esteres de glicerol de la reacción de glicerol con Ácidos dicarboxílicos

7/25/2019 Esteres de Glicerol de La Reaccin de Glicerol Con cidos Dicarboxlicos

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ABSTRACT: Mono- and di-esterified glycerols were synthe-sized by the base catalyzed reaction of glycerol with aliphatic di-carboxylic acid esters (C2C9): 2,3-dihydroxy-propyl oxalate (2),1,3 dioxalyloxy propan-2-ol (3), 1,3-dimethoxyoxalyloxy propan-

2-ol (5), 2,3-dihydroxy-propyl malonate (6), 2,3-dihydroxy-propylmethyl malonate (7), 2,3-dihydroxy-propyl methyl succinate (8),1,3-dimethoxysuccinyloxy propan-2-ol (9), 2,3-dihydroxy-propylmethyl glutarate (10), 1,3-dimethoxyglutaryloxy propan-2-ol(11), 2,3-dihydroxy-propyl methyl azelate (14), and 1,3-dimethoxyazelyloxy propan-2-ol (15). Their structures were elu-cidated by spectrometric methods. Compounds 8, 10, 2,3-dihy-droxy-propl methyl adipate (12) and 14 were found to possesssurface active properties and the ability to reduce the interfacialtension between paraffin and water.

Paper no. S1511 in JSD 9, 147152 (Qtr 2, 2006).

KEY WORDS: Diglycerol ester, dimethyl ester, glycerol,

monoglycerol ester.

The synthesis of monoglycerides from different mono-acyldonors (free fatty acids, fatty acid alkyl ester, and vinyl ester)

with glycerol have been studied extensively by numerous re-searchers (1,2). However, the synthesis of glycerol estersfrom di-acyl donors was limited.

The synthesis of long chain dicarboxylic acid glyceridesfrom japanic acid, COOH(CH2)20COOH, and palmitic acid,CH3(CH2)14COOH, with glycerol, to produce ,-japanin--palmitin glycerides and ,-japanin--palmitin glycerides, wasdescribed by Nagano and Tanaka (3). The synthesis of twodiglyceride (1,3-dioleoyl and 1,3-distearoyl ester) moleculeslinked together with a short chain dibasic acid (fumaric acid,succinic acid, and adipic acid) at position 2 was reported (4,5).These esters can be edible and digestible since fumaric andsuccinic acids occur as metabolites in the Krebs cycle for the

metabolism of fats. In addition, this synthetic ester [bis-(glyc-erol 1,3-distearate) succinate] possesses lubrication properties(5). Mono- and di-esterified glycerol esters which are useful forthe synthesis of biodegradable polymers and surfactants weresynthesized from the enzymatic esterification of glycerol withadipic, sebacic acids, and their dimethyl ester derivatives (6).

The synthesis of oligoesters from oxalic acid and glycerolwas reported by Alksnis and colleagues (7). Polyester films,which are useful in surface coatings industries, were synthe-sized from glycerol with different chain lengths of aliphaticand aromatic dicarboxylic acids (8,9).

As there are only limited reports on the synthesis of glyc-erol with short carbon chain dicarboxylic acid esters, thepresent study on synthesis of glycerol ester by the transes-terification of glycerol with dicarboxylic acid esters (C2C9)represents a contribution to this subject.

Parameters that affect the transesterification were exam-ined in order to optimize the yield of products. In this study,the reaction of glycerol with dimethyl succinate was used asa model, as the formation of monoester can be convenientlyused to monitor the progress of reaction.

EXPERIMENTAL PROCEDURES

Materials. Glycerol (99.2%) was purchased from FisherChemicals (Leicestershire, United Kingdom). The dicar-boxylic acid esters (dimethyl oxalate, dimethyl malonate,dimethyl succinate, dimethyl glutarate, dimethyl adipate,

and dimethyl azelate) and molecular sieves (4 ) were pur-chased from Fluka (Buchs, Switzerland), and potassium hy-droxide was purchased from Merck (Darmstadt, Germany).The solvents used were high-performance liquid chroma-tography (HPLC) grade.

Methods. The alcoholysis was performed in a 250-mLthree-necked flask equipped with a reflux condenser, ther-mometer, and a sampling port. The flask was heated to80C in a water bath, and its contents were stirred magneti-cally. The reagents used were in a molar ratio, 4 mol of glyc-erol 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

*To whom correspondence should be addressed at AOTD-MPOB, Lot9&11, Jalan P10/14, 43650 Bandar Baru Bangi, Selangor Darul Ehsan,Malaysia. E-mail: [email protected]

Abbreviations: APCI, atmospheric pressure chemical ionization;CIMS, chemical ionization with mass spectrometry; EI, electron im-pact; FTIR, Fourier transform infrared; GC, gas chromatography;GCMS, gas chromatography with mass spectrometry; HPLC, high-per-formance liquid chromatography; IR, infrared; LCMS, liquid chroma-

tography with mass spectrometry.

Glycerol Esters from the Reaction of Glycerol with

Dicarboxylic Acid EstersGladys H.P. Choa,b, S.K. Yeongb,*, T.L. Ooib, and C.H. Chuaha

aDepartment of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur, Malaysia,and bAOTD-MPOB, Bandar Baru Bangi, Selangor Darul Ehsan, Malaysia

JOURNAL OF SURFACTANTS AND DETERGENTS, VOL. 9, NO. 2 (QTR 2, 2006)

147

COPYRIGHT 2006 BY AOCS PRESS


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washed with water and the glycerol ester extracted withchloroform.

Spectrometric analysis.A Nicolet magna FT-IR 550 (Madi-son, Wisconsin) spectrometer was used to record theFourier transform infrared (FTIR) spectra. Gas chromato-graphic (GC) analyses of glycerol esters were performedon an Agilent 6890N (Palo Alto, California) gas chromato-graph equipped with a flame ionization detector. An Agi-lent DB Wax (Palo Alto, California) 30 m 0.32 mm 0.25m column was used for the separation. The oven temper-ature was programmed from 60 to 230C at 2C/min. Theinjector port was set at 240C and detector at 260C. Gaschromatography with mass spectrometry (GCMS) wasperformed on an Agilent 6893 (Palo Alto, California) se-ries gas chromatograph fitted with an Agilent DB Wax(Palo Alto, California) 30 m 0.32 mm 0.25 m capillarycolumn and temperature programming was similar to theGC conditions. Liquid chromatography with mass spec-trometry (LCMS) was performed on PE Sciex API 100

LCMS (Wellesley, Massachusetts) fitted with an SGE GLWakosil (United States) 150 mm 2 mm 5m C-18 col-umn, PerkinElmer LC Series 2000 LC pump, and What-man zero air generator. Distilled water with 0.1% of formicacid and methanol with 0.1% of formic acid in a 55:45ratio served as the mobile phase for flow injector analysis(FIA). HPLC was performed on a Jasco PU-1580 (Tokyo,

Japan) fitted with an Inertsil Octadecylsilane-3 (UnitedStates), 25 cm long, 4.6 mm internal diameter, with a 5 mparticle size 8 reversed-phase column. Distilled water andmethanol in a 55:45 ratio served as the mobile phase. Themeasurements of surface tension were performed by using

the Sigma 70 tensiometer (Finland). Interfacial tensionswere measured by using the same instrument and paraffinoil was used as the lighter phase. Cloud points were deter-mined by heating 25 mL of 10% (vol/vol) glycerol estersolution in a standard test jar. The cloud point was deter-mined by visual observation. The temperature at which thesolution becomes obviously turbid was recorded as thecloud point. The reproducibility of cloud point measure-ment is 0.2C.

RESULTS AND DISCUSSION

The glycerol esters (Fig. 1, Table 1) were synthesized by thebase catalyzed reaction of glycerol with aliphatic dicarboxylicacid esters (dimethyl oxalate, dimethyl malonate, dimethyl suc-cinate, dimethyl glutarate, dimethyl adipate, and dimethyl aze-late). This study consists of 11 new and four reported com-pounds. The new compounds are 2, 3, 5, 6, 7, 8, 9, 10, 11, 14,and 15. The general scheme of synthesis is illustrated inScheme 1. Synthesized compounds are identified and de-scribed herein.

Products identified from reaction of glycerol with dimethyl ox-

alate. (i) 4-Hydroxymethyl-1,3-dioxolan-2-one (1). Infrared (IR)max cm

1: 3414, 2946, 1751, 1217. EI/GCMS m/z (rel.int.): 118 [M+, 6], 117 (M+ H, 100%), 75 (C3H7O2

+, 10),

61 (C2H5O2+, 15), 57 (C3H5O

+, 50). Atmospheric pressurechemical ionization (APCI)/LCMS m/z (rel. int.): 119[(M+H)+, 100%].

(ii) 2,3-Dihydroxy-propyl oxalate (2). IR max cm1: 3414,

2946, 1751, 1644, 1405, 1217. EI/GCMS m/z(rel. int.): 147(M+ OH, 4), 103 (C3H3O4

+, 100%), 89 (C2HO4+, 23), 73

(C2HO3+

, 10), 61 (C2H5O2+

, 30). APCI/LCMS m/z(rel.int.): 165 [(M+H)+, 100%].(iii) 1,3-Dioxalyloxy propan-2-ol (3). IR max cm

1: 3414,2946, 1751, 1644, 1405, 1217. EI/GCMS m/z(rel. int.): 147(C5H7O5

+, 2), 103 (C3H3O4+, 100%), 89 (C2HO4

+, 17), 73(C2HO3

+, 9), 61 (C2H5O2+, 23). APCI/LCMS m/z (rel.

int.): 237 [(M+H)+, 100%].(iv) 2,3-Dihydroxy-propyl methyl oxalate (4). IR max cm

1:3414, 2946, 1751, 1644, 1405, 1217. EI/GCMS m/z(rel. int.):147 (M+ OCH3, 10), 103 (C3H3O4

+, 100%), 117 (C4H5O4+,

5), 87 (C3H3O3+, 6), 75 (C3H7O2

+, 45), 59 (C2H3O2+, 43).

APCI/LCMS m/z(rel. int.): 179 [(M+H)+, 100%].(v) 1,3-Dimethoxyoxalyloxy propan-2-ol (5). IR max cm

1:

3414, 2946, 1751, 1644, 1405, 1217. EI/GCMS m/z(rel.int.): 233 (M+ OCH3, 6), 147 (C5H7O5

+, 5), 103 (C3H3O4+,

100%), 87 (C3H3O3+, 2), 75 (C3H7O2

+, 44), 59 (C2H3O2+,

37). APCI/LCMS m/z(rel. int.): 265 [(M+H)+, 100%].Products identified from reaction of glycerol with dimethyl mal-

onate. (i) 2,3-Dihydroxy-propyl malonate (6). IRmax cm1: 3404,

2955, 1737, 1642, 1444, 1206. EI/GCMS m/z(rel. int.): 103(C3H3O4

+, 100%), 87 (C3H3O3+, 1), 75 (C3H7O2

+, 69), 61(C2H5O2

+, 83), 59 (C2H3O2+, 3). APCI/LCMS m/z (rel.

int.): 179 [(M+H)+, 100%].(ii) 2,3-Dihydroxy-propyl methyl malonate (7). IR max cm

1:3404, 2955, 1737, 1642, 1444, 1206. EI/GCMS m/z(rel.

int.): 133 (C5H9O4+

, 10), 117 (C3H3O4+

, 100%), 75(C3H7O2+, 17), 61 (C2H5O2

+, 28), 59 (C2H3O2+, 20).

APCI/LCMS m/z(rel. int.): 193 [(M+H)+, 100%].Products identified from reaction of glycerol with dimethyl succi-

nate. (i) 2,3-Dihydroxy-propyl methyl succinate (8). IR max cm1:

3408, 2953, 1727, 1641, 1433, 1217. EI/GCMS m/z (rel.int.): 189 (M+ OH, 1), 175 (M+ OCH3, 5), 147 (C6H11O4

+,5), 115 (C5H7O3

+, 100%), 59 (C2H3O2+, 20). APCI/LCMS

m/z(rel. int.): 207 [(M+H)+, 100%].(ii) 1,3-Dimethoxysuccinyloxy propan-2-ol (9). IR max cm

1:3408, 2953, 1727, 1641, 1433, 1217. EI/GCMS m/z(rel.int.): 320 [M+, 2], 289 (M+ OCH3, 5), 189 (C8H13O5

+, 7),175 (C

7H

11O

5

+, 10), 115 (C5H

7O

3

+, 100%), 59 (C2H

3O

2

+,20). APCI/LCMS m/z(rel. int.): 321 [(M+H)+, 100%].

Products identified from reaction of glycerol with dimethyl glu-

tarate. (i) 2,3-Dihydroxy-propyl methyl glutarate (10). IRmax cm1:

3443, 2951, 1726, 1640, 1444, 1216. EI/GCMS m/z(rel. int.):220 [M+, 3], 203 (M+ OH, 1), 189 (M+ OCH3, 10), 129(C6H9O3

+, 100%), 101 (C5H9O2+, 45), 59 (C2H3O2

+, 53).APCI/LCMS m/z(rel. int.): 221 [(M+H)+, 100%].

(ii) 1,3-Dimethoxyglutaryloxy propan-2-ol (11). IR max cm1:

3443, 2951, 1726, 1640, 1444, 1216. EI/GCMS m/z(rel. int.):289 (M+ C(=O)OCH3, 5), 189 (C8H13O5, 7), 129 (C6H9O3

+,100%), 101 (C5H9O2

+, 10), 87 (C4H7O2+, 11), 59 (C2H3O2

+,20). APCI/LCMS m/z(rel. int.): 349 [(M+H)+, 100%].

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G.H.P. CHO ET AL.



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149

GLYCEROL ESTERS

TABLE 1Composition of Base-Catalyzed Reaction Based on GC Chromatogram

Reaction of Dicarboxylicglycerol with Glycerol (%) acid ester (%) Monoester (%) Diester (%)

Dimethyl oxalate 1.74 90.99 5.16 2.11Dimethyl malonate 1.14 71.60 27.26 nda

Dimethyl succinate 1.01 37.09 54.03 7.87Dimethyl glutarate 1.06 22.75 65.34 10.85Dimethyl adipate 1.61 7.60 75.57 15.79Dimethyl azelate 1.57 3.55 78.75 16.13and, not detected.

OH

O

O

C O

H

H

H

H

H

1

O

O H

O H

C

O

C

O

O H(C H 2)n

H

H

H

H

H

2 n= 0

6 n= 1

O

O H

O

C

O

C

C

O

C

O

O H

O

O H

H

H

H

H

H

O

O H

O H

C

O

(C H2)n C

O

O C H3

H

H

H

H

H

O

O H

O

C

O

(C H2)n C

O

O CH3

C

O

(C H2)n C

O

O CH 3

H

H

H

H

H

3 4 n= 0

7 n= 1

8 n= 2

10 n= 3

12 n= 4

14 n= 7

5 n= 0

9 n= 2

11 n= 3

13 n= 4

15 n= 7

FIG. 1. Structure of synthesized compounds.


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Products identified from reaction of glycerol with dimethyl adipate.

(i) 2,3-Dihydroxy-propyl methyl adipate (12). IR max cm1: 3410,

2951, 1724, 1639, 1442, 1213. EI/GCMS m/z(rel. int.): 203(M+ OCH3, 5), 175 (M

+ C(=O)OCH3, 10), 173 (C8H13O4+,

22), 161 (C7H13O4+, 15), 143 (C7H11O3

+, 100%), 115(C6H11O2

+, 30), 59 (C2H3O2+, 21). APCI/LCMS m/z(rel.

int.): 235 [(M+H)+, 100%].

(ii) 1,3-Dimethoxyadipyloxy propan-2-ol (13

). IR max cm1

:3410, 2951, 1724, 1639, 1442, 1213. EI/GCMS m/z(rel.int.): 345 (M+ OCH3, 3), 317 (M

+ C(=O)OCH3, 7), 303(C14H23O7

+, 15), 143 (C7H11O3+, 100%), 115 (C6H11O2

+,40), 73 (C3H5O2

+, 20), 59 (C2H3O2+, 18). APCI/LCMS

m/z(rel. int.): 377 [(M+H)+, 100%].Products identified from reaction of glycerol with dimethyl aze-

late. (i) 2,3-Dihydroxy-propyl methyl azelate (14). IR max cm1:

3412, 2950, 1723, 1637, 1443, 1215. EI/GCMS m/z(rel.int.): 276 [M+, 2], 259 (M+ OH, 5), 217 (M+ C(=O)OCH3, 7), 215 (C11H19O4

+, 15), 203 (C10H19O4+,

20), 185 (C10H17O3+, 100%), 157 (C9H17O2

+, 20), 59(C

2

H3

O2

+, 25). APCI/LCMS m/z(rel. int.): 277 [(M+H)+,100%].

(ii) 1,3-Dimethoxyazelyloxy propan-2-ol (15). IR max cm1:

3412, 2950, 1723, 1637, 1443, 1215. EI/GCMS m/z(rel.int.): 429 (M+ OCH3, 7), 401 (C21H37O7

+, 10), 303(C14H23O7

+, 20), 185 (C10H17O3+, 100%), 157 (C9H17O2

+,20), 73 (C3H5O2

+, 25), 59 (C2H3O2+, 30). APCI/LCMS

m/z(rel. int.): 461 [(M+H)+, 100%].All compounds showed broad peak at IR bands at

34043443 cm1 that are characteristic of the OH stretch-ing from glycerol, along with the 17231751 cm1 band(C=O stretching for glycerol esters), 16371644 cm1 band(C=O stretching of dicarboxylic acid esters), and 1230 cm1

band (bending of the C-O-C group in ester).Chemical ionization with mass spectrometry (CIMS) spec-

trum gave molecular ion (M+H) peaks for compounds 1,2,3,4, 5,6, 7,8,9, 10,11,12,13, 14, and 15 at m/z118, 164, 236,178, 264, 178, 192, 206, 320, 220, 348, 234, 376, 276, and 460,

which correspond to the molecular formula C4H6O4, C5H8O-

6, C7H8O9, C6H10O6, C9H12O9, C6H10O6, C7H12O6, C8H14O6,C13H20O9, C9H16O6, C15H24O9, C10H18O6, C17H28O9,C13H24O6, and C23H40O9, respectively. The EIMS spectrumrevealed that the most important ions with highest abundanceare associated with cleavage to the oxygen atoms of ester toproduce ions of type [C(=O)(CH2)nC(=O)OCH3]

+. These

ions serve the primary function of marking the position of

substitution in the glycerol chain. The characteristic fragmention shown in compound 5was m/z87; 6 and 7were m/z101; 8and 9were m/z115; 10 and 11were m/z129; 12 and 13werem/z 143; and 14 and 15 were m/z 185, respectively. Theacylium ion, M+ 31, is due to the loss of the methoxyl groupby simple -cleavage. In compound 5 it resulted in m/zat 233,8 in m/zat 175, 9 in m/zat 289, 10 in m/zat 189, and 15 in m/z

at 429, respectively. Another significant ion in methyl estercleavage was m/z59, [CH3OC(=O)]+, which was also due to

the -cleavage in ester linkage (10). Besides that, EIMS indi-cated that simple cleavage of the hydroxyl group, M-OH, oc-curred in compound 8 at m/z189, 10 at m/z203, and 14 at m/z259, respectively.

Various parameters that may affect the transesterificationwere studied in order to optimize the yield of products. Thefirst parameter studied was the effect of substrate molarratio. The reactions were carried out by varying the glyc-erol/ester molar ratio. Accumulated studies (1113) sug-gest that an excess of the acid ester is essential for alcoholy-sis reaction to be completed. Molar ratios from 1:1 to 6:1,glycerol to acid ester, were investigated. The optimum ratio

was 4:1 (Fig. 2), whereby the quantity of the monoester was60% after 8 h. The conversion decreased slightly when themolar ratio exceeded 4:1. A similar result was obtained byRoxana and colleagues (13) in 1999 in their study on enzy-matic synthesis.

Although similar reactions are known to be catalyzedby acids, bases, or enzymes (1216), only potassium hy-droxide was selected; the resulting base added at several

150

G.H.P. CHO ET AL.


OC(CH2)nCOMe

OH

OC(CH2)nCOMe

O O

OO

OH

OH

OH

MeOC(CH2)nCOMe

O O

+

OC(CH2)nCOMe

OH

OH

O O

KOH

H

H

H

H

H H

H

H

HH

H

H

HH

H

SCHEME 1. Synthesis of glycerol esters (n = 0, 1, 2, 3, 4, 7).

0

10

20

30

40

50

60

0 5 10 15 20

Percentconversion(

%)

Reaction time (hours)

FIG. 2. Effect of glycerol:dimethyl succinate molar ratio at 1:1 (); 2:1(); 3:1 (); 4:1 (x); 5:1 (); and 6:1 () (80C, 0.2 wt% KOH, and 2 wt%

molecular sieve).


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concentrations (00.6 wt%) showed an increase of reac-tion rate (Fig. 3), but the optimal value was about 0.2

wt%.

The reaction temperature also influences the rate ofreaction and the yield of glycerol esters. Therefore differ-ent reaction temperatures were studied to determine theoptimum temperature. Reaction temperatures studied

were 80C, 100C, and 120C. At higher temperatures, theamount of monoester in the reaction mixture increasedand it reached a maximum level after 6 h when the reac-tion was carried out at 100 to 120C, whereas it took 8 hat a lower temperature (Fig. 4). Furthermore, the forma-tion of diester from monoester was faster when the tem-perature was higher. However, the overall yield at the endof the reaction was not affected by temperature. In this

case, the formation of both monoester and diester wereproduced in an overall yield of 80% after 15 h of reactiontime.

Esterification is a reversible reaction. Water is the by-product formed during the process and it would cause theester to hydrolyze. The equilibrium will shift to the forma-tion of ester if water is removed during the reaction. Thiscan be done with the assistance of molecular sieves (13). Inthis case, molecular sieves were deliberately added to has-

ten the reaction. The rate of reaction accelerated whenwater was constantly removed from the reaction mixture bythe molecular sieve as shown in Figure 5.

In consideration of the above factors, molar ratio of 4:1of glycerol to ester, reaction temperature at 80C, 0.2 wt%KOH as catalyst, and 2 wt% of molecular sieves were cho-sen as the optimum reaction conditions for all the subse-quent reactions, which are reactions of glycerol with di-methyl oxalate, dimethyl malonate, dimethyl succinate,dimethyl glutarate, dimethyl adipate, and dimethyl aze-late. The GC composition of the reactions is shown inTable 1.

The results indicate that long chain dicarboxylic acid es-ters are easier to react with glycerol and formed glycerol es-ters than shorter chain length dicarboxylic acid esters. Thisis expressed by the yield of glycerol: dimethyl azelate washighest and followed by dimethyl adipate, dimethyl glu-tarate, dimethyl succinate, dimethyl malonate, and di-methyl oxalate.

Compounds 8, 10, 12, and 14with 90% purity were iso-lated by HPLC and the physical properties were tested.The measurement of surface tension, interfacial tension,and cloud point are summarized in Table 2. Surface ten-sion of compounds 8, 10, 12, and 14were in the range of30 to 31 mN/m and decreased when the carbon chainlength of dimethyl ester increased (Table 2). These val-ues are close to those of the surface tension of the indus-trial surfactants, which range from 26 to 28 mN/m (17).Interfacial tensions of compounds 8, 10, 12, and 14against paraffin oil were found to be 16.8, 14.5, 10.4, and9.9 mN/m, respectively (Table 2). Compound 14 has the

lowest interfacial tension compared with compounds8

,10, and 12. This is probably due to the interaction of thehydrophobic portion of monoglycerol ester with the liq-uid surface of paraffin oil. The cloud points of synthe-sized monoesters were more than 100C (Table 2). Fromthe literature, mono- and di-glycerides are mild surfac-tants and widely used in food industries. They also can befurther reacted to produce more complex biosurfactantssuch as the phospholipids (18). The synthesized succinate


151

GLYCEROL ESTERS

0

10

20

30

40

50

60

70

0 5 10 15 20


Percentconversion(%)

FIG. 3. Effect of catalyst (KOH) concentration on the reaction of glycerolwith dimethyl succinate: without catalyst (); 0.1 wt% (); 0.2 wt% (); 0.4wt% (x); and 0.6 wt% (+) (molar ratio 4:1, 80C, and 2 wt% molecular sieve).

0

10

20

30

40

50

60

0 5 10 15 20


Percentconvers

ion(%)

Monoester

Diester

FIG. 4. The effect of temperature on the reaction of glycerol with di-methyl succinate for monoester at 80C (); 100C (); 120C () anddiester at 80C (); 100C (); 120C () (molar ratio 4:1, 0.2 wt%

KOH, and 2 wt% molecular sieve).

0

10

20

30

40

50

60

70

80

0 5 10 15 20

Monoester

Diester


Percentconversio

n(%)

FIG. 5. The influence of molecular sieve on the reaction of glycerol withdimethyl succinate for monoester without molecular sieve () and with 2wt% molecular sieve (); and for diester without molecular sieve () and

with 2 wt% molecular sieve () (molar ratio 4:1, 80C, and 0.2 wt% KOH).


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glycerides (8) could be used in conjunction with harsh de-tergents like sodium lauryl sulfate to reduce the irritationof the sulfate ester.

ACKNOWLEDGMENTS

The authors would like to thank the Director General of MalaysianPalm Oil Board (MPOB) for the permission to publish this article

and the research grant given through MPOB graduate scholarship.In addition, the authors are also grateful to the University ofMalaya for the facilities provided.

REFERENCES

1. Bancquart, S., Y. Pouilloux, and J. Barrault, Selective GlycerolTransesterification over Mesoporous Basic Catalysts, C.R.Chimie 7:593599 (2004).

2. Waldinger, C., and M. Schneider, Enzymatic Esterification ofGlycerol III. Lipase-Catalyzed Synthesis of RegioisomericallyPure 1,3-sn-Diacylglycerols and 1(3)-rac-Monoacylglycerols De-rived from Unsaturated Fatty Acids, J. Am. Oil Chem. Soc.73:15131519 (1996).

3. Nagano, Y., and T. Tanaka, Synthesis of Dibasic Acid Glyc-

erides, Yukagaku 11:209211 (1962).4. Ward, T.L., A.T. Gros, and R.O. Feuge, New Fat Products: Glyc-eride Esters of Adipic Acid,J. Am. Oil Chem. Soc. 36:667671(1959).

5. Feuge, R.O., and T.L. Ward, 1,3-Diolein and 1,3-Distearin Esterof Fumaric, Succinic and Adipic Acids, J. Am. Chem. Soc.80:63386341 (1958).

6. Villeneuve, P., T.A. Foglia, T.J. Mangos, and A. Nuez, Synthe-sis of Polyfunctional Glycerol Esters: Lipase-Catalyzed Esterifi-cation of Glycerol with Diesters, J. Am. Oil Chem. Soc.75:15451549 (1998).

7. Alksnis, A.F., I.V. Gruzin, and Ya.A. Surna, Synthesis of Oli-goesters from Oxalic Acid and Glycerol, J. Polym. Sci. Poly.Chem. Ed. 14:26312638 (1976).

8. Nagata, M., T. Kiyotsukuri, H. Ibuki, N. Tsutsumi, and W.

Sakai, Synthesis and Enzymatic Degradation of Regular Net-work Aliphatic Polyesters, Reactive Functional Polymers30:165171 (1996).

9. Kiyotsukuri, T., M. Kanaboshi, and N. Tsutsumi, Network Poly-ester Film from Glycerol and Dicarboxylic Acids, Polym. Inter.33:18 (1994).

10. McLafferty, F.W., and F. Turecek, Interpretation of Mass Spectra:

Mass Spectra of Common Compound Classes, University ScienceBooks, Sausalito, United States, 1993, p. 168.

11. Robles, A.M., L.C. Esteban, A.G. Gimnez, B.P. Camacho,M.J.G. Ibez, and E.G. Molina, Lipase Catalyzed Esterificationof Glycerol and Polyunsaturated Fatty Acids from Fish and Mi-croalgae Oils,J. Biotech. 70:379391 (1999).

12. Darnoko, D., and C. Munir, Kinetics of Palm Oil Transesterifi-cation in a Batch Reactor,J. Am. Oil Chem. Soc. 77:12631267(2000).

13. Roxana, R., Y. Mamoru, I. Yugo, and Y. Tsuneo, Enzymatic Syn-thesis of Symmetrical 1,3-Diacylglycerols by Direct Esterifica-tion of Glycerol in Solvent Free System,J. Am. Oil Chem. Soc.76:839843 (1999).

14. Klare, S.,Fatty Acids: Their Chemistry, Properties, Production, andUses, Interscience Publishers, London, England, 1968, p. 342.

15. Ulf, S., S. Ricardo, and M.V. Rogrio, Transesterification ofVegetable Oils: A Review,J. Braz. Chem. Soc. 9:199210 (1998).

16. Otera, J., Review Transesterification, Chem. Rev. 93:1449-1470(1993).

17. Jnsson, B., B. Lindman, K. Holmberg, and B. Kronberg, In-troduction to Surfactants, in Surfactants and Polymers in AqueousSolution,John Wiley & Sons, West Sussex, England, 1999, p. 28.

18. Coupland, K., Surfactants in Lipid Chemistry-Recent Synthetic,Physical and Biodegradative Studies, in Natural Base Surfac-

tants-Some Aspects of their Chemistry and Uses, edited by J.H.P.Tyman, Royal Society of Chemistry, Cambridge, Great Britain,1992, p. 158.

[Received August 25, 2006; accepted February 14, 2006]

Gladys H.P. Cho is a masters degree student at the Department of

Chemistry, University of Malaya, Malaysia. She majors in oleo-

chemical chemistry.

Dr. S.K. Yeong is a senior research officer at the Advanced Oleo-

chemical Technology Division, Malaysian Palm Oil Board. Her re-

search involves the development of household and industrial chemical

products from palm based oleochemicals.

Dr. T.L. Ooi is a principal research officer at the Advanced Oleo-chemical Technology Division, Malaysian Palm Oil Board. He cur-

rently heads the Oleochemical Products Development Unit.

Dr. C.H. Chuah is a professor at the Department of Chemistr y,

University of Malaya, Malaysia. His research interest is in palm

oil chemistry.

152

G.H.P. CHO ET AL.


TABLE 2Physical Data of 10% (vol/vol) Monoglycerol Esters

Temperature Compound Compound Compound CompoundProperties (C) 8 10 12 14

Light yellow Light yellow Light yellow Light yellowAppearance 25 liquid liquid liquid liquid

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

Cloud point (C) >100 >100 >100 >100

esteres de glicerol de la reacción de glicerol con Ácidos dicarboxílicos

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