U.S. patent application number 11/667779 was filed with the patent office on 2009-04-23 for benzotriazole compositions.
Invention is credited to Samuel Evans, Isabelle Rapenne-Jacob, Peter Rohrbach, Martin Von Buren.
Application Number | 20090105102 11/667779 |
Document ID | / |
Family ID | 34929906 |
Filed Date | 2009-04-23 |
United States Patent
Application |
20090105102 |
Kind Code |
A1 |
Rapenne-Jacob; Isabelle ; et
al. |
April 23, 2009 |
Benzotriazole Compositions
Abstract
The invention relates to novel (benzo)triazole compositions
comprising mixtures of benzotriazoles and N-substituted
benzotriazoles in functional liquids, e.g. mineral oil. The
mixtures can be prepared from readily obtainable starting
materials, such as tolutriazole (TTA), alkyl aldehydes and
cycloalkanols. The invention furthermore relates to a process for
protecting metals, which are in contact with functional liquids
comprising the mixtures.
Inventors: |
Rapenne-Jacob; Isabelle;
(Mulhouse, FR) ; Evans; Samuel; (Marly, CH)
; Rohrbach; Peter; (Liestal, CH) ; Von Buren;
Martin; (Muttenz, CH) |
Correspondence
Address: |
JoAnn Villamizar;Ciba Corporation/Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Family ID: |
34929906 |
Appl. No.: |
11/667779 |
Filed: |
November 14, 2005 |
PCT Filed: |
November 14, 2005 |
PCT NO: |
PCT/EP05/55934 |
371 Date: |
May 15, 2007 |
Current U.S.
Class: |
508/281 |
Current CPC
Class: |
C10N 2030/10 20130101;
C10N 2020/02 20130101; C10N 2030/14 20130101; C10M 133/44 20130101;
C10M 141/06 20130101; C10M 2203/1006 20130101; C10M 2215/064
20130101; C10N 2050/023 20200501; C10M 2207/289 20130101; C10M
2205/0285 20130101; C10N 2040/08 20130101; C10M 2207/026 20130101;
C10N 2040/20 20130101 |
Class at
Publication: |
508/281 |
International
Class: |
C10M 133/44 20060101
C10M133/44 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 22, 2004 |
EP |
04105973.4 |
Claims
1. A composition comprising A) A mixture consisting essentially of:
a) A benzotriazole compound: ##STR00021## Wherein R.sub.1
represents hydrogen or C.sub.1-C.sub.4alkyl; R.sub.2 represents a
substituent selected from the group consisting of
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl; b) A
benzotriazole compound: ##STR00022## Wherein R.sub.1 represents
hydrogen or C.sub.1-C.sub.4alkyl; and, optionally, c) A triazole
compound: ##STR00023## Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; R.sub.2 represents a substituent selected
from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl; and
B) A functional fluid selected from the group consisting of
lubricants, hydraulic agents, metal working fluids and coating
agents.
2. A composition comprising A) A mixture consisting essentially of
a) A benzotriazole compound: ##STR00024## Wherein R.sub.1
represents hydrogen or methyl; R.sub.2 represents
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl; R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.7cycloalkyl and
phenyl or an isomer of the compound (I'); and b) A benzotriazole
compound: ##STR00025## Wherein R.sub.1 represents hydrogen or
methyl; and C) A functional fluid selected from the group
consisting of lubricants, hydraulic agents, metal working fluids
and coating agents.
3. A composition according to claim 1 comprising A) A mixture
consisting essentially of a) A benzotriazole compound: ##STR00026##
Wherein R.sub.1 represents hydrogen or methyl; R.sub.2 represents a
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.7cycloalkyl and
phenyl or an isomer of the compound (I'); b) A benzotriazole
compound: ##STR00027## Wherein R.sub.1 represents hydrogen or
methyl; and c) A triazole compound: ##STR00028## Wherein R.sub.1
represents hydrogen or methyl; R.sub.2 represents a
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl and
phenyl or an isomer of the compound (III'); and B) A functional
fluid selected from the group consisting of lubricants, hydraulic
agents, metal working fluids and coating agents.
4. A composition according to claim 2 comprising A) A mixture
consisting essentially of a) A benzotriazole compound (I'), wherein
R.sub.1 represents hydrogen or methyl; R.sub.2 represents
C.sub.5-C.sub.7cycloalkyl; and R.sub.3 represents
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl or an isomer of
the compound (I'); and b) A benzotriazole compound (II), wherein
R.sub.1 represents hydrogen or methyl; and B) A functional fluid
selected from the group consisting of lubricants, hydraulic agents,
metal working fluids and coating agents.
5. A composition according to claim 1 comprising A) A mixture
consisting essentially of a) A benzotriazole compound (I'), wherein
R.sub.1 represents hydrogen or methyl; R.sub.2 represents
C.sub.5-C.sub.7cycloalkyl; and R.sub.3 represents
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl or an isomer of
the compound (I'); b) A benzotriazole compound (II), wherein
R.sub.1 represents hydrogen or methyl; and c) A triazole compound
(III'), wherein R.sub.1 represents hydrogen or methyl; R.sub.2
represents C.sub.5-C.sub.7cycloalkyl; and R.sub.3 represents
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl or an isomer of
the compound (I'); and B) A functional fluid selected from the
group consisting of lubricants, hydraulic agents, metal working
fluids and coating agents.
6. A composition according to claim 1, which comprises additional
additives selected from the group consisting of metal deactivators,
antioxidants, rust inhibitors, viscosity index improvers,
pour-point depressants, dispersants, surfactants, extreme-pressure
additives and antiwear additives.
7. A mixture comprising a) A benzotriazole compound (I), wherein
R.sub.1 represents hydrogen or C.sub.1-C.sub.4alkyl; R.sub.2
represents a substituent selected from the group consisting of
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl; b) A
benzotriazole compound (II), wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; and, optionally, c) A triazole compound
(III'), wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; R.sub.2 represents a substituent selected
from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl.
8. A method for improving the functional properties of lubricants,
hydraulic or metal-working fluids or coating compositions, which
comprises adding to a functional fluid the mixture according to
claim 7 and, optionally, further additives.
Description
[0001] The invention relates to novel benzotriazole compositions
comprising mixtures of benzotriazoles and N-substituted
benzotriazoles, the process for preparing N-substituted
benzotriazoles and a method for improving the functional properties
of lubricants, hydraulic or metal-working fluids or coating
compositions.
[0002] Additives, which can be used as metal deactivators display
their protective action in functional liquids, such as mineral oil
or fuels, by deactivating the metal ions, such as copper or iron,
contained therein. These metal ions can have catalytic effects in
undesired oxidative decomposition processes of mineral oil or
fuels. The protective action is explained by the formation of
film-like layers on the surface of metals or by complex formation
with metal ions.
[0003] EP-A-365 476 discloses benzotriazole compounds:
##STR00001##
[0004] Wherein R.sub.1 represents C.sub.1-C.sub.12 straight or
branched chain alkyl; and
[0005] R.sub.2 represents C.sub.1-C.sub.12 straight or branched
chain alkyl interrupted by one or more O-atoms or represents
C.sub.5-C.sub.12cycloalkyl;
and lubricant compositions comprising these benzotriazole
compounds.
[0006] Owing to their volatility at high operating temperatures of
machines, metal deactivators of the triazole type are problematic.
Because of high temperatures, in particular in internal combustion
engines and turbines, which are exposed to oils and fuels, the
deactivator concentration can rapidly decrease with a corresponding
reduction in the protective action.
[0007] It is the object of the invention to prepare, from readily
obtainable starting materials, such as tolutriazole (TTA), alkyl
aldehydes and cycloalkanols, additive components which can be used
in lubricant compositions as metal deactivators, possess improved
solubility and, in functional liquids, have lower volatility than
tolutriazole itself.
[0008] This object is achieved by the present invention, which
relates to novel benzotriazole compositions comprising mixtures of
benzotriazoles and N-substituted benzotriazoles.
[0009] The invention relates to a composition comprising [0010] A)
A mixture consisting essentially of: [0011] a) A benzotriazole
compound:
[0011] ##STR00002## [0012] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; [0013] R.sub.2 represents a substituent
selected from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl,
[0013] ##STR00003## [0014] Wherein R.sub.1' is as defined as
R.sub.1; [0015] The index a represents a numeral from 1 to 10; and
[0016] The index n represents a numeral from 2 to 8; and [0017]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl;
[0018] b) A benzotriazole compound:
[0018] ##STR00004## [0019] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; and, optionally, [0020] c) A triazole
compound:
[0020] ##STR00005## [0021] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; [0022] R.sub.2 represents a substituent
selected from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl,
[0022] ##STR00006## [0023] Wherein R.sub.1' is as defined as
R.sub.1; and [0024] The index a represents a numeral from 1 to 10;
[0025] The index n represents a numeral from 2 to 8; and [0026]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl;
[0027] B) A functional fluid selected from the group consisting of
lubricants, hydraulic agents, metal working fluids and coating
agents.
[0028] A more specific embodiment of the invention relates to a
composition comprising [0029] A) A mixture consisting essentially
of: [0030] a) A benzotriazole compound:
[0030] ##STR00007## [0031] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; [0032] R.sub.2 represents a substituent
selected from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and [0033] R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl;
[0034] b) A benzotriazole compound:
[0034] ##STR00008## [0035] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; and, optionally, [0036] c) A triazole
compound:
[0036] ##STR00009## [0037] Wherein R.sub.1 represents hydrogen or
C.sub.1-C.sub.4alkyl; [0038] R.sub.2 represents a substituent
selected from the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl; and [0039] R.sub.3
represents hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl; and
[0040] B) A functional fluid selected from the group consisting of
lubricants, hydraulic agents, metal working fluids and coating
agents.
[0041] The compositions defined above are prepared by conventional
mixing procedures and are suitable as metal deactivators in
functional liquids.
[0042] The expressions and terms used above and below are
preferably defined as follows in the description of the present
invention:
Component A)
[0043] The compounds (I) present in the compositions according to
the invention are defined by the following isomeric structures:
##STR00010##
[0044] Wherein R.sub.1, R.sub.2 and R.sub.3 are as defined
above.
[0045] The term isomer includes any structural and positional
isomers, tautomeric forms, cis-trans isomers and stereoisomers,
e.g. enantiomeric forms and racemic mixtures.
[0046] R.sub.1 and R.sub.1' defined as C.sub.1-C.sub.4alkyl
represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or
tert-butyl. According to a preferred embodiment, R.sub.1 represents
methyl.
[0047] R.sub.2 represents a substituent selected from the group
consisting of C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl or
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl.
[0048] R.sub.2 defined as C.sub.1-C.sub.12alkyl represents
C.sub.1-C.sub.4alkyl as defined above with regard to R.sub.1 and
R.sub.1' and additionally represents straight chain or branched
C.sub.5-C.sub.12alkyl, e.g. pentyl, hexyl, heptyl, octyl, nonyl,
undecyl or dodecyl.
[0049] R.sub.2 defined as C.sub.5-C.sub.7cycloalkyl is preferably
cyclopentyl or cyclohexyl.
[0050] R.sub.2 defined as
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl is
preferably cyclopentyl or cyclohexyl substituted with
C.sub.1-C.sub.4alkyl, e.g. methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl or tert-butyl.
[0051] R.sub.2 defined as
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl is e.g.
cyclopentylmethyl, cyclohexylmethyl, cyclopentyl-1,1-ethyl,
cyclohexyl-1,1-ethyl, cyclopentyl-1,2-ethyl or
cyclohexyl-1,2-ethyl.
[0052] In the compound (I) the index a represents a numeral from 1
to 10, and the index n represents a numeral from 2 to 8.
[0053] According to a preferred embodiment, the index a represents
a numeral from 1 to 6, and the index n represents a numeral from 2
to 6.
[0054] According to a highly preferred embodiment, the index a
represents a numeral from 1 to 4, and the index n represents a
numeral from 2 to 4.
[0055] R.sub.3 represents a substituent a substituent selected from
the group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl.
[0056] R.sub.3 defined as C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl has the same
meanings as defined above with regard to R.sub.2.
[0057] R.sub.3 defined as phenyl, phenyl-C.sub.1-C.sub.4alkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3phenyl and
(C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl is, for
example, phenyl, benzyl, 1- or 2-phenylethyl, 4-methyl or 4-ethyl,
cumyl or 4-methylbenzyl.
[0058] Compounds of the formula (I) are known from the disclosure
of EP 0 365 476, or can be pre-pared in a manner analogous to the
methods as described therein, e.g. by the acid catalysed reaction
of the R.sub.1-substituted benzotriazole, e.g. tolutriazole
(tolyltriazole), with the aldehyde R.sub.3--C(.dbd.O)--H and the
alcohol R.sub.2--OH in a solvent inert to the reactants, while
continuously removing an azeotropic mixture of solvent and water
formed during the reaction.
[0059] Suitable acid catalysts include mineral acids, e.g.
sulphuric acid, acid clays, e.g. bentonite, montmorillonite,
Bleicherde Tonsil.RTM. (Supreme 110 FF, 126 FF) or Fuller's earth,
acid ion-exchange resins, e.g. Amberlyst.RTM. 15, and sulphonic
acids, e.g. p-toluene sulphonic acid.
[0060] The inert solvent may be cyclohexane, benzene, toluene,
xylene or carbon tetrachloride.
[0061] Compounds (I) wherein R.sub.2 represents a group of the
partial formulae (A) or (B), can be pre-pared in an analogous
manner by the acid catalysed reaction of the R.sub.1-substituted
benzotriazole, e.g. tolutriazole (tolyltriazole), with the diol
HO--(CH.sub.2).sub.2-3O--(CH.sub.2-3O).sub.a--(CH.sub.2-3)--OH and
2 equivalents of the aldehyde R.sub.3--(C.dbd.O)--H, or with the
diol HO--(CH.sub.2).sub.n--OH and 2 equivalents of the aldehyde
R.sub.3--(C.dbd.O)--H.
[0062] In a compound (II) R.sub.1 defined as C.sub.1-C.sub.4alkyl
represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or
tert-butyl. According to a preferred embodiment, R.sub.1 represents
methyl.
[0063] Compounds (II) are known and are commercially available,
e.g. Irgamet.RTM. (Ciba Specialty Chemicals) TTA.
[0064] The compounds (III) present in the compositions according to
the invention are preferably defined by the following isomeric
structure:
##STR00011##
[0065] Wherein R.sub.1, R.sub.2 and R.sub.3 are as defined
above.
[0066] Compounds (III), according to the optional component c), can
be prepared in a manner analogous to EP 0 365 476, e.g. by the acid
catalysed reaction of a R.sub.1-substituted triazole, e.g. triazole
or methyltriazole, with the aldehyde R.sub.3--C(.dbd.O)--H and the
alcohol R.sub.2--OH.
[0067] Compounds (III), wherein R.sub.2 represents a group of the
partial formula (A) or (B), can be pre-pared in an analogous manner
by the acid catalysed reaction of the R.sub.1-substituted triazole,
e.g. triazole or methyltriazole, with the diol
HO--(CH.sub.2).sub.2-3O--(CH.sub.2-3O).sub.a--(CH.sub.2-3)--OH and
2 equivalents of the aldehyde R.sub.3--(C.dbd.O)--H, or with the
diol HO--(CH.sub.2).sub.n--OH and 2 equivalents of the aldehyde
R.sub.3--(C.dbd.O)--H.
Component B)
[0068] The term functional liquid selected from the group
consisting of lubricants, hydraulic agents, metal working fluids
and coating agents includes non-aqueous, partially aqueous and
aqueous liquids which are in contact with metals to be deactivated,
in particular copper or iron.
[0069] Examples of non-aqueous functional liquids are fuels, e.g.
hydrocarbon mixtures comprising mineral oil fractions which are
liquid at room temperature and are suitable for use in internal
combustion engines, e.g. internal combustion engines with external
(petrol engines) or internal ignition (diesel engines), e.g. petrol
having different octane contents (regular grade or premium grade
petrol) or diesel fuel, and lubricants, hydraulic fluid, metal
working fluid, engine coolants, transformer oil and switch gear
oil.
[0070] Examples of suitable partially aqueous functional liquids
are hydraulic fluids based on aqueous polyglycol/polyglycol ether
mixtures or glycol systems, water-in-oil or oil-in-water systems
and engine cooling systems based on aqueous glycol.
[0071] Examples of aqueous functional liquids are industrial
cooling water, filling compositions of a water conditioning plant,
steam generation systems, sea water evaporation systems, sugar
evaporation systems, irrigation systems, hydrostatic boilers and
heating systems or cooling systems having a closed circulation.
[0072] The compositions according to the invention preferably
comprise 0.01 to 5.0% by weight, in particular 0.02 to 1.0% by
weight, of a compound (I), based on the weight of the functional
liquid.
[0073] Non-aqueous functional liquids are preferred, in particular
base oils of lubricating viscosity, which can be used for the
preparation of greases, metal working fluids, gear fluids and
hydraulic fluids.
[0074] Suitable greases, metal working fluids, gear fluids and
hydraulic fluids are based, for example, on mineral or synthetic
oils or mixtures thereof. The lubricants are familiar to a person
skilled in the art and are described in the relevant literature,
such as, for example, in Chemistry and Technology of Lubricants;
Mortier, R. M. and Orszulik, S. T. (Editors); 1992 Blackie and Son
Ltd. for GB, VCH-Publishers N.Y. for U.S., ISBN 0-216-92921-0, cf.
pages 208 et seq. and 269 et seq.; in Kirk-Othmer Encyclopedia of
Chemical Technology, Fourth Edition 1969, J. Wiley & Sons, New
York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance
Testing of Hydraulic Fluids; R. Tourret and E. P. Wrght, Hyden
& Son Ltd. GB, on behalf of The Institute of Petroleum London,
ISBN 0 85501 317 6; Ullmann's Encyclopedia of Ind. Chem., Fifth
Completely Revised Edition, Verlag Chemie, DE-Weinheim,
VCH-Publishers for U.S., Vol. A 15, page 423 et seq. (Lubricants),
Vol. A 13, page 165 et seq. (Hydraulic Fluids).
[0075] The lubricants are in particular oils and greases, for
example based on mineral oil or vegetable and animal oils, fats,
tallow and wax or mixtures thereof. Vegetable and animal oils,
fats, tallow and wax are, for example, palm kernel oil, palm oil,
olive oil, colza oil, rapeseed oil, linseed oil, soy bean oil,
cotton wool oil, sunflower oil, coconut oil, maize oil, castor oil,
walnut oil and mixtures thereof, fish oils, and chemically
modified, e.g. epoxidised or sulphoxidised, forms or forms prepared
by genetic engineering, for example soy bean oil prepared by
genetic engineering.
[0076] Examples of synthetic lubricants include lubricants based on
aliphatic or aromatic carboxylic esters, polymeric esters,
polyalkylene oxides, phosphoric acid esters, poly-.alpha.-olefins
or silicones of the diester of a dibasic acid with a monohydric
alcohol, e.g. dioctyl sebacate or dinonyl adipate, of a triester of
trimethylolpropane with a monobasic acid or with a mixture of such
acids, e.g. trimethylolpropane tripelargonate, trimethylolpropane
tricaprylate or mixtures thereof, of a tetra ester of
pentaerythritol with a monobasic acid or with a mixture of such
acids, e.g. pentaerythrityl tetracaprylate, or of a complex ester
of monobasic and dibasic acids with polyhydric alcohols, e.g. a
complex ester of trimethylolpropane with caprylic and sebacic acid
or of a mixture thereof. Particularly suitable in addition to
mineral oils are, for example, poly-.alpha.-olefins, ester-based
lubricants, phosphates, glycols, polyglycols and polyalkylene
glycols and mixtures thereof with water.
[0077] Said lubricants or mixtures thereof can also be mixed with
an organic or inorganic thickener (base fat). Metal working fluids
and hydraulic fluids can be prepared on the basis of the same
substances as described above for the lubricants. These are
frequently also emulsions of such substances in water or other
liquids.
Additional Components
[0078] A further embodiment of the invention relates to a
composition, which comprises additional additives selected from the
group consisting of metal deactivators, antioxidants, rust
inhibitors, viscosity index improvers, pour-point depressants,
dispersants, surfactants, extreme-pressure additives, and antiwear
additives.
[0079] Such additives are added in the amounts customary in each
case for the purpose, each in the range from 0.01 to 10.0% by
weight. Examples of further additives are listed below: [0080] 1.
Phenolic antioxidants [0081] 1.1. Alkylated monophenols:
2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethyl-phenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-iso-butylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethyl-phenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or
nonylphenols which are branched in the side chain, e.g.
2,6-dinonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methyl-undec-1'-yl)-phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)-phenol,
2,4-dimethyl-6-(1'-methyl-tridec-1'-yl)-phenol and mixtures thereof
[0082] 1.2. Alkylthiomethylphenols:
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methyl phenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonyl-phenol [0083] 1.3. Hydroquinones
and alkylated hydroquinones: 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone,
2,6-diphenyl-4-octadecyl-oxyphenol, 2,6-di-tert-butyl-hydroquinone,
2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenylstearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate [0084] 1.4.
Tocopherols: .alpha.-, .beta.-, .gamma.- or .delta.-tocopherols and
mixtures thereof (vitamin E) [0085] 1.5. Hydroxylated thiodiphenyl
ethers: 2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thio-bis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis-(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxy-phenyl)disulphide [0086] 1.6.
Alkylidene bisphenols:
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
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'-methylene-bis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethyl
benzyl)-4-nonylphenol], 4,4'-methylenebis(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-methyl-phenyl)-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'-methyl-benzyl)-6-tert-butyl-4-methyl-p-
henyl]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-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane [0087]
1.7. O--, N- and S-benzyl compounds:
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl
4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulphide, isooctyl
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate [0088] 1.8.
Hydroxybenzylated malonates: dioctadecyl
2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, dioctadecyl
2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl
mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydr-
oxybenzyl)malonate [0089] 1.9. Hydroxybenzyl aromatics:
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl
benzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol [0090]
1.10. Triazine compounds:
2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin-
e,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-tri-
azine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate
[0091] 1.11. Acylaminophenols: 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate [0092] 1.12. Esters
of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid: with
monohydric or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane [0093]
1.13. Esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid: with
monohydric or polyhydric alcohols, e.g. the alcohols with methanol,
ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol, tris(hydroxyethyl)isocyanurate, N
N'-bis(hydroxyethyl)-oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane [0094]
1.14. Esters of beta-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic
acid: with monohydric or polyhydric alcohols, e.g. the alcohols
stated under 13 [0095] 1.15. Ester of
3,5-di-tert-butyl-4-hydroxyphenylacetic acid: with monohydric or
polyhydric alcohols, e.g. the alcohols stated under 13 [0096] 1.16.
Amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid:
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenedi-
amine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenedia-
mine, N N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine
[0097] 1.17. Ascorbic acid (vitamin C) [0098] 1.18. Amine
antioxidants: N,N'-diisopropyl-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-methyl-heptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-di-(naphth-2-yl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenyl enediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulphonamido)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxy-diphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,
p'-di-tert-octyidiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylamino-phenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
di-(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenyl methane,
1,2-di-[(2-methyl-phenyl)-amino]ethane,
1,2-di-(phenylamino)-propane, (o-tolyl)biguanide,
di-[4-(1',3'-dimethyl-butyl)phenyl]amine, tert-octylated
N-phenyl-1-naphthylamine, mixture of mono- and dialkylated
tert-butyl/tert-octyidiphenylamines, mixture of mono- and
dialkylated nonyidiphenylamines, mixture of mono- and dialkylated
dodecyldiphenylamines, mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines, mixtures of mono- and dialkylated
tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
mixture of mono- and dialkylated tert-butyl
tert-octylphenothiazines, mixture of mono- and dialkylated
tert-octylphenothiazines, mixture of mono- and dialkylated
nonylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-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-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol [0099] 2. Further antioxidants:
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-trithiamidecane
and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane
[0100] 3. Further metal deactivators, e.g. for copper: [0101] 3.1.
Benzotriazoles and derivatives thereof: 2-mercaptobenzotriazole,
2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazoles (e.g.
tolutriazole) and derivatives thereof,
4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole;
Mannich bases of benzotriazole or tolutriazole, such as
1-[di(2-ethylhexylaminomethyl)]tolutriazole and
1-[di(2-ethylhexylaminomethyl)]benzotriazole;
alkoxyalkylbenzotriazoles, such as
1-(nonyloxymethyl)-benzotriazole, 1-(1-butoxyethyl)benzotriazole
and 1-(1-cyclohexyloxybutyl)tolutriazole [0102] 3.2.
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
[0103] 3.3. Imidazole derivatives:
4,4'-methylenebis(2-undecyl-5-methylimidazole),
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether [0104] 3.4.
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
[0105] 3.5. Amino compounds: salicylidenepropylenediamine,
salicylaminoguanidine and salts thereof [0106] 4. Corrosion
inhibitors [0107] 4.1. Organic acids, their esters, metal salts,
amine salts and anhydrides: e.g. alkyl- and alkyenylsuccinic acids
and partial esters thereof with alcohols, diols or
hydroxycarboxylic acids, partial amides of alkyl- and
alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and
alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid,
dodecyloxy(ethoxy)acetic acid and amine salts thereof, and
furthermore N-oleoylsarcosine, sorbitan monooleate, lead
naphthenate, alkenylsuccinic anhydrides, e.g. dodecenylsuccinic
anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts
thereof, in particular sodium salts and triethanolamine salts
[0108] 4.2. Nitrogen-containing compounds: [0109] 4.2.1 Tertiary
aliphatic and cycloaliphatic amines and amine salts of organic and
inorganic acids, e.g. oil-soluble alkylammonium carboxylates, and
furthermore
1-[N,N-bis-(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol
[0110] 4.2.2 Heterocyclic compounds, e.g. substituted imidazolines
and oxazolines, e.g. 2-heptadecenyl-1-(2-hydroxyethyl)-imidazoline
[0111] 5. Sulphur-containing compounds: barium
dinonyinaphthalenesulphonates, calcium petroleum sulphonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulphocarboxylic acids and salts thereof [0112] 6.
Viscosity index improvers: polyacrylates, polymethacrylates,
vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidiones,
polybutenes, olefin copolymers, styrene/acrylate copolymers,
polyethers [0113] 7. Pour point depressants: poly(meth)acrylates,
ethylene-vinyl acetate copolymers, alkyl polystyrenes, fumarate
copolymers, alkylated naphthalene derivatives [0114] 8.
Dispersants/Surfactants: polybutenylsuccinamides or
polybutenylsuccinimides, polybutenylphosphonic acid derivatives,
basic magnesium, calcium and barium sulphonates and phenolates
[0115] 9. High pressure and antiwear additives: sulphur- and
halogen-containing compounds, e.g. chlorinated paraffins,
sulphonated olefins or vegetable oils (soy bean oil, rapeseed oil),
alkyl or aryl di- or trisulphides, benzotriazoles or derivatives
thereof, such as bis(2-ethylhexyl)aminomethyl tolutriazoles,
dithiocarbamates, such as methylenebisdibutyl dithiocarbamate,
derivatives of 2-mercaptobenzothiazole, such as
1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,
derivatives of 2,5-dimercapto-1,3,4-thiadiazole, such as
2,5-bis(tert-nonyidithio)-1,3,4-thiadiazole [0116] 10. Substances
for reducing the coefficient of friction: lard oil, oleic acid,
tallow, rapeseed oil, sulphurised fats, amines. Further examples
are stated in EP-A-0 565 487 [0117] 11. Special additives for use
in water/oil metal processing and hydraulic fluids: [0118] 11.1
Emulsifiers: petroleum sulphonates, amines, such as
polyoxyethylated fatty amines, non-ionic surface-active substances
[0119] 11.2 Buffers: alkanolamines [0120] 11.3 Biocides: triazines,
thiazolinones, trisnitromethane, morpholine, sodium pyridinethiol
[0121] 11.4 Processing speed improvers: calcium sulphonates and
barium sulphonates.
[0122] Said components can be mixed with the lubricants in a manner
known per se. It is also possible to prepare a concentrate or a
so-called additive packet, which can be diluted to the
concentrations of use for the corresponding lubricant according to
consumption.
[0123] A preferred embodiment of the invention relates to a
composition comprising [0124] A) A mixture consisting essentially
of [0125] a) A benzotriazole compound:
[0125] ##STR00012## [0126] Wherein R.sub.1 represents hydrogen or
methyl; [0127] R.sub.2 represents a substituent selected from the
group consisting of C.sub.1-C.sub.8alkyl,
C.sub.5-C.sub.7cycloalkyl,
[0127] ##STR00013## [0128] Wherein R.sub.1' is as defined as
R.sub.1; [0129] The index a represents a numeral from 1 to 10;
[0130] The index n represents a numeral from 2 to 8; and [0131]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.7cycloalkyl
and phenyl or an isomer of the compound (I'); and [0132] b) A
benzotriazole compound:
[0132] ##STR00014## [0133] Wherein R.sub.1 represents hydrogen or
methyl; and [0134] A) A functional fluid selected from the group
consisting of lubricants, hydraulic agents, metal working fluids
and coating agents.
[0135] A highly preferred embodiment of the invention relates to a
composition comprising [0136] A) A mixture consisting essentially
of [0137] a) A benzotriazole compound:
[0137] ##STR00015## [0138] Wherein R.sub.1 represents hydrogen or
methyl; [0139] R.sub.2 represents a substituent selected from the
group consisting of C.sub.1-C.sub.8alkyl,
C.sub.5-C.sub.7cycloalkyl,
[0139] ##STR00016## [0140] Wherein R.sub.1' is as defined as
R.sub.1, [0141] The index a represents a numeral from 1 to 10;
[0142] The index n represents a numeral from 2 to 8, and [0143]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.7cycloalkyl
and phenyl or an isomer of the compound (I'); [0144] b) A
benzotriazole compound:
[0144] ##STR00017## [0145] Wherein R.sub.1 represents hydrogen or
methyl; and [0146] c) A triazole compound:
[0146] ##STR00018## [0147] Wherein R.sub.1 represents hydrogen or
methyl; [0148] R.sub.2 represents a substituent selected from the
group consisting of C.sub.1-C.sub.8alkyl,
C.sub.5-C.sub.7cycloalkyl,
[0148] ##STR00019## [0149] Wherein R.sub.1' is as defined as
R.sub.1; and [0150] The index a represents a numeral from 1 to 10;
[0151] The index n represents a numeral from 2 to 8; and [0152]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl and phenyl; and [0153] B) A functional
fluid selected from the group consisting of lubricants, hydraulic
agents, metal working fluids and coating agents.
[0154] The invention particularly refers to a composition
comprising [0155] A) A mixture consisting essentially of [0156] a)
A benzotriazole compound (I'), wherein [0157] R.sub.1 represents
hydrogen or methyl; [0158] R.sub.2 represents
C.sub.5-C.sub.7cycloalkyl or the group (A'), wherein R.sub.1' is as
defined as R.sub.1; [0159] And the index a represents a numeral
from 1 to 8; and [0160] R.sub.3 represents C.sub.1-C.sub.8alkyl or
C.sub.5-C.sub.7cycloalkyl or an isomer of the compound (I'); and
[0161] b) A benzotriazole compound (II), wherein [0162] R.sub.1
represents hydrogen or methyl; and [0163] B) A functional fluid
selected from the group consisting of lubricants, hydraulic agents,
metal working fluids and coating agents.
[0164] Another highly preferred embodiment of the invention relates
to composition comprising [0165] A) A mixture consisting
essentially of [0166] a) A benzotriazole compound (I'), wherein
[0167] R.sub.1 represents hydrogen or methyl; [0168] R.sub.2
represents C.sub.5-C.sub.7cycloalkyl or the group (A'), wherein
R.sub.1' is as defined as R.sub.1; [0169] And the index a
represents a numeral from 1 to 8; and [0170] R.sub.3 represents
C.sub.1-C.sub.8alkyl or C.sub.5-C.sub.7cycloalkyl or an isomer of
the compound (I'); [0171] b) A benzotriazole compound (II), wherein
[0172] R.sub.1 represents hydrogen or methyl; and [0173] c) A
triazole compound (III), wherein [0174] R.sub.1 represents hydrogen
or methyl; [0175] R.sub.2 represents C.sub.5-C.sub.7cycloalkyl or
the group (B), wherein R.sub.1' is as defined as R.sub.1; and
[0176] The index a represents a numeral from 1 to 8; and [0177]
R.sub.3 represents C.sub.1-C.sub.8alkyl or
C.sub.5-C.sub.7cycloalkyl or an isomer of the compound (I'); and
[0178] B) A functional fluid selected from the group consisting of
lubricants, hydraulic agents, metal working fluids and coating
agents.
[0179] A further embodiment of the invention relates to a mixture
comprising [0180] a) A benzotriazole compound (I), wherein [0181]
R.sub.1 represents hydrogen or C.sub.1-C.sub.4alkyl; [0182] R.sub.2
represents a substituent selected from the group consisting of
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl or represents the
group (A), [0183] Wherein R.sub.1' is as defined as R.sub.1; and
[0184] The index a represents a numeral from 1 to 10; and [0185]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl;
[0186] b) A benzotriazole compound (II), wherein [0187] R.sub.1,
represents hydrogen or C.sub.1-C.sub.4alkyl; and, optionally,
[0188] c) A triazole compound (III), wherein [0189] R.sub.1
represents hydrogen or C.sub.1-C.sub.4alkyl; [0190] R.sub.2
represents a substituent selected from the group consisting of
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl and
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl or represents the
group (B), wherein [0191] R.sub.1' is as defined as R.sub.1; and
[0192] The index a represents a numeral from 1 to 10; and [0193]
R.sub.3 represents hydrogen or a substituent selected from the
group consisting of C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.7cycloalkyl,
(C.sub.1-C.sub.4alkyl).sub.1-3C.sub.5-C.sub.7cycloalkyl,
C.sub.5-C.sub.7cycloalkyl-C.sub.1-C.sub.4alkyl, phenyl,
phenyl-C.sub.1-C.sub.4alkyl, (C.sub.1-C.sub.4alkyl).sub.1-3phenyl
and (C.sub.1-C.sub.4alkyl).sub.1-3phenyl-C.sub.1-C.sub.4alkyl.
[0194] The mixtures defined above is particularly useful in method
for improving the functional properties of lubricants, hydraulic or
metal-working fluids or coating compositions, which comprises
adding to a functional fluid the mixture defined above and,
optionally, further additives.
[0195] The following examples illustrate the invention:
EXAMPLE 1
##STR00020##
[0197] 99.9 g (0.75 mol) tolutriazole (IRGAMET TTA, 2:3 mixture of
4(5)-methyl-1H-benzotriazole (2:3)), 75.15 g (0.75 mol)
cyclohexanol (Riedel 24217) and 18.8 g (7% per weight based on the
weight of all reactants) Montmorillonite K5 (Fluka 69908) are added
to 147.0 g cyclohexane. The suspension is stirred and heated under
reflux conditions. The water from the earth clay is removed for 30
min. in the gas phase and separated. 90.06 g (0.789 mol) heptanal
are added within a time period of 30 min. The mixture is stirred
and heated for 4 h under reflux conditions and, when the separation
of water ceases, cooled to room temperature and filtered. The
solvent is removed from the yellowish filtrate in the vacuum and a
yellowish oil is obtained, which contains less than 1% TTA (HPLC).
In the gas chromatogram 0.7% TTA, 1.1% heptanal and 0.8%
cyclohexanol are found.
Elemental Analysis [%]:
TABLE-US-00001 [0198] C H N Calc. 72.91 9.48 12.75 Found
72.85/72.86 9.60/9.64 12.52/12.51
[0199] According to an alternative embodiment of the process,
Montmorillonit is replaced with Bleicherde Tonsil.RTM. Supreme
110FF.
EXAMPLE 2
[0200] Mixtures comprising different amounts of tolutriazole (I)
with regard to the condensation product (II) are prepared in a
manner analogous to Example 1 by adding excess amounts of (I) to
the reaction mixture:
TABLE-US-00002 Amounts [% by weight] Components B-1 B-2 B-3 B-4 B-5
B-6 B-7 (II) 95.0 92.5 90.0 87.5 85.0 82.5 80.0 (I) 5.0 7.5 10.0
12.5 15.0 17.5 20.0 Total Weight (I) 112.7 119.1 125.5 131.9 138.3
147.7 151.1 Excess of (I) 12.8 19.2 25.6 32.0 38.4 47.8 51.2
EXAMPLE 3
Application Tests
3.1 Methods
3.1.1 Rotary Bomb Oxidation Test ASTM D-2272
[0201] A 0.05% solution of the test composition in a mineral oil of
turbine quality is prepared, which oil has a viscosity of 26.2
mm.sup.2/sec (40.degree. C.) and 4.8 mm.sup.2/sec (100.degree. C.)
and a sulphur content of 0.54%. The solution can also contain a
phenolic or amine antioxidant. The time required at a temperature
of 150.degree. C. for a minimum pressure drop of 1.75 bar starting
from the maximum pressure of 6.2 bar is measured.
3.1.2 Modified ASTM D-130 Copper Strip Test
[0202] A 0.04% solution of the test composition in a
poly-alpha-olefin (PAO), which has a viscosity of 7.7-8.0 cSt
(100.degree. C.) and a content of 50 ppm of elemental sulphur, is
prepared. A copper strip (50.times.10.times.1 mm) is polished with
grade 150 silicon carbide, which was absorbed with a wool pad wet
with high-boiling petroleum ether. The polished strip is then
completely immersed in the prepared solution, which is kept at
100.degree. C. for two hours. The strip is then removed, washed
with isooctane and dried and its colour is compared with the
standardized colour samples of the tarnish chart, which is
applicable for the corrosion test of copper strips according to
ASTM D130.
3.2 Compositions Tested
TABLE-US-00003 [0203] Composition Tested [% by weight] Components
Control 1 Control 2 Control 3 1 (B-1) 2 (B-2) 3 (B-3) 4 (B-4) 5
(B-5) 6 (B-6) 7 (B-7) Base Fluid.sup.1) Bal. Bal. Bal. Bal. Bal.
Bal. Bal. Bal. Bal. Bal. Antifoam.sup.2) 0.05 0.05 0.05 0.05 0.05
0.05 0.05 0.05 0.05 0.05 Base -- 0.38 0.38 0.38 0.38 0.38 0.38 0.38
0.38 0.38 Formulation.sup.3) (II) -- -- 0.04 Blends -- -- 0.04 0.04
0.04 0.04 0.04 0.04 0.04 .sup.1)Group II, ISO 46 (blend of Jurong
150 and 500) .sup.2)IRGALUBE AF 1 .sup.3)Base Formulation
Components Amount [% by weight] IRGANOX L57 39.5 IRGANOX L135 39.5
PANA 15.8 IRGACOR NPA 2.6 Sarkosyl O 2.6
3.3 Results
TABLE-US-00004 [0204] Composition Tested [% by weight] Test Control
1 Control 2 Control 3 1 (B-1) 2 (B-2) 3 (B-3) 4 (B-4) 5 (B-5) 6
(B-6) 7 (B-7) RPVOT.sup.1) 28 452 507 581 582 646 640 640 645 651 D
130 rating 4a 4a 3b 1b+ 1b+ 1b+ 1b+ 1b+ 1b+ 1b+ .sup.1)RPVOT:
Average of duplicates, minutes; ASTM D 2272 .sup.2)Copper corrosion
per ASTM D 130, 3 h at 125.degree. C. with 50 ppm elemental sulphur
present
[0205] The findings in the RPVOT show outstanding antioxidative
properties exerted by representative compositions in a non-aqueous
functional fluid in the presence of phenolic and aminic
antioxidants.
[0206] The findings in the copper corrosion test show outstanding
deactivation of copper, which is achieved in a non-aqueous
functional fluid in the presence of representative blends.
* * * * *