Note: Descriptions are shown in the official language in which they were submitted.
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
Succinic acid semi-amides as anti-corrosive agents
The present invention relates to compositions comprising succinic acid semi-
amides and to
the use of those compositions in improving the use properties of lubricants,
such as hydraulic
or metal-working fluids, greases, gear oils or engine oils.
Additives that have to fulfil demanding tasks, such as a high load-bearing
capacity, protection
against wear and corrosion, and antioxidant action, are added to lubricants.
In addition, the
properties of lubricants should not be modified disadvantageously in the
presence of con-
taminants. Often, in mineral oil industry enterprises, oils are admixed with
commercially avai-
lable additive concentrates or "packages". Contamination with water, calcium
detergents and
residues of other lubricants may occur during the mixing process. As a result,
the action of
the additive components with respect to corrosion is reduced, for example
owing to formation
of hydrolysis products and precipitation of poorly soluble calcium residues,
the latter being
especially disadvantageous because they block filter systems.
The present invention relates to the problem of producing lubricant
compositions that provide
improved protection against corrosion, combined with good compatibility with
calcium ions.
U.S. Patent Specification 4 462 918 discloses lubricant compositions providing
protection
against wear and corrosion, which comprise a component of the N-acyl-N-
alkylaminosuccinic
acid ester type (aspartic acid esters, aspartates).
U. S. Patent Specification 5 275 749 discloses lubricant compositions
providing protection
against wear and corrosion, which comprise a component of the N-acyl-N-
alkoxyalkylamino-
succinic acid ester type.
It has now been found, surprisingly, that succinic acid semi-amides, which are
obtainable by
reacting succinic acid anhydride with ~3-amino acid derivatives, improve the
corrosion protec-
tion in lubricant compositions whilst at the same time the formation of
precipitation products
and residues is reduced.
The invention relates to compositions comprising
a) At least one compound of formula
R2
R~~N~X
O R3
O
O~Y''
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-2-
Wherein
R~ is a substituent selected from the group consisting of C1-Czzalkyl, Cz-
Czzalkyl sub-
stituted by hydroxy, Cz-Czzalkyl interrupted by -C(=O)-, -O-C(=O)- or by
-NRa C(=O)-, C3-Czzalkyl interrupted by -O-, -S-, -NRa , -C(=O)-O- or by
-C(=O)-NRa , wherein Ra denotes hydrogen or C~-Czzalkyl, phenyl, benzyl, 1- or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl, 1-naphthylmethyl,
cyclohexyl,
cyclohexylmethyl, and isobornyl;
Rz and R3 are hydrogen, or one of Rz and R3 is hydrogen and the other is
methyl; and
X is carboxy or carboxylate and Y+ is a salt-forming cation suitable for
lubricant com-
positions; or
X is derivatised carboxy selected from the group consisting of cyano, carboxy
esteri-
fied by C,-Czzalkyl, carboxy esterified by hydroxy-Cz-Czzalkyl, carboxy
esterified by
Cz-Czzalkyl interrupted by -C(=O)-, -C(=O)-O- or by -C(=O)-NRa , carboxy
esterified
by C3-Czzalkyl interrupted by -O-, -S-, -NRa , -O-C(=O)- or by -NRa (C=O)-,
wherein
Ra denotes hydrogen or C1-Czzalkyl, carboxy esterified by phenyl, benzyl, 1-
or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl, 1-naphthylmethyl,
cyclohexyl,
cyclohexylmethyl, isobornyl, and carbamoyl of the partial formula
O~~
-R
~Nv
R
Wherein Rb and R~ are each independently of the other hydrogen, Ci-Czzalkyl or
2-hydroxyethyl, or Rb and R~ together are Cz-C8alkylene, Cz-C8alkenylene,
Cz-C8alkadienylene or Cz-Cealkylene, Cz-Cealkenylene or Cz-Caalkadienylene
inter-
rupted by -O- or by -NRa with Ra being as defined; and
Y+ is a hydrogen ion or is a salt-forming cation suitable for lubricant
compositions; and
b) A base oil of lubricating viscosity.
The compounds (I) have excellent corrosion-inhibiting action combined with
good compatibil-
ity with calcium ions, which may be present in lubricants especially as
constituents of deter-
gents.
A preferred embodiment relates to compositions comprising
a) At least one compound (I), wherein
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-3-
R, is a substituent selected from the group consisting of C,-C22alkyl, CZ-
C22alkyl substi-
tuted by hydroxy, C2-C2zalkyl interrupted by -C(=O)-, -O-C(=O)- or by -NRa
C(=O)-,
C3-C22alkyl interrupted by -O-, -S-, -NRa , -C(=O)-O- or by -C(=O)-NRa ,
wherein Ra de-
notes hydrogen or C,-C2Zalkyl, phenyl, benzyl, 1- or 2-phenylethyl, 2-
phenoxyethyl,
furfuryl, 1-naphthyl, 1-naphthylmethyl, cyclohexyl, cyclohexylmethyl and
isobornyl;
R2 and R3 are hydrogen, or one of R2 and R3 is hydrogen and the other is
methyl;
X is derivatised carboxy selected from the group consisting of cyano, carboxy
esterified
by C,-C22alkyl, carboxy esterified by hydroxy-C2-C22alkyl, carboxy esterified
by
C2-C22alkyl interrupted by -C(=O)-, -C(=O)-O- or by -C(=O)-NRa , carboxy
esterified by
C3-C22alkyl interrupted by -O-, -S-, -NRa , -O-C(=O)- or by -NRa (C=O)-,
wherein Ra de-
notes hydrogen or C,-C22alkyl, carboxy esterified by phenyl, benzyl, 1- or 2-
phenylethyl,
2-phenoxyethyl, furfuryl, 1-naphthyl, 1-naphthylmethyl, cyclohexyl,
cyclohexylmethyl,
isobornyl, and carbamoyl of the partial formula (A), wherein Rb and R~ are
each inde-
pendently of the other hydrogen, C,-C22alkyl or 2-hydroxyethyl, or Rb and R~
together
are C2-C$alkylene, C2-CBalkenylene, Cz-C8alkadienylene or C2-Csalkylene, C2-
CBalk-
enylene or C2-CBalkadienylene interrupted by -O- or by -NRa , Ra being as
defined; and
Y+ is a hydrogen ion or is a salt-forming cation suitable for lubricant
compositions; and
b) A base oil of lubricating viscosity.
An especially preferred embodiment corresponds to the following compositions
comprising
a) At least one compound (I), wherein
R, is a substituent selected from the group consisting of C,-C22alkyl, C2-
C22alkyl inter-
rupted by -C(=O)- or by -O-C(=O)-, C3-C22alkyl interrupted by -O- , -S- or by -
C(=O)-O-,
phenyl and benzyl;
R2 and R3 are hydrogen;
X is derivatised carboxy selected from the group consisting of cyano, carboxy
esterified
by C,-C22alkyl, carboxy esterified by hydroxy-CZ-C22alkyl, carboxy esterified
by
C2-C22alkyl interrupted by -C(=O)- or by -C(=O)-O-, carboxy esterified by C3-
CZZalkyl
interrupted by -O-, -S- or by -O-C(=O)-, and carbamoyl of the partial formula
(A) defined
as heterocyclylcarbonyl; and
Y+ is a hydrogen ion, ammonium, (C,-C4alkyl),_4ammonium or (2-hydroxyethyl),_4-
ammonium; and
b) A base oil of lubricating viscosity.
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-4-
A very especially preferred embodiment relates to compositions comprising
a) At least one compound (I), wherein
Ri is a substituent selected from the group consisting of C~-C22alkyl, C3-
C22alkyl inter-
rupted by -O-, phenyl, and benzyl;
R2 and R3 are hydrogen;
X is derivatised carboxy selected from the group consisting of cyano, carboxy
esterified
by C,-C2zalkyl, carboxy esterified by C3-CZZalkyl interrupted by -O-, and
carbamoyl of
the partial formula (A) defined as piperidinocarbonyl, piperazinylcarbonyl or
morpholi-
nocarbonyl; and
Y+ is a hydrogen ion, ammonium, (C,-C4alkyl)i.~ammonium or (2-hydroxyethyl)1_a-
ammonium; and
b) A base oil of lubricating viscosity.
A likewise very especially preferred embodiment relates to compositions
comprising
a) At least one compound (I), wherein
Ri is a substituent selected from the group consisting of Ci-ClBalkyl, C3-
ClBalkyl interrupted
by -O-, phenyl, and benzyl;
R2 and R3 are hydrogen;
X is carboxy and Y is ammonium, (Ci-C4alkyl)~.~ammonium or (2-hydroxyethyl)1_a-
ammonium; or
X is carboxylate or derivatised carboxy selected from the group consisting of
cyano, car
boxy esterified by C1-ClBalkyl, carboxy esterified by C3-Ci8alkyl interrupted
by -O-, and
morpholinocarbamoyl; and
Y+ is hydrogen, ammonium, (C~-C4alkyl)i.~ammonium or (2-
hydroxyethyl)i~ammonium; and
b) A base oil of lubricating viscosity.
The compounds (I) are prepared in a manner known per se, for example by
addition of a
primary amine R1-NH2 to an acrylic acid derivative:
R2~X
H R3 (X = carboxy, carboxylate or derivatised carboxy)
(Addition of amines to a,~3-unsaturated carbonyl compounds) to form a ~3-amino
acid deriva-
tive:
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-5-
R2
R1'N X
I
H R
3
s
Which is acylated with a reactive, functional derivative of succinic acid, for
example succinic
anhydride or succinic acid monochloride.
DE-A-2 054 649 describes the addition of primary amines to acrylic acid esters
and the sub-
sequent reaction with succinic anhydride. The compounds described therein can
be used,
inter alia, as textile adjuvants.
The terms and general designations used in the description of the present
invention are pref-
erably defined as follows:
Component a) Compounds (I)
R1 and Ra defined as Ci-C22alkyl include saturated, unbranched or, where
possible, bran-
ched hydrocarbon groups, especially Ci-C9alkyl, e.g. methyl, ethyl, isopropyl,
n-butyl, iso-
butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-
methylpentyl, 1,3-di-
methylbutyl, n-heptyl, 3-heptyl, 1-methylhexyl, isoheptyl, n-octyl, 2-
ethylhexyl, 1,1,3,3-tetra-
methylbutyl, 1-methylheptyl, n-nonyl or 1,1,3-trimethylhexyl, and also Cio-
C22alkyl, especially
straight-chain Cio-C22alkyl, e.g. n-decyl, n-dodecyl, n-tetradecyl, n-
hexadecyl or n-octadecyl
or branched Cio-C22alkyl, e.g. 1,1,3-trimethylhexyl, 1-methylundecyl, 2-n-
butyl-n-octyl,
isotridecyl, 2-n-hexyl-n-decyl or 2-n-octyl-n-dodecyl, or higher homologues
thereof.
R1 defined as C2-C22alkyl substituted by hydroxy includes saturated,
unbranched hydrocar-
bon groups having preferably from 2 to 9 carbon atoms, e.g. 2-hydroxyethyl or
2- or 3-hy-
droxypropyl.
Ri defined as C2-C22alkyl interrupted by -C(=O)-, -O-C(=O)- or by -NRa C(=O)-
includes un-
branched or branched hydrocarbon groups preferably having from 2 to 9 carbon
atoms, e.g.
acetonyl, acetoxycarbonylmethyl, 2-acetoxycarbonylethyl, 2-tert-
butoxycarbonylethyl or N,N-
diethylcarbamoyl.
R1 defined as C3-C22alkyl interrupted by -O-, -S-, -NRa , -C(=O)-O- or by -
C(=O)-NRa in-
cludes unbranched or branched hydrocarbon groups preferably having from 3 to
18 carbon
atoms, e.g. 2-methoxyethyl, 2- or 3-methoxypropyl, 2-, 3- or 4-methoxybutyl, 2-
ethoxyethyl,
2- or 3-ethoxypropyl, 2-, 3- or 4-ethoxybutyl, 2-n-propoxyethyl, 2- or 3-n-
propoxypropyl, 2-, 3-
or 4-n-propoxybutyl, 2-isopropoxyethyl, 2- or 3-isopropoxypropyl, 2-, 3- or 4-
isopropoxybutyl,
2-n-butoxyethyl, 2- or 3-n-butoxypropyl, 2-, 3- or 4-n-butoxybutyl, 2-tert-
butoxyethyl, 2- or
3-tert-butoxypropyl, 2-, 3- or 4-tert-butoxybutyl, 2-methylthioethyl, 2- or 3-
methylthiopropyl, 2-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-6-
ethylthioethyl, 2-dimethylaminoethyl, 2- or 3-dimethylaminopropyl, 2-
diethylaminoethyl, 2- or
3-diethylaminopropyl, 2-acetoxyethyl or 2-(N-acetoxy-N-methyl)-ethyl.
In compounds (I), R2 and R3 are hydrogen, or one of R2 and R3 is hydrogen and
the other is
methyl. Preferably, R2 and R3 are hydrogen.
When X in compounds (I) is carboxy or carboxylate [-C(=O)-O'], Y+ is a salt-
forming cation
suitable for lubricant compositions, e.g. ammonium, tetramethylammonium,
tetraethylammo-
nium or 2-hydroxyethyltrimethylammonium. There is present only one carboxy
group in sub-
stantially undissociated form [-C(=O)-OH] or in salt form [-C(=O)-O'], e.g.
with ammonium
ions, e.g. ammonium, tetramethylammonium, tetraethylammonium or 2-hydroxyethyl-
trimethylammonium.
In a preferred embodiment, X is derivatised carboxy or unsubstituted or
substituted car-
bamoyl as defined hereinbelow. Y+ is then a hydrogen ion or a salt-forming
cation suitable for
lubricant compositions.
X defined as carboxy esterified by C1-C22alkyl is, for example, a carboxy
group which is es-
terified by the Ci-CZZalkyl groups defined hereinabove for R,, e.g. saturated,
unbranched or,
where possible, branched hydrocarbon groups, e.g. methyl, ethyl, isopropyl, n-
butyl, isobutyl,
tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-
methylpentyl, 1,3-dimethyl-
butyl, n-heptyl, 3-heptyl, 1-methylhexyl, isoheptyl, n-octyl, 2-ethylhexyl,
1,1,3,3-tetramethyl-
butyl, 1-methylheptyl, n-nonyl or 1,1,3-trimethylhexyl, and also by Cio-
C22alkyl, especially
straight-chain Cio-C22alkyl, e. g. n-decyl, n-dodecyl, n-tetradecyl, n-
hexadecyl or n-octadecyl.
X defined as carboxy esterified by hydroxy-C2-C22alkyl is, for example, a
carboxy group that
is esterified by hydroxy-C2-C22alkyl defined hereinabove for Ri, e.g. 2-
hydroxyethoxy-
carbonyl or 2- or 3-hydroxypropoxycarbonyl.
X defined as carboxy esterified by C2-C22alkyl interrupted by -C(=O)-, -C(=O)-
O- or by
-C(=O)-NRa is, for example, a carboxy group esterified by CZ-C22alkyl, defined
hereinabove
for R1, interrupted by -C(=O)-, -C(=O)-O- or -C(=O)-NRa , e.g.
acetonyloxycarbonyl, acetoxy-
carbonylmethoxycarbonyl or 2-acetoxycarbonylethoxycarbonyl.
X defined as carboxy esterified by C3-C22alkyl interrupted by -O-, -S-, -NRa ,
-O-C(=O)- or by
-NRa (C=O)- is, for example, a carboxy group esterified by C3-C22alkyl
(defined hereinabove
for R1) interrupted by -O-, -S-, -NRa-, -O-C(=O)- or by -NRa (C=O)-, e.g. 2-
methoxyethoxy-
carbonyl, 2- or 3-methoxypropoxycarbonyl, 2-, 3- or 4-methoxybutoxycarbonyl, 2-
ethoxyeth-
oxycarbonyl, 2- or 3-ethoxypropoxycarbonyl, 2-, 3- or 4-ethoxybutoxycarbonyl,
2-methylthio-
ethoxycarbonyl, 2- or 3-methylthiopropoxycarbonyl, 2-ethylthioethoxycarbonyl,
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
_7-
2-dimethylaminoethoxycarbonyl, 2- or 3-dimethylaminopropoxycarbonyl, 2-
diethylamino-
ethoxycarbonyl, 2- or 3-diethylaminopropoxycarbonyl, 2-acetoxyethoxycarbonyl
or 2-(N-
acetoxy-N-methyl)-ethoxycarbonyl.
X defined as carbamoyl of the partial formula A is, for example, carbamoyl,
dimethyl- or di-
ethyl-carbamoyl. In addition, Rb and R~ may be linked to one another by C2-
Caalkylene, e.g.
1,4-n-butylene or 1,5-n-pentylene, by CZ-CBalkenylene, e.g. 2-butenylene, or
by C2-CBalka-
dienylene, e.g. 1,3-butadienylene and, together with -N<, form a heterocycle
which may, in
turn, contain further hetero atoms, e.g. N or O. In that case, the partial
formula A corre-
sponds to a heterocyclylcarbonyl substituent, e.g. piperidinocarbonyl,
piperazinylcarbonyl or
morpholinocarbonyl.
In the compounds (I) described hereinabove, the sum of the carbon atoms
present in R1 and
X is preferably greater than ten.
The definition used for Y+, "a salt-forming cation suitable for lubricant
compositions", includes
those cations of salt-formers that together with the carboxylate group form
metal salts suit-
able for lubricant compositions, e.g. alkali metal, alkaline earth metal, zinc
(Zn2+) or copper
(Cu2+) salts, e.g. sodium, potassium, calcium, zinc2+ or Cu2+ ions.
In a preferred embodiment of the invention, the definition used for Y+, "a
salt-forming cation
suitable for lubricant compositions", is understood to mean those cations of
salt-formers that
together with the carboxylate group form suitable, non-metallic salts, e.g.
ammonium,
(C1-C22alkyl),~ammonium or (2-hydroxyethyl)1_4ammonium, e.g.
tetramethylammonium, tet-
raethylammonium or 2-hydroxyethyltrimethylammonium.
The compounds (I) are readily soluble in oils and can be admixed with a base
oil of lubricat-
ing viscosity, e.g. a lubricant, in a manner known per se.
Component b) Base oil
The definition "base oil of lubricating viscosity" includes, for example,
lubricants that can be
used for hydraulic or metal-working fluids, greases, gear oils or engine oils.
Suitable lubricants are based, for example, on mineral or synthetic oils or
mixtures thereof.
The person skilled in the art will be familiar with the lubricants, which are
described in the
relevant technical literature, for example in Chemistry and Technology of
Lubricants; Mortier,
R. M. and Orszulik, S. T. (Edifors); 1992 Blackie and Son Ltd. for GB, VCH-
Publishers N. Y, for
U. S., ISBN 0-216-92921-0, see pages 208 ff and 269 ff; in Kirk-Othmer
Encyclopedia of
Chemical Technology, Fourth Edition 1969, J. Wiley & Sons, New York, VoG 13,
page 533 ff
(Hydraulic Fluids); Performance Tesfing of Hydraulic Fluids; R. Tourret and
E.P. Wright, Hy-
den & Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN D
85501 317 6;
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
_g-
Ullmann's Encyclopaedia of Ind. Chem., Fifth Completely Revised Edition,
Verlag Chemie,
DE-liVeinheim, VCH-Publishers for U.S., Vol. A 15, page 423 ff (Lubricants),
Vol. A 13, page
165 ff (Hydraulic Fluids).
The lubricants are especially oils and greases, for example based on mineral
oil or vegetable
and animal oils, greases, tallow and wax or mixtures thereof. Vegetable and
animal oils,
greases, tallow and wax are, for example, palm-kernel oil, palm oil, olive
oil, rapeseed oil,
rape oil, linseed oil, soybean oil, cottonseed oil, sunflower oil, coconut
oil, maize oil, castor
oil, tree nut oil and mixtures thereof, fish oils, and their chemically
modified forms, for exam-
ple epoxidised and sulphoxidised forms, or forms produced by genetic
engineering, for
example soybean oil produced by genetic engineering.
Examples of synthetic lubricants include lubricants based on aliphatic or
aromatic carboxylic
acid esters, polymeric esters, polyalkylene oxides, phosphoric acid esters,
poly-c~olefins or
silicones, diesters of a divalent acid with a monohydric alc~hol, such as, for
example, dioctyl
sebacate or dinonyl adipate, triesters of trimethylolpropane with a monovalent
acid or with a
mixture of such acids, such as, for example, trimethylolpropane
tripelargonate, trimethylol-
propane tricaprylate or mixtures thereof, tetraesters of pentaerythritol with
a monovalent acid
or with a mixture of such acids, such as, for example, pentaerythritol
tetracaprylate, or com-
plex esters of monovalent and divalent acids with polyhydric alcohols, for
example a complex
ester of trimethylolpropane with caprylic and sebacic acid, or a mixture
thereof. Apart from
mineral oils there are especially suitable, for example, poly-a-olefins, ester-
based lubricants,
phosphates, glycols, polyglycols and polyalkylene glycols, and also mixtures
thereof with
water.
An organic or inorganic thickener can also be added to the mentioned
lubricants or mixtures
thereof (base grease). Metal-working fluids and hydraulic fluids can be
prepared on the basis
of the same substances as described hereinabove for the lubricants. Such
fluids are fre-
quently also emulsions of such substances in water or other liquids.
The compositions advantageously contain from 0.005 to 10.0 % by weight,
preferably from
0.01 to 5.0 °l° by weight, especially from 0.01 to 0.9 % by
weight, of compounds (I).
The compositions are used, for example, in hydraulic or metal-working fluids,
greases, gear
oils, or oils for engines of the Otto, diesel, two-stroke, Wankel or orbital
type.
The mentioned lubricants may additionally comprise other additives that are
added in order
to improve their basic properties still further; such additives include:
antioxidants, metal de-
activators, rust inhibitors, viscosity index improvers, pour-point
depressants, dispersants,
detergents, extreme-pressure additives, anti-wear additives and friction
reducers. Such addi-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
_g_
tives are added in the customary amounts in each case, in the range of about
from 0.01 to
10.0 % by weight of each. The following are examples of further additives:
Phenolic antioxidants
1-Alkvlated monoahenols: 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-
dimethylphenol, 2,6-
di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-
butyl-4-isobutyl-
phenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-
dimethylphenol, 2,6-
dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-
methoxymethyl-
phenol, linear nonylphenols or nonylphenols branched in the side-chain, e.g.
2,6-dinonyl-
4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)-phenol, 2,4-dimethyl-6-
(1'-methyl-
heptadec-1'-yl)-phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)-phenol and
mixtures thereof.
2. Alkylthiometh r~l phenols: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-
dioctylthiomethyl-6-
methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-
nonylphenol.
3. Hydroauinones and alk lay ted hydroauinones: 2,6-di-tert-butyl-4-
methoxyphenol, 2,5-di-
tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-
octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-
butyl-4-hy-
droxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-
butyl-4-hydroxy-
phenyl) adipate.
4. Tocoaherols: a-, [i-, 'y or b-tocopherols and mixtures thereof (vitamin E).
5. Hydroxylated thiodiahenyl ethers: 2,2'-thiobis(6-tert-butyl-4-
methylphenol), 2,2'-thiobis(4-
octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-
butyl-2-methyl-
phenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-
hydroxyphenyl)
disulphide.
6. Alkylidene bisphenols: 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-
methylene-
bis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-
methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-
methylphe-
nol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-
tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis(6-(a-
methylbenzyl)-4-
nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-
methylene-
bis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-
butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-
hydroxybenzyl)-4-
methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-
bis(5-tert-butyl-
4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis(3,3-
bis(3'-tert-
butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-
phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-
tert-butyl-4-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-10-
methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-
bis(3,5-di-
tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tart-butyl-4-hydroxy-2-
methylphenyl)-4-n-
dodecylmercaptobutane, 1,1,5,5-tetra(5-tart-butyl-4-hydroxy-2-
methylphenyl)pentane.
7. O-. N- and S-benzyl compounds: 3,5,3',5'-tetra-tart-butyl-4,4'-
dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-
di-tert-
butylbenzyl mercaptoacetate, tris(3,5-di-tart-butyl-4-hydroxybenzyl)amine,
bis(4-tart-butyl-
3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3,5-di-tart-butyl-4-
hydroxybenzyl)
sulphide, isooctyl-3,5-di-tart-butyl-4-hydroxybenzyl mercaptoacetate.
8. Hvdrox rb~ylated malonates: dioctadecyl 2,2-bis(3,5-di-tart-butyl-2-
hydroxybenzyl)malo-
nate, dioctadecyl 2-(3-tart-butyl-4-hydroxy-5-methylbenzyl)malonate,
didodecylmercap-
toethyl 2,2-bis(3,5-di-tart-butyl-4-hydroxybenzyl)malonate, di-[4-(1,1,3,3-
tetramethylbu-
tyl)phenyl] 2,2-bis(3,5-di-tart-butyl-4-hydroxybenzyl)malonate.
9. Hvdroxybenzyl aromatic compounds: 1,3,5-tris(3,5-di-tart-butyl-4-
hydroxybenzyl)-2,4,6-
trimethylbenzene, 1,4-bis(3,5-di-tart-butyl-4-hydroxybenzyl)-2,3,5,6-
tetramethylbenzene,
2,4,6-tris(3,5-di-tart-butyl-4-hydroxybenzyl)phenol.
10. Triazine compounds: 2,4-bisoctylmercapto-6-(3,5-di-tart-butyl-4-
hydroxyanilino)-1,3,5-.
triazine, 2-octylmercapto-4,6-bis(3,5-di-tart-butyl-4-hydroxyanilino)-1,3,5-
triazine, 2-octyl-
mercapto-4,6-bis(3,5-di-tart-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-
tris(3,5-di-tert-
butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tart-butyl-4-
hydroxybenzyl) iso-
cyanurate, 1,3,5-tris(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
2,4,6-
tris(3,5-di-tart-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-
tart-butyl-4-hy-
droxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-
hydroxyben-
zyl) isocyanurate.
11. Acylaminophenols: 4-hydroxylauric acid anilide, 4-hydroxystearic acid
anilide, N-(3,5-di-
tart-butyl-4-hydroxyphenyl)carbamic acid octyl ester.
12. Esters of beta-(3,5-di-tart-butyl-4-hydro phenyl propionic acid with mono-
or poly-hydric
alcohols, for example with methanol, ethanol, n-octanol, isooctanol,
octadecanol, 1,6-hex-
anediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-
thiapentadecanol, trimethyl-
hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicy-
clo[2.2.2]octane.
13. Esters of beta-(5-tart-but~rl-4-hydroxy-3-methylphen~ propionic acid (with
mono- or poly-
hydric alcohols): with methanol, ethanol, n-octanol, isooctanol, octadecanol,
1,6-hexane-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-11-
diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene gly-
col, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-
thiapentadecanol, trimethyl-
hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-
trioxabicyclo[2.2.2]oc-
tane.
14. Esters of beta-(3,5-dicyclohexyl-4-hydroxyphenyl~aroaionic acid with mono-
or poly-hy-
dric alcohols, e.g. with the alcohols mentioned under 13..
15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or poly-
hydric alcohols,
e.g. with the alcohols mentioned under 13..
16. Amides of beta-(3,5-di-tert-butyl-4-hydrox rpwllaroaionic acid, for
example N,N'-
bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-
bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-
4-hydroxy-
phenylpropionyl)hydrazine.
Amine-type antioxidants
N,N'-Di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-
dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-
phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-
phenylenediamine, N,N'-
diphenyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylenediamine, N-
isopropyl-N'-
phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-me-
thylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-
phenylenediamine, 4-(p-
toluenesulphonamido)-diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-
phenylenediamine,
diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-
naphthyl-
amine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine,
octylated di-
phenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-
butylaminophenol, 4-butyryl-
aminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-
octadecanoylamino-
phenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-
dimethylaminomethylphenol, 2,4'-dia-
minodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-
diaminodi-
phenylmethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,2-
di(phenylamino)propane, (o-tolyl)-
biguanide, di[4-(1',3'-dimethylbutyl)phenylJamine, tert-octylated N-phenyl-1-
naphthylamine,
mixture of mono- and di-alkylated tert-butyl-/tert-octyl-diphenylamines,
mixture of mono- and
di-alkylated nonyldiphenylamines, mixture of mono- and di-alkylated
dodecyldiphenylamines,
mixture of mono- and di-alkylated isopropyl-/isohexyl-diphenylamines, mixtures
of mono- and
di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-
benzothiazine, phe-
nothiazine, mixture of mono- and di-alkylated tert-butyl-/tert-octyl-
phenothiazines, mixture of
mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-12-
1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperidin-4-yl-
hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethypiperidin-4-
one, 2,2,6,6-
tetramethylpiperidin-4-ol.
Further antioxidants
Ascorbic acid (vitamin C), aliphatic or aromatic phosphites, esters of
thiodipropionic acid or
thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid,
2,2,12,12-tetramethyl-
5,9-dihydroxy-3,7,11-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-
3,7,10,14-
tetrathiahexadecane.
Metal deactivators, for example for copper
1- Benzotriazoles and derivatives thereof: 2-mercaptobenzotriazole, 2,5-
dimercaptobenzo-
triazole, 4- or 5-alkylbenzotriazoles (e.g, tolutriazole) and derivatives
thereof, 4,5,6,7-tet-
rahydrobenzotriazole, 5,5'-methylene-bisbenzotriazole; Mannich bases of
benzotriazole or
tolutriazole, such as 1-[di(2-ethylhexyl)aminomethyl]tolutriazole and 1-[di(2-
ethylhexyl)-
aminomethyl]benzotriazole; alkoxyalkylbenzotriazoles, such as 1-
(nonyloxymethyl)ben-
zotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-
cyclohexyloxybutyl)tolutriazole.
2. 1.2.4-Triazoles and derivatives thereof: 3-alkyl- (or aryl-)1,2,4-
triazoles, Mannich bases of
1,2,4-triazoles, such as 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole;
alkoxyalkyl-1,2,4-
triazoles, such as 1-(1-butoxyethyl)-1,2,4-triazole; acylated 3-amino-1,2,4-
triazoles.
3. Imidazole derivatives: 4,4'-methylenebis(2-undecyl-5-methylimidazole);
bis[(N-methyl)-
imidazol-2-yl]carbinol-octyl ether.
4. Sulphur-containing heterocyclic compounds: 2-mercaptobenzothiazole, 2,5-
dimercapto-
1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof; 3,5-
bis[di(2-
ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one.
5. Amino compounds: salicylidene-propylenediamine, salicylaminoguanidine and
salts
thereof.
Rust inhibitors
1. Organic acids, their esters, metal salts, amine salts and anhydrides: alkyl-
and alkenyl-
succinic acids and their partial esters with alcohols, diols or
hydroxycarboxylic acids, par-
tial amides of alkyl- and alkenyl-succinic acids, 4-nonylphenoxyacetic acid,
alkoxy- and
alkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid,
dodecyloxy(ethoxy)acetic
acid and amine salts thereof, and also N-oleoyl-sarcosine, sorbitan
monooleate, lead
naphthenate, alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid
anhydride, 2-
(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof, especially
sodium and
triethanolamine salts thereof.
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-13-
2. Nitrogen-containinq compounds:
2.1. Tertiary aliphatic or cycloaliphatic amines and amine salts of organic
and inorganic
acids, e.g. oil-soluble alkylammonium carboxylates, and also 1-[N,N-bis(2-hy-
droxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
2.2. Heterocyclic compounds, e.g. substituted imidazolines and oxazolines,
e.g. 2-hepta-
decenyl-1-(2-hydroxyethyl)-imidazoline.
3. Sulphur-containing compounds: barium dinonylnaphthalenesulphonates, calcium
petroleum sulphonates, alkylthio-substituted aliphatic carboxylic acids,
esters of aliphatic
2-sulphocarboxylic acids and salts thereof.
Extreme pressure and anti-wear additives
Sulphur-containing and halogen-containing compounds, for example, chlorinated
paraffins,
sulphurated olefins or vegetable oils (soybean/rapeseed oil), alkyl- or aryl-
di- or -tri-sulph-
ides, benzotriazoles or derivatives thereof such as bis(2-
ethylhexyl)aminomethyltolutriazole,
dithiocarbamates such as methylene-bis-dibutyldithiocarbamate, derivatives of
2-mercapto-
benzothiazole such as 1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-
benzothia-
zole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole such as 2,5-bis(tert-
nonyldithio)-1,3,4-
thiadiazole.
Friction coefficient reducing agents
Lard oil, oleic acid, tallow, rapeseed oil, sulphurated fats, amines. Further
examples are
given in EP-A-0 565 487.
Further additives
1. Viscosity index improvers: polyacrylates, polymethacrylates,
vinylpyrrolidone/methacrylate
copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers,
styrene/acrylate co
polymers, polyethers.
2. Pour-point depressants: poly(meth)acrylates, ethylene/vinyl acetate
copolymer, alkyl-
polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.
3. Dispersants/surfactants: polybutenylsuccinic acid amides or imides,
polybutenylphos-
phonic acid derivatives, basic magnesium, calcium and barium sulphonates and
phe-
nolates.
Special additives
For use in water/oil metal-working fluids and hydraulic fluids
1. Emulsifiers: petroleum sulphonates, amines, such as polyoxyethylated fatty
amines, non-
ionic surface-active substances;
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-14-
2. Buffers: alkanolamines;
3. Biocides: triazines, thiazolinones, tris-nitromethane, morpholine, sodium
pyridenethiol;
4. Processing speed improvers: calcium and barium sulphonates.
The mentioned ingredients are added to the composition using customary mixing
methods in
a manner known per se. It is also possible, using the compounds (I) or
mixtures thereof and,
optionally, further additives, to prepare a concentrate or so-called additive
package, which is
diluted, as required for use, to a concentration for use in the lubricant in
question. The com-
position of the components in the concentrate is such that the concentrate is
liquid at room
temperature without further addition of component b) or a solvent.
The present invention relates also to a concentrate comprising a) at least one
compound (I)
wherein Ri, R2, R3, X and Y are as defined, optionally further additives, and
b) a base oil of
lubricating viscosity.
The invention relates also to a method of improving the use properties of
lubricants, which
comprises adding to the lubricants a composition comprising at least one
compound (I)
wherein R1, R2, R3, X and Y are as defined.
The following Examples illustrate the invention:
Examples
Temperatures are given in °C; h: hour(s); min.: minutes; m.p.: melting
point; drying in vacuo
(100°C, about. 0.05 mbar)
Synthesis Examples
Example '1
N-(2-n-Butoxycarbonylethyl)-N-(n-octadecyl)-succinic acid monoamide
O O
n-octadecyl-NHZ + ~O-(n-butyl) ~ n-octadecyl-H~O-(n-butyl)
o O
n-octadecyl~N~O-(n-butyl)
o O
O
OH
1.1 14.1 g (0.110 mol) of acrylic acid n-butyl ester are added drop wise, at
60°C, over the
course of 10 min., to 28.4 g (0.100 mol) of n-octadecylamine and the clear
reaction
mixture is stirred at 100° for 2 h; the cooled crude product is
dissolved in 100 ml of
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-15-
hexane, filtered and washed twice with 50 ml of water. The organic phase is
concen-
trated by evaporation in a rotary evaporator, the residue is dried in vacuo
and 40.0 g of
a clear, colourless, medium-viscosity oil are obtained.
1.2 3.1 g (0.030 mol) of succinic anhydride are added to 11.9 g (0.030 mol) of
the resulting
intermediate product, and the clear reaction solution is stirred at
100° for 1 h. The
cooled crude product is dissolved in 100 ml of hexane, filtered and washed
twice with
40 ml of water. The hexane solution is concentrated by evaporation in a rotary
evapo-
rator and the residue is dried in vacuo. 13.7 g (92 % of theory) of a clear
yellow oil,
which crystallises on standing are obtained.
M.p.: 50-52°C; elemental analysis: 70.24 % C (calc. 69.98), 10.91 % H
(calc. 11.14),
2.80 % N (calc. 2.81 ).
Example 2
~3-n-Butox p~yl)-N-(2-n-dodecyloxycarbon~h~)-succinic acid monoamide
O
3-(n-butoxy)-propyl-NH2 + ~ ~ O
~O-(n-dodecyl) 3-(n-butoxy)-propyl~N~O- n-dodec I
H ( y)
o O
3-(n-butoxy)-propyl~N~O- n-dodec I
o ( Y)
O'
O
OH
2.1 26.7 g (0.10 mol) of acrylic acid n-dodecyl ester are added drop wise,
over the course
of 20 min., to 13.3 g (0.100 mol) of 3-n-butoxypropylamine and the reaction
mixture is
stirred at 100° for 2 h; the cooled crude product is dried in vacuo and
37.0 g of a clear,
colourless, low-viscosity oil are obtained.
2.2 4.2 g (0.040 mol) of succinic anhydride are added to 14.9 g (0.040 mol) of
the resulting
intermediate product and the reaction mixture is stirred for 2 h; the cooled
crude prod-
uct is dissolved in 100 ml of hexane, filtered and washed three times with 30
ml of wa-
ter. The hexane solution is concentrated by evaporation in a rotary
evaporator, the re-
maining product is dried in vacuo and 18.0 g (95 % of theory) of a clear
yellow oil of
medium viscosity are obtained.
np2° 1.4670; elemental analysis: 66.85 % C (calc. 66.21 ), 10.54 % H
(calc. 10.47),
2.72 % N (calc. 2.97).
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-16-
np2° 1,4670; elemental analysis: 66.85 % C (calc. 66.21 ), 10.54 % H
(calc. 10.47),
2.72 % N (calc. 2.97).
Example 3
N-(2-Morpholinocarbon I~yl)-N-(n-octadecyl)-succinic acid monoamide
oleyl-NH2 + ~ /~ ~ O
~N~ oleyl~
0
0
0 oleyI~N~N~
~O
O'
O
H
3.1 5.8 g (0.040 mol) of 4-acryloylmorpholine are added drop wise, at
60°, over the course
of 10 min., to 10.7 g (0.040 mol) of oleylamine (Armeen00), the reaction
mixture is
stirred at 100° for 1 h and the cooled crude product is dried in vacuo.
16.0 g of a clear,
light-yellow, low-viscosity oil are obtained.
3.2 4.1 g (0.040 mol) of succinic anhydride are added to 16 g (0.040 mol) of
the resulting
intermediate product, the reaction solution is stirred at 100° for 1 h
and the cooled
crude product is shaken with 200 ml of hexane and 100 ml of brine (NaCI-
saturated).
The middle phase of the three phases is washed a further three times using 30
ml of
brine each time and is dissolved in 100 ml of toluene, filtered and
concentrated by
evaporation in a rotary evaporator; the remaining product is dried in vacuo.
15.6 g
(77 % of theory) of a clear yellow oil which becomes turbid on cooling are
obtained.
Elemental analysis: 68.24 % C (calc. 68.47), 10.23 % H (calc. 10.30), 5.34 % N
(calc.
5.51 ).
Example 4
The following compounds (I) can be prepared analogously to Examples 1-3:
R2
R~~N X
O R3
O RZ, R3, Y: H
OY
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-17-
Table 1
Ex. R, X Yield Appearance Analysis [found
[% (cal-
of culated)]
theory]
4.1 oleyl -C(=O)-O-(n-butyl)99 clear, light-yellow,70.79 % C (70.26)
medium-viscosity10.58 % H (10.78)
oil
npz 1.4761 2.82 % N (2.83)
4.2 oleyl -C(=O)-O-methyl 93 clear, yellow,69.97 % C (70.08)
vis-
cous oil 10.40 % H (10.44)
zo
np 1.4804 3.10 % N (3.10)
4.3 oleyl -C(=O)-O(CHz)z-O-ethyl96 clear, yellow,69.02 % C (68.07)
me-
dium-viscosity10.50 % H (10.44)
oil
zo
no 1.4768 2.77 % N (2.74)
4.4 oleyl -C(=O)-O-(isobutyl)77 clear, yellow,70.04 % C (70.26)
me-
dium-viscosity10.76 % H (10.78)
oil
zo
np 1.4748 2.80 l N (2.83)
4.5 oleyl -C(=O)-O-ethyl 69 clear, yellow,68.85 % C (69.34)
me-
dium-viscosity10.50 % H (10.56)
oil
npz 1.4769 2.97 % N (2.99)
4.6 isotridecyl-C(=O)-O-(n-butyl)90 clear, light-yellow,67.56 % C (67.41
)
viscous oil 10.59 % H (10.61)
zo
no 1.4711 3.35 % N (3.28)
4.7 isotridecyl-C(=O)-O-(isobutyl)87 clear, light-yellow,67.63 % C (67.41
)
viscous oil 10.66 % H (10.61)
zo
np 1.4709 3.36 % N (3.28)
4.8 n-butyl -C(=O)-O-oleyl 95 clear, yellow,70.80 % C (70.26)
me-
dium-viscosity10.79 % H (10.78)
oil
zo
no 1.4752 2.56 % N (2.83)
4.9 n-dodecyl-C(=O)-O-ethyl 82 clear, light-yellow,65.78 % C (65.42)
medium-viscositylp,3g l H (10.20)
oil
npz 1.4706 3.72 % N (3.63)
4.10 oleyl Nitrite 87 clear, light-yellow,72.13 % C (71.39)
viscous oil 10.73 % H (10.54)
zo
no 1.4783 6.23 % N (6.66)
4.11 n-octyl -C(=O)-O-oleyl 97 clear, yellow,72.04 % C (71.69)
vis-
cous oil 11.05 % H (11.30)
zo
np 1.4745 2.41 % N (2.53)
4.12 oleyl -C(=O)-O-(CHz)zOH59 clear, light-yellow,66.92 % C (67.05)
viscous oil 9.99 % H (10.21)
n~z 1.4855 2.86 % N (2.90)
4.13 oleyl -C(=O)-NHz 82 clear, yellow,68.10 % C (68.45)
vis-
cous oil 10.44 % H (10.57)
zo
np 1.4745 6.26 % N (6.39)
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-18-
Table 1 (ctd.)
Ex. R~ X Yield Appearance Analysis [found
[% (cal-
of culated)]
theory]
4.14 coconut -C(=O)-O-(n-butyl)87 clear, light-yellow,67.68 % C (67.73)
oil
amine viscous oil 10.50 % H (10.18)
(C~z mix) no2 1.4701 3.31 % N (3.29)
4.15 n-butoxy-pro--C(=O)-O-oleyl 97 clear, yellow,69.75 % C (69.40)
me-
pyl dium-viscosity10.66 % H (10.74)
oil
zo
n~ 1.4744 2.40 % N (2.53)
4.16 Ca-C~oalkyl--C(=O)-O-(n-butyl)95 clear, yellow,63.72 % C
me-
O(CH2)a dium-viscosity10.00 % H
oil
noz 1.4680 3,1 g % N
4.17 isodecyl--C(=O)-O-(n-butyl)96 clear, yellow,64.75 % C (64.98)
me-
O(CH2)s dium-viscosity10.11 % H (10.22)
oil
zo
no 1
4699
. 3,14 % N (3.16)
4.18 2-ethylhexyl-C(=O)-O-(n-dodecyl)96 clear, light-yellow,69.60 % C
(69.04)
medium-viscosity10.69 % H (10.94)
oil
no2 1,4684 2.67 % N (2.98)
4.19 methoxy- -C(=O)-O-(n-dodecyl)98 wax-like solid64.99 % C (64.31
)
propyl 10.14 % H (10.09)
2.91 % N (3.26)
4.20 CB-C~oalk-nitrite 97 clear, yellow,63.62 % C (64.38)
me-
O(CH2)a dium-viscosity9.61 % H (9.67)
oil
20
no 1.4731 7,6g % N (7.90)
4.21 benzyl -C(=O)-O-(n-dodecyl)97 wax-like solid70.02 % C (69.77)
8.99 % H (9.23)
3.10 % N (3.13)
4.22 oleyl -C(=O)-O-cyclohexyl98 clear, yellow,71,35% C (71,36)
me-
dium-viscosity10,12% H (10.62)
oil
no2 1,4864 2,72% N (2,68)
4.23 oleyl -C(=O)-O-(CH2)2-O-98 clear, yellow,71,20% C (70,81
me- )
phenyl dium-viscosityg,57% H (9,54)
oil
20
np 1,5025 2,43% N (2,50)
4.24 oley) -C(=O)-O-(CHz)z-O-94 clear, yellow,67,82% C (67.43)
me-
methyl dium-viscosity10,26% H (10.51
oil )
20
no 1,4791 2,85% N (2,81)
4.25 oleyl -C(=O)-O-(CH2)2-O-94 clear, yellow,66.55% C (67.54)
me-
(CH2)2-O-ethyl dium-viscosity10,55% H (10.34)
oil
zo
np 1,4771 2,51 % N (2,52)
4.26 benzyl -C(=O)-O-dodecyl98 yellowish,
wax-like
solid
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-19-
Table 1 (ctd.)
4.27 2-ethylhexyl-C(=O)-O-dodecyl96 clear, yellow,69,60% C (69,04)
me-
dium-viscosity10,69% H (10,94)
oil
20
np 1,4684 2.67% N (2,98)
4.28 n-butyl -C(=O)-O-i-decyl91 clear, yellow,65,24% C (65,42)
me-
dium-viscosity10,20% H (10,20)
oil
20
no 1,4708 3,43% N (3,63)
4.29 methyl-O--C(=O)-O-dodecyl99 yellowish, 64,99% C (64,31)
wax-like
(CHz)a solid 10,14% H (10,09)
2,91 % N (3,26)
4.30 ethyl-O- -C(=O)-O-dodecyl95 clear, yellow,65.25% C (64.98)
me-
(CHz)a dium-viscosity10,28% H (10,22)
oil
np2 1,4681 2,85% N (3,16)
4.31 ethyl-O- -C(=O)-O-oleyl 95 clear, yellowish,69,09% C (68,53)
(CH2)a medium-viscosity10,76% H (10,54)
oil
np2 1,4755 2,57% N (2.66)
4.32 i-propyl-O--C(=0)-O-oleyl 96 clear, yellow,68,19% C (68,98)
me-
(CH2)a dium-viscosity10,09% H (10,64)
oil
20
no 1,4741 2,55% N (2,59)
4.33 i-decyl-O--C(=O)-O-n-butyl96 clear, yellow,64,75% C (64,98)
me-
(CH2)s dium-viscosity10,11% H (10,22)
oil
20
no 1,4699 3,14% N (3,16)
4.34 i-decyl-O--C(=O)-O-i-butyl95 clear, yellow,64,87% C (64,98)
me-
(CH2)s dium-viscosity10,38% H (10,22)
oil
20
np 1,4696 3,25% N (3,16)
4.35 octadecyl-O--C(=O)-O-i-butyl96 clear, yellow,66,76% C (67,30)
me-
(CHz)a dium-viscosity10,72% H (10,69)
oil
20
no 1,4682 2,91 % N (2.80)
4.36 oleyl -C(=O)-N(CH2)s 94 clear, yellow,70,76% C (71,10)
me-
dium-viscosity10,98% H (10,74)
oil
20
no 1,4985 5,24% N (5,53)
Application Examples
Example 5
Testing of corrosion protection properties (of active ingredient-containing
industrial, circulat-
ing. turbine and hydraulic oils) according to ASTM D 665 (= DIN 51585)
300 ml of formulated oil are mixed with 30 ml of synthetic seawater by
stirring for 24 h at 60°
whilst simultaneously immersing a steel round-section bar.
After being in contact for that period, the steel bar is subjected to a visual
corrosion test.
Each test is carried out in duplicate. The base formulation is based on a
mineral oil of speci-
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-20-
fication SN VG46, which has been stabilised using antioxidants and metal
deactivators. The
active ingredients under test are used in a concentration of 0.1 mmol/kg
(corresponding to
0.03 - 0.06 % by weight or 300 - 600 ppm). See Table 2 for results.
~ 0: no corrosion
~ 1: light corrosion (< 6 corrosion sites less than 1 mm in diameter)
~ 2: moderate corrosion (< 5 % of the surface corroded)
~ 3: heavy corrosion (> 5 % of the surface corroded)
Example 6
Testing for filterability in the presence of calcium ions
0.3 g of distilled water and 30 ppm of calcium in the form of a calcium
detergent (6.9 % Ca)
are added to 300 g of the test formulation. The mixture is homogenised in a
four-blade mixer
at the maximum speed of rotation for 5 min.. The emulsion is stored for 96
hours at 70°C
(+/- 2°C) and then for a further 48 hours at room temperature in the
dark. If precipitation is
observed, the test is stopped. Before filtration, the test mixture is
homogenised again by
shaking vigorously for one minute. It is then filtered through a 0.8 N
Millipore0 filter (type
AAWP 04700) using compressed air at 1 bar (+/- 0.05 bar) positive pressure.
The times re-
quired to filter 50, 100, 200 and 300 ml of test mixture are measured. The
filtration index FI is
calculated, as the mean of two measurements, in accordance with the following
formula (see
AFNOR NFE 48-691):
FI = (t3oomi - t2oomi)/ 2 (t100m1 - t50m1)
FI =1 means that no resistance is built up at the filter.
FI < 2 is the requirement for passing the test.
In the event of the filter becoming blocked, a note is made after 60 min. of
the volume of oil
filtered up until then.
CA 02496696 2005-02-28
WO 2004/026811 PCT/EP2003/010115
-21 -
Table 2
Example Degree of corrosion,Filterability
according to in the pres-
ASTM D 665 ence of Ca2+
Filtration index
FI
Base formulation 3 / 3 1.25
1 1/0
2 . 0 / 0 1.20
3 O / 0 1.25
4.1 0 / 0 1.13
4.2 O/0 1.11
4.3 0 / 0 1.05
4.4 1 / 1 1.05
4.5 0 / 1 1.1
4.6 1 / 0
4.7 0/0
4.8 0 ! 0 1.05
4.9 0/0
4.10 0 / 0 1.05
4.11 1 / 1
4.12 1 / 1
4.13 1 / 1 1.20
4.14 1 / 0
4.15 0/0
