U.S. patent application number 13/062586 was filed with the patent office on 2011-07-07 for emulsifiers for metal working fluids.
Invention is credited to Matthias Hof, Tanja Luedtke.
Application Number | 20110162425 13/062586 |
Document ID | / |
Family ID | 40056164 |
Filed Date | 2011-07-07 |
United States Patent
Application |
20110162425 |
Kind Code |
A1 |
Hof; Matthias ; et
al. |
July 7, 2011 |
Emulsifiers for Metal Working Fluids
Abstract
Disclosed is the use of an alkoxylated fatty alcohol of formula
(I), RO--(CH.sub.2--CHR'--O).sub.n--(CH.sub.2CH.sub.2--O).sub.m--H,
wherein R stands for a saturated and/or unsaturated alkyl moiety
containing 12 to 22 carbon atoms, R' is methyl, ethyl or propyl, m
represents a number of 1 to 12, preferably 4 to 10, and n
represents a number of 1 to 10, preferably 2 to 8, as an emulsifier
in metalworking fluids which also contain at least water and one
oil component, non-miscible with water, and, optionally, further
ingredients, and where the fatty alcohol which forms the R moiety
has a iodine value of 15 to 75 g I.sub.2/100 g.
Inventors: |
Hof; Matthias; (Duisburg,
DE) ; Luedtke; Tanja; (Rommerskirchen, DE) |
Family ID: |
40056164 |
Appl. No.: |
13/062586 |
Filed: |
August 27, 2009 |
PCT Filed: |
August 27, 2009 |
PCT NO: |
PCT/EP2009/006228 |
371 Date: |
March 7, 2011 |
Current U.S.
Class: |
72/42 ;
508/579 |
Current CPC
Class: |
C10N 2050/011 20200501;
C10N 2070/02 20200501; C10M 173/00 20130101; C10N 2040/20 20130101;
C10M 173/02 20130101; C10M 2201/02 20130101; B01F 17/0021 20130101;
C10N 2030/24 20200501; C10M 2209/104 20130101; B01F 17/0085
20130101; C10M 2209/107 20130101; C10N 2020/013 20200501; C10N
2030/18 20130101; B01F 17/0028 20130101; C10M 145/36 20130101; C10M
2209/104 20130101; C10M 2209/106 20130101; C10M 2209/104 20130101;
C10M 2209/105 20130101 |
Class at
Publication: |
72/42 ;
508/579 |
International
Class: |
B21B 45/02 20060101
B21B045/02; C10M 169/04 20060101 C10M169/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 5, 2008 |
EP |
08015630 |
Claims
1-13. (canceled)
14. A method of metalworking comprising the step of treating metal
with a metalworking fluid, comprising: (a) one or more oil
components which are non-miscible with water, (b) water, (c) one or
more emulsifiers selected from the group consisting of alkoxylated
fatty alcohols of formula (I)
RO--(CH.sub.2--CHR'--O).sub.n(CH.sub.2CH.sub.2--O).sub.m--H (I)
wherein R stands for a saturated and/or unsaturated alkyl group
containing 12 to 22 carbon atoms, and is derived from a fatty
alcohol; R' is methyl, ethyl or propyl; m represents a number of 1
to 12; and n represents a number of 1 to 10, and (d) optionally,
further ingredients, wherein said fatty alcohol which forms the R
moiety has an iodine value of 15 to 75 g I.sub.2/100 g.
15. The method of claim 14, wherein m is 4 to 10.
16. The method of claim 14, wherein n is 2 to 8.
17. The method of claim 14, wherein R comprises oleyl, and R'
comprises methyl.
18. The method of claim 14, wherein component (c) comprises a
mixture of at least two different compounds of formula (I), and
wherein one compound contains an unsaturated R group, and the other
compound contains a saturated R group.
19. The method of claim 18, wherein one R group comprises oleyl,
and the other R group comprises cetyl.
20. The method of claim 1, wherein said one or more emulsifiers of
formula (I) are present in the metalworking fluid in an amount of
0.1 to 25% by weight.
21. The method of claim 20, wherein said emulsifiers are present in
1 to 20% by weight.
22. The method of claim 21, wherein said emulsifiers are present in
1.5 to 10% by weight.
23. The method of claim 1, wherein said iodine value is in the
range of 20 to 55 g I.sub.2/100 g.
24. The method of claim 1, wherein said metalworking fluid is an
emulsion.
25. The method of claim 24, wherein said emulsion is an
oil-in-water emulsion.
26. The method of claim 1, wherein R' is methyl, and the ethylene
oxide and propylene oxide moieties of formula (I) are distributed
randomly.
27. The method of claim 1, wherein R' is methyl, and the oxides are
distributed block-wise, with the propylene oxide block adjacent to
the fatty alcohol group, followed by the ethylene oxide block.
28. The method of claim 1, wherein n is a number in the range of 1
to 5.
29. The method of claim 28, wherein n is a number in the range of 1
to 3.
30. The method of claim 1, excluding the co-use of diesters of
dicarboxylic acids.
31. An emulsion concentrate, comprising: (a) one or more oil
components, (b) water, (c1) 2-30% by weight, based on the
concentrate, of one or more emulsifiers of formula (I)
RO--(CH.sub.2--CHR'--O).sub.n(CH.sub.2CH.sub.2--O).sub.m--H (I)
wherein R stands for a saturated and/or unsaturated alkyl group
containing 12 to 22 carbon atoms, and is derived from a fatty
alcohol; R' is methyl, ethyl or propyl; m represents a number of 1
to 12; and n represents a number of 1 to 10, (c2) at least one
additional emulsifier, (d1) a corrosion inhibitor system, and (d2)
optionally, other ingredients.
32. The method of claim 31, wherein the amount of said one or more
emulsifiers of formula (I) is 3-25% by weight, based on the
concentrate.
33. A metalworking fluid, comprising: (a) an oil phase which is not
miscible with water, (b) a water phase, (c) 0.1-20% by weight,
based on the fluid, of one or more emulsifiers of formula (I)
RO--(CH.sub.2--CHR'--O).sub.n(CH.sub.2CH.sub.2--O).sub.m--H (I)
wherein R stands for a saturated and/or unsaturated alkyl group
containing 12 to 22 carbon atoms, and is derived from a fatty
alcohol; R' is methyl, ethyl or propyl; m represents a number of 1
to 12; and n represents a number of 1 to 10, and (d) one or more
additional compounds selected from the group consisting of
corrosion inhibitors, yellow metal deactivators, defoamers, and
biocides.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is the US National Stage application
under 35 U.S.C. .sctn.371 of International application number
PCT/EP2009/006228, filed on Aug. 27, 2009, which claims the benefit
of priority of European application number 08015630, filed on Sep.
5, 2008, the disclosures of both of which are hereby incorporated
by reference herein in their entireties.
FIELD OF THE INVENTION
[0002] The present invention pertains to emulsifiers, useful in
metalworking fluids, as well as to metalworking fluids, containing
those emulsifiers.
BACKGROUND OF THE INVENTION
[0003] Metalworking fluids, either based on petrochemical or
natural oils, are well known in the art and utilized throughout the
industry for a variety of processes including rolling, stamping,
drawing, pickling, cutting and extruding. Aqueous formulations of
various oils are widely used as the rolling oil in the cold rolling
of steel to provide lubrication and to cool the rolls. In addition
to providing effective lubrication and effective cooling of the
workpiece/working elements, there are other criteria which must be
met by metalworking fluids. Rolling oils, for example, must be
capable of providing a continuous coating on the surface of the
metal. Furthermore, this coating or film must have a minimum
thickness and must be substantive enough to the metal so that it
will be maintained at the high pressures which occur in the roll
bite. Above and beyond these lubrication considerations it is
particularly advantageous if the rolling oil provides some measure
of corrosion protection to the rolled strip and burns off cleanly
during the annealing operation. Residual rolling oil must
volatilize cleanly and should not leave any carbonaceous deposits
or surface discoloration. In view of variations in the metals being
worked and the different operating conditions and application
methods employed, numerous metalworking fluids have been developed
in an attempt to obtain the optimum balance of properties. Most of
these variations have involved the use of different fats and oils
or replacement of a portion of the fat or oil with a petroleum
product, e.g. mineral oil, or a synthetic lubricant, e.g. a
synthetic hydrocarbon or ester.
[0004] Emulsifier systems have also been widely varied and
additives have been employed to enhance the characteristics of
these oils. Unfortunately, emulsions are quite unstable fluids. For
example, they often show tendency to coalescence resulting in an
increased mean particle size, changed particle size distribution
and finally in oil and/or water separation. This instability is
even more pronounced when operating under varying and severe
process conditions. In this respect variables like make-up water
quality/composition, temperature, pH, tramp oil and metal fines in
the emulsion are considered important and crucial. In view of the
above it is emphasized that the values of these variables can vary
over wide ranges, well-known to those skilled in the art. For
example, water hardness values of between 0.degree. dH
(demineralized water) and 40.degree. dH for make-up water are
observed. Also known is that after preparation of the emulsion the
ionic strength and/or water hardness may change/increase
significantly during the operation due to evaporation of water or
incoming metal fines and ions, resulting in a reduction or loss of
relevant properties like emulsion stability, film forming
properties and dispersing capacity. Such instabilities of emulsions
are highly undesirable. Users of metalworking emulsions strongly
prefer stable emulsions having properties/performance which do not
change over time. Therefore, in the research and development area,
producers of these emulsions strive for maximization of the
emulsion stability, especially under practical, varying operating
conditions.
[0005] Unexpectedly, it has now been found that the stability
problems of metalworking fluids, being oil-in-water emulsions, or
even multiple emulsions, can be solved by using one or more
alkoxylated fatty alcohols as emulsifiers. Surprisingly, this type
of emulsion not only shows high emulsion stability under varying
and severe processing conditions, but also provides good foam
behavior, and shows good lubricating properties. Also the
above-mentioned type of emulsifier shows high responsiveness to
concentration changes. By varying the content of the emulsifier,
the formulator can influence directly the size of the oil droplets
in the emulsion, as desired.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a graph displaying foam height versus time for
emulsifiers of formula (I), versus a commercial standard.
[0007] FIG. 2 is a graph displaying foam height versus time for
inventive metalworking formulations including the emulsifiers of
formula (I), versus a commercial standard.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0008] A first embodiment of the present invention is directed to
the use of an alkoxylated fatty alcohol characterized by the
general formula (I)
RO--(CH.sub.2--CHR'--O).sub.n(CH.sub.2CH.sub.2--O).sub.m--H (I)
wherein R stands for a saturated and/or unsaturated alkyl moiety,
containing 12 to 22 C-Atoms, R' is a methyl-, ethyl-, or
propyl-group, m represents an number of 1 to 12, and preferably 4
to 10, n represents a number of 1 to 10, and preferably 2 to 8, as
an emulsifier in metalworking fluids, containing at least water and
one oil component, non-miscible with water, and optionally further
ingredients. The R moiety in formula (I) shows an iodine value of
between 15 and 75 g I.sub.2/100 g.
[0009] The compounds according to formula (I) are generally known.
It is preferred to have an unsaturated alkyl moiety in the fatty
alcohol part; mono-, di-, tri- and poly-unsaturated alkyl groups
are all suitable. The alkyl moiety "R" can be branched or linear.
Preferred fatty alcohols, used to prepare the compounds according
to formula (I) are selected from mono-unsaturated fatty alcohols
having 12 to 22, preferably 14 to 20 carbon atoms. Linear alcohols
are preferred over the branched ones.
[0010] Preferred unsaturated fatty alcohols in this context are
10-undecen-1-ol, (Z)-9-octadecen-1-ol (common name, oleyl alcohol),
(E)-9-octadecen-1-ol (common name, elaidyl alcohol),
(Z,Z)-9,12-octadecadien-1-ol (common name, linoleyl alcohol),
(Z,Z,Z)-9,12,15-octadecatrien-1-ol (common name, linolenyl
alcohol), (Z)-13-docosen-1-ol (common name, erucyl alcohol), and
(E)-13-docosen-1-ol (common name, brassidyl alcohol). Most
preferred is oleyl alcohol.
[0011] Preferred saturated fatty alcohols in this context are
1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol,
1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol,
1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol,
1-nonadecanol, 1-eicosanol, 1-heneicosanol and 1-behenylalcohol. In
addition, saturated, branched alcohols, such as Guerbet-type
alcohols are also suitable. Most preferred is cetyl alcohol
(hexadecane-1-ol).
[0012] As far as the alcohol-derived group "R" in formula (I) is
concerned, the iodine value is also important. Preferred ranges for
the iodine value (measured, for example, according to DGF-Method,
C-V 17a) are from 15 to 75, more preferably from 20 to 75, still
more preferably from 20 to 55, and most preferably from 25 to 50 g
I.sub.2/100 g. This value refers to the fatty alcohol stock, or
mixture, used to prepare the alkoxylates according to formula
(I).
[0013] The components according to formula (I) are mixed
alkoxylates, i.e. containing at least ethylene oxide moieties
together with propylene oxide, butylene oxide or pentylene oxide,
whereby the most preferred alkoxides are ethylene oxide and
propylene oxide. The indices m and n are numbers and may be
integers or fractional numbers, as the alkoxides are statistically
distributed during preparation. However, the teaching of the
present invention encompasses alkoxides with a narrow range of
alkoxides as well.
[0014] The alkoxylated components according to formula (I) are
prepared by standard methods known by the skilled person. The fatty
alcohol is reacted with the alkoxides in the presence of alkaline
catalysts at a temperature of about 120 to 220.degree. C. and a
pressure of about 100 to 500 kPa, to form the alkoxylated
end-product.
[0015] It is especially preferred to use such components according
to formula (I) wherein the amount of ethylene oxide is equal to or
higher than the amount of the other alkoxide, i.e. m.gtoreq.n.
Preferred values for m are in the range from 4 to 10, and in
particular 4 to 8; preferred values for n are in the range from 1
to 8, in particular from 1 to 5, and most preferably from 1 to 3.
However, also preferred are compounds where n stands for 4 to 6. In
addition, a preferred selection encompasses compounds according to
formula (I) wherein m is 4 to 10, and n is 1 to 8, or 1 to 5, or 1
to 3.
[0016] In the compounds according to formula (I) the sequence of
addition of ethylene oxide and the other alkoxide is not critical,
and can be randomized (mixed sequence of different alkoxides) or
block-wise.
[0017] However, it is a preferred embodiment that the compound
according to formula (I) contains two blocks: preferably, the first
one, adjacent to the alkyl moiety, contains the alkoxide,
preferably propylene oxide, and the last block contains the
ethylene oxide. Such compounds can be described with the general
formula RO--(CH.sub.2CR'--O).sub.n(CH.sub.2--CH.sub.2--O).sub.m--H,
or more simply as RO--(PO).sub.n-(EO).sub.m--H.
[0018] However, the above described general formula (I) is not to
be understood as being limited to any specific sequence of the
alkoxides moieties. Thus, this formula covers also block-wise
alkoxylated products like RO-(EO).sub.m--(PO).sub.n--H, and also
randomly distributed homologues thereof.
[0019] Generally, those compounds according to formula (I) are
preferred in which R' stands for a methyl group, i.e. those
compounds contain both ethylene oxide and propylene oxide
together.
[0020] A further preferred embodiment of the present invention
pertains to the use of a blend of components according to formula
(I), in which R represents in the one compound a saturated moiety,
and in the other compound an unsaturated moiety. The blends of
saturated and unsaturated compounds according to formula (I) may
vary across a broad range of weight ratio, for example the
saturated compound is present in amounts from 1 to 99% by weight,
and the unsaturated compound is present in amounts from 99 to 1% by
weight. But, in cases when those combinations of saturated and
unsaturated compounds are used, the amount of saturated compounds
of formula (I) could be greater than the amount of unsaturated
compounds according to formula (I). For example, the amount of the
unsaturated compound is in the range from 51 to 99% by weight, and
the amount of the saturated compound is from 1 to 49% by weight in
a preferred embodiment of the present invention.
[0021] However, a most preferred blend according to the invention
contains oleyl-(C18') and cetyl (C14)-based compounds according to
formula (I) together. These compounds may be present together in
weight ratios from 99:1 to 1:99, and particularly in the ratio from
4:1 to 1:4, and most particularly in the weight ratio from 9:1 to
3:1. It is particularly useful to have an excess of the oleyl-based
compound.
[0022] The use of alkoxylated fatty alcohols as emulsifiers for
metalworking fluids is not new per se. GB 1 462 357 discloses, for
the purpose of emulsifying, a combination of fatty alcohol
alkoxylates together with diesters of dicarboxylic acids. However,
GB 1 462 357 disclosed in the examples only ethoxylated fatty
alcohols, having saturated alkyl moieties. In contrast the present
invention selects alkoxylated fatty alcohols having at least two
different kinds of alkoxylates in the molecule. It is further
preferred to avoid the use of such diesters of dicarboxylic esters
in using the claimed process of the present invention. From WO
2008/089857 A1 cooling lubricants for the wet machining of aluminum
alloyed magnesium are known. In particular the use of water
miscible emulsions, containing particular fatty alcohols,
propoxylated and ethoxylated, in combination with selected
corrosion inhibitors for this purpose are disclosed. On page 15 in
"Tabelle 1" a specific fatty alcohol, based on a blend of C12-C14
alcohols, and being ethoxylated and propoxylated (3 EO+6 PO) is
disclosed. Those compounds are not preferred in the meaning of the
present teaching, and could be excluded from protection therefore.
The same is true in regard to the particular blend of the
ethoxylated oleyl alcohol, and the propoxylated oleyl/cetyl alcohol
as given in this "Tabelle 1" on page 15 of WO 2008/089857 A1. From
WO 2008/071582 A2 it is known, that propoxylated and ethoxylated
tallow fatty alcohols with an iodine value below 1 g I.sub.2/100 g,
can be used as emulsifiers.
[0023] Concerning the oil component of the emulsions according to
the invention it is stated that such a component can be selected
from the group consisting of mineral oils, synthetic lubricants,
natural triglycerides and blends of all mentioned base fluids.
Mineral oils are obtained by oil drilling and then fractionated and
purified. Other known oil components useful in metalworking fluids
according to the present invention are esters, poly-alpha-olefins,
polyglycols, and the like, all having a hydrophobic character and
for that reason suitable for the preparation of the metalworking
fluids according to the invention. In particular, esters may be
selected from the group consisting of (a) natural esters like
vegetable and animal fats and oils, being triglycerides of glycerol
and fatty acids, and (b) synthetic esters of polyalcohols (polyols)
and fatty acids of natural and synthetic origin. Examples of
synthetic esters include, without limitation, esters of fatty acids
and polyols, the latter including pentaerythritol,
trimethylolpropane, neopentylglycol, and the like.
[0024] As the metalworking fluids according to the invention are
preferably oil-in-water emulsions, in their final use the oil
content is generally at most 20 weight-%, preferably less than 15
weight-% and most preferably less than 10 weight-%. However, for
concentrated emulsions the oil content may even be up to 60
weight-%, for instance 50 weight-%.
[0025] Generally, those compounds according to formula (I) are
preferred in which R' stands for a methyl group, i.e. those
compounds contain both ethylene oxide and propylene oxide
together.
[0026] The emulsifier according to the invention is present in the
final metalworking fluids in amounts of preferably 0.1 to 25
weight-%, more preferably in amounts from 1 to 15 weight-%, and
most preferably in amounts from 1.5 to 10 weight-%.
[0027] The metalworking fluids according to the invention are
preferably oil-in water (o/w)-emulsions and more particularly
(o/w)-macro-emulsions having a mean particle size above 0.1 .mu.m.
Preferred ranges are from 0.1 to 100 .mu.m, and most preferred from
0.1 to 45 .mu.m.
[0028] Further, the metalworking fluids may comprise typical
additives, such as sulfur additives, for instance, a sulfurized oil
or fat, anti-wear agents and/or extreme pressure additives, as well
as corrosion inhibitors, defoamers, biocides and yellow metal
deactivators, and/or solubilizers. Thus, a preferred embodiment of
the invention encompasses the use of an alkoxylated fatty alcohol
characterized by the general formula (I) as an emulsifier in
metalworking fluids, containing at least water and one oil
component, non-miscible with water, and optionally, further
ingredients selected from the group of sulfur additives, anti-wear
agents, extreme pressure additives, corrosion inhibitors,
defoamers, biocides, yellow metal deactivators and
solubilizers.
[0029] A corrosion inhibitor is a highly preferred additive in the
metalworking fluids according to the invention. Corrosion
inhibitors are typically selected from, but not limited to, a
system containing a blend of fatty acids, fatty acid amides, and/or
fatty acid alkylamides, and/or fatty acid alkanolamides.
[0030] A typical yellow metal deactivator can be selected from the
families of the azoles. Illustrative azole-type corrosion
inhibitors are benzotriazole, tolutriazole, the sodium salt of
mercapto-benzotriazole, naphthotriazole, methylene
bis-benzotriazole, dodecyltriazole and butylbenzotriazole,
preferably tolutriazole.
[0031] Besides the emulsifiers according to the invention,
additional emulsifiers of different structure are preferred
components in the metalworking fluids. Typically, one emulsifier is
hydrophobic in nature, where the other emulsifier is more
hydrophilic. Co-emulsifiers are, for example, selected from
ethoxylated fatty alcohols, alkoxylated fatty acids or phenol-type
emulsifiers. Up to five different emulsifiers can be present in a
metalworking fluid.
[0032] The emulsifiers according to the present invention will be
preferably combined or blended together with other additives,
preferably corrosion inhibitors and co-emulsifiers, together with
the oil and water to form a concentrate, which itself is then used
to form a ready-made metalworking fluid.
[0033] Thus, a further embodiment of the present invention pertains
to an emulsion concentrate, containing at least one emulsifier
according to formula (I), one co-emulsifier, a corrosion inhibitor,
an oil component and, optionally, other ingredients, characterized
in that the amount of emulsifier according to formula (I) is at
least 2% by weight, more preferably at least 5% by weight, and at
maximum 30% by weight, preferably 25% by weight. Emulsion
concentrates are commonly the commercial forms of water-miscible
metalworking fluids. These concentrates contain typically an
emulsifier system, comprising at least two different emulsifiers, a
corrosion inhibitor system, and a base oil (mineral oils, ester
oils, polyglycols and the like), and optionally, additional
ingredients such as defoamers, biocides, solubilizers and extreme
pressure and/or anti wear additives (so-called EP/AW additives).
The amount of emulsifiers in such concentrates ranges from 5 to 30%
by weight, the base oil is present preferably in amounts from 50 to
75% by weight, corrosion inhibitors are present in amounts from 5
to 15% by weight, biocides are used in amounts from 0.01 to 1% by
weight, solubilizers are preferably present in amounts from 1 to 5%
by weight, and the EP/AW-additives are used in amounts from 2 to
10% by weight, with the proviso that the sum of all ingredients is
100% by weight. Water can be present also in smaller amounts, such
as 5 to 25% by weight, but it is only an optional ingredient.
[0034] The emulsions according to the invention can be obtained in
two different ways. Directly, the emulsions (in their final use)
are prepared by emulsification in water of an emulsifiable oil
containing the alkoxylated fatty alcohols according to the
invention. Indirectly, the emulsions can be prepared in 2 steps by
first making a concentrated emulsion (or using a concentrate, as
described above), and second by simply diluting this concentrated
emulsion with water. The concentrated emulsion is an oil-in-water
emulsion of about 60 weight-% oil in water stabilized with the
alkoxylated fatty alcohol emulsifiers. The final emulsion can be
prepared by simply diluting the concentrated emulsion with
water.
[0035] A further aspect of the invention is directed to the use of
the metalworking fluids in metalworking processes. Typical
metalworking processes involve elastic deformation, plastic
deformation and cold working of metals, with or without metal
removal. In some of these operations the metal piece is deformed
only; like in rolling and drawing of steel and aluminum, while in
others metal is removed rather than deformed, like in cutting,
grinding, broaching, machining and drilling of metals. The metallic
material from which the metalworking apparatus and articles to be
fabricated are made, include steel, cast iron, and ferrous alloys,
as well as aluminum alloys and other non-ferrous alloys, including
such components as titanium, magnesium, copper, tin and brass.
[0036] A last embodiment of the current application pertains to a
metalworking fluid, containing at least a water-phase, an oil-phase
which is not miscible with water, an emulsifier, and additional
compounds, selected from the group of emulsifiers, co-emulsifiers,
corrosion inhibitors, yellow metal deactivators, defoamers,
biocides, EP- and/or AW-additives, and solubilizers, characterized
that the fluid contains in amounts of 0.1 to 20.0% by weight as
emulsifier of at least one compound according to formula (I).
Examples
[0037] Two new emulsifiers were synthesized using standard
alkoxylation methods and run through different application tests in
comparison to a commercial nonionic emulsifier containing 5 parts
of ethylene oxide.
1. Synthesis of Emulsifier A
[0038] 333 g of oleyl/cetyl-alcohol were mixed with 1.4 g KOH
solution and dried under vacuum. Then 221 g of propylene oxide (PO)
was added first at 170-180.degree. C. and a pressure of at maximum
5 bars. After the propoxylation reaction had taken place, 146 g of
ethylene oxide (EO) were added under the same conditions. After
successful take-up of the oxides, the reaction was continued for
another 60 minutes. Then the reaction mixture was cooled,
neutralized, and filtered through TONSIL.RTM. brand bleaching
earth, and CELATOM.RTM. brand diatomaceous earth, to yield a pale
yellow, liquid product. The following physical data were measured
to characterize the material:
TABLE-US-00001 Density at 15.degree. C. 0.9520 g/cm.sup.3 Viscosity
at 40.degree. C. 24.8 mm.sup.2/s Viscosity at 100.degree. C. 6.0
mm.sup.2/s VI 172 Cloud point 4.degree. C. Pourpoint 3.degree. C.
Turbidity point in butyl 62.degree. C. diglycol HLB value 10.5
[0039] All measurements where carried out according to DIN
methods.
2. Synthesis of Emulsifier B
[0040] 244 g of oleyl/cetyl-alcohol were mixed with 1.4 g KOH
solution and dried under vacuum. Then 214 g of propylene oxide was
added first at 170-180.degree. C. and a pressure of at maximum 5
bars. After the propoxylation reaction had taken place, 243 g of
ethylene oxide was added under the same conditions. After
successful take-up of the oxides the reaction was continued for
another 60 minutes. Then the reaction mixture was cooled down,
neutralized, and filtered through TONSIL.RTM. brand bleaching
earth, and CELATOM.RTM. brand diatomaceous earth, to yield a pale
yellow, liquid product. The same data as with Emulsifier A were
measured to characterize the material:
TABLE-US-00002 Density at 15.degree. C. 0.978 g/cm.sup.3 Viscosity
at 40.degree. C. 40.6 mm.sup.2/s Viscosity at 100.degree. C. 8.4
mm.sup.2/s VI 188 Cloud point 8.degree. C. Pourpoint 0.degree. C.
Turbidity point in butyl 68.degree. C. diglycol HLB value 14.0
3. Comparison of Foaming Behavior
[0041] Emulsifier A, emulsifier B and a commercial nonionic
emulsifier with 5 EO were compared in terms of foaming. To evaluate
the 3 components a test was used as described below, using the SITA
FOAM TESTER.RTM. R-2000: [0042] Prepare a 1% solution in water
[0043] Place 300 ml of the solution in a beaker [0044] Run test
under stifling using the following parameters:
TABLE-US-00003 [0044] Sample volume: 300 ml Temperature: 20.degree.
C. tolerance: +/-0.5.degree. C. Stirrer velocity: 1100 min.sup.-1
Time of stirring: 10 sec. Cycles: 3 Interval of measurement: 10
sec. Time of foam decomposition: 20 min/0 ml foam height Cleaning:
shortened
[0045] The foam height is recorded for each interval and the decay
over 20 minutes. [0046] Average values of foam height versus time
are displayed in a diagram.
[0047] The build-up and decrease of the foam is showed in FIG. 1
for Emulsifier A and B in comparison with the commercial 5 EO
product. It can be clearly seen that both new emulsifiers generate
much less foam than the commercial 5 EO emulsifier, which has a
higher foaming tendency despite the higher HLB values of the new
emulsifiers A and B.
4. Lubrication Behaviour
[0048] The three previously tested emulsifiers were used in a basic
frame formulation containing base fluid, corrosion protection
package and emulsifier package. The following formulations were
used to evaluate Emulsifier A and B:
TABLE-US-00004 Content (w/w) Formulation A Formulation B
Formulation C 50.00% Ester Ester Ester 5.80% Monoethanolamine
Monoethanolamine Monoethanolamine 2.20% Triethanolamine
Triethanolamine Triethanolamine 14.00% Tall oil fatty acid Tall oil
fatty acid Tall oil fatty acid 3.80% Fatty Acid C8 Fatty Acid C8
Fatty Acid C8 6.00% Alkanolamide Alkanolamide Alkanolamide 10.60%
Hydrophobic Hydrophobic Hydrophobic emulsifier emulsifier
emulsifier 2.70% Butyldiglycol Butyldiglycol Butyldiglycol 4.90%
Emulsifier A Emulsifier B Commercial 5 EO product
[0049] The three frame formulations were tested for lubricating
performance using the Reichert Rig. The recorded wear scars are
listed below.
TABLE-US-00005 Formulation A Formulation B Formulation C Wear Scar
14.7 15.0 15.5
[0050] Both new emulsifiers show matching performance to other
commercial emulsifier.
5. Comparison of Foaming Behavior of Formulations
[0051] All three formulations prepared for the lubrication test
were run through the same foam test as the pure emulsifiers.
[0052] The build-up and decrease of the foam is showed in FIG. 2
for Formulation A and B in comparison with Formulation C. The
results and conclusions of the pure emulsifiers could be clearly
mirrored in the respective frame formulations.
6. Emulsion Behaviour in Different Base Fluids
[0053] To show the versatility towards different base fluids the
three emulsifiers were blended in specific percentage in 4
different fluids: two esters of different chemical structure
(Trimethylolpropane-trioleate, TMP-trioleate; 2-ethylhexyloleate,
2-EH-oleate) and 2 petrochemical fluids (Naphthenic oil; Paraffinic
oil).
[0054] These concentrates were then diluted 5% in water for a
particle size measurement. Average, median and maximum values of
the oil droplet distribution were recorded. All three values should
ideally be very equal. But due to the logarithmic scale of the x
axis higher deviations can be accepted when bigger droplets are
present. The average value equals the particle size, which
represents the arithmetic middle particle size when recognizing the
logarithmic scale. The median value represents the particle size,
till which 50% of all oil droplets are measured. The maximum value
represents the particle size, of which the high percentage is
present in the emulsion.
[0055] The results are given in tables 1 and 2, below, for both of
the new emulsifiers in the 4 different base fluids.
TABLE-US-00006 TABLE 1 Concentration Appearance Appearance Average
Value Median Value Maximum Value Base Oil Emulsifier Emulsifier
Concentrate Emulsion [.mu.m] [.mu.m] [.mu.m] TMP-trioleate A 10%
Clear OK 13.69 6.21 4.87 20% Clear OK 6.281 5.831 8.537 25% Clear
OK 15.29 10.16 23.82 2-EH-oleate A 10% Little Haze separated 16.82
11.72 34.59 20% Little Haze OK 12.7 7.806 7.084 25% Little Haze OK
10.02 6.756 6.45 Naphthenic Oil A 10% Cloudy OK 12.28 10.91 18 20%
Cloudy OK 18.87 18.29 21.7 25% Cloudy OK 14.14 7.69 4.05 Paraffinic
Oil A 10% Little Haze OK 11.69 7.973 13.61 20% Little Haze OK 3.035
2.706 3.06 25% Little Haze OK 0.46 0.486 0.688
TABLE-US-00007 TABLE 2 Concentration Appearance Appearance Average
Value Median Value Maximum Value Base Oil Emulsifier Emulsifier
Concentrate Emulsion [.mu.m] [.mu.m] [.mu.m] TMP-trioleate B 20%
Little Haze Creaming 24.99 13.95 34.59 2-EH-oleate B 10% Little
Haze separated 20.11 14.73 41.68 20% Little Haze OK 13.76 9.806
34.59 25% Little Haze OK 4.235 1.384 0.117 Naphthenic Oil B 10%
Little Haze OK 12.33 7.733 12.4 20% Clear OK 8.968 6.991 9.026 25%
Clear OK 0.131 0.088 0.088 Paraffinic Oil B 10% Haze Creaming 17.02
11.59 26.15 20% Little Haze OK 6.452 2.329 2.313 25% Clear OK 0.123
0.122 0.117
[0056] It can be seen, that Emulsifier A is highly suitable for all
kinds of base fluids, while Emulsifier B is more effective in terms
of mono-esters in higher concentrations and in general for
petrochemical base oils.
[0057] As comparative example the same measurements as for
Emulsifiers A and B where carried out for Example C. As can be seen
in Table 3 the droplet size is only weakly influenced by the
concentration of emulsifier C, and the properties of the emulsions
are less advantageous than the emulsions prepared in accordance
with the invention. In particular, the concentration of the
emulsifier C does not trigger the droplet size in the same manner
as the inventive emulsifiers A and B.
TABLE-US-00008 TABLE 3 Concentration Appearance Appearance Average
Value Median Value Maximum Value Base Oil Emulsifier Emulsifier
Concentrate Emulsion [.mu.m] [.mu.m] [.mu.m] TMP-trioleate C 5%
Clear OK 4.91 3.005 2.539 10% Little Haze Creaming 3.379 2.263
2.107 30% Cloudy Separate 4.806 2.842 2.539
* * * * *