A Novel Method to Determine the Chemical Composition of

Polyisobutylene-Based Oil-Soluble Dispersants by Fluorescence

Solmaz Pirouz, Yulin Wang, Michael Chong, Jean Duhamel
Institute of Polymer Research (IPR), Department of Chemistry, University of Waterloo

INTRODUCTION RESULTS Table 1. Summary of PIBSA and PIBSI Chemical Compositions

SOLUTION

14
Succinimide dispersants are among the most 1H
FT-IR
Determination of Chemical Composition Dispersants NMR GPC UV-Vis
important additives that are currently used in (Peak Height)
UFPs which are smaller than 100 nm in diameter have
engine oils. They adsorb on the surface of polar groups on their surface which are generated by the
a) Fourier Transform Infrared (FTIR)
PIBSA NSA / NIB 1:55±2 1:49±1 1:52 -
carbon-rich particles generated during engine oxidation of the oil during engine operation. In apolar oil,
Partially
hydrated CH3 1390 cm-1
operation, stabilizing them in solution, and UFPs self–aggregate into large particles (LPs, dLP= ~1 PIBSA b-PIBSI NSI / NIB 1:31±3 1:39±2 - -
consequently reducing the emission of ultrafine μm) to minimize their surface exposure to the oil.
m-PIBSI-
particles (UFPs) and the formation of sludge. NSI / NIB 1:45 1:44 - 1:55
LPs PyNH2
This research intends to characterize the dehydrated C=O 1785 cm-1
UFPs PIBSA Pirouz, S.; Wang, Y.; Chong, M.; Duhamel, J. “Characterization of the Chemical Composition of
chemical composition of a series of succinimide- Polyisobutylene-Based Oil-Soluble Dispersants by Fluorescence”, J. Phys. Chem. B 2014, 118, 3899-3911

based dispersants. The chemical composition of e) Fluorescence Measurements

polyisobutylene succinic anhydride (PIBSA) C=O 1705 cm-1

20
b-PIBSI
b-PIBSI b-PIBSI-HMDA
b-P
and a series of polyisobutylene succinimide Polar Apolar
b-PIBSI-DETA
b-P
b-P
b-PIBSI-TETA
(PIBSI) dispersants were determined by more b
b-PIBSI-TEPA
b
-P
b-PIBSI-PEHA
-P
common characterization methods such as 1H
NMR, FTIR, UV-Vis, and a procedure based on Figure 3. UFPs in the oil: (top) aggregated UFPs in the absence
of dispersant, (bottom) stabilized UFPs in the presence of
GPC analysis. Steady-state and time-resolved
dispersant
fluorescence measurements were used as a new b) Nuclear Magnetic Resonance (1H NMR)
LPs can cause sludge formation resulting in oil blockage
and unique method to determine the chemical and engine failure. Therefore, dispersants are added to the 1H 2 H O
composition of PIBSI dispersants. engine oil to minimize UFPs aggregation into LPs. 3H
O 2+3
Dispersants are typically composed of a polar head group H
n
O
1
and an oil-soluble apolar tail. The polar core of the
PROBLEMS dispersant is expected to be adsorbed onto the surface of O H H
the UFPs, whereas the apolar tail stabilizes the particle in
H H O
H
H
H
N 5 NH N H

the oil. NH NH n
n O
O 4 5
2+3
4
R
SYNTHESIS PROTOCOL 7 6 5 4 3 2 1 0 ppm
c) Gel Permeation Chromatography (GPC) SUMMARY
Figure 1. Lung failure caused by UFPs emission in to the air
2 mole equivalent
¾The chemical composition of PIBSA and PIBSI
H H O O H H
H O
H
(-1x H20) b-PIBSI PIBSA
UFPs are typically formed by the incomplete
H H
H N N
2
H
O
H2N NH2
H
n N
H m n H
dispersants were characterized quantitatively by using a
oxidation of fuel during ignition and can be
n NH O O
O m
PIBSA b-PIBSI novel characterization method
released into the air. Since releasing UFPs
Scheme 1. Synthesis of succinimide dispersants. ¾This study confirmed the existence of H-bonds between
from engines into the air can cause heart and
IP
the secondary amines of the polyamine spacer and the
lung failure, governmental regulations were
Diethylenetriamine (DETA) H2N-(CH2CH2-NH)1-CH2CH2-NH2 succinimide carbonyls of the b-PIBSI dispersants
issued to reduce their emission. This, in turn,
results in higher concentrations of UFPs in the ¾Stern−Volmer plots of the ratios I0/I and τo/τ as a
Triethylenetetramine (TETA) H2N-(CH2CH2-NH)2-CH2CH2-NH2
engine oil which leads to sludge formation. To function of the number of secondary amines showed a
prevent this phenomenon, dispersants were Tetraethylenepentamine (TEPA) H2N-(CH2CH2-NH)3-CH2CH2-NH2 linear behavior suggesting that fluorescence quenching
d) UV-Visible Spectrophotometry (UV-Vis)
g oil.
added to the engine measurements can provide a reliable measure of the
Pentaethylenehexamine (PEHA) H2N-(CH2CH2-NH)4-CH2CH2-NH2
Solid secondary amine content of a given b-PIBSI dispersant.
d-Chloloform
Hexamethylenediamine (HMDA) H2N-(CH2)6-NH2

ACKNOWLEDGMENTS
The authors thank Imperial Oil and NSERC for
Figure 2. Sludge formation caused by circulating the exhaust funding.
gas back into the oil