Modified TMP Esters as Multifunctional Additives in

Metalworking Fluids

T. Mathiesen Esti Chem A / S , Koege, Denmark

This paper looks at newly developed trimethylolpropane (TMP)esters, which

have multifunctional properties as additives in aqueous metalworking fluids.
Such TMP esters can replace the previous monofinctional esters, which
provided only lubrication.
New TMP esters are obtained by chemical modification of traditional
TMP esters, and provide the finctions of lubrication, corrosion protection,
and co-emulsification in one product. The paper looks at the chemistry of
these esters, and their properties. Some experimental products are also
examined.

KEYWORDS: fatty acid esters, lubricant additives, metalworking, TMP,

trimethylolpropane,formulation
INTRODUCTION

In recent years, fatty acid esters have found application as lubricant additives
in metalworking fluids. Such esters are typically reaction products of natural
fatty acids and mono- or polyfunctional alcohols, are non-miscible with water,
and have low acid numbers (in the range of 1-15 mg KOWg). A list of stan-
dard esters used in metalworking fluids is shown in Table 1 (overleaf). These
products are all characterised by having only one function in the metalwork-
ing fluid, lubrication. Emulsifiers, corrosion inhibitors, coupling agents, and
so on, must be added to the formulation to obtain the performance necessary
for a modern metalworking fluid.
Increased concern about environmental and health and safety issues has
had an effect on the formulation of metalworking fluids. Secondary alkanol
amines are now being brought into question, and this discussion has promoted
the use of combinations of primary and tertiary alkanol amines. The use of
chlorinated paraffins in metalforming lubricants is in doubt and formulators
are looking for alternative base materials. Another approach to reducing
health risks for machine operators is the use of mineral oil-free metalworking
fluids. The base oil in such fluids can be triglycerides, fatty acid esters, PAOs,
or other synthetic hydrocarbons.'

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Table 1 Standard fatty acid esters used in metalworking fluids

Unsaturated

2-ethylhexyl oleate

propylene glycol dioleate

neopentylglycol dioleate

TMP trioleate

penta tetraoleate

rapeseed oil

blown rapeseed oil

castor oil (incl. EP derivatives)

ricinoleic acid esters

Partly unsaturated

isobutyl tallowate

Saturated

2-ethylhexyl palrnitatektearate

12-hydroxystearic acid esters

An ester is traditionally one of the expensive components in a metalwork-

ing fluid. The use of a multifunctional ester that improves several performance
parameters is a useful way to improve the price/performance ratio of the for-
mulation. The present paper discusses how multifunctional esters can be ob-
tained by chemical modification of traditional trimethylolpropane (TMP)
esters.’
These multifunctional esters have three main functions in a metalworking
fluid: lubrication, corrosion protection, and co-emulsification.
With this new ester, it is now possible to reduce the content of other base
materials in the formulation, each providing only one of the properties men-
tioned above. Alternatively, the dilution rate of the metalworking fluid could
be increased.
Modified TMP esters have been increasingly used in metalworking fluids
during the last few years.3 This paper will concentrate on the latest develop-
ment of acid-functional TMP esters for use in water-dilutable cutting fluids.
Such esters can also be used in metalforming lubricants.

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Modified TMP Esters as Multifunctional Additives in Metalworking Fluids 383

Table 2 Important properties of a multifunctional ester molecule

Lubrication

Corrosion protection

Self-emulsifyingor co-emulsifying

Hydrolytic stability

Foaming

Oxidation stability

Toxicity

Biodegradability

Table 3 A comparison of two commercial TMP esters with a multifunctional

ester

Property TMP trioleate TMP trincinolate Multifunctional ester

Acid value, 1-2 10-1 5 50-90

mg KOH/g

Viscosity, 51 85 80-1 50
CPl25"C

Molecular weight 920 1.000 700-1.1 00

Emulsion Typical properties Contains free Contains COOH-groups

properties of a neutral ester OH-groups linked to the ester mole-
oil, must be emul- linked to the ester cule, much higher acid
sified with tailor- molecule and a number than TMP triricino-
made emulsifier certain amount of late, very easy to emulsify,
system free fatty acids, better hard-waterstability
more hydrophilic as the acid group is linked
than TMP tri- to the ester molecule (not
oleate, easier to presentas free fatty acids).
emulsify The neutralised ester is a
part of the emulsifier and
corrosion inhibitor system

Function in the lubricant additive lubricant additive lubricant additive

metalworkingfluid corrosion inhibitor
co-emulsifier

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Table 4 Ideal product profile for a multifunctional ester

Good lubricating properties

(high viscosity)

Good corrosion protection properties

(high acid number)

Partly or fully self-emulsifying

Easy to split from the used emulsion

(by acid-splitting or ultrafiltration)

Good hydrolytic stability

(sterically hindered)

Low foaming

Good oxidation stability

(low iodine number)

Low toxicity

Biostable in the metalworking fluid

(when separation from the used emulsion is possible using
conventional techniques)

Properties

The most important properties of a multifunctional ester for use in metalwork-

ing fluids are listed in Table 2. The ester should lubricate and contribute to
corrosion protection and emulsification of the base oil. Also, hydrolytic
stability should be as good as possible to prevent degradation in the diluted
metalworking fluid, foaming should be minimised, toxicity should be low,
and the product should not biodegrade during use.
Table 3 gives a comparison of the properties of two commercial TMP es-
ters (TMP trioleate and TMP triricinolate) with the new multifunctional ester.
From the table it can be seen that the new multifunctional ester is a logical step
in the development of esters for use in an aqueous system, such as a water-
dilutable metalworlung fluid. A product profile for an ideal product can be
generated, as shown in Table 4. The final product will always be a compro-
mise between the different requirements, but, with proper formulation, multi-
functional esters can be tailor-made to fulfil the requirements for the various
metalworking fluids: fluids with high mineral oil content, semi-synthetics,
fully-synthetics or amine-free fluids.

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Modified TMP Esters as Multifunctional Additives in Metalworking Fluids 385

Table 5 Raw materials for ester synthesis - important parameters

Saturated or unsaturated
Straight chained or branched
Long or short chained
Mono- or polyfunctional

Figure 1 Molecular structure for self-emulsifying ester

R1

R2 R1, R2, and R3:alkyl chains

DESIGN OF THE ESTER MOLECULE

Esters are formed by the reaction of a carboxylic acid and an alcohol. The
properties of the ester can be controlled by correct selection of base materials
for the ester synthesis. Typical parameters are shown in Table 5. The degree
of steric hindrance in the molecule controls the hydrolytic stability of the
product, and partly also the biodegradability. Saturated raw materials have
better oxidation stability than unsaturated materials, but also have a signifi-
cantly higher pour point. This negative effect can be controlled by introducing
a certain degree of branching in the C-C chain, or by using blends of various
carboxylic acids and alcohols. The commercial availability of the various raw
materials will naturally limit the possibilities when designing the ester mole-
cule. However, as the petrochemical industry has developed many new car-
boxylic acids and alcohols, it is possible to develop combinations of synthetic
materials and naturally derived products, and to obtain products with much
enhanced performance.

PHYSICAL AND CHEMICAL PROPERTIES OF EXPERIMENTAL

PRODUCTS

Based on theoretical considerations, a number of experimental products were

developed, in order to investigate the relationship between molecule structure
and phy sicalkhemical properties.

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Table 6 Comparison of two experimental products

Parameter A3 A4

Acid value, mg KOHIg 57 78

Viscosity, cPI25"C 320 310

Average molecular weight 1100 700

Appearance of a 5% emulsion of Milky emulsion Semi-transparent

ester neutralised with alkanol emulsion
amines

Foaming tendency Low Low

The basic molecular structure is shown in Figure 1. All products can be

described as TMP esters, with varying degrees of alkoxylation and fatty acid
composition. The molecule carries a free carboxylic acid function, providing
the three important properties in a metalworking fluid: lubrication, corrosion
protection and co-emulsification. The properties of two experimental prod-
ucts, A3 and A4, are compared in Table 6. The two esters have the same basic
molecular structure, but differ in the carboxylic acid composition. The prop-
erties presented in Table 6 show that it is possible to create products with
broad variations in chemical and physical properties by changing the raw ma-
terial composition. When neutralising the experimental products A3 and A4
with alkanolamines, and mixing with water, two very different emulsions can
be observed: Product A3 forms a milky emulsion, whereas the emulsion based
on the A4 product is semi-transparent and very stable. The emulsion quality
can be further improved by the addition of non-ionic emulsifiers.
Another important parameter for esters used in water-dilutable metal-
working fluids is hydrolytic stability. Hydrolysis of the ester will decrease
corrosion protection, increase foaming, and might lead to instability of the
emulsion. The hydrolytic stability of five selected experimental products was
tested under the following saponification conditions:

2g ester
10 g KOH solution ( 5 % in demineralised water)
5g demineralised water
83 g ethanolhopropanol mixture (85/15)
50°C temperature

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Modified TMP Esters as Multifunctional Additives in Metalworking Fluids 387

Figure 2 Hydrolytic stability of self-emulsifyingesters compared with PEG-

400 monooleate

PEG-400
monooleate

80

70

:. 60 A3
-1.
50
>
c
8 40 A1 0
30 A308

20 A4
A21 B
10

0
0 5 10 15 20 25 30 35 40 45 50 55 60
Time, min.

Standard ester: PEG-400 monooleate

Self-emulsifying esters: A3, A10, A308, A4, A218

The rate of hydrolysis was determined by titration with 0.05 M HCl with
intervals of 15 min.
The results are shown in Figure 2. A standard ester (PEG 400 mono-
oleate), used for many years as an emulsifier in metalworking fluids, was test-
ed as a comparison. All the experimental products showed much better
stability than the standard ester. The relation between steric hindrance and
hydrolytic stability is very clear: increasing steric hindrance around the ester
bond dramatically increases hydrolytic stability. Substitution of traditional
esters by the multifunctional esters will minimise problems with ester
hydrolysis during storage of the concentrate and use of the diluted fluid.

APPLICATION

To demonstrate the application properties of a modified TMP ester in a

metalworking fluid, a model formulation was made.

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Experimental product A4 50.0%

Alkanol amine mixture 37.0%
Demineralised water 13.O%

The above formulation is purely experimental, but it gives some indication of

the parameters that can be improved by incorporating the self-emulsifying
ester into a metalworking fluid formulation. The properties of the model
formulation are described in Table 7.
The results are very interesting, as the model formulation fulfils the basic
demands of a metalworking fluid without the addition of emulsifiers, corro-
sion inhibitors or other performance additives:

the emulsion is semi-transparent, stable, and low-foaming

a 3% emulsion shows corrosion grade '0'
the emulsions are stable in hard water
the Reichert value for a 5% emulsion is excellent (13.3 mm2)
the dried concentrate is liquid, forms no sticky residues and can easily be
re-emulsified.

Table 7 Properties of a model formulation based on experimental product A4

Model formulation for a cutting fluid concentrate

Experimentalproduct A4 50%

Alkanol amine mixture 37%

Demineralisedwater 13%

Properties of a 3% dilution in 2PdH water

Appearance, 20°C semi-transparentemulsion

pH value 9.25

Iron chip corrosion test 0 (no corrosion)

(DIN 53360, part 2)

Circulation pump test stable, low foaming, no

(2 weeks) separation of calcium soaps

Properties of a 5% dilution in 2O"dH water

Reichert test 13.3 mm2

Drying test 24 h/70°C liquid, not sticky

easy to re-emulsify

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Modified TMP Esters as Multifunctional Additives in Metalworking Fluids 389

These very positive properties indicate good potential for using the experi-
mental product A4 as a multifunctional formulation component to improve
emulsion stability corrosion protection and lubricity.

INDUSTRIAL APPLICATIONS

A number of the experimental products described above have commercial use

in cutting fluids such as fluids with high-mineral oil content, semi-synthetic
fluids and mineral oil-free cutting fluids. In processing aluminium and yellow
metals, the new esters have shown superior performance compared with tra-
ditional TMP esters. Other applications of the self-emulsifying esters are in
rolling oils, deep-drawing lubricants, release agents, rust preventives and
other industrial functional fluids.
The acid value provided by the new TMP esters is neutralised with alka-
line components as a part of the formulation. Initial tests have shown good po-
tential for using KOH as a neutralising component instead of alkanol amines.
This feature opens the possibility of using modified TMP esters in amine-free
metalworking fluids.

TOXICOLOGICAL AND ENVIRONMENTAL PROPERTIES

The multifunctional esters have the typical benefits of fatty acid esters:

LD,, values (oral, rat) 25.000 mglkg.

Skin irritation None-to-low skin irritation, depending on the chemical com-
position of the ester.
Biodegradability Varies from readily to slowly biodegradable, depending
on the chemical structure.

The multifunctional esters can generally be considered as safe components for

use in existing and future metalworking fluid formulations.

FUTURE APPLICATIONS

Many industrial functional fluids are being reformulated from mineral oil
bases to aqueous systems. In these, multifunctional esters can be applied with
good results, as they give the formulator more flexibility in the development
of new products. Future applications of modified TMP esters includes

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lubricants for ‘hot’ applications, hydraulic fluids, concrete mould release

agents and textile processing fluids.

CONCLUSION

This paper reports on the possibilities of controlling the physical and chemical
properties of a modified TMP ester by proper selection of base raw materials.
By this technique, tailor-made solutions can be developed for metalworking
fluids and other industrial functional fluids where a special performance pro-
file is needed. Increasing consideration of the environmental and toxicological
behaviour of formulation components has prompted the need for new raw
materials for the formulator. Multifunctional TMP esters are a new group of
materials that provides the chemist with a new-found freedom of formulation.

References

1 , Miiller, J., ‘Wassermischbare Kiihlschmierstoffe - in Zukunft umweltvertraglich?’ in

Proc. International Colloquium Tribologie 2000, Technische Akademie Esslingen, Ostfil-
dern, Germany, 14 January 1992, pp. 12.7-1 - 12.7-16.
2. European Patent 4451 85.
3. Mathiesen, T., ‘New water dilutahle esters for biodegradable metalworking fluids’, in
Proc. International Colloquium Tribologie 2000, op. cit., pp. 12.8-1 - 12.8-9.

An earlier version of this paper was presented at the Technische Akademie Esslingen,
International Colloquium ‘Tribology - Solving Friction and Wear Problems’.

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