Journal of Oleo Science

Copyright ©2015 by Japan Oil Chemists’ Society

doi : 10.5650/jos.ess14162
J. Oleo Sci. 64, (2) 143-151 (2015)

Palm Oil Derived Trimethylolpropane Triesters

Synthetic Lubricants and Usage in Industrial
Metalworking Fluid
Teck-Sin Chang1, Robiah Yunus1, 2＊ , Umer Rashid2, Thomas S.Y. Choong1,
Dayang Radiah Awang Biak1 and Azhari M. Syam2, 3
1
‌Department of Chemical and Environmental Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor,
Malaysia.
2
Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
3
Department of Chemical Engineering, University of Malikussaleh, Lhokseumawe 24351, Indonesia.

Abstract: Trimethylolpropane triesters are biodegradable synthetic lubricant base oil alternative to mineral
oils, polyalphaolefins and diesters. These oils can be produced from trimethylolpropane (TMP) and fatty
acid methyl esters via chemical or enzymatic catalyzed synthesis methods. In the present study, a
commercial palm oil derived winter grade biodiesel (ME18) was evaluated as a viable and sustainable
methyl ester source for the synthesis of high oleic trimethylolpropane triesters (HO-TMPTE). ME18 has
fatty acid profile containing 86.8% oleic acid, 8.7% linoleic acid with the remaining minor concentration of
palmitic acid, stearic acid and linolenic acid. It’s high oleic property makes it superior to produce synthetic
lubricant base oil that fulfills both the good low temperature property as well as good oxidative stability.
The synthetic base oil produced had a viscosity of 44.3 mm2/s at 40℃ meeting the needs for ISO 46 oils. It
also exhibited an excellent viscosity index of 219 that is higher than some other commercial brands of
trimethylolpropane trioleate. Properties of base oil such as cloud point, density, acid value, demulsibility
and soap content were also examined. The oil was then used in the formulation of tapping oil and appraised
in term of adaptability, stability and field test performance.

Key words: TMP ester, renewable, biolubricant, calcium methoxide, straight oil

1 INTRODUCTION applications where the lubricants will be likely to leak into

Lubricant base stocks in the market primarily comprise
mineral oil-based, polyalphaolefins（PAO）, polyalkylene
glycols（ PAG）and other petrochemical origin synthetic
esters1）. Lubricant finished products applied in automotive,
industry, marine etc. typically contain approximately
70-99％ of base stocks in its’formulations. The world lu-
bricant consumption was 38.7 million metric tons in 20122）
while Freedonia Group, US estimated the lubricant con-
sumption growth rate to be at 2.5％ per year having 42.3
million metric tons in 20173）. Conversely, the biodegradable
lubricant usage in the European market was estimated only
121,796 tons in 20064）. Due to the potential environmental
impact by these lubricant oils, environmental friendly
nature biodegradable lubricant base stocks are essential as
the substitute of the currently predominant non-biode-
gradable mineral-based base stocks, especially for those
the environment, i.e. marine, agriculture, metalworking
etc. Among the commonly used biodegradable lubricant
base stocks are from vegetable oils, low molecular weight
（DE）
PAOs, PAGs, dibasic acid esters （PE）
and polyol esters 1）
.
PE is derived synthetically by the reaction of fatty acids
and polyhydric alcohols（also known as polyol）. Examples
of commonly utilized fatty acids are palmitic acid（C16:0）,
stearic acid（C18:0）, oleic acid（C18:1）etc. and polyols are
trimethylolpropane（TMP）, neopenthylglycol（NPG）, pen-
taerythritol（PET） etc. These fatty acids are the products of
oleochemical industries, usually obtained from vegetable
oils like soybean, sunflower, rapeseed, palm etc. PE have
relatively good thermal and hydrolytic stability as com-
pared to its’natural vegetable oils form due to the elimina-
tion of β-carbon after the substitution of glycerol molecular
backbone with polyol. PE appears in either solid or liquid

＊
Correspondence to: Robiah Yunus, Institute of Advanced Technology, University Putra Malaysia, 43400 UPM Serdang, Selangor,
Malaysia.
E-mail: robiah@upm.edu.my
Accepted September 26, 2014 (received for review July 24, 2014)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/  http://mc.manusriptcentral.com/jjocs

143
 T.-S. Chang, R. Yunus, U. Rashid et al.
form depending on the degree of –OH group substitution
on the polyols and the type of the reacted acids. PE are
classified as Group V base oils under the American Petro-
leum Institute（API）base oil classifications, mostly pro-
duced for aircraft turbine lubricants and hydraulic oils uses
due to the good flow ability at extreme temperature condi-
tions and good stability features. TMP triesters are among
the PE of interest in the lubricant industry for its’wide
viscosity range, high flash point and fire retardant attri-
butes. The fatty acids being considered most in the synthe-
sis of TMP triesters are pure caprylic acid5）, oleic acid6）,
rapeseed oil7）, olive oil7）, animal fats7）, palm oil8）, rubber
seed oil9）etc.
The oil palm（Elaeis guineensis）is one of the palm
species under Arecaceae family and Arecoideae subfamily.
Malaysia & Indonesia are currently the world’ s primary
producers as well as exporters of the palm oil products. Oil
palm has the highest oil yield as compared to other oil
crops having a 5 to 10 times better in term of oil yields per
hectare10, 11）, consequently it is currently the most produc-
tive oil source plant species known. Palm oil extracted
from the oil palm mesocarp as well as the oil palm kernel
are extensively used in the oleochemical industries due to
it’s wide fatty acid components ranging from C12 to C24.
Palm oil typically comprises 0.1-0.4％ lauric（C12:0）, 0.7-
1.2％ myristic（C14:0）, 36.7-42.4％ palmitic（C16:0）, 0.1-
0.3％ palmitoleic（C16:1）, 3.3-6.6％ stearic（C18:0）, 46.1-
47.0％ oleic（C18:1）, 5.3-8.6％ linoleic（C18:2）and trace
amount of linolenic（C18:3） and C20-C2412, 13）. Having an ap-
proximately 50-50％ mix of C16 and C18:1, it can be used
as it is in a fatty acids mix or can be processed and frac-
tionated into high cuts, low cuts, saturated or unsaturated
fatty acid fractions. Hence, palm oil has a great advantage
in the biofuels and biolubricants production due to it’ s Palm oil-based winter grade biodiesel（ME18）was ob-
flexibility in making into products with different grades and
application for either tropical or temperate climates. More-
over, it is a perennial tree crop that produces oil all year
round unlike the other annual oil crops like corn and soy
ensuring a consistent supply of raw materials for the indus-
tries uses.
The synthesis of TMP triesters has been reported earlier
via esterification and transesterification synthesizing
methods. Esterification synthesis method involves TMP
and fatty acids using acid catalysts. One of the common
acids used is p-toluene sulfonic acid14）. Transesterification
synthesis employs TMP and methyl esters, can be cata-
lyzed using either enzymatic biocatalysts or base （alkaline）
chemical catalysts. Candida rugosa lipase 15）, Candida
sp.5） and Rhizomucor miehei lipase16） were used as bio-
catalysts whereas sodium methoxide8, 15） calcium methox-
ide7, 17） and organotin18） were used as base chemical cata-
lysts in the synthesis of TMP triesters. TMP triesters cater
the viscosity range of 20-100 mm2/s, more commonly at ap-
proximately 46 mm2/s measured at 40℃ which is known as
144
J. Oleo Sci. 64, (2) 143-151 (2015)
ISO 46 oils or TMP trioleate（TMPTO）. It is currently pro-
duced by a few renowned oleochemicals producers, among
these companies are OLEON, UNDESA and Liacheng
Rujie. Yunus8）studied the potential of palm oil methyl ester
in synthesizing TMP trioleate equivalent synthetic ester
base stock. However, lubricant market forces demand for
low pour point TMP triesters due to the lubricant blending
and adaptability requirements for marketing in cold climate
countries. Therefore, Yunus 19） had also attempted to syn-
thesis TMP triesters with high oleic content from fraction-
ated high oleic methyl esters and achieved a pour point of
＜−30℃ while maintaining the viscosity as well as other
properties. High oleic methyl ester is available commercial-
ly and commercialized as winter grade biodiesel（Carotino
company, Malaysia）. This biodiesel could be an acceptable
material for producing TMP triesters and hence move up
it’s value chain to a more valuable synthetic lubricant
product. Furthermore, this biodiesel would also provide a
more sustainable and viable raw material for this purpose
as it is already a well established commodity in the market.
The objective of the present work was to explore the
utility of ME18 as the raw material for synthesizing high
oleic TMP triesters（HO-TMPTE）. The key characteristics
and physical properties of HO-TMPTE were determined
and compared with the commercial TMPTO products. The
tapping oil formulations were prepared with HO-TMPTE
and tested to examine its adaptability and performances as
metalworking lubricant.
2 EXPERIMENTAL
2.1 Chemicals and Materials
tained from Carotino Sdn. Bhd. Trimethylolpropane （TMP）
（assay ＞98％）purum grade and calcium methoxide
powder（97％）were purchased from Sigma Aldrich Sdn.
Bhd.（Malaysia）. The additives used in the formulation of
tapping oil were BD-0908 from DRD Additives, LLC; Syn-
Ester TM SE-115, Syn-Ester TM GY-25, Lubrizol ® L5333,
ADDCOTM 360-P and SKOSANORTM KSP-93 from Lubrizol
Corporation. BD-0908 is a proprietary mixed esters incor-
porated with boron nanoparticles with multipurpose func-
tions as friction modifier, anti-wear（AW）as well as extreme
pressure（EP）additive. SE-115 is a high molecular weight
polymerized ester containing 15％ w/w of sulfur used as
EP additive. GY-25 is also a high molecular weight polymer-
ized ester used as EP additive. It is an ideal replacement
for common EP used in metalworking industries like sulfur
and chlorine as quoted in the GY-25 product data sheet.
Lubrizol ® L5333 is a sulfurized vegetable oil containing
10％ w/w of active sulfur used as lubricity improver. 360-P
is n alkyl phosphate EP and AW additive. KSP-93 is a tri-
azole derivative used as metal passivator that prevents
 Palm Oil Derived Trimethylolpropane Triesters Synthetic Lubricants and Usage in Industrial Metalworking Fluid
staining of the yellow metals（metals containing copper）
during metal processing at high temperature.
2.2 Preparation of HO-TMPTE
HO-TMPTE was prepared via transesterification reaction
using calcium methoxide solid catalyst as reported in the
previous works at the optimum conditions of 170℃,
50mbar, TMP/ME18 ratio of 6:1 and 0.3％w/w of catalyst
for 8h reaction time17）. The reaction product was filtered to
remove the un-used catalysts, washed to reduce soap as a
result of saponification and finally vacuum-fractionated to
remove the excess ME18.
2.3 Preparation of Tapping Oil
HO-TMPTE prepared from Section 2.2 was blended with
various combinations of additives to formulate tapping oils.
Blending process was completed in a closed glass jar
heated at 40℃ and stirred at 50 rpm for at least 10 min to
ensure well mixed condition. Tapping oil contained primar-
ily HO-TMPTE as the lubricant base oil. The additives in-
cluded lubricity improver, AW additive, EP additive and in
some cases metal passivator where yellow metal（copper
and brass）compatibility is needed. Three tapping oil for-
mulations were prepared using combinations of additives
from two lubricant additives producers, namely Lubrizol
Corporation and DRD Additive, LLC. The compatibility and
performance of HO-TMPTE base oil in each respective for-
mulation was evaluated and compared with commercial
petroleum based tapping oil available from Malaysia’s hard-
ware store. The formulations of examined tapping oils were
as follows:
TO-A: Commercial petroleum based tapping oil
TO-B: 100％ HO-TMPTE as control
TO-C: 95％ HO-TMPTE and 5％ BD-0908
TO-D: 88.8％ HO-TMPTE, 5％ GY-25, 1％ 360-P, 5％
L5333 and 0.2％ KSP-93
TO-E: 90.8％ HO-TMPTE, 8％ GY-115, 1％ 360-P and
0.2％ KSP-93
（All percentages were measured in weight）
2.4 Analysis of Products
Fatty acid profiles（in fatty acid methyl ester form）of
ME18 and purified HO-TMPTE were determined using gas
chromatography（GC）through a method published in an
earlier publication20）. Commercial TMPTO, namely Radial-
ube 7561 and TMPTO-A were transesterified with metha-
nol at molar ratio of 1:24 using sodium methoxide catalyst.
The fatty acid profiles was determined and examined using
GC. The soap content in the synthesized HO-TMPTE was
analyzed using PORIM p2.13 （2005） method.
2.5 Characterization and Physical Property Determina-
tion
The acid number of the oil was measured by PORIM p25
J. Oleo Sci. 64, (2) 143-151 (2015)
（1995）Method. The viscosities at 40℃ and 100℃ were
measured using ASTM D445 method and the viscosity
index（ VI）was calculated based on the ASTM D2270
Method. The pour point（PP）was determined through
ASTM D97 Method. The flash point was determined with
ASTM D93-02a Method and density by ASTM D369
method. The cloud point was determined by ASTM D2500
Method and demulsibility was tested by ASTM 1401-02
Method.
The tapping oil formulations were evaluated based on
the oil appearance, viscosity, temperature stability and
field performance tapping test. The oil appearance was de-
termined by observation in term of color, clarity and homo-
geneity. The viscosity was determined at 40℃ also by
ASTM D445 method. The temperature stability was estab-
lished by IP311/74（ 1994）Method. In this method, the
tapping oil samples were stored at 50℃（in air oven）, 27℃
- 30℃（room temperature）and 5℃（cold water bath）, re-
spectively for 24 h and then examined for characteristics
and homogeneity. The field tapping tests were performed
on a 12.7 mm thickness SS304 stainless steel plate and
mild steel plate where tapping holes were prepared accord-
ing to the taps guidelines as available in Presto Counselor
Handbook. An industrial milling machine（ EME Seiki,
Model 2000）was employed for testing purposes. High
speed steel（HSS）BSP taps ranging from ¼-½”were used
and tapping speed was set at 80 rpm throughout the
testing process.
3 RESULTS AND DISCUSSION
3.1 Ester Profile of ME18
The fatty acids profile of ME18 was used in this work as
determined by GC, given as Table 1. The fatty acid profiles
of palm methyl esters（PME）, the fractionated oleic palm
methyl esters（OPME）from Yunus19） work as well as the
commercial oleic acids（COA-1 and COA-2） were also listed
in Table 1 for comparison purposes. Commercial TMPTOs
are usually synthesized via chemical esterification reaction
using TMP and oleic acid, hence commercial COAs were
considered for the comparison purposes.
Commercial COA-1 and COA-2 contain mainly 73-82％
w/w C18:1, 7-14％ w/w C18:2 and small fractions of satu-
rated C16:0 and C18:0. These mono- and poly-unsaturated
fatty acid chains in contrast to the saturated fatty acid
chains（ C16:0 and C18:0）are important to produce low
pour point oil products. However, poly-unsaturated fatty
acids at the same time may make the oils oxidatively and
hydrolytically unstable21, 22）. PME typically contain high
saturates content of approximately 45％ w/w and this attri-
butes to a higher pour point TMP triesters with pour point
＞0℃19）. TMP triesters produced from PME is therefore
only suitable in the tropical climate countries with no
145
 T.-S. Chang, R. Yunus, U. Rashid et al.

Table 1　Fatty acid profile of ME18, PME, OPME and commercial oleic acids.
Fatty acid ME18a PMEb OPMEc COA-1d COA-2e
C12 － 0.4 0 － －f
C14 － 1.2 0 0 －f
C16 1.8 42.4 7.8 2－7 －f
C16:1 － 0.3 － ＜1 －f
C18 1.8 3.3 6.0 3－6 －f
C18:1 86.8 47.1 66.2 73－82 ＞80.0
C18:2 8.7 5.3 18.3 7－13 ＜14.0
C18:3 0.3 － 0.7 ＜4 －g
Othersh 0.6 － 0.9 ＜3 ＜1.0
a
Commercial palm-based winter grade biodiesel used in this work as obtained by GC.
b
Palm methyl esters produced from crude palm oil. Data from Berchmans and Hirata [11].
c
Fractionated palm methyl ester with high oleic content. As of POTE1, data from Yunus
[18].
d
Commercial oleic acid. Trade name: Radiacid 0215, data from brochure of OLEON
Company.
e
Commercial oleic acid. Trade name: Palmac 770, data from fatty acids specification of
IOI Oleochemical Industries Berhad.
f
<6% w/w total of C6 to C18, if presence.
g
C18:3 is grouped together with "Others", if presence.
h
Fatty acid of this group may consist of saturated and unsaturated C20, or higher carbon
chain fatty acids.

Fig. 1　Gas chromatogram of the ME18 used in this work.

winter season. Conversely, OPME was a modified PME with the production TMP triesters due to it’ s highest C18:1
high oleic content prepared by simple single stage fraction- content（86.8％ w/w）, lowest saturates and poly-unsatu-
ation process. It has relatively much higher C18:1 content rates among all. The gas chromatogram of ME18 is illus-
at 66.2％ w/w and C18:2 at 18.3％ w/w as compared to trated in Fig. 1 with the highest peak at 14.20 min indicated
PME in it’ s original form although it still contain 7.8％ w/w the C18:1, an excellent source of fatty acid methyl esters
of C16. ME18, a commercial palm-based winter grade bio- that give the low pour point properties23）while maintaining
diesel seemed to be a good source of starting material for an acceptable molecular stability to the TMP triesters.
146
J. Oleo Sci. 64, (2) 143-151 (2015)
 Palm Oil Derived Trimethylolpropane Triesters Synthetic Lubricants and Usage in Industrial Metalworking Fluid

ME18 is a highly fractionated PME produced using multiple ing sections.

fractionation technology developed by Malaysian Palm Oil
Board（MPOB）.
3.2 Characteristics and Physical Properties of HO-
TMPTE and Commercial TMPTO
The esters content, characteristics and physical proper-
ties of the HO-TMPTE and commercial TMPTO were sum-
marized in Table 2. These are the important technical pa-
rameters of the synthetic esters to suit into the lubricant
base stocks applications. The properties of these polyol
esters were principally discussed against the TMP triesters
purity and the fatty acids composition. Other factors that
influenced the properties are also discussed in the follow-
3.2.1 Pour Point and Cloud Point
Pour point is always used to validate the suitability of
the lubricant base stock to use at the lowest possible appli-
cation temperature where it maintains it’s flow. TMPTO-A
demonstrated the lowest pour point as compared to Radi-
alube 7561 and HO-TMPTE with −39, −36 and −30℃,
respectively. Both Radialube 7561 and TMPTO-A contained
higher triesters, contributed to the lower pour point even
though HO-TMPTE has higher oleic content. This ex-
plained that the overall molecular structure especially for
multiple branched molecules which have greater influence
to the pour point than it’s branching fatty acids. This is in
agreement with the suggestion in the previous literatures7, 24）.

Table 2　C haracteristics and physical properties of the HO-TMPTE and the
commercial TMP trioleate.
Radialube
Properties HO-TMPTE TMPTO-A
7561
Esters composition (% w/w)
Methyl esters*/fatty acids** 5.1* 0.4** 2.3**
TMP monoesters 0.2 0.7 -
TMP diesters 10.2 3.8 6.1
TMP triesters 84.5 95.1 91.6
a
Soap Content (mg/g) 2.49 0.02 0.02
Fatty acid compositions (% w/w)
C16 1.8 6.4 4.9
C18 1.8 0.9 0.9
C18:1 86.8 78.3 81.8
C18:2 8.7 5.9 1.5
C18:3 0.3 6.1 9.4
c
Others 0.6 2.4 1.5
Characteristics and Physical Properties
Pour Point (℃) -30 -36 -39
Flash Point (℃) 270 306 260
Cloud Point (℃) 0 -3 -6
Density at 20℃ (g/cm3) 0.914 0.928 0.917
Viscosity at 40℃ (mm2/s) 44.3 46.3 47.9
2
Viscosity at 100℃ (mm /s) 9.9 9.3 9.8
Viscosity Index 219 189 196
Acid Value (mgKOH/g) 0.28 0.46 2.97
60 min
Demulsibilityb ＜30 min ＜30 min
5/38/37
a
Measured in mg of soap in oleate per gram of sample
b
Demulsibility time limit at emulsion reduction to 3 ml was set at 30 min. Reported as ＜30
min if the time limit was fulfilled otherwise the volume of oil/water/emulsion remaining at
the reported time in ml
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J. Oleo Sci. 64, (2) 143-151 (2015)
 T.-S. Chang, R. Yunus, U. Rashid et al.
Besides, TMPTO-A showed a lower pour point than Radial-
ube 7561 due to it’ s higher poly-unsaturated content. Poly-
unsaturated fatty acids in natural vegetable oils usually
appear in cis-configuration possessing a weaker intermo-
lecular interaction between the oil molecules and hence
showed a lower pour point. HO-TMPTE contained higher
content of diesters and methyl esters primarily due to the
incomplete transesterification into TMP triesters and also
inefficient fractionation in the removal of the unreacted
methyl esters. These could be improved by specifying the
triesters purity in the production of HO-TMPTE base stock,
preferably ＞95％ w/w of triesters.
Cloud point is the temperature when the oil become
cloudy caused by the crystals formation of the saturated
components and usually occurs above the pour point25）.
Cloud point exhibited in the similar manner as the pour
point where the purity of triesters affected the earlier for-
mation of crystals most followed by the fatty acids level of
saturation. The cloud point of TMPTO-A, Radialube 7561
and HO-TMPTE were −6, −3 and 0℃, respectively.
3.2.2 Flash Point
Flash point is the temperature which the oil must be
heated such that it can be ignited in a mixture of oil vapor
and air. Radialube 7561 exhibited the highest flash point
（306℃）followed by HO-TMPTE（270℃）and TMPTO-A
（260℃）primarily due to it’s highest triesters content as
well as the lowest fraction of low molecular weight compo-
nents of fatty acid . Higher triesters content denoted a
higher overall molecular weight, thus higher energy was
needed to bring the oil to ignite. On the other hand, HO-
TMPTE has higher flash point than TMPTO-A. Monoesters
and diesters consist of polar hydroxyl（-OH）groups which
generate inter-molecule hydrogen bonding between the oil
molecules. HO-TMPTE has higher content of monoesters
and diesters; resultantly oil volatility was relatively
reduced.
3.2.3 Density
Radialube 7561 showed the highest density among three
products with the density of 0.928 g/cm3 as compared to
HO-TMPTE and TMPTO-A with similar densities of 0.914
and 0.917 g/cm3, respectively. The larger molecular struc-
ture of TMP triesters contributed to the higher molecular
density, hence, higher poly-unsaturated levels will render
this effect. Thus, TMPTO-A has lower density than Radial-
ube 7561 but similar to density with HO-TMPTE.
3.2.4 Viscosity and Viscosity Index（VI）
Viscosity of vegetable oil based materials increases with
the presence of partial esters and intermolecular hydrogen
bonding between the hydroxyl group（-OH）of the partial
esters8）. This effect was observed between Radialube 7561
and TMPTO-A where the VI were 196 and 189, respective-
ly. Though, HO-TMPTE possessed the highest VI among
three oils which did not match with the literature. The
lower viscosity of HO-TMPTE can be rationalized by the di-
148
J. Oleo Sci. 64, (2) 143-151 (2015)
lution effect of the high amount of ME18. Higher ME18
content in the HO-TMPTE could have contributed to the
decreased viscosity at 40℃. Higher diesters content con-
tributed to higher viscosity and this effect was particularly
significant at 100℃. Even though higher VI appears to be
good as far as the lubricant formulation is concerned,
however the main drawback would be it’s lower flash point
that making it inadequate for certain applications, for in-
stance, application in fire retardant hydraulic lubricants.
3.2.5 Acid Value and Soap Content
Acid values of the oils were measured in term of milli-
grams of potassium hydroxide（KOH） , required to neutral-
ize the free fatty acids in 1g of oil sample. There was no
standard or reference that explains this parameter for the
synthetic esters and it is very much applications depen-
dant, therefore TMPTO, is available in a few acid value
variations. TMP triesters, would have lower acid value as
the process did not involve the acidic ingredients and
water washing processes. Consequently, acid value of the
HO-TMPTE was only measured at 0.28 mg KOH/g whereas
Radialube 7561 and TMPTO-A, prepared by esterification
route measured 0.46 mg KOH/g and 2.97 mg KOH/g, re-
spectively. The low acid value of the oils after the esterifi-
cation reaction with acid catalysts could be achieved by in-
corporating the neutralization and drying processes. Drying
process is crucial in HO-TMPTE production because water
content in the oil will cause hydrolysis to the oils during
storage time. Conversely, HO-TMPTE prepared with base
catalyst would have higher soap content. Soap improves
the lubricity of the lubricant oils; however it is not pre-
ferred in the lubricant base stocks as soap would influence
the compatibility of other lubricant additives and it would
cause sludge formation in some of the high temperature
applications, for instance, in engine oils and gear oils. The
soap content of HO-TMPTE measured 2.49 mg soap in
oleate/g sample while a small amount was detected in Radi-
alube 7561 and TMPTO-A. Radialube 7561 and TMPTO-A
could have gone through the neutralization processes,
leaving a trace of soap in them.
3.2.6 Demulsibility
Demulsibility property is an important parameter for lu-
bricating oil as an indication of well separated oil-water
mixture over certain specific time interval. This parameter
is particularly crucial for the applications where water will
tend to enter into the lubricating system and formation of
water emulsion could reduce the boundary lubrication
properties of the oils on the metal surfaces. Between the
three investigated products, only HO-TMPTE exhibited an
unsatisfying demulsibility characteristic. This is visibly due
to the existence of high soap content that functioned as an
emulsifying agent in the oil-water mix. The demulsification
properties of HO-TMPTE could be improved by having
soap removal process via water washing and subsequently
drying. The presence of partial esters（monoesters and di-
 Palm Oil Derived Trimethylolpropane Triesters Synthetic Lubricants and Usage in Industrial Metalworking Fluid

esters）in the oil has also contributed to the reduced water
demulsibility property of HO-TMPTO. Fenglan26） reported
a similar result in the previous publication.
3.3 Properties and Performances of Tapping Oils
Tapping oils formulated from the HO-TMPTE were
studied in term of physical properties, stability and perfor-
mances in thread tapping application. The results obtained
from this study were summarized in Table 3. In this work,
three tapping oil formulations were prepared and then
compared against the pure HO-TMPTE（without any addi-
tives）and the commercial petroleum-based tapping oil,
namely New Rapid Tap. Tapping process for internal thread
in the metalworking industries is one of the most challeng-
ing operations usually due to breakage of the costly taps as
well as the wasted metal work piece. Ideally, all tapping oil
formulations should have a clear and homogeneous mix
showing good compatibility between all additives. In some
cases, solid phase additives are added as the AW and EP
additive. However, it must maintain a stable suspension
over certain years of storage.
Among the prepared formulations, TO-D and TO-E were
prepared using liquid phase EP, AW and lubricity additives.
Oil mix compatibility test showed that these two formula-
tions remained clear and stable under different storage
temperatures, thus the additives were considered compati-
ble with HO-TMPTE in the tapping oil formulations. TO-C
was prepared with microcrystalline boron nanoparticles,
namely BD-0908 and it functioned as EP as well as AW ad-
ditive in the formulation. This nanoparticles boron additive
was prepared as a stable suspension in an esters compound
which worked as a lubricity improver as well in the tapping
oil formulation. Due to the presence of the solid nanoparti-
cles phase, the oil preparation appeared to be hazy at room
temperature. Further testing on the storage stability of
TO-C at 5℃ for 24 h resulted slight fallout of the nanopar-
ticles at the bottom. This result established that HO-
TMPTE was not compatible with the base fluids of BD-0908
therefore unable to maintain it in good suspension. This
could be improved by adding a combination of surfactant
and/or other synthetic esters that makes both base oils
compatible better to each other.
Commercial tapping oil, New Rapid Tap （TO-A） examined
in this work was a mineral-vegetable oil mixed oil with a
viscosity of 30.1 mm2/s at 40℃. Other tapping oils formu-
lated with HO-TMPTE were higher than the commercial
one because the base oil itself was ISO46 grade base oil.
However, the viscosity range of tapping oil is not vital as

Table 3　Properties of the formulated high oleic palm based TMP triesters tapping oils as compared to the
commercial product.
Tapping Oila
Properties
TO-A TO-B TO-C TO-D TO-E
Brown, slight
Appearance Amber, Clear Yellow, Clear Amber, Clear Amber, Clear
cloudy
Viscosity at 40℃ (mm2/s) 30.1 44.3 49.6 58.7 52.4
Density at 20℃ (g/cm3) 1.004 0.914 0.918 0.922 0.941
Temperature stability
　At 5℃ No separation No separation Partial separation No separation No separation
　At room temperature No separation No separation No separation No separation No separation
　At 50℃ No separation No Separation No separation No separation No separation
b
Field tapping test performance on SS304 plate
　1/4”BSP Tap Passed Passed Passed Passed Passed
　3/8”BSP Tap Passed Failed Passed Passed Passed
　1/2”BSP Tap Passed Failed Passed Passed Failed*
b
Field tapping test performance on mild steel plate
　1/4”BSP Tap Passed Passed Passed Passed Passed
　3/8”BSP Tap Passed Failed Passed Passed Passed
　1/2”BSP Tap Passed Failed Passed Passed Passed
a
TO-A, New Rapid Tap, commercial tapping oil; TO-B, HO-TMPTE only as control; TO-C, TO-D and TO-E, formulated tapping
oil with HO-TMPTE as in Section 2.3.
‘Passed’indicates successful tapping through all 5/5 of holes on the plate,“Failed*”indicates unsmooth tapping with
b

successful tapping only through 4/5 of holes on the plate and‘Failed’indicates jammed tapping for > 1 hole on the plate.
149
J. Oleo Sci. 64, (2) 143-151 (2015)
 T.-S. Chang, R. Yunus, U. Rashid et al.
long as it has good flow to fill the gap between the metal
surfaces during the taping processes. Densities of the oils
were also measured as indicative parameters. TO-A has a
density of ＞1.0 g/cm3 at 20℃ indicated that the oil was
blended with high percentage of high molecular weight,
polymerized oils as well as mineral based EP and AW addi-
tives, however the details of the additives involved were
not known.
As far as the field thread tapping test was concerned,
TO-A, TO-C and TO-D formulations were able to meet the
testing conditions as set. TO-B which was applied directly
without adding any additives passed the 1/4”BSP thread
on the 12.7 mm SS304 plate, however it failed for 3/8”and
1/2”thread on both SS304 and mild steel plates. Bigger
thread size will have greater metal to metal contact surface
and thus required higher torque when cutting deeper into
the metal plate. Without using any EP and AW additives,
the tap stuck in the tap hole and failed to complete the
thread making process. TO-C showed good performance
for all tapping tests indicated that BD-0908 was an effec-
tive EP/AW additive when blended together with HO-
TMPTE. Boron compound was known to be effective EP/
AW additive in metalworking applications27）. Ferro-borate
film was formed when boron was exposed to high tempera-
ture due to friction heat created by metal-metal sliding, in
this case the test metal and the HSS tap. TO-D and TO-E
were formulated with different degrees of AW and EP
treatments. TO-D was formulated as a heavy duty formula-
tion suitable for applications in hard metals like stainless
steel, duplex stainless steel, hastelloy® etc. It contained an
additional active sulfur EP/AW additive（ L5333）that is
known to be an effective EP treatment agent. Sulfur com-
pound reacted with the metal surfaces to form a sulfide
layer when exposed to high temperature during the cutting
action28）. This layer improved the sliding contact between
metals, preventing scuffing and galling. Conversely, TO-E
was prepared as a light duty formulation. It did not work
perfectly on the SS304 even though GY-115 contains sulfur
compound as the sulfur present was in passive form （sulfu-
rized-vegetable oil） , thus the EP/AW effects was relatively
lower. This formulation was suitable for light duty applica-
tions like thread tapping on carbon steel, mild steel, alu-
minium, brass etc. Sulfur additive on the other hand is
known to create staining effect on the yellow metals
（copper containing metals and alloys）. Hence, KSP-93
metal deactivator was added as a detergent to prevent the
potential staining. However, the yellow metal staining
effect was not considered in this work. 360-P was a phos-
phate-based ashless EP/AW additive. Thick amorphous
iron-phosphate formed during the sliding action has been
reported functioned as EP/AW enhancer 29）. In another
study, Kawamura and Fujita30） suggested that phosphate
reacted with the metal as low as at 100℃ while sulfur
reacted at higher temperature of 200℃ and above. Hence,
150
J. Oleo Sci. 64, (2) 143-151 (2015)
a combination of phosphorus and sulfur EP/AW additive
would be needed for these purposes. In this work, 360-P
was added into TO-D and TO-E as EP/AW supplement to
the sulfur-base additives. However, the effects of phospho-
rus and sulfur loading in metalworking were not investigat-
ed in this work.
4 CONCLUSIONS
High oleic TMP triesters was prepared from commercial
palm-based winter grade biodiesel and trimethylolpropane
by transesterification using calcium methoxide as the cata-
lyst. The oil properties such as pour point, flash point,
cloud point, density, viscosity and others were determined.
The HO-TMPTE synthesized showed comparable proper-
ties with the commercially available trimethylolpropane tri-
oleate. It was most preferable considering it’ s potentially
lower pour point, higher viscosity index and lower acid
number. The oil also demonstrated good compatibility and
adaptability with the commercial lubricant additives in the
formulation of tapping oil. It also exhibited satisfactory
performance in the tapping applications. However, the per-
formance of the formulations was greatly influenced by the
applied additives.
ACKNOWLEDGEMENT
The authors are grateful to the Ministry of Science and
Technology, Malaysia for financial support under the Tech-
nofund grant. The authors also acknowledge the contribu-
tion of Solution Engineeriing Sdn. Bhd. for providing the
additives for the product formulation purposes.
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