WCAM 2013

Suzhou June 4th-7th

Polyisobutenyl Succinic Anhydrides and their derivatives:

Synthesis, characterization and application in automotive and
innovative fields

Riccardo Rausa1, Andrea Pucci 2, Paolo Fiaschi 1

1) S.Donato M.se Eni R&M Research Center

www.eni.it
2) Department of Chemistry and Industrial Chemistry University of Pisa, Italy
 2
R.Rausa WCAM 2013 Suzhou
OUTLINE

PolyIsobutenyl Succinanhydride (PIBSA)

Amphiphilic structure and applications

Synthesis and characteristics

Functional derivatives

Application in the “Automotive field”

New applications

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PIBSA

Poly Iso Butenyl Succinhanydride

Very flexible structure that can be converted in various derivatives

useful in the whole Oil field e.g.:

PIBSE Poly Isobutenyl Succinic Esters

PIBSI Poly Isobutenyl Succinic Imides

PIBS-X Poly Isobutenyl Succinic -X derivative

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 Polyisobutenyl Succinic Anhydrides (PIBSA)

Amphiphilic molecules
Obtained by the addition of maleic anhydride (a polar
head: the hook) onto a polimeric (polyolefinic) chain (the
tail)

“Solubilizing”
Apolar Tail “Ancoring”
Polar Head
O

Oleophilic Polar O

Surface active substances (i.e. lower the interfacial tension)

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Polyisobutenyl Succinic Anhydrides derivatives

“Polar
“Hook” Head” Further conversion of
the Succinic group leads
Solubilizing to various derivatives of
“Apolar Tail” varying strenght and
applications.

A B C
O
O

X----Y
O
X--Y
O
O
n
n

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PIBSA and derivatives in organic phase.
Colloidal characteristics in organic solution

Dispersant in organic phase Depending on their concentration

the molecule can associate in
PIBSA PAM
(apolar ) (polar ) “inverse” micelles and fluoresce

Monomer

Organic
phase

Shining blue-green color

when excited by a long-
range UV lamp at 366 nm

Micelle can serve as dispersant reserve

in equilibrium with dissolved molecules
micelle
and molecules adsorbed onto the surface
of deposits A.Pucci, et al. Macromol. Chem. Phys. (2008) 209,900-906.
Mata et al. Coll.and Surf A:
Phys.and Eng. Aspects 418 (2013) 157-164.

R.Rausa WCAM 2013 Suzhou

 PIBSA AND PIBSA-DERIVATIVES APPLICATIONS

Emulsifiers Used
in Emulsion
Explosives Oil Spill
Al-Sabagh,
Rajapakse. A., Parthasarathy , R.,
J.of Chemical Tech and
and Bhattacharaya, S.N., (2003),
Biotech(1999)
O

X-----Y Cosmetics
(S)

US 2008/0199420 A1
O
n

Antifouling
in refinery
processes Automotive
US 5,194,142 Corrosion
US 5171421
inhibitors
US20110160405
US5989322

Lubricants Innovatives
All figs have been taken from internet
Appl.

R.Rausa WCAM 2013 Suzhou 8

 PIBSA derivatives in High internal phase emulsions

in areas as diverse as explosives, food products and toiletries

In high internal phase emulsions
Aqueous
W/O emulsion .phase

aqueous droplets are stabilized by PIBSA

the polyisobutylene acid amide or
PIBSA-based surfactant, adsorbed at
the water/oil interface

http://www.exploenergy.com In the petroleum area

Stabilize or avoid formation of aggregates

Antifouling, dispersants, detergents

Can help oil spill remediation

Corrosion inhibitors

R.Rausa WCAM 2013 Suzhou 9

Modifying polyolefins to make PIBSA

Addition of Maleic Anhydride

Depending on the starting PIB different reactions are required

to functionalize Polyolefins

They can involve or not the use of chlorine

Classical (Cl2)

Thermal “ene addition”

Catalyzed addition

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PIBSA: traditional chlorination way

Classical synthesis of PIBSA via chlorination

O
single or multiple
step
PIB + Cl2 + MAH O
+ Cl2

O
140-250 °C PIBSA

O O

O
- HCl O

Cl O O
O

O
O
O
O
Some chlorine remains in the final products O
O
J.D.Burrrington et al.
Additives 2011 Oxford 20 March 2001 O
PIBBSA O

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Thermal “ene” addition: The starting matter
PIB: Mainly used (about 60%) as starting molecule for obtaining lube additives
(dispersants) and fuel detergents .

Higher performance additives require “High reactive” PIB (i.e. high content of
vinylidene Hydrogen atoms)

Isobutylene + ~ 85% mol. α-olefin

BF3 cat. ~ 10% mol. β-olefin
~ 3% mol. tetrasubst. olef.

Mn: from 650 to 2300 Da.

Low Molecular weight polidispersity: better low temperature properties
Ashless, “chlorine free” additives for lubricants and fuels with excellent performances

H.Machl.Lubrication Science 11-2, February 1999

12
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PIBSA: Thermal “ene”synthesis

Mono substituted

eccesso MAH

Isomers formation depending on

reaction conditions:
T, PIB/MAH ratio, time,
Disubstituted
A. Pucci, C. Barsocchi, R. Rausa, L. D’Elia, F. Ciardelli, Polymer 2005, 46, 1497

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PIBSA: the Catalytic way
Isomers formation depending on
reaction conditions:T, PIB/MAH ratio,
time, catalyst
100 2.00
1.75
80 No catalyst
1.50
B 1.25

GF NMR
60

% mol,
1.00
40 0.75
0.50
20
0.25
0 0.00

A 0 4
t (ore)
7 14

PIB A B C D GF NMR

100 1,75

1,50
80
1,25
60
1,00

GF NMR
% mol,
0,75
40

C 20
0,50

D 0,25

0 0,00
0 4 7 10 14
t (ore)
PIB A B C D GF NMR

(*) R.Rausa; Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2007), 48(2), 227-228.

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PIBSA: Chemical physical Characteristics

Chlorine content •Depending on the process

(hundred to thousands ppm)

-Cl

•Depending on the starting PIB

Molecular weights (1000-1300-2300) and process

TAN, Functionalisation • Depending on PIB and reaction

conditions
(Mw starting PIB; T; MAH/PIB;
t (h), cat.etc.)
• TAN: 31 – 86 mg KOH/g)
• FD: 1-2.2

Spectroscopical characteristics •Depending on concentration

(e.g.1.45 10-3 M)
(e.g. fluorescence)

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 PIBSA DERIVATIVES

O
O

+ H-Y Y
X
O

O
O
n
n

H-Y : Polyalkylene amines (e.g. TETA, PEHA, HEPA etc.)

PoliIsobutenyl Succinimides
PIBSI
O O

CH 3 CH 3 NH2-(CH2CH2NH)nNH2 CH 3 CH3
H2
O
H2 H2 NH(CH2 CH 2 NH)nNH 2
H2
H3 C C ( C C )n C H3 C C ( C C )nC
O O
CH 3 CH 3 160 °C CH 3 CH3

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PIBSI

Perhaps the most important and diffuse

PIBSA derivatives

Extensively used in Automotive

applications as components for Lubricants
and Fuels

Can be obtained at various degree of

complexity depending on the type of
Polyalkylene amine (PAM) used and
on the coupling ratio (CR)

CR: SA/PAM

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Synthesis of PIBSI: coupling ratio

CR: 1

Mono
Succinimide

CR: 2

Bis
Succinimide

CR: 3

Tris
Succinimide

Tomlinson et al.. Langmuir 1997, 13, 5881-5893

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PIBSI in Automotive applications – Lubricants -

Colloidal characteristics and interaction with soot.

Formation of solide residues occurs inside the engine due to the partial combustion of
the fuel.
In lubricants high content of solid fractal aggregates (100-120 nm) are formed (soot) that lead
to agglomerates of high viscosity, high oil content and thus to adverse reological properties for
the engine.

Incipient
Soot

J. Emert, et al.
ACS National Meeting, N. Y. , Sept 10, 2003

The main function of PIBSA and PIBSI or PIBS-X in this case is directed to prevent
the aggregation of soot (Dispersant action) via “steric stabilization” .

Georges et al.Langmuir 1997, 13, 3454-3463 DISPERSANT ACTION

We Won et al Langmuir 2005, 21, 924-932

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Effect of Dispersant on Soot and Sludge in the engine

OIL Sump

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Dispersant evaluation in Lubricants

Peugeot DV-4 engine -CEC L-093-04 test method

“Mid SAPS” lubricant with a proprietary

PIBSA derivative

Evaluation criteria

Viscosity@6 % soot
Delta viscosity @100°C, soot 6%
Lubricant A Reference
Lube RL223
Viscosity@6 % soot 16.97 28
Delta viscosity 3.25 13.95
@100°C, soot 6%
Prestational limits Pass 8.37
A1/B1-12, A3B3-12,
A3/B4-12, A5/B5-12
Prestational limits Pass 8.37
C1-12,C2-12,C3-12 C4-
C12

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PIBSI and PIBS-X in Automotive applications - Fuel components -

In fuels, products from incomplete combustion lead to the formation of solids that occlude
Injector holes and lead to poor engine peformance in terms of fuel consumption efficiency
(Fuel economy) and increased formation of pollutants.

Detergency evaluation
Engine tests
Clean injector

•Atomization
•Ignition
•Combustion

Injector with
nozzle deposit

DETERGENT ACTION

R.Rausa WCAM 2013 Suzhou

PIBSI and PIBS-X in Automotive applications - Fuel components -

Thanks to their amphiphilic characteristics PIBSA and PIBSI can “clean”

surfaces where deposits have been formed

“Clean up” effect

Fuel Flow

Deposit

Clean surface

R.Rausa WCAM 2013 Suzhou

 Evaluation of detergent properties via engine tests
XUD9 A/L – CEC F-23-A-01 Nozzle fouling test

Engine
Diesel Normally Aspirated
Test Referencing Fluids
4 cylinder - 8 valve -1900
cm³ Indirect Injection •Low Ref RF 93-T-95 :
92 +/- 5% fouling
•High Ref DF 90-01 :
60 +/- 10% fouling

Test Criteria
% of air flow loss accross
injector nozzles between
SOT and EOT European Normated Standard Test
of evaluation of injector detergency
CEC: Co-ordinating European Council

R.Rausa WCAM 2013 Suzhou

Automotive applications. Fuel detergency by PIBSI
CEC – CE F23 –A-01
% Flow recovery at the end of test (EOT)* % fouling at the end of test (EOT)*

TEST XUD-9 - CLEAN UP - Test XUD-9 - Keep Clean-

Nozzle fouling at 0.1 mm needle Lift (%)

80

Nozzle fouling at 0.1 mm

85
85 88
85

needle Lift (%)

75
∆
66 60
65

57
55 51

45 40
REF. PR24 PR44 1
PR34 PR14 PR15 PR16

Flow Recovery %
(Deposits removal efficiency)

F(0) -F(EOT)
∆ = %FDI-%FCI %F = *100
F(0)

F(EOT): Flow EOT

F(0) : Flow at the beginning

(*) R.Rausa. Unpublished results

R.Rausa WCAM 2013 Suzhou

CEC F-98-08 diesel injector fouling test (DW-10)

Detergent additive is the key Peugeot DW10 engine

technology for injector deposit
control
2.0 litre common rail unit with a maximum
injection pressure of 1600 bar, fitted with
Euro V (100 mm hole diameter) injectors

The method directly measures engine

power, which is a function of the level of
injector fouling

•Thirty-two hours running time

•Four (8 hrs) cycles

•Three intermediate`soak’ periods

CEC: Co-ordinating European Council

European Normated Standard Test

of evaluation of injector detergency The basis of the test is a high speed, high load, one
hour cycle

R.Rausa WCAM 2013 Suzhou

Automotive applications: CEC F-98-08 DW-10 diesel injector fouling test

Clean Up procedure
Power % Final Power %
(clean injector)
(new
injector)
∆ Power recovery

(fouled
injector)

PIBSI and PIBS-X effective

additives in reducing injector
fouling and restoring engine
power

Effect depending on their

chemical structure

R.Rausa. Unpublished results

R.Rausa WCAM 2013 Suzhou

Automotive applications: CEC F-98-08 DW-10 diesel injector fouling test

Keep Clean
Keep Testprocedure
Clean

Dw -10 K.C.

8.00 Power remains constant along the run

3.00
POWER %

ENI
-2.00 0 10 20 30

-7.00

-12.00
t (h) PIBSA DERIVATIVES CAN EFFECTIVELY

CONTROL THE FORMATION OF DEPOSITS

INSIDE THE INJECTOR

R.Rausa.Unpublished results

R.Rausa WCAM 2013 Suzhou

 Introduzione
Emerging applications of PIBSA and PIBSA Derivatives
Automotive field
Nanostructures in US2005/0025694 a1 US6419717 US6419717 b2
Fuels and Base oils L. Rickett. et al. (Texas A&M University)
and lubricants Thermal Conductivity Enhancement of PAO fluid using
Multi-Wall nanotubes
containing Pibsa http://reumicro.tamu.edu/activity2009/result/REU2009_Lillie_poster.
derivatives pdf.

MWNT used to Increase some peculiarities of lubricants (Thermal properties)

Thermal conductivity of base oils (PAO)

and lubricants increases in the presence of
dispersed NT

the measured conductivity enhancements, for

nanotube-in-oil suspensions are one order of
magnitude greater than those predicted by
existing theories Zhang et al.(2001)

With 1.0 vol% nanotubes in oil the increase is of

about 160%, while the enhancements predicted by
the theoretical models are not more than 10%.
Adv. Mater. 2011, 23, 2588–2601

Zhang et al. Appl. Phys. Lett. 79, 2252-2254, 2001

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Emerging applications of PIBSA and PIBSA Derivatives

Nanotubes dispersion

Picture borrowed from Internet.

Surface anchor

Solvophilic tail

Dispersant

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MWCNT + PIBS-X: Preparation of Dispersions

Sonication

Power: 400 W
Frequency : 24 kHz

Organic solution of
MWCNT PIBSI;PIBS-X

centrifugation

4000 rpm

MWNT dispersion
Calisi et al.(2013) European Polymer Journal (in Press)

R.Rausa WCAM 2013 Suzhou

PIBSA derivatives as nanotubes dispersants

Commercial nanotubes: C150 P MWCN’t

MWCNt determined
on surnatant
70

60

wt% Dispersion
50

40
30

20
10

0
PIBSI-A PIBSI-B PIBS-C

Dispersions stable after months

R.Rausa.Unpublished results

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CONCLUSIONS

PIBSA and PIBSA derivatives are a very versatile and powerful

class of amphiphilic additives

Their peculiarities permit their use in many industrial fields

and especially in the automotive field as valuable components
of lubricants and fuels

The possibilities offered by a very flexible synthetic pathway suggest

wider potentiality of the additives obtained via conversion of PIBSA in
molecules with new applications in the organic phase (e.g.
nanostructure dispersants)

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ACKNOWLEDGEMENTS

The valuable co-operation of N.Brambati and G.Merlini of the CR-SDM PROD is

acknowledged

The authors are grateful to G.Gioco and A.Pedicillo for their work on engine tests

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 THANKS FOR YOUR ATTENTION

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