Synthesis and characterization of oleic succinic anhydrides: Structure-property relations

Article abstract of DOI:10.1007/s11746-005-1066-5

Alkenyl succinic anhydrides (ASA) were prepared by an -ene reaction of n-alkyl (C₁ to C₅) oleates with maleic anhydride. The purified compounds were characterized by FTIR, ¹H NMR, and MS analytical methods to elucidate their structures. Their physicochemical properties were systematically studied and found to depend on the length of the alkyl radical. Structure-property relations were established for viscosity, m.p., and density. The combination of a long hydrophobic chain and a highly polar group with density values close to that of water implied good emulsification properties for some of these molecules. Comparison of the thermal properties of alkyl oleates and their respective ASA demonstrated that the grafting of maleic anhydride allowed the synthesis of compounds with very low melting temperatures (less than -60°C) and good stability at high temperatures (greater than 350°C) under both air and helium atmospheres. All these properties suggest a strong potential for application in the biolubricant or surfactant fields. The combined influences of the succinic part and variable ester moieties imply that each ASA molecule has its own characteristics, based on which applications could be developed. Copyright

Full text of DOI:10.1007/s11746-005-1066-5

Synthesis and Characterization of Oleic Succinic
Anhydrides: Structure–Property Relations
Laure Candy, Carlos Vaca-Garcia*, and Elisabeth Borredon
Laboratoire de Chimie Agro-industrielle, Unité Mixte de Recherche (UMR) 1010 Institut National de la Recherche
Agronomique (INRA)/Institut National Polytechnique de Toulouse (INP)–Ecole Nationale Supérieure des Ingénieurs en Arts
Chimiques et Technologiques (ENSIACET), 31077 Toulouse Cedex 4, France
ABSTRACT: Alkenyl succinic anhydrides (ASA) were prepared side reactions can take place: enophile polymerization, alkene
by an -ene reaction of n-alkyl (C1 to C5) oleates with maleic an-
hydride. The purified compounds were characterized by FTIR,
1H NMR, and MS analytical methods to elucidate their struc-
tures. Their physicochemical properties were systematically
studied and found to depend on the length of the alkyl radical.
Structure–property relations were established for viscosity, m.p.,
and density. The combination of a long hydrophobic chain and
a highly polar group with density values close to that of water
implied good emulsification properties for some of these mole-
cules. Comparison of the thermal properties of alkyl oleates and
their respective ASA demonstrated that the grafting of maleic
oligomerization, copolymerization between the enophile and
alkene, and thermal decomposition of the ASA (retroene re-
action). Secondary products are black, waxy solids unsuitable
for the major uses of ASA.
Literature concerning the reaction between maleic anhy-
dride and unsaturated molecules can be divided in three peri-
ods. First, the reaction mechanism was studied during the
1940s and up to the early 1950s by using ASA from FA or FA
esters. Demonstration of the -ene reaction mechanism was de-
bated and finally established during this period (9–11). Sec-
anhydride allowed the synthesis of compounds with very low ond, the strong development of petrol resources in the early
melting temperatures (less than –60°C) and good stability at
high temperatures (greater than 350°C) under both air and he-
lium atmospheres. All these properties suggest a strong poten-
tial for application in the biolubricant or surfactant fields. The
combined influences of the succinic part and variable ester moi-
eties imply that each ASA molecule has its own characteristics,
based on which applications could be developed.
1950s favored the production of ASA from straight or
branched olefins or even from polyolefins (4,12). From then
up to the 1990s, the studies aimed at limiting secondary prod-
ucts by adding reaction catalysts, polymerization inhibitors
(8), or an aromatic solvent (13). Third, with the increased in-
terest in renewable resources clearly observed since the
1990s, new ASA have again been synthesized from vegetable
oils and their derivatives. They have essentially been used as
monomers for the fabrication of thermosets (14), as the anhy-
dride moiety can react with diamines, diols and polyols, or
epoxy resins to yield unsaturated polyester-like resins.
Among these works, only a few have been concerned with the
fundamentals of vegetable ASA compounds, such as the one
carried out by Metzger and Biermann (15), who studied the
stereochemistry of ASA obtained from methyl oleate by 1H
and 13C NMR. No study has been concerned with the physic-
ochemical properties of vegetable ASA compounds. Our pur-
pose was therefore to synthesize, purify, and characterize
ASA compounds obtained from oleic acid esters with differ-
ent alkyl groups (Fig. 1). The main objective was to study the
influence of ester chain length on some physicochemical
properties to establish structure–property relations useful for
defining potential fields of application. With this study, we in-
tend to favor the replacement of fossil resources by renew-
able resource-derived ASA.
Paper no. J10734 in JAOCS 82, 271–277 (April 2005).
KEY WORDS: Alkenyl succinic anhydride, degradation tem-
perature, density, dynamic viscosity, fatty acid ester, maleiniza-
tion, melting temperature, renewable resources.
Alkenyl succinic anhydrides (ASA) are widely used in sev-
eral fields, for example, as additives in lubricants (1), inter-
mediates in organic chemistry (2), wood-preservation agents
(3), or paper-sizing agents (4,5). They are obtained by an -ene
reaction (6) between maleic anhydride (enophile) and an
alkene having an allylic hydrogen (-ene). During the reaction,
a new bond is created between two unsaturated termini, with
an allylic shift of the -ene double bond and transfer of the al-
lylic hydrogen to the enophile. Usually, the alkene is a petro-
chemical olefin, but TG or vegetable oil derivatives such as
FA also have been used; in this case, the reaction is com-
monly named maleinization (7). The -ene reaction requires a
Lewis acid and/or high temperature (>200°C) since its acti-
vation energy (Ea) is high (>80 kJ/mol) (8). Even though the
conversion rate is improved at higher temperatures, various
EXPERIMENTAL PROCEDURES
Materials. Methyl oleate (>96%) was supplied by Fluka (St
Quentin Fallavier, France). Oleic acid and oleoyl chloride
(both technical grade >85%), as well as maleic anhydride,
ethanol, propanol, butanol, and pentanol (all >99%), were
*To whom correspondence should be addressed at Laboratoire de Chimie Agro-
industrielle UMR 1010 INRA/INP-ENSIACET, 118 route de Narbonne; 31077
Toulouse Cedex 4, France. E-mail: Carlos.VacaGarcia@ensiacet.fr
Copyright © 2005 by AOCS Press
271
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L. CANDY ET AL.
FIG. 1. Alkenyl succinic anhydrides (ASA) compounds derived from alkyl oleates (R = –CnH2n+1, n = 1–5). Two isomers are possible.
purchased from Sigma (St Quentin Fallavier, France). 4- column (silica-grafted C18) operated at 25°C, with a 1 mL/
Toluene-sulfonic acid (p-TSA, >99%) was supplied by Fluka. min acetonitrile (Riedel-de Haën, St Quentin Fallavier,
All reagents were used as received without further purification. France) flow as the mobile phase.
Preparation of butyl and pentyl oleates. The syntheses of
IR spectroscopy. IR spectra were recorded on KBr win-
butyl and pentyl oleates were based on the complete esterifi- dows using a Perkin-Elmer 1600 FTIR in the 400–4000 cm–1
cation of oleic acid with the corresponding alcohol. Butanol region.
1
or pentanol (2 mol), oleic acid (1 mol), and p-TSA (0.1%
NMR spectroscopy. H NMR spectra were obtained in a
based on total weight) were placed in a 500-mL three-necked Bruker AC200 apparatus at 200 MHz. The samples were ana-
reactor and heated to 95°C. The reactor was equipped with a lyzed in CDCl3 99% (Sigma).
magnetic stirrer, a thermometer, and a distillation column fol-
MS. Mass spectra were obtained in a Nermag R 1010 spec-
lowed by a condenser. The azeotropic mixture formed by trometer. After dilution in CH2Cl2, the samples were chemi-
water and alcohol was distilled off to shift the equilibrium. cally ionized by ammonia (NH3).
Esterification was monitored by quantification of the acid
Density. Density was determined using a 10-mL pycnome-
value of the medium according to ISO Standard 660:1996. ter according to ISO standard 279-1981.
The reaction was stopped when no more azeotropic mixture
Rheometry. Dynamic viscosities were measured with a
was distilled and when the acidity of the medium was mini- Carrimed CSL100 viscometer. The operating conditions for
mal. The cooled reaction medium was washed with a NaCl- oleic esters were as follows: cone angle, 2°; cone diameter, 6
saturated aqueous solution and then vacuum distilled. FA es- cm; truncation, 56 µm; strain, constant 1 N/m2 for 1 min; tem-
ters were distilled between 170 and 190°C under 1 mmHg and perature, 20°C. The operating conditions for ASA were as
used immediately for the -ene reaction.
follows: cone angle, 2°; cone diameter, 4 cm; truncation, 54
Preparation of ethyl and propyl oleates. These esters were µm; strain, linear from 10 to 30 N/m2 for 2 min; temperature,
synthesized by acylation of the alcohol with a FA chloride. variable from 0 to 60°C.
Ethanol or propanol (1 mol) was placed in a 500-mL three-
DSC. Thermal transitions of oleic esters were recorded on
necked reactor equipped with a nitrogen input, a mechanical a PerkinElmer Pyris1 apparatus. The temperature program
stirrer, and a condenser followed by two NaOH solution was –50 to 25°C at 10°C/min. ASA compounds were studied
washers to trap the HCl formed. Oleoyl chloride (0.5 mol) in a Netzsch 204 apparatus. The temperature program was
was added to the reactor under nitrogen at room temperature. −120 to 25°C at 10°C/min. Melting points of these com-
As the HCl evolved, the equilibrium shifted. The temperature pounds were calculated from thermograms according to the
was gently raised to 90°C to complete the reaction. The tangent method.
medium was then washed with a NaCl-saturated aqueous so-
Thermogravimetrical analysis. The degradation tempera-
lution and vacuum distilled. Ethyl and propyl oleates were tures of ASA corresponding to 10 and 50% mass loss were de-
distilled between 160 and 170°C under 1 mmHg and used im- termined in a Setaram TG-DTG 92 apparatus. The samples were
mediately for the -ene reaction.
heated from 20 to 600°C at 10°C/min under air and helium.
Synthesis and purification of ASA. Alkyl oleate (100 g) and
maleic anhydride (1.2 mol/mol of alkyl oleate) were heated at
220°C for 8 h under a static nitrogen atmosphere in a three-
RESULTS AND DISCUSSION
necked reactor equipped with a magnetic stirrer and a con- Synthesis of alkyl oleates. Five oleic acid alkyl esters, from
denser heated at 60°C to reflux the liquid maleic anhydride. methyl to pentyl, with reasonably high purity (>85%) were
At the end of the reaction, the medium was vacuum distilled required for ASA synthesis. Methyl oleate was commercially
(<1 mmHg). Unreacted maleic anhydride and oleic acid es- available. Butyl oleate and pentyl oleate were successfully
ters were distilled at 70°C and between 160 and 190°C, re- synthesized by the esterification technique. After distillation,
spectively. ASA were then distilled between 240 and 260°C no residual oleic acid accompanied the desired product. The
under this pressure. The purity of the distilled fractions (oleic purities of these alkyl oleates were 90 and 87%, respectively,
acid esters and ASA) was evaluated by LC. The HPLC sys- the rest being butyl and pentyl esters of other FA as the initial
tem was composed of a Spectra-Physics pump and a refrac- source, which were of technical grade. On the contrary, the
tometer detector 350RI (Varian) at 35°C. A Spherisorb ODS2 esterification technique was not successful for the synthesis
JAOCS, Vol. 82, no. 4 (2005)

STRUCTURE–PROPERTY RELATIONS OF OLEIC SUCCINIC ANHYDRIDES
273
of ethyl and propyl oleates. These reactions were not com- anhydride, at 917 cm–1. The carbonyl stretching band of the
plete, and significant quantities of oleic acid remained in the alkyl ester appeared at 1732 cm–1.
reaction medium. This was probably due to the low reaction
1H NMR spectra of the samples showed the expected char-
temperature, limited by the boiling temperature of the water– acteristic peaks. ASA from methyl oleate showed a peak at
alcohol azeotrope. Moreover, the distillation of the medium 5.5 ppm (m, 2H) belonging to the –CH of the double bond.
did not allow an effective separation of the ethyl and propyl The peak at 3.6 ppm (s, 3H) belonged to the –CH3 in the ester
oleates from oleic acid. Consequently, the synthesis of the part. The peaks between 3.1 and 2.6 ppm (m, 3H) were as-
former were finally properly achieved by acylation of the cor- signed to –CH belonging to the succinic link and to the anhy-
responding alcohol with oleoyl chloride. Purities of 84 and dride moiety. The peaks at 2.2 ppm (t, 2H) and at 1.5 ppm (m,
89% in ethyl and propyl oleate, respectively, were reached 2H), respectively, were identified as –CH2 in positions α and
after distillation, with no free reagents left. The rest was as- β to the ester group and part of the unsaturated chain. The
sumed to be ethyl or propyl esters of other FA.
peak at 1.9 ppm (d, 2H) belonged to the –CH2 in a position to
Synthesis of ASA. Two isomers of ASA can be formed, the double bond. The peak at 1.2 ppm (m, 20H) was represen-
since the addition reaction of maleic anhydride on oleic acid tative of the –CH2 from the linear fatty chain. Finally, the
esters can occur either on carbon 9 or carbon 10 (atoms con- peak at 0.80 ppm (t, 3H) could be assigned to the terminal
cerned with the double bond) of the unsaturated chain. The –CH3 moiety of the alkyl chain. These spectra provided con-
two isomers could not be separated by vacuum distillation, firmation of the nature of our products.
but the HPLC analysis of the distillate showed two peaks that
Additional confirmation of the structures was obtained
were poorly resolved. They were therefore integrated as a from MS. The M.W. of ASA compounds were obtained from
unique peak for purity calculations based on the following area the formation of ASA–NH4+ ions for m/z 412, 426, 440, 454,
ratios: 95% for methyl oleate succinic anhydride (ASAOM), and 468, which corresponded to the theoretical M.W. of
99% for ethyl oleate succinic anhydride (ASAOE), 99% for ASAOM, ASAOE, ASAOPr, ASAOB, and ASAOPe. Other
propyl oleate succinic anhydride (ASAOPr), 88% for butyl characteristic peaks were m/z 395, 409, 423, 437, and 451,
oleate succinic anhydride (ASAOB), and 98% for pentyl oleate corresponding to the formation of ASA–H+ ions. For each
succinic anhydride (ASAOPe).
MS spectrum, a common peak for m/z 398 was obtained, cor-
ASA characterization. All distilled ASA were clear yel- responding to a NH4+ ionized fragment in which the alkyl part
low, oily liquids (Gardner’s color index from 5 to 7). FTIR of the carboxylic acid ester moiety of ASA was being re-
spectra of oleic ASA presented significant bands representa- moved.
tive of the groups present (Fig. 2). The major IR peaks aris-
Physical properties of ASA. After confirmation of the
ing from anhydride carbonyl stretching were located at 1785 structure of ASA, several physical characteristics were evalu-
and 1863 cm–1. They also showed a stretching vibration band ated. Our conclusions took into account the stereoselectivity,
typical of five-membered cyclic anhydrides, such as succinic the length of the ester moiety, and the influence of the suc-
Wavenumber (cm–1)
FIG. 2. FTIR spectrum of pentyl oleate succinic anhydride.
JAOCS, Vol. 82, no. 4 (2005)

274
L. CANDY ET AL.
cinic moiety. With regard to the stereoselectivity, previous ences the intermolecular arrangement and consequently the
studies (7,15,16) have indicated that the mechanism of the- physical properties of vegetable ASA compounds.
ene reaction for a cis alkene (oleic acid) with a maleic anhy-
Viscosity. The rheological behavior of ASA was studied at
dride leads to 100% trans adducts. This change in configura- 20°C (Fig. 3). The gradient was an increasing linear function
tion and the presence of the ester and succinic moieties influ- of the strain. The viscosity, i.e., the slope of the preceding
0.19 Pa⋅s
0.20 Pa⋅s
0.20 Pa⋅s
0.23 Pa⋅s
0.28 Pa⋅s
CH3
C2H5
C3H7
C4H9
C5H11
Strain (N/m2)
CH3; Ea = –46.3 kJ/mol
C2H5; Ea = –42.9 kJ/mol
C3H7; Ea = –45.1 kJ/mol
C4H9; Ea = –43.7 kJ/mol
C5H11; Ea = –42.8 kJ/mol
1/T (K–1)
FIG. 3. Rheological behavior of ASA. (A) Gradient vs. strain applied. (B) Dynamic viscosity vs. temperature.
Methyl oleate succinic anhydride (CH3), ethyl oleate succinic anhydride (C2H5), propyl oleate succinic an-
hydride (C3H7), butyl oleate succinic anhydride (C4H9), pentyl oleate succinic anhydride (C5H11). For other
abbreviation see Figure 1.
JAOCS, Vol. 82, no. 4 (2005)

STRUCTURE–PROPERTY RELATIONS OF OLEIC SUCCINIC ANHYDRIDES
275
curves, was therefore constant for all strains applied. The vis- relation, S.G. = 0.0003n2 – 0.0065n + 1.0204, with a correla-
cosity values ranged from 0.19 to 0.28 Pa⋅s from methyl to tion coefficient R2 = 0.9796. This type of correlation also was
pentyl. The lowest value was measured for ASAOE. We can found for the corresponding alkyl oleates: S.G. = 0.0007n2 –
propose no explanation for this exception to the tendency. 0.0067n + 0.8830, with R2 = 0.9984. Thus, grafting maleic
ASA appeared to be Newtonian liquids whose viscosities anhydride onto alkyl oleates led to an important densification
were at least 30 times higher than those of the corresponding of the molecule. For each ester, maleinization allowed an in-
alkyl oleates, which ranged from 0.003 to 0.009 Pa⋅s. This crease of about 0.12 kg/m3. This was quite surprising since
was linked to both the increase in M.W. and the presence of a the succinic moiety also could act as a spacer between mole-
new function, branched to the alkenyl chain, corresponding cules. However, because the -ene reaction on alkyl oleates
to the grafted maleic anhydride, which created friction phe- (cis compounds) leads only to trans ASA compounds, we can
nomena between the molecules. The maximal viscosity cor- hypothesize that molecule stacking is more compact for ASA
responded to the shortest alkyl moiety, which was also the than for the oleates. Furthermore, for the vegetable ASA com-
most polar. This compound seemed to undergo the most im- pounds considered, even if they possess a long hydrocarbon
portant friction between molecules even if its M.W. was the chain (C18:1 unsaturated; ester moiety ranging from CH3 to
lowest of the series. The evolution of viscosity with tempera- C5H11), they have an S.G. approximately equal to that of
ture can be mathematically expressed as ln µ = a/T + b what- water. Because ASA molecules consist of a long hydrophobic
ever the strain applied (Fig. 3). This behavior is also charac- chain and two polar groups, we can propose that these ASA
teristic of Newtonian fluids. On the one hand, these equations would be easily emulsified in water and used as wetting
can be used as predictive models for the evaluation of ASA agents. Some preliminary tests have demonstrated a real im-
viscosities at every temperature, which are useful values for provement in emulsion stability when compared with conven-
determining fluid transport conditions. On the other hand, by tional ASA not bearing an ester moiety.
analogy with the Arrhenius law, it is possible to calculate the
DSC. The melting temperatures of alkyl oleates and ASA
Ea as being equal to Ea = –a × R. Except for ASAOE, the Ea were evaluated by DSC (Table 1). The melting temperatures
increases as the length of the ester moiety decreases. The less of vegetable ASA followed a parabolic relation vs. the length
polar the molecule (longest alkyl chain), the lower friction of the ester moiety, whose equation was: Tm = 0.086n2 –
there is between molecules, so the less energy is necessary to 2.514n – 61.48, with R2 = 0.997. The longer the ester moiety,
overcome the initial friction.
the lower the m.p. The thermal transitions in the thermograms
Density. Specific gravities (S.G.) of ASA and alkyl oleates revealed that what we called melting was in reality a phenom-
were evaluated at 20°C according to a standardized method. enon close to glass transition, as the ASA were passing
When the length of the alkyl substituent increased, the S.G. through a mesomorphic state before reaching the liquid state.
of ASA decreased, presumably due to an increase in steric This phenomenon became clearer with the longest alkyl es-
hindrance (Fig. 4). The terminal unit acted as a “spacer” be- ters. In addition, maleinization decreased the melting temper-
tween molecules. The S.G., plotted as a function of the num- atures of alkyl oleates to about 30°C in each case. Because
ber of carbon atoms in the alkyl moiety, followed a parabolic the -ene reaction leads only to trans isomer compounds, the
FIG. 4. Specific gravities of ASA and alkyl oleates as a function of the length of their ester moi-
ety. For abbreviation see Figure 1.
JAOCS, Vol. 82, no. 4 (2005)

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L. CANDY ET AL.
dride moiety and the change to a trans configuration provided
TABLE 1
Melting Temperatures of Alkyl Oleates and Alkenyl Succinic
Anhydrides (ASA)
molecules more stable to high-temperature conditions of at
least 40°C. We also observed that the degradation tempera-
ture increased according to the length of the ester moiety.
ASA of vegetable origin can thus be used at high tempera-
tures with little or no degradation.
Melting temperature (°C)
Ester moiety
Ester
ASA
Methyl
Ethyl
Propyl
Butyl
–18.9
–24.3
–32.8
–35.5
–31.9
–63.8
–66.4
–68.2
–70.0
–72.0
ACKNOWLEDGMENTS
This work was supported in part by research grants from the Organi-
sation Nationale Interprofessionnelle des Producteurs d’Oléagineux
(Paris, France) and the Agence de l’Environnement et de la Maitrise
de l’Energie (Angers, France).
Pentyl
stacking of molecules was changed to a more compact
arrangement. The molecules may be arranged in a way to
minimize steric hindrance between groupings. Layers may be
formed, with vertical chains with ester moieties having a
head-to-tail arrangement and thus an increased mobility.
Therefore, long alkyl moieties act as spacers, significantly de-
creasing the melting temperatures of the corresponding ASA
compounds. For the succinic parts, they can be arranged here
and there from the plan formed by the trans alkenyl chains,
having minimal steric hindrance. Because of the decrease in
melting temperature, the products obtained are then liquids
that can be used under very low temperatures (<–50°C),
which is useful in applications for biolubricants. For alkyl
oleates, the melting temperatures ranged from –19 to –35°C
and were best fitted by a parabolic relation: y = 2.538x2 –
20.496x + 6.28 (correlation coefficient: R2 = 0.9853). The
alkyl oleate melting at the lowest temperature was thus the
butyl one. These data were in good agreement with those
available in the literature (17).
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TABLE 2
Degradation and 10% Weight Loss Temperatures of ASAa Under an Air or Helium
Atmosphere vs. Length of the Alkyl Moiety
10% weight loss temperature (°C)
50% weight loss temperature (°C)
Ester moiety
Under helium
Under air
Under helium
Under air
Methyl
Ethyl
Propyl
Butyl
316.2
316.2
336.8
332.4
341.2
342.6
338.2
326.5
332.3
351.5
363.0
365.2
376.7
377.2
380.8
379.9
383.0
379.6
383.8
389.0
Pentyl
aFor abbreviation see Table 1.
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STRUCTURE–PROPERTY RELATIONS OF OLEIC SUCCINIC ANHYDRIDES
277
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[Received September 22, 2003; accepted March 15, 2005]
JAOCS, Vol. 82, no. 4 (2005)