3 Polyalphaolefins

Ronald L. Shubkin
Polyalphaolefin (PAO) fluids are synthetic hydrocarbons designed to provide superior lubri-
cation performance over a wide temperature operating range.1 They are manufactured by a
two-step process from linear alpha-olefins, which are themselves produced from ethylene.
The first synthesis step entails oligomerization, which simply means a polymerization to rel-
atively low molecular weight products.

alpha-Olefin → Dimer + Trimer + Tetramer + Pentamer, etc.

For the production of low-viscosity (2 to 10 cSt @ 100°C) PAO fluids, the catalyst for
the oligomerization reaction is boron trifluoride. The BF3 catalyst is used in conjunction with
a protic co-catalyst such as water, an alcohol, or a weak carboxylic acid. The BF3· ROH cata-
lyst system is unique because of its ability to form highly branched products with the
oligomer distribution peaking at the trimer. High-viscosity (40 and 100 cSt @ 100°C) PAO
fluids are manufactured using Ziegler-Natta catalysts such as alkylaluminum compounds in
conjunction with organic halides.
The second step in the manufacturing process is hydrogenation of the unsaturated
oligomer to enhance chemical inertness and oxidative stability. The reaction is carried out
over a metal catalyst such as nickel or palladium. Distillation of the reaction mass to give spe-
cific product cuts may be done before or after hydrogenation.
One distinct advantage in the manufacture of PAO fluids is that they can be “tailor-
made” to fit end-use requirements by manipulation of reaction variables which include:2

• Chain length of olefin raw material

• Temperature
• Time
• Catalyst and co-catalyst type and concentration
• Distillation of final product.

Although choice of starting olefin can exert a major influence on product properties,
commercial PAOs are generally derived from 1-decene to provide the broadest range of
operational temperature.
The following tables list properties of various grades of commercial decene-derived PAO
base fluids.3 The widely used convention for designating the PAO grade is to use the kine-
matic viscosity (KV) in centistokes (cSt) at 100°C. In other words, a PAO fluid with KV100°C
of approximately 2 cSt would be referred to as PAO 2. Differences in properties among the
various grades illustrate what can be accomplished by manipulation of the reaction parame-
ters. Some products are coproduced and separated by distillation. The properties listed in
Tables 1 to 5 are typical of base fluids currently available; they do not represent the specifi-
cations of any particular producer and do not include property enhancements that can be
obtained by the proper choice of additives.
Copyright © 1997 CRC Press, LLC.

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1997 by CRC Press LLC
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REFERENCES

1. Shubkin, R. L., Polyalphaolefins, Synthetic Lubricants and High-Performance Functional Fluids Shubkin,
R. L., Ed., Marcel Dekker, New York, 1992, 1–40.
2. Shubkin, R. L. and Kerkemeyer, M. E., Tailor Making PAOs, 7th Int. Colloq. Automotive
Lubrication, Technische Akademie Esslingen, Federal Republic of Germany, January 16–18, 1990;
also, J. Synth. Lubr., 8(2): 115–134, 1991.
3. Shubkin, R. L., Polyalphaolefins, CRC Handbook of Lubrication and Tribology, Vol. 3, Booser, E. R.,
Ed., CRC Press, Boca Raton, FL, 1994, 219–252.

Copyright © 1997 CRC Press, LLC.

 40 Tribology Data Handbook

Copyright © 1997 CRC Press, LLC.

 Polyalphaolefins 41

Copyright © 1997 CRC Press, LLC.