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Synthesis of polyisobutenyl succinic anhydrides.

Product distribution and proposed reaction
mechanism
Conference Paper January 2007
DOI: 10.13140/2.1.3847.8403

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SYNTHESIS OF POLYISOBUTENYL SUCCINIC ANHYDRIDES.

PRODUCT DISTRIBUTION AND PROPOSED REACTION
MECHANISM.

The fate of the various reagents (PIB) and products (PIBSA and PIBBSA)
can be determined and quantified via NMR 2. In this case, results achieved
on samples taken at various times for the reaction carried out without any
acidic catalyst added are reported in Figure.2 .

Riccardo Rausa

100

CR SDM/PROD
ENI R&M
Via Maritano 26
20097 S.Donato M.se, Italy

2,00
1,75

Results and Discussion

The reaction between a reactive PIB and maleic anhydride can generally
occur, in pure thermal conditions with the formation of four main products
(adducts) whose structure is shown in Figure 1.

1,00
40

0,75
0,50
0,25

0,00
0

4
PIB

t (ore)

14
d

GF NMR

Figure 2. Trend of the various molar fraction with time without acidic
catalyst.
Figure 3 shows results obtained for the reaction where 500 ppm of p-toluen
sulphonic acid were added .

100

1,75
1,50

80

1,25
60

1,00

40

0,75
0,50

20

0,25

0,00
0

PIB

4
a

7
t (ore)
b

Figure 3. Trend of the various

time in the presence of acidic catalyst.

Figure 1.
General scheme for the synthesis of PIBSA via thermal
reaction of reactive PIB with maleic anhydride.

GF NMR

1,25

60

GF NMR

Experimental
Materials. All reagents were used without further purification.
Highly reactive polyisobutene (PIB) 2300 was supplied by BASF Italia
S.p.A. and maleic anhydride (98%) was purchased from Polioli Italia
Instrumentation. 1 H -NMR spectra of reagents and products were
obtained on a Varian VXR-400 spectrometer operating at 399.867 MHz at
the following conditions: single pulse excitation, pulse angle 30 , recycle
time : 2 s. Sample concentrations were about 30 % (w/v) in CDCL3
containing 1% TMS as an internal reference.
Synthesis of Polyisobutenyl succinahnydrides. PIBSA derivatives
were prepared according to previously reported procedure 2 via a thermal
ene reaction by reaction with maleic anhydride. The reaction was carried out
either without or with a soluble organic acid ( p-toluen sulphonic acid) at a
concentration of 500 ppm, for reaction times up to 14 h, at temperatures
higher than 200 C.

1,50

20

% mol,

Introduction
Polyisobutenyl succinic anhydrides (PIBSA) are intermediates for the
synthesis of succinimides that are one of the most widely used additives in
automotive applications. They can be prepared
by the reaction of
polyalkenes, generally polyisobutene, with unsaturated anhydrides. When
prepared in the absence of halogens, the synthesis of PIBSA is carried out
using reactive polyolefins and the reactions occurs via an ene reaction.
The formation of PIBSA, in the so called thermal conditions, sometimes is
carried out in the presence of acidic species and/or radical inhibitors at
temperatures ranging between 180 and 245 C to lower the production of
undesirable by-products. Despite the large number of information in the
patent literature1, however, very little is known about the mechanism related
to the formation of PIBSA, on the various species that are formed during the
reaction and products distribution. In this paper results obtained in the
synthesis of high molecular weight PIBSA are reported; trends of the
various adducts formed during the reaction, carried out without or in the
presence of a soluble organic acid, are discussed and a mechanism of
reaction proposed.

% mol,

80

10
d

molar

14
GF NMR

fraction

with

time

In the first case, the preferential formation of the two main adducts of the
reaction (A and B, Figure.1) can be observed. The mono substituted PIBSA
(A) is produced in higher concentration due to less steric hindrance. The
concentration of the bi-adduct (C) increases with time through the conversion
of (A) according to the mechanism of Figure 1. Interstingly, the PIBBSA
(D) in this case seems not to be produced in these conditions because it has
not been detected among the reaction products. The functionalization degree
(GF NMR), calculated from the NMR spectra and shown in the second scale,
after 4 hrs increases and remains constant, reaching the average value of
1.25 succinic groups per molecule of reacted PIB.
When the p-toluen sulphonic acid is added, a new mechanism seems
operating and a new distribution pattern is observed (Figure 3). In this case,
in fact, the conversion of starting PIB is slower than that previously
observed without the acid, and a new distribution of the formed adducts is
obtained. A strong conversion of (A) suddenly occurs, (B) and (D) are the

Polymer Preprints 2007, 48(2), 227

main reaction products and the concentration of (C ) is considerably

constantly lower than that observed without any acid. In this case, due to a
higher concentration of double substituted adducts (D) the functionalization
degree is greater than that obtained for products deriving from the pure
thermal reaction (Figure 2), reaching the value of 1.5 succinic groups per
molecule of reacted PIB.
The observed different reaction could be consistent with the occurrence of a
ionic mechanism catalized by the acid present in the reaction medium and
could be explained following the mechanism proposed in Figure 4.

the formation of double adducts some of which are not detected in the
classical reaction. Their preferential formation leads to high functionalized
PIBSA.

100

1,75
1,50

80

1,00

40

0,75

GF NMR

% mol,

1,25
60

0,50
20

0,25

0,00
0

PIB

4
a

7
t (ore)
b
c

10

14
d

GF NMR

Figure 5. Evolution of the molar fractions of the various adducts obtained

adding p-toluen sulphonic acids after 4 hours.
In conclusion the organic acid when introduced into reaction doesnt only
leads to a decrease in insoluble by-products as reported in the literature 1 but
acts as a catalyst influencing the fate and the characteristics of the final
polyisobutenyl anhydride produced.
Acknowledgements. The author would like to thank Mr.G.Merlini and
Mrs.N.Brambati for their valuable technical help.
Figure 4. Proposed mechanism for the synthesis of PIBSA in the presence of
acidic catalysts.

References

In this mechanism, the attack of protonated maleic anhydride to the reactive

PIB double bond is suggested, leading to the formation of the first
intermediate (1). This intermediate could easily evolve towards the formation
either of unreactive specie (B) which remains one of the most important
adducts formed in these conditions, or to furtherly reactive adducts (A). The
subsequent reaction of (A) with the protonated maleic anhydride can lead
through the intermediate (2) both to (D), the second main reaction product,
and to (C).
The high reactivity of (A) in the presence of the acidic catalyst used in the
reaction has been proved carrying out the reaction in the same conditions but
adding the p-toluen sulphonic acid after 4 hours of conversion.
In this case, as shown in Figure 5, which depicts trends obtained for the
various species in this case, the trend of (A) before adding the acid is very
similar to that obtained without any catalyst (Figure2). Conversely after the
addition of the acid (4 h) a sudden decrease of (A) can be observed and the
product distribution from that point on is almost identical to that previously
obtained when the acid is added from the beginning of the reaction. Also the
distribution of products (as shown in Figure 4 ), is almost the same of that
depicted in Figure 3 where (B) and (D) appear the main reaction products.
The soluble organic acid, therefore, strongly influences reaction pathways
and properties of the resulting final polyisobutenylsuccin anhydrides that are
related to the number of functional groups on the converted PIB.
Conclusions
The reaction of reactive PIB with maleic anhydride to produce polyisobutenyl
succinic anhydrides (PIBSA), in the utilized conditions, is strongly influenced
by the presence of an acidic specie. When the reaction is carried out at pure
thermal conditions, the distribution of products (adducts) mainly lead to
monosubstituted adducts. Conversely in the presence of soluble organic
acids, the evolution of the intermediate products during the reaction is
significantly different suggesting that a new mechanism of formation of PIB
derived succinic derivatives occurs. This mechanism, probably ionic in
nature, could involve the formation and evolution of intermediates leading to

(2) Polymer 46 (2005) 14971505

(1) US PATENT 02260032 A1, Dec.23, 2004

Polymer Preprints 2007, 48(2), 228