LUBRICATION SCIENCE Synthetic Lubrication

Lubrication Science (2011)

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/ls.166

Poly-a-olefin-based synthetic lubricants: a short review on various

synthetic routes

Saptarshi Ray*,†, Peddy V. C. Rao and Nettem V. Choudary

Corporate Research and Development Centre, Bharat Petroleum Corporation Limited, Plot-2A, Udyog Kendra,
Surajpur Industrial Area, Greater Noida, Uttar Pradesh 201306, India

ABSTRACT
This paper reviews various synthetic protocols for poly-a-olefin (PAO) synthetic lubricant base stocks
that have evolved over the years. Apart from conventional Lewis acid catalysts known for the synthesis
of poly-a-olefins, such as aluminium trichloride and boron trifluoride, several new catalysts such as
metallocenes and ionic liquids have been reported by various researchers. With increasing options of
catalytic processes available, it is now possible to produce tailor made PAOs and thus control the
properties of the end products, such as viscosity and the viscosity index. Although 1-decene is the most
widely used monomer for PAO application, researchers have used a wide range of monomers from 1-hexene
to 1-tetradecene and internal olefins in some cases. Copyright © 2011 John Wiley & Sons, Ltd.

Received 24 April 2011; Revised 16 June 2011; Accepted 21 July 2011

KEY WORDS: synthetic lubricant; group IV lube base stock; poly-a-olefin; oligomerisation catalyst; PAO

INTRODUCTION

Poly-a-olefins (PAOs) are oligomers of linear a-olefins, which are used as base stocks for synthetic
lubricants for automotive and industrial applications. Synthetic base stocks exhibit better performance
when compared with the conventional mineral base stock. Various properties such as kinematic
viscosity (KV) and viscosity index (VI), pour point (PP) and volatility (Table I), thermal and oxidative
stability, response to antioxidants and flash and auto ignition points are superior when compared with
mineral base stocks.
Since 1990s, a major driving force for the strong growth of synthetic lubes is in the automotive
sector such as synthetic automotive crankcase oils and gear oils. In addition, PAO-based synthetic
lubricants also find several niche applications in military, polymer industries, food grade applications,
cosmetics, refrigeration, textile, dielectric fluids, brake fluids, shock absorption and others. Synthetic
lubricants are more expansive when compared with conventional mineral oils. However,

*Correspondence to: Saptarshi Ray, Corporate Research and Development Centre, Bharat Petroleum Corporation
Limited, Plot-2A, Udyog Kendra, Surajpur Industrial Area, Greater Noida, Uttar Pradesh 201306, India.
†
E-mail: saptarshiray@bharatpetroleum.in

Copyright © 2011 John Wiley & Sons, Ltd.

 S. RAY, P. V. C. RAO AND N. V. CHOUDARY

Table I. Physical properties of various lubricating oils.1

Properties Group I Group III Group IV Group I Group II Group III Group IV
4.0 cSt oil 6.0 cSt oil
KV at 100 C (cSt) 3.81 3.75 3.84 6.31 5.77 5.14 5.98
KV at 40 C (cSt) 18.6 16.2 16.7 40.8 33.1 24.1 30.9
VI 89 121 124 102 116 149 143
PP ( C) 15 27 72 15 15 15 64
Flash point ( C) 200 206 213 212 220 230 235
Noack (% loss) 3.0 22.2 11.8 18.8 16.6 8.8 6.1

considerations such as performance, toxicity of the existing lubricating fluids, reduced wear and tear
and maintenance of the machineries, minimising disposal problem and satisfying the ever increasing
norms for health, safety and environmental standards are forcing the users to replace mineral base
stocks by PAOs that are superior in terms of various physicochemical properties.
Although in recent years, PAOs are facing strong challenge in the market from relatively low cost
group III lubricants and emerging gas to liquid technology; however, with the ever increasing demand
in the engine performance and stringent emission norms, demand for PAOs shall remain high in the
years to come.
Even though the worldwide use of lubricant is estimated at around 38 MTPA, its growth in USA,
Western Europe and Japan is dropping, whereas its growth in the Asia-Pacific region is robust, with
focus on India and China. Currently, the Asia-Pacific region accounts for one-third of the global
lubricant demand, and India is the fifth largest lubricant market in the world. India’s base stock
production stands at 1.1 MTPA, and the demand for various lubricants is projected to grow 4% per
annum, with one-third of it contributed by higher quality groups II and III base stocks. Expanding
automobile market in India results in the growing demand for high-quality lubricants.
The total share of synthetic lubricant in the global lubricant business is only 2.5%; however, as more
and more new application is emerging, demand for synthetic lubricants is expected to grow. The world
market for synthetic lubricant is projected to grow at an average annual rate of 2.5% per year on a
volume basis. Current worldwide volume of synthetic lubricant is ~1000 TMT in 2011.
One of the industrial practices is to market lubricants that are partially synthetic. This can be
achieved by blending the mineral base stocks, having lower KV and VI, with synthetic group IV base
stocks having superior KV and VI, resulting in a product with properties somewhere in between. A
good compilation of the properties and application of PAOs can be found in the review by Rudnick
and Shubkin.1
Synthesis of PAOs is primarily carried out through oligomerisation of linear a-olefins using
various polymerisation and oligomerisation catalysts and majority of the processes reported, using
1-decene as the monomer. However, the use of C8, C12 and C14 a-olefins are also found in the
literature. In some of the reports, mixtures of various olefins are used for the production of
PAOs. Proper choice of catalysts and the reaction conditions can produce PAOs with tailor made
properties.
This paper encompasses a literature and patent review of various synthetic protocols reported by
researchers. Even though it is not exhaustive, it discusses all the important synthetic routes for
PAO-based synthetic lube base stock.

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 PAO SYNTHESIS: A SHORT REVIEW

Synthesis of Poly-Α-Olefins

In addition to the conventional Zeigler–Natta catalytic route for the polymerisation of a-olefins,
synthesis of PAOs are carried out with a wide range of catalytic routes and reaction conditions. The
most widely studied are the Lewis acids catalysts, namely boron trifluoride and aluminium chloride.
In addition, several other catalytic routes have been discussed in the patent and published literature,
which include catalysts containing metals such as titanium, chromium, vanadium, tantalum, and
catalysts such as metallocenes, Fisher–Tropsh catalysts, clays and zeolites (ZSM-5, etc.). Examples
of catalytic routes using peroxide, ionic liquids and noncatalytic routes such as thermal polymerisation
have also been reported. Depending on the catalytic routes and reaction conditions, the properties of
the PAOs, such as KV, VI, flash point and PPs, can widely vary.

Aluminium chlorides and boron trifluoride catalysts

Aluminium chloride (AlCl3) is often used as a catalyst for a-olefin polymerisation along with a
second moiety, for example water and various alcohols (Table II). The second moiety is primarily
the co-activator that produces the active intermediate along with the liberation of the hydrogen chloride.
Hiroshi Mandai et al.2 reported the use of aluminium powder and polyester along with AlCl3 as
the catalyst mixture for the oligomerisation of a mixture of a and internal olefins, followed by
hydrogenation using Raney Nickel. The inventors demonstrated that on using aluminium powder
during the oligomerisation, halogen free PAO could be obtained. Kumar and Davis3 worked on the
polymerisation of 1-decene using a combination of AlCl3 and various alcohol proton donors, such
as methanol, ethanol, propanol, butanol and methoxyethanol. The results indicated that the viscos-
ity of the product decreased with the increased molecular weight of the alcohol. Kenneth D Hope
and coworkers in 2002 have reported polymerisation of 1-decene using a 2 : 1 mixture of AlCl3 and
trimethylamine hydrochloride as the proton donor.4 They claimed that KV at 40 C and 100 C and
VI obtained were lower when the oligomerisation was performed in the presence of a diluent (heptane)
compared with oligomerisation performed in bulk. Surana et al., in 2006, have reported the use of a
mixture of AlCl3 and deionised water to oligomerise a combination of 1-olefins in a continuous
process.5 No diluent was used during oligomerisation process. Very similar work reported by Kramer
et al. in 2007 on polymerisation of mixtures containing 1-hexene, 1-octene, 1-decene and 1-dodecene
using AlCl3 and water in the molar ratio of 1 : 0.5 as catalysts and obtained polymers of molecular
weight in the 4000–10 000 range and VI varying from 145 to 173.6
AlCl3 is also known as a very effective Fridel–Craft catalyst for the alkylation of aromatic ring using
alkyl halides or olefins. This property of AlCl3 has also been exploited by researchers in producing
high VI lube base stocks. For example, Schenach was granted a patent on the polymerisation
of 1-octene, 1-decene, 1-dodecene and 1-tetradecene in the presence of benzene or toluene.7 The
reactions were conducted at 60 C and 90 C. It was demonstrated that the VIs of products obtained
from 1-octene were relatively lower compared with other olefins. The inventors claimed the product
to be a mixture of alkylated aromatics and PAOs considering the facts that the bromine number is
lower suggesting lower concentration of olefin component but higher VI suggesting the presence of
PAOs in addition to alkylated aromatics.
Several heterogeneous aluminium chloride catalysts have been reported (Table II); for example,
Suzzy C. Ho and coworkers reported the silica supported EtAlCl2 to polymerise 1-decene with H2O

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 Copyright © 2011 John Wiley & Sons, Ltd. Table II. Aluminium chloride and boron trifluoride catalysed oligomerisation of a-olefins.
No. Reference Catalyst type
1 US 4031159 AlCl3, cocatalyst: various
polyesters such as diethyl
malonate, diethyl adipate
and diethyl succinate
2 US 5196635 AlCl3, cocatalyst: various
alcohols such as methanol,
propanol, butanol, octanol,
decanol and methoxyethanol
3 US 6395948 AlCl3, cocatalyst:
trimethylamine
hydrochloride
4 US 2006/0161034 AlCl3, cocatalyst:
DI H2O
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Reaction Polymer Product
condition microstructure properties
AlCl3, polyester and Al powder mixed Not reported KV at 100 F,
at 100 C for 1 h, followed by dropwise 47.23–90.42 cSt;
addition of 1-olefins (mixture of C6, C8 VI 124–132,
and C10, alternatively 1-octene) and hydrogenated product
reaction for 5 h. Hydrogenated using Br number 0.2–0.3
Raney Ni at 150 C for 3 h and
10 kg cm 2 pressure
1-decene oligomerised using AlCl3 Not reported Using 4 wt.% of AlCl3
S. RAY, P. V. C. RAO AND N. V. CHOUDARY
(1–6 wt.%) and various alcohols and 1.25 mol% of
(0.15–0.83 wt.%) at 25–30 C using various alcohols: KV
heptane as the diluent. Conversion at 40 C, 2140–4610 cSt;
>90% using various alcohols using KV at 100 C, 165–359
3% AlCl3 and various concentration cSt; VI 158–235
of 1-octanol
1-decene oligomerised using 2 : 1 Not reported Bulk: KV at 40  C,
ratio of AlCl3 and TMA
HCl 283 cSt; KV at 100 C,
at 22 C (monomer addition 31.6 cSt; VI 152;
at 0 C). t = 1 h, Hydrogenation PP 39 C, Noack
using Ni catalyst volatility: 1.68%
With heptane: KV at
40 C, 109 cSt; KV
at 100 C, 15 cSt;
VI 143; PP 45 C
Linear -olefins of C8–C14 range Not reported Varied properties based
oligomerised either as a single on the composition,
component or as blends using e.g. with 60/40
various %AlCl3 and reaction C12/C14, using 2.45%
condition. The products were AlCl3 add time 3 h,
dechlorinated and thermally hold time 1 h; KV at
hydrogenated over 40 C, 1234 cSt;
VI 181; PP 21 C
and with 55/45
C10/C12’ using 1.45%
AlCl3 add time 3 h,
(Continues)
 Copyright © 2011 John Wiley & Sons, Ltd. Table II.
Table 2. (Continued)

Reaction Polymer Product

No. Reference Catalyst type condition microstructure properties
hold time 1 h, KV
at 40 C, 386 cSt;
VI 152; PP 42 C
5 US 2007/0225533 AlCl3, cocatalyst: Linear α-olefins of C6–C12 Not reported High VI products using
DI H2O range oligomerised in various combinations of
various blend composition, with olefins
AlCl3 0.8–4.0%,
H2O/AlCl3 0.5 M ratio
6 US 4011166 AlCl3, benzene, Alkylation of benzene using Not reported Mixture of alkylated/

PAO SYNTHESIS: A SHORT REVIEW

1-decene/1-octene/ various olefins dialkylated aromatics
1-dodecene at 60–85 C and PAOs
7 US 5451704 Silica (calcined 1-decene oligomerisation using Molecular weight High viscosity and VI
at 600 C) H2O and methanol cocatalyst, (Mw and Mn) of (up to 150) PAOs
supported EtAlCl2 T = 24–100 C, t = 24 h, [Cocat]: heterogeneous and obtained; effect of
[Cat] = 0.5 and 1.0 homogeneous cocatalyst, particle size,
catalysts silica calcination
are similar. Slightly temperature on the PAO
broader polydispersity properties were reported
of the heterogeneous
catalyst with
respect to
homogeneous catalyst
8 US 6002060 Silica (dried at 1-decene oligomerised in presence Varied oligomer PAOs obtained with
140 C) supported of various diluents and reaction distribution high VI up to 139
AlCl3 + Et2AlCl conditions such as temperature obtained
and volume of diluent
9 US 4045508 BF3 + butanol 1-decene oligomerised in a two stage Oligomer distribution High conversion rate up
Lubrication Science (2011)

process, containing a stirred tank reported to 97.8%

reactor followed by a coiled reactor.
wt.% of butanol 0.6%, BF3
pressure 50 psig, T = 48.9 C
DOI: 10.1002/ls

10 US 4218330 BF3
2H2O α-olefin mixture containing Not reported VI in the range of

C12–C16 plus internal olefin and 13–140; PP up
vinylidene olefins oligomerised at to 30 C

(Continues)
 Copyright © 2011 John Wiley & Sons, Ltd. Table II.
Table 2. (Continued)

Reaction Polymer Product

No. Reference Catalyst type condition microstructure properties
98 C. The recycled product further
oligomerised in combination with
1-tetradecene. In another example,
C14, C14/C16 mixture and C12/C14
W
mixture were oligomerised
11 US 4400565 BF3 + Nafion C13–C14 internal olefins oligomerised Oligomeric VI up to 132 and
at 85 C for 2 h. The resulting product distribution PP < 50 C
was hydrogenated using various reported

S. RAY, P. V. C. RAO AND N. V. CHOUDARY

hydrogenation catalysts.
12 US 5068487 BF3 + alcohol 1-decene oligomerisation Oligomeric Low viscosity
alkoxylates distribution products obtained
[(RO-CHR’-CHR”-O)n-H] reported
13 US 5191140 BF3 + butanol/H2O + various 1-decene oligomerisation Oligomeric High olefin conversion
acid anhydrides distribution using both butanol and
reported acid anhydrides, VI
124–138
14 US 7592497 BF3 + 1-propanol/1-butanol/ C10, C12 and C8–C12 Not reported Low viscosity PAOs
1-pentanol mixture oligomerisation with high VI and PP
15 WO 2009/073135 BF3 + butanol + butyl acetate Mixture of tetradecene and Oligomer distribution KV at 100 C, 3.94 cSt;
C16 vinylidene oligomerised, reported KV at 40 C; VI 124;
t = 30 min, T = 43 C PP 66 C
KV, kinematic viscosity; VI, viscosity index; PP, pour point; PAO, poly-a-olefin.
Lubrication Science (2011)
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 PAO SYNTHESIS: A SHORT REVIEW

as the co-initiator.8 The surface supported species was apparently Si-O-AlCl2. Moderately high VI is
reported. Using EtAlBr2 instead of AlCl3 as the catalyst precursor showed considerably reduced con-
version. Other aspects such as the effect of cocatalyst methanol vis-à-vis water, particle size of the sil-
ica support and silica calcinations temperature were also examined. Also, reported molecular weights
of the PAOs obtained from the heterogeneous and homogenous catalysts are similar, although the mo-
lecular weight distribution of the PAOs obtained from the heterogeneous catalysts is slightly broader
compared with those obtained from the homogeneous catalysts route.
Sinha Ray et al.9 reported one silica supported catalyst consisting of mixture of AlCl3 and EtAlCl2.
Sarin et al.10 have used similar catalyst for the polymerisation of 1-decene. The inventors have indi-
cated that a mixture of aluminium chloride and organoaluminium catalyst offers a good balance of
catalytic activity and control over distribution of oligomers. Oligomerisation of 1-decene produced
base stocks of VI in the range of 138–140.
Boron trifluoride (BF3) is also a widely used catalyst for the oligomerisation of 1-olefins (Table II).
In particular BF3 has been employed for the production of low viscosity oil, suitable for low
temperature applications. Barrett L Cupples and his coworkers reported a two-stage continuous
process of 1-decene oligomerisation using BF3/butanol catalyst.11 The process included a stirred tank
reactor, the outlet of which was connected to a coiled tube reactor. It was claimed that the relative pro-
portions of various oligomers and thus the product viscosity could be controlled by this two-stage
process by controlling the percentage of conversion taking place in each stage and the total conversion.
In 1980, Shubkin reported co-oligomerisation of various long-chain a-olefins in the range of C12–C16,
internal olefins and vinylidene using BF3
2H2O catalyst, the resulting oils showing low KV and VI in
the range of 130–145.12 There are other examples of internal olefins oligomerisation using boron tri-
fluoride as the initiator. Darden and coworkers reported oligomerisation of C13–14 internal olefins using
BF3 and NafionW as the co-initiator, followed by hydrogenation. The resulting oligomers showed mod-
erate VI (e.g. 123).13 In another patent, the same research group demonstrated the oligomerisation
of a and internal olefin mixture using BF3/butanol.14 In 1991, Theriot reported oligomerisation of
1-decene using BF3 in combination with alcohol alkoxylates of formula (RO-CHR’-CHR”-O)n-H.15
Akatasu et al. reported oligomerisation of 1-octene, 1-decene and 1-dodecene, using BF3/alcohol
and/or water in the presence of various acid anhydrides.16 The inventors claimed that low-viscosity
oligomers could be obtained at high yield and less time. In some recent patents, Clarembeau reported
the co-oligomerisation of 1-decene and 1-dodecene using BF3 and various alcohols,17 and Yang and
Nandapurkar reported co-oligomerisation of 1-octene, 1-decene and 1-dodecene using BF3 plus various
alcohols, in a two-stage continuous stirred-tank reactor process. The product obtained was low-
viscosity PAOs with high VI and excellent low-temperature properties.18 The inventors have demon-
strated that a careful controlled composition of various olefins can reduce the PP of the product to a
desired level. In 2009, Bagheri and coworkers have reported oligomerisation of 1-tetradecene and
C16 vinylidene monomers using BF3/butanol in presence of butyl acetate.19 The oil obtained after
the removal of unreacted monomers and volatiles, followed by hydrogenation, showed viscosity of
3.93 cSt at 100 C and 17.3 cSt at 40 C with VI of 124 and PP of 63 C. The product thus obtained
was comparable to commercially available 4.0 cSt PAO.
Thus, it can be summarised that although AlCl3 is capable of producing high viscosity and VI base
stock (>130 and up to 200), BF3 is a preferred choice for the synthesis of low-viscosity products. The
difference can be attributed to the Lewis acid strengths of the two catalysts. BF3 being a stronger Lewis
acid, formation of the carbonium ion that initiates the oligomerisation of the olefins, should be faster,
leading to low molecular weight products.

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
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 S. RAY, P. V. C. RAO AND N. V. CHOUDARY

Chromium-based and Titanium-based catalysts

There are several reports of chromium-based catalysts for the oligomerisation of linear a-olefins
(Table III). Chromium catalysts used for this purpose are in the reduced state, most of the time supported
on the surface of an inert carriers such as silica. PAOs synthesised by chromium-based catalysts are
generally having very high viscosity and VI, often termed as HVI-PAO, and are characterised by rela-
tively lower branch ratio. Several patents reported in the late 1980s/early 1990s of using chromium-
based catalysts. In 1989, Margaret Wu described the synthesis of PAOs with high VIs and low PP.
The compositions were characterised by uniform molecular structures and low branch ratio.20 The
catalyst was prepared by anchoring a chromium precursor (chromium (II) acetate in this case) onto
the surface of silica, followed by reduction using carbon monoxide. Although the active site was not
determined, it can be considered to be supported chromium (II) species with carbonyl ligands. Detailed
studies were cited in the literature, such as the relationship between the branch ratio, silica calcinations
temperature and reaction conditions with VI of the oil produced. In the subsequent year, Wu and
Parline reported regeneration studies of the silica supported chromium catalysts for a-olefin oligomer-
isation.21 In 1993, Wu disclosed oligomerisation of 1-decene in the presence of hydrogen using the
same catalyst and demonstrated that this can control the viscosity of the products and thereby making
them suitable for lubricant applications.22 Addition of hydrogen during the oligomerisation led to
lower molecular weight and lower branching, the latter due to lowering of isomerisation. In another
patent in 1991, the same inventor disclosed a process for the oligomerisation of ethylene and propylene
using the above catalyst composition.23 In the case of propylene, the VI obtained was 78 using the sup-
ported chromium (II) catalyst, whereas the VI obtained by using AlCl3
HCl and BF3
H2O under simi-
lar conditions were 38 and 46, respectively. Oligomerisation using a combination of ethylene and
propylene in a tubular reactor yielded a VI up to 144. In 1993, Johnson et al. were granted a patent
for generating active chromium species upon synthetic layered silicate materials.24 The resulting oligo-
mers of 1-decene produced were of high VI (>190) and low PP.
Various reports of titanium-based catalysts for the oligomerisation of a-olefins have also been found
in the literature (Table III). For example, Frederick C. Loveless reported oligomerisation of 1-decene
using the titanium tetrachloride/triethylaluminium catalyst in presence of organic chlorides such as
allyl chlorides and t-butyl chloride.25 It was claimed that the presence of organic chloride controlled
the molecular weight of the resulting polymer and therefore the viscosity of the product. Using TiCl4
with Ti : Al ratio 1 : 1 and allyl chloride resulted in the product with the KV of 12.51 cSt at 100 C,
81.90 cSt at 40 C and the VI 151. While doubling the concentration of the allyl chloride with the con-
centration of TiCl4 and AlEt3 constant, the KV of the polymer changed to 39.7 cSt at 100 C and
409.53 cSt at 40 C and VI 146.
In 1992, Sanderson et al. reported oligomerisation of olefins using halogen free titanium salts and
clay, namely Engelhard Grade F2C.26 In the subsequent year, Beach et al. reported the oligomerisation
of 1-octene and 1-decene using TiCl4/AlEt3 catalyst in the presence of hydrogen.27 The resulting oli-
gomers, when blended with low-viscosity oligomers, increased the viscosity of the blends very signifi-
cantly. Sarin et al. reported a combination of AlCl3 and titanium alkoxides in 10 : 1 ratio for the
oligomerisation of 1-decene.28 It was claimed that by selecting the proper ratio of Al : Ti, the viscosity
of the resulting oligomers can be controlled.
Supported titanium catalysts have also been reported for the oligomerisation of a-olefins. In
2005, Huang et al. have reported oligomerisation of 1-decene using MgCl2-supported TiCl4 catalyst,
in combination with Et2AlCl cocatalyst.29 Effect of Al/Ti and the polymerisation time on the

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 Copyright © 2011 John Wiley & Sons, Ltd. Table III. Chromium-based and titanium-based catalysts for the oligomerisation of a-olefins.

Catalyst Reaction Product

No. Reference type condition Polymer microstructure properties
1 US 4827064 Silica-supported 1-hexene and 1-decene oligomerisation Low branch ratio reported, High viscosity and
chromium catalyst MW and MWD reported high VI up to 246
obtained
a. Continuous process: tubular reactor
b. Batch process: for
1-hexene: T = 55 C, t = 2 h; for 1-decene:
t = 16–20 h, 1-decene/catalyst ratio = 40
2 US 5264642 Silica-supported 1-hexene and 1-decene oligomerisation Low branch ratio reported Oligomerisation in the
chromium catalyst presence of hydrogen

PAO SYNTHESIS: A SHORT REVIEW

can control the
viscosity and VI
a. Continuous process: tubular reactor
b. Batch process: for
1-hexene: T = 55 C, t = 2 h; for 1-decene:
t = 16–20 h, 1-decene/catalyst ratio = 40
3 US 4990709 Silica supported Propylene and ethylene–propylene Oligomeric distribution For propylene
chromium catalyst oligomerisation: (C6–C30+) reported oligomerisation VI:
78; for ethylene–
propylene
oligomerisation in
a tube reactor VI
up to 144
a. Fixed bed reactor: T = 180–190 C,
P = 220 psig, t = 16 h,
b. Tubular reactor: T = 190 C,
P = 200–300 psig, t = 15 h
4 US 5243114 chromium catalyst 1-decene oligomerisation, Not reported High VI up to 191
Lubrication Science (2011)

supported onto T = 140–180 C, t = 16 h obtained

synthetic layered silicate
5 US 4642410 TiCl4 + allyl 1-decene oligomerisation by slow Not reported High VI up to 151
chloride/t-butyl chloride addition of catalyst (90 min) at 42 C, obtained
DOI: 10.1002/ls

+ triethyl aluminium/ followed by stirring for 15 min

diethylaluminium chloride
6 US 5146030 Sulphates of titanium/ Oligomeric distribution Not reported
(Continues)
 Copyright © 2011 John Wiley & Sons, Ltd. TableIII.
Table 3. (Continued)

Catalyst Reaction Product

No. Reference type condition Polymer microstructure properties
zirconium + clay C10 and C14 olefins oligomerised at reported
Engelhard’s grade F2C 140–160 C for 5 h
7 US 5922636 Aluminium chloride + 1-decene oligomerisation, T = 100 C, Not reported KV at 100 C 22.1; VI
titanium isopropoxide/ t = 2 h, Al : Ti ratio 21 140; PP 27 C
isobutoxide
8 European MgCl2 supported 1-decene oligomerisation in presence Oligomeric distribution at Not reported
Polymer TiCl4 + Et2AlCl of hydrogen, T = 40–80 C, t = 1 h, various conditions measured by
Journal 2005; [Ti] = 7.3  10 3 mmol, 1-decene GC–MS, microstructures

S. RAY, P. V. C. RAO AND N. V. CHOUDARY

41: 2909 20 ml, toluene 20 ml, Al/Ti = 40 characterised by 13 C NMR
MW, molecular weight; MWD, molecular weight distribution; VI, viscosity index; KV, kinematic viscosity; PP, pour point;
GC–MS, gas chromatography–mass spectrometry.
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 PAO SYNTHESIS: A SHORT REVIEW

catalytic activities and the microstructures of the oligomers using 13C NMR spectroscopy were also
discussed.
In summary, most of the reported literature on chromium-based catalysts for olefin oligomerisation
are silica-supported catalysts producing very high viscosity and VI base stocks.

Metallocenes catalysts
Metallocenes have widely been employed as catalysts for the synthesis of PAOs (Table IV, Figure 1).
Kaminsky et al. first demonstrated the use of metallocene in conjunction with methylaluminoxane
(MAO) as a highly active catalysts for ethylene polymerisation.30 Almost all the reports are based
on bridged metallocenes catalysts, as they offer lesser steric hindrance during the insertion of the
monomer to the metal centre. In 2002, Dimaio et al. have been granted a patent on the oligomerisation
of 1-decene using Ph2C(Cp-9-Flu)ZrCl2 and Ph2C(3-nBuCp-9-Flu)ZrCl2 in combination with MAO.31
Several parameters such as the effect of temperature, concentration of hydrogen and catalyst/MAO
ratio on the properties of PAOs were discussed. VI in excess of 300 could be obtained using the afore-
mentioned catalyst combination. Comparative examples were illustrated using Cp2ZrCl2, (nBuCp)
2ZrCl2, Me2SiCp2ZrCl2, rac-Et(Ind)2ZrCl2 and rac-Me2Si(2Me-Ind)2ZrCl2; in some of the cases, the
polymers obtained were not amorphous in nature and thus found not suitable for lubricant applications.
In the subsequent year, Dimaio et al. filed a patent for the copolymerisation of 1-decene and norbor-
nene.32 One interesting observation made by the authors was that the addition of norbornene during
the polymerisation can control the molecular weight and the viscosity of the resulting polymer. In
2007, Mihan illustrated trimerisation of 1-butene, 1-hexene and 1-decene using Cp2TiCl2, in combin-
ation with MAO.33 Margaret Wu also demonstrated formation of HVI-PAO by oligomerisation of
1-decene using (Me2Cp)2ZrCl2 and Me2SiCp2ZrCl2 catalysts; the viscosities as well as VIs of the re-
sulting polymers were obtained from the catalyst with substituted Cp ring being higher.34 In 2008, Wu
et al. have demonstrated blending a very high viscosity (600 cSt at 100 C) base stock obtained via metal-
locene catalysis, with a very low viscosity (4 cSt at 100 C) base stock to have an intermediate viscosity
product.35 Recently in 2009, Knowles et al. have been granted a patent on the polymerisation method
of 1-decene using Ph2C(Cp-9-Flu)ZrCl2/MAO catalyst36 and demonstrated the recyclability of the
monomer and the catalyst. Using this catalyst KV at 100 C was up to 280 cSt. In 2010, Hiroshi Fujita
reported oligomerisation of 1-decene using Cp2ZrCl2/MAO catalyst system,37 where selective dimer-
isation, trimerisation and tetramerisation of 1-decene were demonstrated. The resulting lube compos-
ition, when blended to various other additives such as VI improver, transmission fluid additives and
esters gave the VI of the resulting product up to 166. In 2009, Kissin et al. reported oligomerisation
of 1-hexene and separately 1-decene using nBuCp2ZrCl2 and MAO with Al/Zr molar ratio of 200.38
They have demonstrated that by changing the temperature from 70 C to 90 C, the percentage of dimer
increased from 60% to 71%. The dimers obtained from two cases were further polymerised using
AlCl3-supported, EtAlCl2-supported and silica-supported EtAlCl2, and the products were analysed
using gas chromatography. In a separate scheme, the authors have also shown oligomerisation of 4-
methyl-1-pentene using the aforementioned metallocene/MAO combination and post-oligomerisation
of the dimer using silica-supported EtAlCl2.
Thus, metallocenes are also capable of producing very high viscosity base stocks similar to
supported chromium catalysts. Most of the metallocenes used were bridged metallocenes with high
Cp-M-Cp angle due to the higher steric demand for the higher a-olefins.

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 Copyright © 2011 John Wiley & Sons, Ltd. Table IV. Metallocenes catalysed oligomerisation of a-olefins.
Catalyst Reaction Polymer
No. Reference type condition microstructure Product properties
1 WO 02/014384 1. Ph2C(Cp-9-Flu) C6 to C10 LAOs oligomerisation, Triad distribution, Very high KV up to
ZrCl2/MAO T = 70–150 C, P = 2000 psig pentad distribution 2400 cSt at 100 C
measured using 13C obtained and VI up
NMR to 344
2. Ph2C(3-nBuCp-
9-Flu)ZrCl2/MAO
2 WO 03/051943 Various metallocenes/ 1-decene + 2-norbornene MW, MWD, DSC Varied KV and VI,
MAO oligomerisation at 120 C, analysis reported dependent up on the

S. RAY, P. V. C. RAO AND N. V. CHOUDARY

P = 2000 psig, concentration of
2-norbornene
3 US 7279609 1. CpTiCl3/MAO 1-butene, 1-hexene, Oligomer distribution Not reported
1-decene oligomerisation, reported
T = 40 C, [Ti]/[Al] 100–500.
2. Me5CpTiCl3/MAO
3. PriCpTiCl3/MAO
[Me2NHPh]+[(C6F5)4B]
used in some examples
4 US 2007/0000807 1. (Me2Cp)2ZrCl2/MAO 1-decene polymerisation, Not reported Very high KV up to
T = 20–25 C, t = 16 h 312 cSt at 100 C
and VI = 250 obtained
2. Me2SiCp2ZrCl2/MAO
5 US 2009/0281360 Ph2C(Cp-9-Flu) Two-stage process Detailed triad and
ZrCl2/MAO pentad analysis (13 C
Stage 1: 1-decene oligomerisation, NMR), MW and
P = 300 psig, T = 150 C MWD discussed
Stage 2: crude polydecene oligomerisa-
tion, using pre-made catalyst, P = 240
Lubrication Science (2011)

psig, T = 115 C
6 US 2010/0062954 Cp2ZrCl2/MAO 1-decene oligomerisation, Selective trimerisation Not reported
[Al]/[Ti] = 10, T = 40 C, t = 20 h, and tetramerisation
hydrogenation was carried out by
DOI: 10.1002/ls

Co(acac)3 and triisobutyl aluminium

7 Journal of Applied (nBuCp)2ZrCl2/MAO Two-stage process Oligomer composition as Not reported

(Continues)
 Copyright © 2011 John Wiley & Sons, Ltd. Table
TableIV.
4. (Continued)

Catalyst Reaction Polymer

No. Reference type condition microstructure Product properties
Polymer Science a function of reaction
2009; 111: 273–280 condition reported
Stage 1: 1-hexene or 1-decene or
4-methyl 1-pentene oligomerisation,
T = 40–100 C, [Al]/[Zr] = 200,
scavenger iBu3Al, t = 4 h
Stage 2: dimers and trimer products
oligomerised using AlCl3, EtAlCl2
and silica-supported EtAlCl2

PAO SYNTHESIS: A SHORT REVIEW

LAO, linear a-olefin; KV, kinematic viscosity; VI, viscosity index; MAO, methylaluminoxane; MW, molecular weight; MWD, molecular weight distribution; DSC, dif-
ferential scanning calorimetry.
Lubrication Science (2011)
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 S. RAY, P. V. C. RAO AND N. V. CHOUDARY

Figure 1. Various metallocene structures.

Ionic liquid catalysts

In the recent years, there have been several reports on oligomerisation of a-olefins using ionic liquids
(Table V). One advantage, as indicated by various researchers, is that the oligomerisation can be per-
formed with the use of any diluent. In 2002, Kenneth D. Hope and coworkers reported oligomerisation
of 1-decene using the binary catalyst composed of aluminium trichloride and trimethylamine hydro-
chloride in 2 : 1 ratio.39 They have claimed that the use of this catalyst composition is ‘particularly ad-
vantageous due to ease of preparation, ready commercial availability of the components, and the
relatively low cost’. KV of 31.6 cSt at 100 C and 283 cSt at 40 C with VI of 152 and PP of 39 C
could be obtained when the oligomerisation was performed in the absence of any diluent. With the
addition of heptane as diluent, a substantial drop in the viscosity values (15 cSt at 100 C and
109 cSt at 40 C) and the VI (143). However, there was a reduction in the PP ( 45 C). In 2004,
Kenneth D. Hope with another group of coworkers was granted two separate patents on the subject.
The first one described preparation of the ionic liquid AlCl3
TMA
HCl in 2 : 1 M ratio40 that was pre-
sumably used for the oligomerisation processes in the subsequent patent.41 In this, oligomerisation of
1-decene and 1-dodecene at different temperature and catalyst concentration were also reported. Both
batch and continuous processes were discussed, and detailed distributions of various oligomeric
products were illustrated. Viscosity and VI data were provided in the case of oligomerisation of 1-
dodecene in the continuous mode.
Saleh Elomari and coworkers of have reported the use of 1-butylpyridinium chloroaluminate for the
oligomerisation of 1-decene and mixture of 1-hexene, 1-octene and 1-decene.42,43 In a second step, the
resultant oligomers were alkylated using isobutane. The olefinicity of the oligomer was reduced, and
percentage of the low boiling cuts increased. In a recently filed patent, the same group of researchers

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 PAO SYNTHESIS: A SHORT REVIEW

Table V. Ionic liquids catalysed oligomerisation of a-olefins.

Catalyst Reaction Polymer Product

No. Reference type condition microstructure properties
1. US 2002/ AlCl3 + Me3NH+Cl 1-decene added dropwise Not reported KV at 40 C, 283 cSt;
0128532 to the catalyst at 0 C and KV at 100 C,
temperature raised to 22 C. 31.6 cSt; VI 152;
Time 1 h, hydrogenation PP 28 C: Noack
using Ni catalyst 1.68%
Addition of heptane:
VI 143
2. US 2004/ Me3N + HCl + AlCl3 1-decene or 1-dodecene Oligomeric Very high VI up to
0030075 oligomerised at various distribution, 172 reported
temperature MW and
MWD reported
3. US 2007/ N-butylpyridinium Oligomerisation of 1-decene, Detailed TBP Very high VI up to
0142684 chloroaluminate followed by alkylation using cuts reported 191 reported
isobutene. Oligomerisation of
1-decene in the presence
of isobutene, and
oligomerisation of 1 : 1 : 1
mixture of 1-hexene, 1-octene
and 1-decene
KV, kinematic viscosity; VI, viscosity index; PP, pour point; MW, molecular weight; MWD, molecular weight distribution;
TBP, true boiling point.

have reported alkylation of 1-decene with isobutane and oligomerisation of 1-decene in varying con-
centration of isobutane.44

Synthetic zeolites catalysts

Several zeolite-based catalysts have been extensively reported for the oligomerisation a-olefins
(Table VI). Patents can be found as early as 1976 when Edwin N. Givens used HZSM-5, Cr–ZSM-
5 and Zn–ZSM-5 for the oligomerisation of propylene.45 In 1983, Stephen J. Miller evaluated various
catalysts for the hydrogen transfer reaction, which include ZSM-5, Zn–ZSM-5, silicalite, ultrastable-Y,
dealuminated mordenite, and have concluded that the catalyst with minimum hydrogen transfer ability
should be best suited for oligomerisation of olefins.46 The researcher also demonstrated Zn–ZSM-5
containing 0.8% Zinc for the oligomerisation of various olefins. VI obtained in the case of oligomer-
isation of 1-decene and 1-tetradecene mixture was 105.
Various researchers concluded that a two-stage process, in which lower olefins in the range of
C2–C6 should be oligomerised in the first stage, produce oligomeric intermediates that can be further
oligomerised to produce high VI products. Catalysts such as ZSM-5 and ZSM-22 were of particular
interest for first stage of such processes. Chen and Tabak patented such a process in which an olefinic
feedstock containing 27% propylene, 36.1% butene, 10.7% propane and 26.1% butane was first
reacted with HZSM-5, which is previously pre-treated with 2, 6-(tert-butyl)-pyridine.47 The authors
have proposed a model for the oligomerisation of propylene, which include simultaneous oligomerisa-
tion, isomerisation and interpolymerisation (Figure 2). The purpose of treating the HZSM-5 with a
bulky amine is to prevent the amine to enter into the channels of HZSM-5 and thereby selectively

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 Copyright © 2011 John Wiley & Sons, Ltd. Table VI. Zeolites catalysed oligomerisation of a-olefins.
Catalyst Reaction Polymer Product
No. Reference type condition microstructure properties
1. US 4417088 Zn–ZSM-5 Mixture of 1-decene and 1-tetradecene Not reported VI 105, PP 6.7 C
oligomerised at 232 C, hydrocarbon
pressure 27.2 bars, LHSV 1. 329 C
fraction hydrofinished
2. US 4568786 HZSM-5 treated with 2,6-t-butyl- Two-stage process, stage 1: C3–C4 Not reported Moderate VI up to
pyridine, BF3/butanol olefinic feedstock reacted to HZSM-5, 119 could be
WHSV 0.4, P = 1000 psig, stage 2: obtained
C9–C18 fraction of the stage 1 reacted

S. RAY, P. V. C. RAO AND N. V. CHOUDARY

to BF3/
butanol at 0–5 C
3. US 5026933 HZSM-23 extrudate (35% Oligomerisation of propylene and Effect of temperature, C15 fraction oligo-
alumina binder); pre-treated 1-butene, under various conditions, pressure, zeolite pre- merised using BF3/
with 2, 6-t-butyl-pyridine and T = 160–225 C, P = 250–1250 psig treatment on the C12 H3PO4: 75 wt.% of
2, 4, 6-collidine in some selectivity, methyl C = 25 fraction
examples branching and oligomer obtained whose
distribution reported VI = 128 and KV
at 100 C, 8.2 cSt
4. US 2009/0093663 HZSM-22 pre-treated with Propylene and 2-butene Effect of oligomeric Not reported
collidine or oxides of yttrium oligomerisation using untreated and distribution on changing
and lanthanum variously treated ZSM-22 extrudated the catalyst reported
using alumina binder in a fixed bed
reactor
5. US 5243112 ZSM-22 (SAR 70) Propylene oligomerisation; Not reported KV at 40 C,
T = 200–235 C, t = 4 days 9.83 cSt; KV at
100 C, 2.57 cSt;
VI 85.7
6. US 5134243 Ultra large pore MCM-41 Propylene and 1-decene Greater trimer and Not reported
Lubrication Science (2011)

oligomerisation, T = 96 C, tetramer selectivity,

P = 500 psig compared with ZSM-5
and ZSM-23
7. US 5714661 Y-zeolite, normal (SAR 4–5) Various olefin–paraffin petroleum Not reported KV at 100 C in
DOI: 10.1002/ls

and super-dealuminated fractions (de-aromatised) oligomerised the range of

(SAR 10–80) 5.29–2.02 cSt

(Continues)
 Copyright © 2011 John Wiley & Sons, Ltd. Table
TableVI.
6. (Continued)

Catalyst Reaction Polymer Product

No. Reference type condition microstructure properties
at T = 160–180 C, t = 3–8
hydrogenated by Pd–C catalyst
8. US 2001/0004972 1. Zn–ZSM-5 Oligomerisation of several olefin Dimer selectivity for Of the C10 + C15–20
fractions (e.g. C10 + C15–20 fractions various catalysts in case oligomerisation
oligomerised at 300 psig, 450 F, of 1-decene reported products
2. Ni–ZSM-5 0.25 LHSV, 200 h)Oligomerisation 700–800 F
of 1-decene using 1% Et3Al2Cl3/ fraction: KV at
Ni–ZSM-5, SAPO-11, 40 C, 11.21 cSt;
montmorillonite, MCM-41 KV at 100 C,

PAO SYNTHESIS: A SHORT REVIEW

and MCM-22 2.97 cSt; VI 120
3. Et3Al2Cl3/Ni–ZSM-5 800 F+ fraction:
KV at 40 C,
49.98 cSt; KV at
100 C, 8.41 cSt;
VI 144
4. SAPO-11
5. Montmorillonite
6. MCM-41 and MCM-22
KV, kinematic viscosity; VI, viscosity index; PP, pour point; WHSV, weight hourly space velocity; LHSV, liquid hourly space velocity.
Lubrication Science (2011)
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 S. RAY, P. V. C. RAO AND N. V. CHOUDARY

Figure 2. Oligomerization model of propylene using HZSM-5 as proposed by Chen et al.47

block the surface acidic sites. Oligomerisation was thus taking place inside the channels, resulting in
the production of linear hydrocarbon chains. The final conformations of the polymer molecules were
influenced by the pore structures of the catalysts. For the higher carbon numbers, the structures are es-
sentially methyl-branched straight olefinic chain with the maximum chain length determined by the
pore dimension. In the second stage of the process, the product obtained from the first stage was
reacted in presence of unmodified HZSM-5. The process is slow, and after 236.7 h, 31% of conversion
could be obtained with VI of the product being 120. In another example, the second stage of oligomer-
isation was performed using BF3. Catherine Chen and Margaret Wu have demonstrated that relatively
low VI product obtained from such two-stage processes can be blended with high VI base stock to pro-
duce intermediate VI base stocks.48
Blain et al. reported the use of ZSM-23 for the oligomerisation of propylene and 1-butene.49 High
C12 selectivity could be obtained in case of propylene, and the methyl branching index for the same
was very low, which signifies that the oligomerisation predominantly took place inside the pores of
the zeolites. In another example, the surface of the ZSM-23 was treated with bulky amines such as
2, 6-(tert-butyl)-pyridine and 2, 4, 6-collidine before the oligomerisation of propylene that led to the
significant drop in the C12 selectivity. The C15 fraction obtained from ZSM-23 oligomerisation was
further oligomerised using BF3/phosphoric acid, and the resulting product contained 75% of the C25

+ fraction. The VI of the product was 123, and the KV at 100 C was 8.2 cSt. In 2009, Cheng et al.
reported use of ZSM-22 surface treated with oxides of yttrium and lanthanum for the oligomerisation
of propylene and 2-butene.50 The results indicated that the dimer selectivity in both the cases was high
using the oxide-treated ZSM-22 compared with ZSM-22 deactivated with collidine and low branching
when compared with untreated ZSM-22. In 1993, Chester et al. reported propylene oligomerisation
using ZSM-22.51 During the same time, Bhore et al. reported oligomerisation of propylene and 1-
decene using acidic MCM-4152 and claimed higher activity and higher trimer and tetramer selectivity
compared with ZSM-5 and ZSM-23. In 1998, Tuli et al. have reported the formation of synthetic lu-
bricant base stocks using various types of Y Zeolites,53 namely as-synthesised Y zeolites with SiO2/
Al2O3 ratio in the range of 4.0–5.0, dealuminated as well as ‘super-dealuminated’ Y zeolites whose
SiO2/Al2O3 ratio is >10 and up to 80. Various olefin fractions have been oligomerised using the afore-
mentioned zeolites and viscosity of 2.51–5.29 cSt could be obtained at 100 C with high degree of con-
version in some cases.
Recently, there have been a few reports on the oligomerisation of higher a-olefins, using various
zeolites. Stephen J Miller and coworkers reported oligomerisation of C10 and C15–20 cuts using Zn–
ZSM-5 (1% Zn) at 300 psig, 450 F and 0.25 liquid hourly space velocity.54 After 200 h, the 700 F+
product was removed, and the catalyst was rejuvenated by stripping with hydrogen, and the run
restarted using the 625 F fraction. The product was hydrogenated and fractionated at 700–800 F

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
DOI: 10.1002/ls
 PAO SYNTHESIS: A SHORT REVIEW

and 800 F+ fractions. In the same patent, the inventors have demonstrated the oligomerisation of 1-
decene using 1% Et3Al2Cl3 in Ni–ZSM-5 and various other catalysts, namely SAPO-11, pillared
and acidic clays and mesoporous aluminosilicates such as MCM-41 and MCM-22.
In 2007, Marja Tiitta and coworkers have been granted a patent on oligomerisation of 1-decene and
1-hexadecene using zeolites Y and zeolite Beta and mesoporous MCM-41.55 They have demonstrated
that by using the zeolite Y, high percentage of dimer selectivity could be obtained.

PAOs from refinery streams and feedstock

It has been the endeavour of an oil refiner to add value to its various streams. Accordingly, there are
several reports of using refinery feedstocks for the production of lube base stocks; for example, Sarin
et al. reported using refinery stream containing 20% a-olefins in the carbon number range of C9 to C13,
2% internal olefins and the balance paraffin.10 Polymerisation was conducted at 120 C using silica-
supported catalysts containing 5 wt.% of AlCl3 and 30 wt.% of Et2AlCl. The product was filtered
through alumina, and the paraffin distilled off. The oligomeric mixture thus obtained containing
25% dimer, 41% trimer, 17% tetramer, 17% pentamer with an overall conversion of 99%. The product
PAO, after hydrogenation, had VI of 138 and PP of 45 C. By adding extra Et2AlCl and by reducing
the temperature to 100 C, the VI was improved to 141.
Chen and Tabak in their patent (see previous section) have used an olefinic stream containing a mix-
ture of propylene, butene, propane and butane and cofed with a gasoline recycle to a fixed bed reactor
for oligomerisation.47 Although it is not explicitly mentioned that a refinery stream was used, the feed
indeed resembles refinery streams. Similarly, Miller et al. have reported the use of C10 and C15–20 cuts
from wax thermal cracker.54 In our laboratory at Bharat Petroleum R&D centre, lab scale experiments
were conducted using olefin rich streams from cracker units, and the results are promising. The pro-
ducts obtained showed properties similar to PAOs obtained from modified silica supported catalysts
(internal report).

CONCLUSIONS

As discussed in this review, a large variety of processes are available for the synthesis of poly-a-
olefins. Although majority of the reports, both in patent and published literature, have used 1-decene
for the synthesis of PAO-based lube base stocks, several other monomers have also been successfully
used for the same purpose, starting from propylene to tetradecene. Several catalytic systems were used
for oligomerisation of a-olefin, namely Lewis acids such as aluminium chloride and boron trifluoride,
metallocenes, ionic liquids and synthetic zeolites. On the basis of the choice of the catalysts, the prop-
erties of the products can be fine tuned, e.g. low viscosity/VI product using BF3
2H2O to very high
viscosity/VI products using metallocene and heterogeneous chromium (II) catalysts. Also, by proper
choice of catalysts and the reaction conditions, the polymeric microstructure of the product can also
be controlled, e.g. low branch ratio in the case of supported chromium catalysts and linearity in case
of surface poisoned HZSM-5. There are several reports of two-stage processes where in the first stage,
a linear olefin is obtained using oligomerisation catalyst, which can be further oligomerised to produce
high viscosity products.
In the years to come, PAOs may face technical challenges from the base oils produced from other
emerging technologies, e.g. ‘ultraperformance’ base oil from the wax produced via Fisher–Tropsh

Copyright © 2011 John Wiley & Sons, Ltd. Lubrication Science (2011)
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 S. RAY, P. V. C. RAO AND N. V. CHOUDARY

route and group III base stocks derived from various hydroprocessing technologies. However, in
the scenario of spiralling crude oil prices, PAOs will certainly be a technocommercial option for
refiners to explore and gear up to face future challenges. It is also imperative that PAOs find different
niche areas due to growing application areas and increasing demand from customers in terms of
improved properties.

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