester.
11.
ACKNOWLEDGMENTS
12.
13.
REFERENCES
14.
15.
16.
17.
18.