675
ISSN 1560-0904, Polymer Science, Series B, 2016, Vol. 58, No. 6, pp. 675–680. © Pleiades Publishing, Ltd., 2016.
Poly(n-octyl methacrylate) Viscosity Index Improver:
Kinetic Study via On-line
1
H-NMR Technique
1
Seyed Mehrdad Jalilian
a
, Hassan Farhadnejad
b
*, Farshid Ziaee
a
,
Behrouz Furughi Nia
c
, Hossein Abdollahi
a
, and Vahid Najafi
a
a
Iran Polymer and Petrochemical Institute, Tehran, 14975-112 Iran
b
Students’ Research Committee, Department of Pharmaceutics and Pharmaceutical Nanotechnology,
School of Pharmacy, Shahid Beheshti University of Medical Sciences, Tehran, Iran
c
Dezful University of Medical Sciences, Dezful, Iran
*e-mail: farhadnejad123@gmail.com
Received January 27, 2016;
Revised Manuscript Received June 24, 2016
Abstract– The free radical solution polymerization of n-octyl methacrylate has been studied in benzene-d
6
in
the presence of 2,2'-azobisisobutyronitrile as thermal initiator. An on-line nuclear magnetic resonance spec-
troscopy was applied to record the reaction data and to determine the monomer conversion at different times
during the polymerization reaction. Effect of monomer and initiator concentration as well as reaction tem-
perature on polymerization rate was studied. The order of the reaction with respect to initiator (0.45) was con-
sistent with the classical kinetic rate equation, while the order of reaction with respect to monomer (1.87) was
much greater than unity. An overall activation energy (E
a
= 53.8 kJ/mol) was obtained over the temperature
range 328−338 K. Also, the efficiency of the synthesized poly(n-octyl methacrylate) for improving the vis-
cosity index of the lube oil was investigated.
DOI: 10.1134/S1560090416060087
INTRODUCTION
Modern lubricants were formulated by using the
base oils and chemical additives. The lubricant creates
a separating fluid layer between moving surfaces and
keeps friction at a low level. Many properties of the
lubricants are improved or created by addition of spe-
cial chemical additives to the base oil. Chemical addi-
tives used in the lube oils may be classified as: viscosity
index improver [1], pour point depressant [2], antiox-
idant [3], corrosion inhibitor [4], extreme pressure
agent [5], etc. Viscosity index improvers are liner, long
chain, high molecular weight and oil soluble polymers
that applied to resist the variation of viscosity the base
oil by enhancing the relative viscosity of oil more at
high temperatures than at low temperatures [6–9].
The efficiency of viscosity index improvers is often
expressed in terms of viscosity index, which is an arbi-
trary scale that shows the extent of changes in viscosity
with changes of temperature [10]. The efficiency of
polymers as viscosity index improvers depends on the
behavior of the polymer chains in the oil solution such
as polymer solubility, molecular weight, concentra-
tion and structure of polymer and resistance to shear
degradation [9].
The increase in the temperature of lube oil make to
reduce its viscosity, but the polymer molecule expands
because of the increase in the solvation power and
thus, the size of micelle enhances. It counterbalances
the reduction in the lube oil viscosity and, therefore,
makes to decrease the change in the viscosity with the
temperature. The process of coil expansion is entirely
reversible [11–13]. For this purpose, homopolymers
and copolymers of n-alkyl acrylates and methacrylates
are often applied as pour point depressants or flow
improvers, viscosity index improvers in crude and
lubricating oils and etc. [14, 15]. One of the most
important oil-soluble and synthetic polymers based
on alkyl methacrylate is poly(n-octyl methacrylate).
On the other hand, one of the most important effec-
tive factors on viscosity index is molecular weight of
polymer [11–13]. Thus, according to the very high
importance of poly(n-octyl methacrylate) and its
copolymers as polymeric additives for lube oil, it is
necessary to study its polymerization kinetic precisely,
to optimize the polymerization process and control
the characteristics (molecular weight and molecular
weight distribution) of the final product.
There are several methods for kinetic studies of
radical polymerization of vinylic monomers, in which
one of the reaction varying factors have been followed
as continual. The most usual methods can be summa-
1
The article is published in the original.
SYNTHESIS