U.S. patent application number 10/526694 was filed with the patent office on 2005-12-01 for succinic acid semi-amides as anti-corrosives agents.
Invention is credited to Camenzind, Hugo, Hanggi, Peter.
Application Number | 20050267003 10/526694 |
Document ID | / |
Family ID | 32000111 |
Filed Date | 2005-12-01 |
United States Patent
Application |
20050267003 |
Kind Code |
A1 |
Camenzind, Hugo ; et
al. |
December 1, 2005 |
Succinic acid semi-amides as anti-corrosives agents
Abstract
The invention relates to improved compositions based on
lubricants and comprising succinic acid semi-amides and to the use
of those lubricant compositions in improving the use properties of
lubricants, such as hydraulic or metal-working fluids, greases,
gear oils or engine oils.
Inventors: |
Camenzind, Hugo; (Bern,
CH) ; Hanggi, Peter; (Giffers, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
32000111 |
Appl. No.: |
10/526694 |
Filed: |
March 3, 2005 |
PCT Filed: |
September 11, 2003 |
PCT NO: |
PCT/EP03/10115 |
Current U.S.
Class: |
508/447 ;
508/477; 508/500 |
Current CPC
Class: |
C10M 2215/226 20130101;
C10M 133/24 20130101; C10N 2040/04 20130101; C10N 2040/20 20130101;
C10N 2040/25 20130101; C10M 2215/22 20130101; C10M 2215/12
20130101; C10M 2215/08 20130101; C10M 2215/16 20130101; C10N
2030/12 20130101; C10N 2040/08 20130101; C10M 133/38 20130101; C10N
2070/00 20130101; C10M 133/16 20130101 |
Class at
Publication: |
508/447 ;
508/477; 508/500 |
International
Class: |
C10M 133/16 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 19, 2002 |
CH |
2002 1588/02 |
Claims
What is claimed is:
1. A composition comprising a) At least one compound of formula
9Wherein R.sub.1 is a substituent selected from the group
consisting of C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkyl
substituted by hydroxy, C.sub.2-C.sub.22alkyl interrupted by
--C(.dbd.O)--, --O--C(.dbd.O)-- or by --NR.sub.a--C(.dbd.O)--,
C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--C(.dbd.O)--O-- or by C(.dbd.O)--NR.sub.a--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, phenyl, benzyl, 1- or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl,
1-naphthylmethyl, cyclohexyl, cyclohexylmethyl and isobomyl;
R.sub.2 and R.sub.3 are hydrogen, or one of R.sub.2 and R.sub.3 is
hydrogen and the other is methyl; and X is carboxy or carboxylate
and Y.sup.+ is a salt-forming cation suitable for lubricant
compositions; or X is derivatised carboxy selected from the group
consisting of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl,
carboxy esterified by hydroxy-C.sub.2-C.sub.22alkyl, carboxy
esterified by C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, carboxy esterified
by C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--O--C(.dbd.O)-- or by --NR.sub.a--(C.dbd.O)--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, 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 10Wherein R.sub.b
and R.sub.c are each independently of the other hydrogen,
C.sub.1-C.sub.22alkyl or 2-hydroxyethyl, or R.sub.b and R.sub.c
together are C.sub.2-C.sub.22alkylene, C.sub.2-C.sub.8alkenylene,
C.sub.2-C.sub.8alkadienylene or C.sub.2-C.sub.8alkylene,
C.sub.2-C.sub.8alkenylene or C.sub.2-C.sub.8alkadienylene
interrupted by --O-- or by --NR.sub.a--, with R.sub.a being as
defined; and Y.sup.+ is a hydrogen ion or is a salt-forming cation
suitable for lubricant compositions; and b) A base oil of
lubricating viscosity.
2. A composition according to claim 1, comprising a) At least one
compound (I), wherein R.sub.1 is a substituent selected from the
group consisting of C.sub.1-C.sub.2alkyl, C.sub.2-C.sub.22alkyl
substituted by hydroxy, C.sub.2-C.sub.22alkyl interrupted by
--C(.dbd.O)--, --O--C(.dbd.O)-- or by --NR.sub.a--C(.dbd.O)--,
C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, phenyl, benzyl, 1- or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl,
1-naphthylmethyl, cyclohexyl, cyclohexylmethyl, and isobornyl;
R.sub.2 and R.sub.3 are hydrogen, or one of R.sub.2 and R.sub.3 is
hydrogen and the other is methyl; X is derivatised carboxy selected
from the group consisting of cyano, carboxy esterified by
C.sub.1-C.sub.22alkyl, carboxy esterified by
hydroxy-C.sub.2-C.sub.22alkyl, carboxy esterified by
C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, carboxy esterified
by C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, NR.sub.a--,
--O--C(.dbd.O)-- or by --NR.sub.a--(C.dbd.O)--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, 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
R.sub.b and R.sub.c are each independently of the other hydrogen,
C.sub.1-C.sub.22alkyl, or 2-hydroxyethyl, or R.sub.b and R.sub.c
together are C.sub.2-C.sub.8alkylene, C.sub.2-C.sub.8alkenylene,
C.sub.2-C.sub.8alkadienylene or C.sub.2-C.sub.8alkylene,
C.sub.2-C.sub.8alkenylene or C.sub.2-C.sub.8alkadienylene
interrupted by --O-- or by --NR.sub.a--, with R.sub.a being as
defined; and Y.sup.+ is a hydrogen ion or is a salt-forming cation
suitable for lubricant compositions; and b) A base oil of
lubricating viscosity.
3. A composition according to claim 1, comprising a) At least one
compound (I), wherein R.sub.1 is a substituent selected from the
group consisting of C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkyl
Interrupted by --C(.dbd.O)-- or by --O--C(.dbd.O)--,
C.sub.3-C.sub.22alkyl interrupted by --O--, --S-- or by
--C(.dbd.O)--O--, phenyl and benzyl; R.sub.2 and R.sub.3 are
hydrogen; X is derivatised carboxy selected from the group
consisting of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl,
carboxy esterified by hydroxy-C.sub.2-C.sub.22alkyl, carboxy
esterified by C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)-- or
by --C(.dbd.O)--O--, carboxy esterified by C.sub.3-C.sub.22alkyl
interrupted by --O--, --S-- or by --O--C(.dbd.O)--, and carbamoyl
of the partial formula (A) defined as heterocyclylcarbonyl; and
Y.sup.+ is a hydrogen ion, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammonium or
(2-hydroxyethyl).sub.1-4ammonium; and b) A base oil of lubricating
viscosity.
4. A composition according to claim 1, comprising a) At least one
compound (I), wherein R.sub.1 is a substituent selected from the
group consisting of C.sub.1-C.sub.2alkyl, C.sub.3-C.sub.22alkyl
interrupted by --O--, phenyl, and benzyl; R.sub.2 and R.sub.3 are
hydrogen; X is derivatised carboxy selected from the group
consisting of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl,
carboxy esterified by C.sub.3-C.sub.22alkyl interrupted by --O--,
and carbamoyl of the partial formula (A) defined as
piperidinocarbonyl, piperazinylcarbonyl or morpholinocarbonyl; and
Y.sup.+ is a hydrogen ion, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammoni- um or
(2-hydroxyethyl).sub.1-4ammonium; and b) A base oil of lubricating
viscosity.
5. A composition according to claim 1, comprising a) At least one
compound (I), wherein R.sub.1 is a substituent selected from the
group consisting of C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl
interrupted by --O--, phenyl and benzyl; R.sub.2 and R.sub.3 are
hydrogen; X is carboxy and Y is ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammonium or
(2-hydroxyethyl).sub.1-4ammonium; or X is carboxylate or
derivatised carboxy selected from the group consisting of cyano,
carboxy esterified by C.sub.1-C.sub.18alkyl, carboxy esterified by
C.sub.3-C.sub.18alkyl interrupted by --O--, and
morpholinocarbamoyl; and Y is hydrogen, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammonium or
(2-hydroxyethyl).sub.1-4ammonium; and b) A base oil of lubricating
viscosity.
6. A composition according to claim 1, comprising b) A base oil of
lubricating viscosity which is used for hydraulic or metal-working
fluids, greases, gear oils or engine oils.
7. A concentrate comprising at least one compound (I) wherein
R.sub.1, R.sub.2, R.sub.3, X and Y are as defined in claim 1.
8. A method of improving the use properties of lubricants, which
comprises adding to the lubricants at least one composition
according to claim 1.
Description
[0001] 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.
[0002] Additives that have to fulfill 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 contaminants. Often, in mineral oil industry
enterprises, oils are admixed with commercially available 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.
[0003] The present invention relates to the problem of producing
lubricant compositions that provide improved protection against
corrosion, combined with good compatibility with calcium ions.
[0004] U.S. Pat. No. 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).
[0005] U.S. Pat. No. 5,275,749 discloses lubricant compositions
providing protection against wear and corrosion, which comprise a
component of the N-acyl-N-alkoxyalkylaminosuccinic acid ester
type.
[0006] It has now been found, surprisingly, that succinic acid
semi-amides, which are obtainable by reacting succinic acid
anhydride with .beta.-amino acid derivatives, improve the corrosion
protection in lubricant compositions whilst at the same time the
formation of precipitation products and residues is reduced.
[0007] The invention relates to compositions comprising
[0008] a) At least one compound of formula 1
[0009] Wherein
[0010] R.sub.1 is a substituent selected from the group consisting
of C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkyl substituted by
hydroxy, C.sub.2-C.sub.22alkyl interrupted by --C(--O)--,
--O--C(.dbd.O)-- or by --NR.sub.a--C(.dbd.O)--,
C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, phenyl, benzyl, 1- or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl,
1-naphthylmethyl, cyclohexyl, cyclohexylmethyl, and isobornyl;
[0011] R.sub.2 and R.sub.3 are hydrogen, or one of R.sub.2 and
R.sub.3 is hydrogen and the other is methyl; and
[0012] X is carboxy or carboxylate and Y.sup.+ is a salt-forming
cation suitable for lubricant compositions; or
[0013] X is derivatised carboxy selected from the group consisting
of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl, carboxy
esterified by hydroxy-C.sub.2-C.sub.22alkyl, carboxy esterified by
C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, carboxy esterified
by C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--O--C(.dbd.O)-- or by --NR.sub.a(C.dbd.O)--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, 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 2
[0014] Wherein R.sub.b and R.sub.c are each independently of the
other hydrogen, C.sub.1-C.sub.22alkyl or 2-hydroxyethyl, or R.sub.b
and R.sub.c together are C.sub.2-C.sub.8alkylene,
C.sub.2-C.sub.8alkenylene, C.sub.2-C.sub.8alkadienylene or
C.sub.2-C.sub.8alkylene, C.sub.2-C.sub.8alkenylene or
C.sub.2-C.sub.8alkadienylene interrupted by --O-- or by
--NR.sub.a-- with R.sub.a being as defined; and
[0015] Y.sup.+ is a hydrogen ion or is a salt-forming cation
suitable for lubricant compositions; and
[0016] b) A base oil of lubricating viscosity.
[0017] The compounds (I) have excellent corrosion-inhibiting action
combined with good compatibility with calcium ions, which may be
present in lubricants especially as constituents of detergents.
[0018] A preferred embodiment relates to compositions
comprising
[0019] a) At least one compound (I), wherein
[0020] R.sub.1 is a substituent selected from the group consisting
of C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkyl substituted by
hydroxy, C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)--,
--O--C(.dbd.O)-- or by --NR.sub.a--C(.dbd.O)--,
C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a--,
--C(.dbd.O)--O-- or by C(.dbd.O)NR.sub.a, wherein R.sub.a denotes
hydrogen or C.sub.1-C.sub.22alkyl, phenyl, benzyl, 1- or
2-phenylethyl, 2-phenoxyethyl, furfuryl, 1-naphthyl,
1-naphthylmethyl, cyclohexyl, cyclohexylmethyl and isobornyl;
[0021] R.sub.2 and R.sub.3 are hydrogen, or one of R.sub.2 and
R.sub.3 is hydrogen and the other is methyl;
[0022] X is derivatised carboxy selected from the group consisting
of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl, carboxy
esterified by hydroxy-C.sub.2-C.sub.22alkyl, carboxy esterified by
C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)--,
--C(.dbd.O)--O-- or by --C(.dbd.O)--NR.sub.a--, carboxy esterified
by C.sub.3-C.sub.22alkyl interrupted by --O--, --S--, --NR.sub.a,
--O--C(.dbd.O)-- or by --NR.sub.a--(C.dbd.O)--, wherein R.sub.a
denotes hydrogen or C.sub.1-C.sub.22alkyl, 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
R.sub.b and R.sub.c are each independently of the other hydrogen,
C.sub.1-C.sub.22alkyl or 2-hydroxyethyl, or R.sub.b and R.sub.c
together are C.sub.2-C.sub.8alkylene, C.sub.2-C.sub.8alkenylene,
C.sub.2-C.sub.8alkadienylene or C.sub.2-C.sub.8alkylene,
C.sub.2-C.sub.8alkenylene or C.sub.2-C.sub.8alkadienylene
interrupted by --O-- or by --NR.sub.a--, R.sub.a being as defined;
and
[0023] Y.sup.+ is a hydrogen ion or is a salt-forming cation
suitable for lubricant compositions; and
[0024] b) A base oil of lubricating viscosity.
[0025] An especially preferred embodiment corresponds to the
following compositions comprising
[0026] a) At least one compound (I), wherein
[0027] R.sub.1 is a substituent selected from the group consisting
of C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkyl interrupted by
--C(.dbd.O)-- or by --O--C(.dbd.O)--, C.sub.3-C.sub.22alkyl
interrupted by --O--, --S-- or by --C(.dbd.O)--O--, phenyl and
benzyl;
[0028] R.sub.2 and R.sub.3 are hydrogen;
[0029] X is derivatised carboxy selected from the group consisting
of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl, carboxy
esterfied by hydroxy-C.sub.2-C.sub.22alkyl, carboxy esterified by
C.sub.2-C.sub.22alkyl interrupted by --C(.dbd.O)-- or by
--C(.dbd.O)--O--, carboxy esterified by C.sub.3-C.sub.22alkyl
interrupted by --O--, --S-- or by --O--C(.dbd.O)--, and carbamoyl
of the partial formula (A) defined as heterocyclylcarbonyl; and
[0030] Y.sup.+ is a hydrogen ion, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4- ammonium or
(2-hydroxyethyl).sub.1-4ammonium; and
[0031] b) A base oil of lubricating viscosity.
[0032] A very especially preferred embodiment relates to
compositions comprising
[0033] a) At least one compound (I), wherein
[0034] R.sub.1 is a substituent selected from the group consisting
of C.sub.1-C.sub.22alkyl, C.sub.3-C.sub.22alkyl interrupted by
--O--, phenyl, and benzyl;
[0035] R.sub.2 and R.sub.3 are hydrogen;
[0036] X is derivatised carboxy selected from the group consisting
of cyano, carboxy esterified by C.sub.1-C.sub.22alkyl, carboxy
esterified by C.sub.3-C.sub.22alkyl interrupted by --O--, and
carbamoyl of the partial formula (A) defined as piperidinocarbonyl,
piperazinylcarbonyl or morpholinocarbonyl; and
[0037] Y.sup.+ is a hydrogen ion, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4- ammonium or
(2-hydroxyethyl).sub.1-4ammonium; and
[0038] b) A base oil of lubricating viscosity.
[0039] A likewise very especially preferred embodiment relates to
compositions comprising
[0040] a) At least one compound (I), wherein
[0041] R.sub.1 is a substituent selected from the group consisting
of C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl interrupted by
--O--, phenyl, and benzyl;
[0042] R.sub.2 and R.sub.3 are hydrogen;
[0043] X is carboxy and Y is ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammon- ium or
(2-hydroxyethyl).sub.1-4ammonium; or
[0044] X is carboxylate or derivatised carboxy selected from the
group consisting of cyano, carboxy esterified by
C.sub.1-C.sub.18alkyl, carboxy esterified by C.sub.3-C.sub.18alkyl
interrupted by --O--, and morpholinocarbamoyl; and
[0045] Y.sup.+ is hydrogen, ammonium,
(C.sub.1-C.sub.4alkyl).sub.1-4ammoni- um or
(2-hydroxyethyl).sub.1-4ammonium; and
[0046] b) A base oil of lubricating viscosity.
[0047] The compounds (I) are prepared in a manner known per se, for
example by addition of a primary amine R.sub.1--NH.sub.2 to an
acrylic acid derivative: 3
[0048] (Addition of amines to .alpha., .beta.-unsaturated carbonyl
compounds) to form a .beta.-amino acid derivative: 4
[0049] Which is acylated with a reactive, functional derivative of
succinic acid, for example succinic anhydride or succinic acid
monochloride.
[0050] DE-A-2 054 649 describes the addition of primary amines to
acrylic acid esters and the subsequent reaction with succinic
anhydride. The compounds described therein can be used, inter alia,
as textile adjuvants.
[0051] The terms and general designations used in the description
of the present invention are preferably defined as follows:
[0052] Component a) Compounds (I)
[0053] R.sub.1 and R.sub.a defined as C.sub.1-C.sub.22alkyl include
saturated, unbranched or, where possible, branched hydrocarbon
groups, especially C.sub.1-C.sub.9alkyl, e.g. methyl, ethyl,
isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl,
isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl,
1,3-dimethylbutyl, n-heptyl, 3-heptyl, 1-methylhexyl, isoheptyl,
n-octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl- , 1-methylheptyl,
n-nonyl or 1,1,3-trimethylhexyl, and also C.sub.10-C.sub.22alkyl,
especially straight-chain C.sub.10-C.sub.22alkyl, e.g. n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl or branched
C.sub.10-C.sub.22alkyl, 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.
[0054] R.sub.1 defined as C.sub.2-C.sub.22alkyl substituted by
hydroxy includes saturated, unbranched hydrocarbon groups having
preferably from 2 to 9 carbon atoms, e.g. 2-hydroxyethyl or 2- or
3-hydroxypropyl.
[0055] R.sub.1 defined as C.sub.2-C.sub.22alkyl interrupted by
--C(.dbd.O)--, --O--C(.dbd.O)-- or by --NR.sub.a--C(.dbd.O)--
includes unbranched 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.
[0056] R.sub.1 defined as C.sub.3-C.sub.22alkyl interrupted by
--O--, --S--, --NR.sub.a--, --C(.dbd.O)--O-- or by
--C(.dbd.O)--NR.sub.a-- includes 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-ethylthioethyl,
2-dimethylaminoethyl, 2- or 3-dimethylaminopropyl,
2-diethylaminoethyl, 2- or 3-diethylaminopropyl, 2-acetoxyethyl or
2-(N-acetoxy-N-methyl)-ethyl.
[0057] In compounds (I), R.sub.2 and R.sub.3 are hydrogen, or one
of R.sub.2 and R.sub.3 is hydrogen and the other is methyl.
Preferably, R.sub.2 and R.sub.3 are hydrogen.
[0058] When X in compounds (I) is carboxy or carboxylate
[--C(.dbd.O)--O.sup.-], Y.sup.+ is a salt-forming cation suitable
for lubricant compositions, e.g. ammonium, tetramethylammonium,
tetraethylammonium or 2-hydroxyethyltrimethylammonium. There is
present only one carboxy group in substantially undissociated form
[--C(.dbd.O)--OH] or in salt form [--C(.dbd.O)--O.sup.-], e.g. with
ammonium ions, e.g. ammonium, tetramethylammonium,
tetraethylammonium or 2-hydroxyethyltrimethylammonium.
[0059] In a preferred embodiment, X is derivatised carboxy or
unsubstituted or substituted carbamoyl as defined hereinbelow.
Y.sup.+ is then a hydrogen ion or a salt-forming cation suitable
for lubricant compositions.
[0060] X defined as carboxy esterified by C.sub.1-C.sub.22alkyl is,
for example, a carboxy group which is esterified by the
C.sub.1-C.sub.22alkyl groups defined hereinabove for R.sub.1, 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-dimethylbutyl, n-heptyl, 3-heptyl,
1-methylhexyl, isoheptyl, n-octyl, 2-ethylhexyl,
1,1,3,3-tetramethylbutyl, 1-methylheptyl, n-nonyl or
1,1,3-trimethylhexyl, and also by C.sub.10-C.sub.22alkyl,
especially straight-chain C.sub.10-C.sub.22alkyl, e. g. n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[0061] X defined as carboxy esterified by
hydroxy-C.sub.2-C.sub.22alkyl is, for example, a carboxy group that
is esterified by hydroxy-C2-C22alkyl defined hereinabove for
R.sub.1, e.g. 2-hydroxyethoxycarbonyl or 2- or
3-hydroxypropoxycarbonyl.
[0062] X defined as carboxy esterified by C.sub.2-C.sub.22alkyl
interrupted by --C(.dbd.O)--, --C(.dbd.O)--O-- or by
--C(.dbd.O)--NR.sub.a-- is, for example, a carboxy group esterified
by C.sub.2-C.sub.22alkyl, defined hereinabove for R.sub.1,
interrupted by --C(.dbd.O)--, --C(.dbd.O)--O-- or
--C(.dbd.O)--NR.sub.a--, e.g. acetonyloxycarbonyl,
acetoxycarbonylmethoxycarbonyl or
2-acetoxycarbonylethoxycarbonyl.
[0063] X defined as carboxy esterified by C.sub.3-C.sub.22alkyl
interrupted by --O--, --S--, --NR.sub.a--, --O--C(.dbd.O)-- or by
--NR.sub.a--(C.dbd.O)-- is, for example, a carboxy group esterified
by C.sub.3-C.sub.22alkyl (defined hereinabove for R.sub.1)
interrupted by --O--, --S--, --NR.sub.a--, --O--C(.dbd.O)-- or by
--NR.sub.a--(C.dbd.O)--, e.g. 2-methoxyethoxycarbonyl, 2- or
3-methoxypropoxycarbonyl, 2-, 3- or 4-methoxybutoxycarbonyl,
2-ethoxyethoxycarbonyl, 2- or 3-ethoxypropoxycarbonyl, 2-, 3- or
4-ethoxybutoxycarbonyl, 2-methylthioethoxycarbonyl, 2- or
3-methylthiopropoxycarbonyl, 2-ethylthioethoxycarbonyl,
2-dimethylaminoethoxycarbonyl, 2- or
3-dimethylaminopropoxycarbonyl, 2-diethylaminoethoxycarbonyl, 2- or
3-diethylaminopropoxycarbonyl, 2-acetoxyethoxycarbonyl or
2-(N-acetoxy-N-methyl)-ethoxycarbonyl.
[0064] X defined as carbamoyl of the partial formula A is, for
example, carbamoyl, dimethyl- or diethyl-carbamoyl. In addition,
R.sub.b and R.sub.c may be linked to one another by
C.sub.2-C.sub.8alkylene, e.g. 1,4-n-butylene or 1,5-n-pentylene, by
C.sub.2-C.sub.8alkenylene, e.g. 2-butenylene, or by
C.sub.2-C.sub.8alkadienylene, 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 corresponds to a heterocyclylcarbonyl substituent, e.g.
piperidinocarbonyl, piperazinylcarbonyl or morpholinocarbonyl.
[0065] In the compounds (I) described hereinabove, the sum of the
carbon atoms present in R.sub.1 and X is preferably greater than
ten.
[0066] The definition used for Y.sup.+, "a salt-forming cation
suitable for lubricant compositions", includes those cations of
salt-formers that together with the carboxylate group form metal
salts suitable for lubricant compositions, e.g. alkali metal,
alkaline earth metal, zinc (Zn.sup.2+) or copper (Cu.sup.2+) salts,
e.g. sodium, potassium, calcium, zinc.sup.2+ or Cu.sup.2+ ions.
[0067] In a preferred embodiment of the invention, the definition
used for Y.sup.+, "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,
(C.sub.1-C.sub.22alkyl).sub.1-4ammonium or
(2-hydroxyethyl).sub.1-4ammoni- um, e.g. tetramethylammonium,
tetraethylammonium or 2-hydroxyethyltrimethylammonium.
[0068] The compounds (I) are readily soluble in oils and can be
admixed with a base oil of lubricating viscosity, e.g. a lubricant,
in a manner known per se.
[0069] Component b) Base Oil
[0070] 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.
[0071] 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
(Editors); 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, Vol. 13, page 533 ff
(Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R.
Tourret and E P. Wright, Hyden & Son Ltd. GB, on behalf of The
Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann's
Encyclopaedia of Ind. Chem., Fifth Completely Revised Edition,
Verlag Chemie, DE-Weinheim, VCH-Publishers for U.S., Vol. A 15,
page 423 ff (Lubricants), Vol. A 13, page 165 ff (Hydraulic
Fluids).
[0072] 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 example epoxidised and sulphoxidised forms, or forms
produced by genetic engineering, for example soybean oil produced
by genetic engineering.
[0073] Examples of synthetic lubricants include lubricants based on
aliphatic or aromatic carboxylic acid esters, polymeric esters,
polyalkylene oxides, phosphoric acid esters, poly-.alpha.-olefins
or silicones, diesters of a divalent acid with a monohydric
alcohol, 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, trimethylolpropane 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 complex 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-.alpha.-olefins, ester-based lubricants, phosphates,
glycols, polyglycols and polyalkylene glycols, and also mixtures
thereof with water.
[0074] 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 frequently also emulsions of such
substances in water or other liquids.
[0075] The compositions advantageously contain from 0.005 to 10.0%
by weight, preferably from 0.01 to 5.0% by weight, especially from
0.01 to 0.9% by weight, of compounds (I).
[0076] The compositions are used, for example, in hydraulic or
metal-working fluids, greases, gear oils, or oils for engines of
the Ofto, diesel, two-stroke, Wankel or orbital type.
[0077] 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
deactivators, rust inhibitors, viscosity index improvers,
pour-point depressants, dispersants, detergents, extreme-pressure
additives, anti-wear additives and friction reducers. Such
additives 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:
[0078] Phenolic Antioxidants
[0079] 1. Alkylated monophenols: 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-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimeth- ylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, 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'-methylhe- ptadec-1'-yl)-phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)-phenol and mixtures
thereof.
[0080] 2. Alkylthiomethylphenols:
2,4-dioctylthiomethyl-6-tert-butylphenol- ,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylpheno- l,
2,6-didodecylthiomethyl-4-nonylphenol.
[0081] 3. Hydroquinones and alkylated hydroquinones:
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-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0082] 4. Tocopherols: .alpha.-, .beta.-, .gamma.- or
.delta.-tocopherols and mixtures thereof (vitamin E).
[0083] 5. Hydroxylated thiodiphenyl ethers:
2,2'-thiobis(6-tert-butyl-4-me- thylphenol),
2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-meth-
ylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxypheny- l) disulphide.
[0084] 6. Alkenylene bisphenols:
2,2'-methylenebis(6-tert-butyl-4-methylph- enol),
2,2'-methylene-bis(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-bu- tyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol-
], 4,4'-methylene-bis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-b- utyl-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-methylphenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]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.
[0085] 7. O-, N- and S-benzyl compounds:
3,5,3',5'-tetra-tert-butyl-4,4'-d- ihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate,
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-but- yl-4-hydroxybenzyl mercaptoacetate.
[0086] 8. Hydroxybenzylated malonates: dioctadecyl
2,2-bis(3,5-di-tert-but- yl-2-hydroxybenzyl)malonate, dioctadecyl
2-(3-tert-butyl-4-hydroxy-5-methy- lbenzyl)malonate,
didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydro-
xybenzyl)malonate,
di-[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-t-
ert-butyl-4-hydroxybenzyl)malonate.
[0087] 9. Hydroxybenzyl aromatic compounds:
1,3,5-tris(3,5-di-tert-butyl-4-
-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydrox-
ybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydrox- ybenzyl)phenol.
[0088] 10. Triazine comoounds:
2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-
-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-
-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-tert-but-
yl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydrox- yphenoxy)-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-tr-
iazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,-
3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)
isocyanurate.
[0089] 11. Acylaminophenols: 4-hydroxylauric acid anilide,
4-hydroxystearic acid anilide,
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carba- mic acid octyl
ester.
[0090] 12. Esters of
beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or poly-hydric alcohols, for example with methanol, ethanol,
n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)o- xalic
acid diamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-- trioxabicyclo[2.2.2]octane.
[0091] 13. Esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid (with
mono- or poly-hydric alcohols): with methanol, ethanol, n-octanol,
isooctanol, octadecanol, 1,6-hexanediol, 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, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o- ctane.
[0092] 14. Esters of
beta-(3.5-dicyclohexyl-4-hydroxyphenyl)progionic acid with mono- or
poly-hydric alcohols, e.g. with the alcohols mentioned under
13.
[0093] 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.
[0094] 16. Amides of
beta-(3.5-di-tert-butyl-4-hydroxphenyl)propionic acid, for example
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hex-
amethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)tri-
methylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydr-
azine.
[0095] Amine-Type Antioxidants
[0096] N,N'-Di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylene- diamine,
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-phenylen- ediamine,
N,N'-diphenyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylen-
ediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-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-naphthylamine- , N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
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'-diaminodiphenylmethane,
1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)propane,
(o-tolyl)-biguanide, di[4-(1',3'-dimethylbutyl)phenyl]amine,
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-fisohexyl-diphenylamines, mixtures of mono-
and di-alkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
mixture of mono- and di-alkylated tert-butyl-/tert-octyl-p-
henothiazines, mixture of mono- and di-alkylated
tert-octylphenothiazines, 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-tetramethypiperi- din-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0097] Further Antioxidants
[0098] 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-trit- hiatridecane and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiah-
exadecane.
[0099] Metal Deactivators, for Example for Copper
[0100] 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'-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)benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)tolutriazole.
[0101] 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-triazol- es, such as
1-(1-butoxyethyl)-1,2,4-triazole; acylated
3-amino-1,2,4-triazoles.
[0102] 3. Imidazole derivatives:
4,4'-methylenebis(2-undecyl-5-methylimida- zole);
bis[(N-methyl)-imidazol-2-yl]carbinol-octyl ether.
[0103] 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.
[0104] 5. Amino compounds: salicylidene-propylenediamine,
salicylaminoguanidine and salts thereof.
[0105] Rust Inhibitors
[0106] 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, partial
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.
[0107] 2. Nitrogen-containing compounds:
[0108] 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-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
[0109] 2.2. Heterocyclic compounds, e.g. substituted imidazolines
and oxazolines, e.g.
2-heptadecenyl-1-(2-hydroxyethyl)-imidazoline.
[0110] 3. Sulphur-containing compounds: barium
dinonylnaphthalenesulphonat- es, calcium petroleum sulphonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulphocarboxylic acids and salts thereof.
[0111] Extreme-Pressure and Anti-Wear Additives
[0112] Sulphur-containing and halogen-containing compounds, for
example, chlorinated paraffins, sulphurated olefins or vegetable
oils (soybean/rapeseed oil), alkyl- or aryl-di- or -tri-sulphides,
benzotriazoles or derivatives thereof such as
bis(2-ethylhexyl)aminomethy- ltolutriazole, dithiocarbamates such
as methylene-bis-dibutyidithiocarbama- te, derivatives of
2-mercaptobenzothiazole such as 1-[N,N-bis(2-ethylhexyl-
)aminomethyl]-2-mercapto-1 H-1,3-benzothiazole, derivatives of
2,5-dimercapto-1,3,4thiadiazole such as
2,5-bis(tert-nonyldithio)-1,3,4-t- hiadiazole.
[0113] Friction Coefficient Reducing Agents
[0114] Lard oil, oleic acid, tallow, rapeseed oil, sulphurated
fats, amines. Further examples are given in EP-A-0 565 487.
[0115] Further Additives
[0116] 1. Viscosity Index improvers: polyacrylates,
polymethacrylates, vinylpyrrolidone/methacrylate copolymers,
polyvinylpyrrolidones, polybutenes, olefin copolymers,
styrene/acrylate co-polymers, polyethers.
[0117] 2. Pour-point depressants: poly(meth)acrylates,
ethylene/vinyl acetate copolymer, alkyl-polystyrenes, fumarate
copolymers, alkylated naphthalene derivatives.
[0118] 3. Dispersants/surfactants: polybutenylsuccinic acid amides
or imides, polybutenylphosphonic acid derivatives, basic magnesium,
calcium and barium sulphonates and phenolates.
[0119] Special Additives
[0120] For use in water/oil metal-working fluids and hydraulic
fluids
[0121] 1. Emulsifiers: petroleum sulphonates, amines, such as
polyoxyethylated fatty amines, non-ionic surface-active
substances;
[0122] 2. Buffers: alkanolamines;
[0123] 3. Biocides: triazines, thiazolinones, tris-nitromethane,
morpholine, sodium pyridenethiol;
[0124] 4. Processing speed improvers: calcium and barium
sulphonates.
[0125] 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
composition 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.
[0126] The present invention relates also to a concentrate
comprising a) at least one compound (I) wherein R.sub.1, R.sub.2,
R.sub.3, X and Y are as defined, optionally further additives, and
b) a base oil of lubricating viscosity.
[0127] 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 R.sub.1,
R.sub.2, R.sub.3, X and Y are as defined.
[0128] The following Examples illustrate the invention:
EXAMPLES
[0129] Temperatures are given in .degree. C.; h: hour(s); min.:
minutes; m.p.: melting point; drying in vacuo (100.degree. C.,
about. 0.05 mbar)
Synthesis Examples
Example 1
N-(2-n-Butoxycarbonylethyl)-N-(n-octadecyl)-succinic acid
monoamide
[0130] 5
[0131] 1.1 14.1 g (0.110 mol) of acrylic acid n-butyl ester are
added drop wise, at 60.degree. 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.degree. for 2 h; the cooled crude product
is dissolved in 100 ml of hexane, filtered and washed twice with 50
ml of water. The organic phase is concentrated 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.
[0132] 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.degree. 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 evaporator and the residue
is dried in vacuo. 13.7 g (92% of theory) of a clear yellow oil,
which crystallises on standing are obtained.
[0133] M.p.: 50-52.degree. C.; elemental analysis: 70.24% C, (calc.
69.98), 10.91% H, (calc. 11.14), 2.80% N, (calc. 2.81).
Example 2
N-(3-n-Butoxypropyl)-N-(2-n-dodecyloxycarbonylethyl)-succinic acid
monoamide
[0134] 6
[0135] 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.degree. for 2 h; the cooled crude product is dried in vacua and
37.0 g of a clear, colourless, low-viscosity oil are obtained.
[0136] 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 product is
dissolved in 100 ml of hexane, filtered and washed three times with
30 ml of water. The hexane solution is concentrated by evaporation
in a rotary evaporator, the remaining product is dried in vacuo and
18.0 g (95% of theory) of a clear yellow oil of medium viscosity
are obtained.
[0137] n.sub.D.sup.20 1.4670; elemental analysis: 66.85% C, (calc.
66.21), 10.54% H, (calc. 10.47), 2.72% N, (calc. 2.97).
n.sub.D.sup.20 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-Morpholinocarbonylethyl)-N-(n-octadecyl)-succinic acid
monoamide
[0138] 7
[0139] 3.1 5.8 g (0.040 mol) of 4-acryloylmorpholine are added drop
wise, at 60.degree., over the course of 10 min., to 10.7 g (0.040
mol) of oleylamine (Armeen.RTM.O), the reaction mixture is stirred
at 100.degree. 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.
[0140] 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.degree. for 1 h and the cooled crude
product is shaken with 200 ml of hexane and 100 ml of brine
(NaCl-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.
[0141] Elemental analysis: 68.24% C, (calc. 68.47), 10.23% H,
(calc. 10.30), 5.34% N, (calc. 5.51).
Example 4
[0142] The following compounds (I) can be prepared analogously to
Examples 1-3: 8
1TABLE 1 Yield [% of Analysis [found Ex. R.sub.1 X theory]
Appearance (calculated)] 4.1 oleyl --C(.dbd.O)--O-(n-butyl) 99
clear, light-yellow, 70.79% C (70.26) medium-viscosity oil 10.58% H
(10.78) n.sub.D.sup.20 1.4761 2.82% N (2.83) 4.2 oleyl
--C(.dbd.O)--O-methyl 93 clear, yellow, 69.97% C (70.08) viscous
oil 10.40% H (10.44) n.sub.D.sup.20 1.4804 3.10% N (3.10) 4.3 oleyl
--C(.dbd.O)--O(CH.sub.2).sub.2--O-ethyl 96 clear, yellow, 69.02% C
(68.07) medium-viscosity oil 10.50% H (10.44) n.sub.D.sup.20 1.4768
2.77% N (2.74) 4.4 oleyl --C(.dbd.O)--O-(isobutyl) 77 clear,
yellow, 70.04% C (70.26) medium-viscosity oil 10.76% H (10.78)
n.sub.D.sup.20 1.4748 2.80% N (2.83) 4.5 oleyl --C(.dbd.O)--O-ethyl
69 clear, yellow, 68.85% C (69.34) medium-viscosity oil 10.50% H
(10.56) n.sub.D.sup.20 1.4769 2.97% N (2.99) 4.6 isotridecyl
--C(.dbd.O)--O-(n-butyl) 90 clear, light-yellow, 67.56% C (67.41)
viscous oil 10.59% H (10.61) n.sub.D.sup.20 1.4711 3.35% N (3.28)
4.7 isotridecyl --C(.dbd.O)--O-(isobutyl) 87 clear, light-yellow,
67.63% C (67.41) viscous oil 10.66% H (10.61) n.sub.D.sup.20 1.4709
3.36% N (3.28) 4.8 n-butyl --C(.dbd.O)--O-oleyl 95 clear, yellow,
70.80% C (70.26) medium-viscosity oil 10.79% H (10.78)
n.sub.D.sup.20 1.4752 2.56% N (2.83) 4.9 n-dodecyl
--C(.dbd.O)--O-ethyl 82 clear, light-yellow, 65.78% C (65.42)
medium-viscosity oil 10.39% H (10.20) n.sub.D.sup.20 1.4706 3.72% N
(3.63) 4.10 oleyl Nitrile 87 clear, light-yellow, 72.13% C (71.39)
viscous oil 10.73% H (10.54) n.sub.D.sup.20 1.4783 6.23% N (6.66)
4.11 n-octyl --C(.dbd.O)--O-oleyl 97 clear, yellow, 72.04% C
(71.69) viscous oil 11.05% H (11.30) n.sub.D.sup.20 1.4745 2.41% N
(2.53) 4.12 oleyl --C(.dbd.O)--O--(CH.sub.2).sub.2OH 59 clear,
light-yellow, 66.92% C (67.05) viscous oil 9.99% H (10.21)
n.sub.D.sup.20 1.4855 2.86% N (2.90) 4.13 oleyl
--C(.dbd.O)--NH.sub.2 82 clear, yellow, 68.10% C (68.45) viscous
oil 10.44% H (10.57) n.sub.D.sup.20 1.4745 6.26% N (6.39) 4.14
coconut oil --C(.dbd.O)--O-(n-butyl) 87 clear, light-yellow, 67.68%
C (67.73) amine(C.sub.12 mix) viscous oil 10.50% H (10.18)
n.sub.D.sup.20 1.4701 3.31% N (3.29) 4.15 n-butoxy-pro-
--C(.dbd.O)--O-oleyl 97 clear, yellow, 69.75% C (69.40) pyl
medium-viscosity oil 10.66% H (10.74) n.sub.D.sup.20 1.4744 2.40% N
(2.53) 4.16 C.sub.8--C.sub.10alkyl- --C(.dbd.O)--O-(n-butyl) 95
clear, yellow, 63.72% C O(CH.sub.2).sub.3 medium-viscosity oil
10.00% H n.sub.D.sup.20 1.4680 3.19% N 4.17 isodecyl-
--C(.dbd.0)--O-(n-butyl) 96 clear, yellow, 64.75% C (64.98)
O(CH.sub.2).sub.3 medium-viscosity oil 10.11% H (10.22)
n.sub.D.sup.20 1.4699 3.14% N (3.16) 4.18 2-ethylhexyl
--C(.dbd.O)--O-(n-dodecyl) 96 clear, light-yellow, 69.60% C (69.04)
medium-viscosity oil 10.69% H (10.94) n.sub.D.sup.20 1.4684 2.67% N
(2.98) 4.19 methoxy- --C(.dbd.O)--O-(n-dodecyl) 98 wax-like solid
64.99% C (64.31) propyl 10.14% H (10.09) 2.91% N (3.26) 4.20
C.sub.8--C.sub.10alk- nitrile 97 clear, yellow, 63.62% C (64.38)
O(CH.sub.2).sub.3 medium-viscosity oil 9.61% H (9.67)
n.sub.D.sup.20 1.4731 7.69% N (7.90) 4.21 benzyl
--C(.dbd.O)--O-(n-dodecyl) 97 wax-like solid 70.02% C (69.77) 8.99%
H (9.23) 3.10% N (3.13) 4.22 oleyl --C(.dbd.O)--O-cyclohexyl 98
clear, yellow, 71.35% C (71.36) medium-viscosity oil 10.12% H
(10.62) n.sub.D.sup.20 1.4864 2.72% N (2.68) 4.23 oleyl
--C(.dbd.O)--O--(CH.sub.2).sub.2--O- 98 clear, yellow, 71.20% C
(70.81) phenyl medium-viscosity oil 9.57% H (9.54) n.sub.D.sup.20
1.5025 2.43% N (2.50) 4.24 oleyl
--C(.dbd.O)--O--(CH.sub.2).sub.2--O- 94 clear, yellow, 67.82% C
(67.43) methyl medium-viscosity oil 10.26% H (10.51) n.sub.D.sup.20
1.4791 2.85% N (2.81) 4.25 oleyl
--C(.dbd.O)--O--(CH.sub.2).sub.2--O-- 94 clear, yellow, 66.55% C
(67.54) (CH.sub.2).sub.2--O-ethyl medium-viscosity oil 10.55% H
(10.34) n.sub.D.sup.20 1.4771 2.51% N (2.52) 4.26 benzyl
--C(.dbd.O)--O-dodecyl 98 yellowish, wax-like solid 4.27
2-ethylhexyl --C(.dbd.O)--O-dodecyl 96 clear, yellow, 69.60% C
(69.04) medium-viscosity oil 10.69% H (10.94) n.sub.D.sup.20 1.4684
2.67% N (2.98) 4.28 n-butyl --C(.dbd.O)--O-i-decyl 91 clear,
yellow, 65.24% C (65.42) medium-viscosity oil 10.20% H (10.20)
n.sub.D.sup.20 1.4708 3.43% N (3.63) 4.29 methyl-O--
--C(.dbd.O)--O-dodecyl 99 yellowish, wax-like 64.99% C (64.31)
(CH.sub.2).sub.3 solid 10.14% H (10.09) 2.91% N (3.26) 4.30
ethyl-O-- --C(.dbd.O)--O-dodecyl 95 clear, yellow, 65.25% C (64.98)
(CH.sub.2).sub.3 medium-viscosity oil 10.28% H (10.22)
n.sub.D.sup.20 1.4681 2.85% N (3.16) 4.31 ethyl-O--
--C(.dbd.O)--O-oleyl 95 clear, yellowish, 69.09% C (68.53)
(CH.sub.2).sub.3 medium-viscosity oil 10.76% H (10.54)
n.sub.D.sup.20 1.4755 2.57% N (2.66) 4.32 i-propyl-O--
--C(.dbd.O)--O-oleyl 96 clear, yellow, 68.19% C (68.98)
(CH.sub.2).sub.3 medium-viscosity oil 10.09% H (10.64)
n.sub.D.sup.20 1.4741 2.55% N (2.59) 4.33 i-decyl-O--
--C(.dbd.O)--O-n-butyl 96 clear, yellow, 64.75% C (64.98)
(CH.sub.2).sub.3 medium-viscosity oil 10.11% H (10.22)
n.sub.D.sup.20 1.4699 3.14% N (3.16) 4.34 i-decyl-O--
--C(.dbd.O)--O-i-butyl 95 clear, yellow, 64.87% C (64.98)
(CH.sub.2).sub.3 medium-viscosity oil 10.38% H (10.22)
n.sub.D.sup.20 1.4696 3.25% N (3.16) 4.35 octadecyl-O--
--C(.dbd.O)--O-i-butyl 96 clear, yellow, 66.76% C (67.30)
(CH.sub.2).sub.3 medium-viscosity oil 10.72% H (10.69)
n.sub.D.sup.20 1.4682 2.91% N (2.80) 4.36 oleyl
--C(.dbd.O)--N(CH.sub.2).sub.5 94 clear, yellow, 70.76% C (71.10)
medium-viscosity oil 10.98% H (10.74) n.sub.D.sup.20 1.4985 5.24% N
(5.53)
Application Examples
Example 5
Testing of Corrosion Protection Properties (of Active
Ingredient-Containing Industrial, Circulating, Turbine and
Hydraulic Oils) According to ASTM D 665 (=DIN 51585)
[0143] 300 ml of formulated oil are mixed with 30 ml of synthetic
seawater by stirring for 24 h at 60.degree. whilst simultaneously
immersing a steel round-section bar.
[0144] 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
specification 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.
[0145] 0: no corrosion
[0146] 1: light corrosion (<6 corrosion sites less than 1 mm in
diameter)
[0147] 2: moderate corrosion (<5% of the surface corroded)
[0148] 3: heavy corrosion (>5% of the surface corroded)
Example 6
Testing for Filterability in the Presence of Calcium Ions
[0149] 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.degree. C. (+/-2.degree. 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 .mu. Millipore.RTM. filter (type MWP
04700) using compressed air at 1 bar (+/-0.05 bar) positive
pressure. The times required 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):
[0150] FI=(t.sub.300 ml-t.sub.200 ml)/2(t.sub.100 ml-t.sub.50
ml)
[0151] FI=1 means that no resistance is built up at the filter.
[0152] FI<2 is the requirement for passing the test.
[0153] In the event of the filter becoming blocked, a note is made
after 60 min. of the volume of oil filtered up until then.
2TABLE 2 Degree of corrosion, Filterability in the according to
presence of Ca.sup.2+ Example ASTM D 665 Filtration index FI Base
formulation 3/3 1.25 1 1/0 2 0/0 1.20 3 0/0 1.25 4.1 0/0 1.13 4.2
0/0 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
* * * * *