U.S. patent application number 10/112436 was filed with the patent office on 2002-10-17 for bisdithiophosphoric acid derivatives as lubricant additives.
Invention is credited to Schumacher, Rolf, Zinke, Horst.
Application Number | 20020151444 10/112436 |
Document ID | / |
Family ID | 4218272 |
Filed Date | 2002-10-17 |
United States Patent
Application |
20020151444 |
Kind Code |
A1 |
Zinke, Horst ; et
al. |
October 17, 2002 |
Bisdithiophosphoric acid derivatives as lubricant additives
Abstract
There are disclosed compounds of formula I 1 wherein R.sub.1 and
R.sub.2 are each independently of the other C.sub.3-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.24alkylphenyl or, taken together, are 2 R.sub.3 is
C.sub.2-C.sub.18alkylene which is interrupted by -O-, -S-, or
-NR.sub.4-, or is a group of formula 3 R.sub.4 is hydrogen,
C.sub.1-C.sub.18alkyl, phenyl-C.sub.1-C.sub.4alkyl, phenyl or
C.sub.1-C.sub.6alkyl-substituted phenyl, R.sub.5 is hydrogen or
methyl. These compounds are particularly suitable for use as
additives for lubricant compositions, hydraulic fluids and
machining fluids.
Inventors: |
Zinke, Horst; (Reichelsheim,
DE) ; Schumacher, Rolf; (Marly, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
4218272 |
Appl. No.: |
10/112436 |
Filed: |
March 28, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10112436 |
Mar 28, 2002 |
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08451378 |
May 26, 1995 |
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6380139 |
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08451378 |
May 26, 1995 |
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08068377 |
May 27, 1993 |
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Current U.S.
Class: |
508/426 ;
252/78.5; 558/160 |
Current CPC
Class: |
C10M 167/00 20130101;
C10N 2040/253 20200501; C10M 137/105 20130101; C10M 2201/02
20130101; C10N 2040/252 20200501; C10N 2040/26 20130101; C10N
2040/255 20200501; C10N 2040/251 20200501; C10N 2040/25 20130101;
C07F 9/1651 20130101; C10N 2040/08 20130101; C10N 2040/28 20130101;
C10M 2223/047 20130101 |
Class at
Publication: |
508/426 ;
252/78.5; 558/160 |
International
Class: |
C10M 137/10; C07F
009/16 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 2, 1992 |
CH |
1773/92-4 |
Claims
1. A compound of formula 17wherein R.sub.1 and R.sub.2 are each
independently of the other C.sub.3-C.sub.18alkyl,
C.sub.5-C.sub.12cycloal- kyl, C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.24alkylphenyl or, taken together, are 18R.sub.3 is
(-CH.sub.2-).sub.b, C.sub.4-C.sub.40alkylene which is interrupted
by -O-, -S-, or -NR.sub.4-, or is a group of formula 19R.sub.4 is
hydrogen, C.sub.1-C.sub.18alkyl, phenyl-C.sub.1-C.sub.4alkyl,
phenyl or C.sub.1-C.sub.6alkyl-substituted phenyl, R.sub.5 is
hydrogen or methyl, and b is an integer from 3 to 18.
2. A compound according to claim 1, wherein R.sub.1 and R.sub.2 are
each independently of the other C.sub.3-C.sub.10alkyl,
C.sub.5-C.sub.6cycloalk- yl, C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.18alkylphenyl or, taken together, are 20and R.sub.3
is (-CH.sub.2-).sub.b, C.sub.4-C.sub.20alkylene which is
interrupted by -O- or NR.sub.4, or is a group of formula 21R.sub.4
is hydrogen or C.sub.1-C.sub.4alkyl, and b is an integer firom 3 to
10.
3. A compound according to claim 1, wherein R.sub.3 is
(-CH.sub.2-).sub.b, C.sub.4-C.sub.12alkylene which is interrupted
by -O- or NR.sub.4, or is 22R.sub.4 is C.sub.1-C.sub.4alkyl and b
is an integer from 3 to 6.
4. A compound according to claim 1, wherein R.sub.1 and R.sub.2 are
C.sub.3-C.sub.6alkyl.
5. A compound according to claim 1, wherein R.sub.5 is
hydrogen.
6. A composition comprising a) a lubricant, a machining fluid or
hydraulic fluid, and b) at least one compound of formula I
according to claim 1.
7. A composition according to claim 6, wherein R.sub.1 and R.sub.2
are each independently of the other C.sub.3-C.sub.10alkyl,
C.sub.5-C.sub.6cycloalkyl, C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.18alkylphenyl or, taken together, are 23R.sub.3 is
(-CH.sub.2-).sub.b, C.sub.4-C.sub.20alkylene which is interrupted
by -O- or NR.sub.4, or is a group of formula 24R.sub.4 is hydrogen
or C.sub.1-C.sub.4alkyl, and b is an integer from 3 to 10.
8. A composition according to claim 6, wherein R.sub.3 is
(-CH.sub.2-).sub.b, C.sub.4-C.sub.12alkylene which is interrupted
by -O- or NR.sub.4, or is 25R.sub.4 is C.sub.1-C.sub.4alkyl and b
is an integer from 3 to 6.
9. A composition according to claim 6, wherein R.sub.5 is
hydrogen.
10. A composition according to claim 6, wherein component a) is a
lubricant.
11. A composition according to claim 10, wherein the lubricant is
an engine oil.
12. A composition according to claim 6, which additionally
comprises further stabilisers selected from the group consisting of
antioxidants, metal deactivators, further extreme-pressure and
antiwear additives and pour-point depressants.
13. A process for enhancing the performance properties of lubricant
compositions, hydraulic fluids and machining fluids, which
comprises adding thereto at least one compound of formula I as
claimed in claim 1.
Description
[0001] The present invention relates to novel bisdithiophosphoric
acid derivatives, to the use thereof as additives in lubricants,
machining fluids and hydraulic fluids, and to compositions
containing said derivatives.
[0002] Mixed oxothiophosphoric acids are disclosed as lubricant
additives in US-A 4 544 492.
[0003] Methyl esters of formula 4
[0004] R'.sub.2 are hydrocarbon radicals and R'.sub.3 is hydrogen
or lower alkyl, are disclosed for the same utility in GB 1 347
845.
[0005] Dithiophosphoric acid derivatives which contain -C.dbd.C-
double bonds or -C(OH)- groups are disclosed in US-A 4 081 387.
[0006] Adducts of dithiophosphoric acids and acrylates are
disclosed in US-A 3 784 588. These adducts are esters of monohydric
to hexahydric alcohols. The use of such compounds in hydraulic oils
is disclosed in EP 465 156.
[0007] Surprisingly, it has been found that some esters of dihydric
alcohols have particularly good properties as lubricant
additives.
[0008] Specifically, the invention relates to compounds of formula
5
[0009] wherein R.sub.1 and R.sub.2 are each independently of the
other C.sub.3-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.24alkylphenyl or, taken together, are 6
[0010] R.sub.3 is (-CH.sub.2-).sub.b, C.sub.4-C.sub.40alkylene
which is interrupted by -O-, -S-, or -NR.sub.4-, or is a group of
formula 7
[0011] R.sub.4 is hydrogen, C.sub.1-C.sub.18alkyl,
phenyl-C.sub.1-C.sub.4a- lkyl, phenyl or
C.sub.1-C.sub.6alkyl-substituted phenyl, R.sub.5 is hydrogen or
methyl, and b is an integer from 3 to 18.
[0012] Preferred compounds of formula I are those wherein R.sub.1
and R.sub.2 are each independently of the other
C.sub.3-C.sub.10alkyl, C.sub.5-C.sub.6cycloalkyl,
C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.18alkylphenyl or, taken together, are 8
[0013] R.sub.3 is (-CH.sub.2-).sub.b, C.sub.4-C.sub.20alkylene
which is interrupted by -O- or NR.sub.4, or is a group of formula
9
[0014] R.sub.4 is hydrogen or C.sub.1-C.sub.4alkyl, and b is an
integer from 3 to 10, and compounds wherein R.sub.5 is
hydrogen.
[0015] Also preferred are compounds wherein R.sub.3 is
(-CH.sub.2-).sub.b, C.sub.4-C.sub.12alkylene which is interrupted
by -O- or NR.sub.4, or is 10
[0016] R.sub.4 is C.sub.1-C.sub.4alkyl and b is an integer from 3
to 6.
[0017] Further preferred compounds are those wherein R.sub.1 and
R.sub.2 are C.sub.3-C.sub.6alkyl.
[0018] b is preferably 4 to 6 and, most preferably, 4.
[0019] R.sub.4 is preferably hydrogen or C.sub.1-C.sub.4alkyl.
[0020] R.sub.1 and R.sub.2 defined in the above formulae as
C.sub.3-C.sub.18alkyl are branched or unbranched radicals.
Illustrative examples are propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl,
2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl,
1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl,
1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl or
1-methylundecyl.
[0021] R.sub.1 and R.sub.2 defined as C.sub.5-C.sub.12cycloalkyl
may typically be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl
or cyclododecyl. Cyclopentyl and cyclohexyl are preferred.
Cyclohexyl is most preferred.
[0022] R.sub.1 and R.sub.2 defined as
C.sub.5-C.sub.6cycloalkylmethyl will be taken to mean
cyclopentylmethyl and, preferably, cyclohexylmethyl.
[0023] R.sub.1 and R.sub.2 defined as
C.sub.9-C.sub.10bicycloalkylmethyl are typically decalinylmethyl.
R.sub.1 and R.sub.2 defined as C.sub.9-C.sub.10tricycloalkylmethyl
are preferably a group of formula 11
[0024] R.sub.1 and R.sub.2 defined as C.sub.9-C.sub.24alkylphenyl
are phenyl groups which are substituted by one or more than one
alkyl group, preferably by 1 to 3, most preferably 1 or 2, alkyl
groups together containing 3 to 18 carbon atoms. Typical examples
of such alkyl groups are methyl and ethyl and those cited
above.
[0025] R.sub.1 and R.sub.2 are preferably identical.
[0026] Interrupted C.sub.4-C.sub.40alkylene R.sub.3 is preferably
straight-chain and preferably contains ethylene units with
alternating O, S or NR.sub.4. The interruption is preferably by
oxygen, resulting in polyethylene glycol groups.
[0027] The invention further relates to compositions comprising
[0028] a) a lubricant, a machining fluid or hydraulic fluid,
and
[0029] b) at least one compound of formula I as described
above.
[0030] Preferred compositions are those wherein R.sub.1 and R.sub.2
are each independently of the other C.sub.3-C.sub.10alkyl,
C.sub.5-C.sub.6-Cycloalkyl, C.sub.5-C.sub.6cycloalkylmethyl,
C.sub.9-C.sub.10bicycloalkylmethyl,
C.sub.9-C.sub.10tricycloalkylmethyl, phenyl,
C.sub.7-C.sub.18alkylphenyl or, taken together, are 12
[0031] R.sub.3 is (-CH.sub.2-).sub.b, C.sub.4-C.sub.20alkylene
which is interrupted by -O- or NR.sub.4, or is a group of formula
13
[0032] hydrogen or C.sub.1-C.sub.4alkyl and b is an integer from 3
to 10.
[0033] Particularly preferred compositions are those wherein
R.sub.3 is (-CH.sub.2-).sub.b, C.sub.4-C.sub.12alkylene which is
interrupted by -O- or NR.sub.4, or is 14
[0034] R.sub.4 is C.sub.1-C.sub.4alkyl and b is an integer from 3
to 6, and also compositions wherein R.sub.5 is hydrogen.
[0035] Compositions meriting special interest are those wherein
R.sub.1 and R.sub.2 are C.sub.3-C.sub.6alkyl.
[0036] The lubricants, machining fluids or hydraulic fluids
contained in the inventive compositions can decompose readily to a
greater or lesser degree under the action of heat, mechanical
stress (especially induced by shear forces) and chemical reagents
(especially atmospheric oxygen).
[0037] The compounds of formula I afford protection against such
influences and will conveniently be present in the novel
compositions in amounts of 0.01 to 10% by weight, typically 0.05 to
5% by weight, preferably 0.05 to 3% by weight and, most preferably,
0.1 to 2% by weight. The novel compositions may contain one or more
than one of these compounds, and the percentages by weight are
based on the total amount of said compounds. The basis of
calculation is the total weight of the lubricant, machining fluid
or hydraulic fluid without the compounds of formula I.
[0038] The invention thus also relates to the use of compounds of
formula I as additives for lubricants, hydraulic fluids and
machining fluids, especially as extreme-pressure and antiwear
additives as well as friction modifiers.
[0039] Such a utility also entails a process for enhancing the
performance properties of lubricants, hydraulic fluids and
machining fluids. The novel utility also encompasses the protection
of the metal parts to be lubricated against mechanical wear
(antiwear protection).
[0040] The suitable lubricants, hydraulic fluids and machining
fluids are typically based on mineral or synthetic oils or mixtures
thereof. The lubricants are known to the skilled person and are
described in the relevant literature, inter alia in Dieter Klamann,
"Schmierstoffe and verwandte Produkte" (Lubricants and Related
Products) (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "Das
Schmiermittel-Taschenbuch" (Handbook of Lubricants) (Dr. Alfred
Huthig-Verlag, Heidelberg, 1974), and in "Ullmanns Enzyklopidie der
technischen Chemie" (Ullmann's Encyclopedia of Industrial
Chemistry), Vol. 13, pages 85-94 (Verlag Chemie, Weinheim,
1977).
[0041] The lubricants are preferably oils and fats are typically
derived from a mineral oil. Oils are preferred.
[0042] A further group of lubricants suitable for use in the
practice of this invention comprises vegetable or animal oils,
fats, tallows and waxes or mixtures with one another or with the
mineral or synthetic oils referred to above. Vegetable and animal
oils, fats, tallows and waxes are typically palm nut oil, palm oil,
olive oil, beet oil, rapeseed oil, linseed oil, ground nut oil,
soybean oil, cottonseed oil, sunflower seed oil, pumpkin seed oil,
coconut oil, corn oil, castor oil, walnut oil and mixtures thereof,
fish oils, the tallows of slaughter animals, e.g. beef tallow,
neat's foot and bone oil, as well as the modified, epoxidised and
sulfoxidised forms thereof, typically epoxidised soybean oil.
[0043] The mineral oils are based in particular on hydrocarbon
compounds.
[0044] Synthetic lubricants typically comprise lubricants based on
aliphatic or aromatic carboxylates, polymeric esters, polyalkylene
oxides, phosphates, poly-.alpha.-olefins or silicones, on a diester
of a divalent acid with a monohydric alcohol, typically dioctyl
sebacate or dinonyl adipate, on a triester of trimethylolpropane
with a monovalent acid or with a mixture of acids, conveniently
trimethylolpropane tripelargonate, trimethylolpropane tricaprylate
or mixturtes thereof, on a tetraester of pentaerytlritol with a
monovalent acid or with a mixture of such acids, typically
pentaerythritol tetracaprylate, or on a complex ester of monovalent
and divalent acids with polyhydric alcohols, for example a complex
ester of trimethylolpropane with caprylic and sebacic acid or of a
mixture thereof. Especially suitable lubricants are, in addition to
mineral oils, typically poly-.alpha.-olefins, ester-based
lubricants, phosphates, glycols, polyglycols and polyalkylene
glycols and mixtures thereof with water.
[0045] Machining fluids and hydraulic fluids can be prepared from
the same substances as those described above in connection with the
lubricants. Often they are also emulsions of such substances in
water or other liquids.
[0046] The lubricating compositions of this invention are used,
inter alia, for combustion engines, typically for motor vehicles
powered by engines of the Otto-cycle, diesel, two-stroke, Wankel or
orbital type.
[0047] The compounds of formula I are readily soluble in
lubricants, machining fluids and hydraulic fluids and are therefore
especially suitable for use as additives for lubricants, machining
fluids and hydraulic fluids. Their surprisingly good antiwear
properties merit special mention.
[0048] The invention thus further relates to a process for
enhancing the performance properties of lubricants, machining
fluids and hydraulic fluids, which comprises adding thereto
compounds of formula I.
[0049] The compounds of formula I can be blended with the
lubricating compositions in a manner known per se. The compounds
are, for example, readily soluble in oils. It is also possible to
prepare a masterbatch, which can be diluted in accordance with
consumption to suitable concentrations with the appropriate
lubricant. In such cases, concentrations higher than 10% by weight
are also possible.
[0050] The lubricants, machining fluids and hydraulic fluids of
this invention may also contain other additives which are added for
further enhancement of the basic properties. These further
additives comprise antioxidants, metal deactivators, rust
inhibitors, viscosity improvers, pour-point depressants,
dispersants, detergents, other extreme-pressure and antiwear
additives.
[0051] Illustrative examples of such further additives are:
[0052] Examples of phenolic antioxidants
[0053] 1. Alkylated monophenols, for example
2,6di-tert-butyl4-methylpheno- l, 2-tert-butyl-4,6-dimethylphenol,
2,6di-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.-methylcyclo-hexyl)-4,6-dimet- hylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol,
2,6-dinonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylhep- tadec-1'-yl)phenol,
2,4-di-methyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0054] 2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert- -butylphenol,
2,4-di-octylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol and
2,6-didodecyl-thiomethyl-4-nonylp- henol.
[0055] 3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol,
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 and
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0056] 4. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis-(6-tert-butyl-2-m- ethylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol) and
4,4'-bis-(2,6-di-methyl-4-hydroxyphenyl) disulfide.
[0057] 5. Alkylidene bisphenols, for example
2,2'-methylenebis(6-tert-buty- l-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-nony- l-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis-(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-b- utyl4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol-
], 4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-bu- tyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6bis(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-dodecylmer-captobutane-
, 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(3,5di-tert-butyl-4hydroxyphenyl)propane,
2,2-bis(5-tert-butyl-4-h-
ydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane and
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0058] 6. O-, N- and S-Benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl
4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,
tris(3,5-di-tert-butyl-4-hy- droxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiote-
rephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and
isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0059] 7. Hydroxybenzylated malonates, for example dioctadecyl
2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl
2(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
didodecylmercaptoethyl
2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate and
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydrox-
ybenzyl)malonate.
[0060] 8. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene
and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0061] 9. Triazine compounds, for example
2,4-bis(octylmercapto)-6(3,5di-t-
ert-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-butyl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-tert-but- yl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydrox- ybenzyl) isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzy- l)
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-triazine and 1,3,5-tris(3,5-di-cyclohexyl-4-hydroxybenzyl)
isocyanurate.
[0062] 10. Benzylphosphonates, for example dimethyl
2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
5-tert-butyl-4hydroxy-3-methylbenzylphosphonate and the calcium
salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
[0063] 11. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide and octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carb- amate.
[0064] 12. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, for example with methanol, ethanol,
octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0065] 13. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propion- ic acid with
mono- or polyhydric alcohols, for example with methanol, ethanol,
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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.
[0066] 14. Esters of .beta.-(3,5
dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or
polyhydric alcohols, for example with methanol, ethanol,
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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane.
[0067] 15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid
with mono- or polyhydric alcohols, for example with methanol,
ethanol, 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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0068] 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)he-
xamethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)tr-
imethylenediamine and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-
hydrazine.
[0069] Examples of aminic antioxidants:
[0070] N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylened- iamine,
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'-bis(2-naphthyl)-p-phenyle-
nediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p- -phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-
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,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethan- e, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetra-methyl-4,4'-diaminodipheny- lmethane,
1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis-(phenylamino)prop-
ane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-l-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-di-methyl-4H-1,4-be- nzothiazine, phenothiazine,
N-allylphenothiazine, N,N,N',N'-tetra-phenyl-1-
,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylene- diamine,
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,
2,2,6,6-tetramethylpiperidin-4-one and
2,2,6,6-tetramethylpiperidin-4-ol.
[0071] Examples of other antioxidants:
[0072] Aliphatic or aromatic phosphites, esters of thiodipropionic
acid or of thiodiacetic acid, or salts of dithiocarbamic or
dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11
-trithiatridecane and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.
[0073] Examples of metal deactivators, for example for copper,
are:
[0074] a) Benzotriazoles and derivatives thereof, for example 4 or
5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof,
4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole;
Mannich bases of benzotriazole or tolutriazole, e.g.
1-[bis(2-ethylhexyl)aminomethyl)tolutriazole and
1-[bis(2-ethylhexyl)amin- omethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)-benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)-tolutriazole.
[0075] b) 1,2,4-Triazoles and derivatives thereof, for example
3-alkyl(or aryl)-1,2,4-triazoles, and Mannich bases of
1,2,4-triazoles, such as
1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazol- es such as
1-(1-butoxyethyl)-1,2,4-triazole; and acylated
3-amino-1,2,4-triazoles.
[0076] c) Imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5- -methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether.
[0077] d) Sulfur-containing heterocyclic compounds, for example
2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and
derivatives thereof; and
3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-on-
e.
[0078] e) Amino compounds, for example
salicylidenepropylenediamine, salicylaminoguanidine and salts
thereof.
[0079] Examples of rust inhibitors are:
[0080] a) Organic acids, their esters, metal salts, amine salts and
anhydrides, for example alkyl- and alkenylsuccinic acids and their
partial esters 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
the amine salts thereof, and also N-oleoylsarcosine, sorbitan
monooleate, lead naphthenate, alkenylsuccinic anhydrides, for
example dodecenylsuccinic anhydride,
2-(carboxyethyl)-1-dodecyl-3-methylglycerol and the amine salts
thereof.
[0081] b) Nitrogen-containing compounds, for example:
[0082] I. Primary, secondary or tertiary aliphatic or
cycloaliphatic amines and amine salts of organic and inorganic
acids, for example oil-soluble alkylammonium carboxylates, and also
l-[N,N-bis(2-hydroxyethy-
l)amino]-3-(4-nonyl-phenoxy)propan-2-ol.
[0083] II. Heterocyclic compounds, for example: substituted
imidazolines and oxazolines, and
2-heptadecenyl-1-(2-hydroxyethyl)imidazoline.
[0084] c) Phosphorus-containing compounds, for example: Amine salts
of phosphoric acid partial esters or phosphonic acid partial
esters, and zinc dialkyldithiophosphates.
[0085] d) Sulfur-containing compounds, for example: barium
dinonylnaphthalenesulfonates, calcium petroleum sulfonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulfocarboxylic acids and salts thereof.
[0086] e) Glycerol derivatives, for example: glycerol monooleate,
1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,
1-(alkylphenoxy)-3-(2,3-dih- ydroxypropyl)glycerols and
2-carboxyalkyl-1 ,3-dialkylglycerols.
[0087] Examples of viscosity index improvers are:
[0088] Polyacrylates, polymethacrylates,
vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones,
polybutenes, olefin copolymers, styrene/acrylate copolymers and
polyethers.
[0089] Examples of pour-point depressants are:
[0090] Polymethacrylate and alkylated naphthalene derivatives.
[0091] Examples of dispersants/surfactants are:
[0092] Polybutenylsuccinic amides or -imides, polybutenylphosphonic
acid derivatives and basic magnesium, calcium and barium sulfonates
and phenolates.
[0093] Examples of antiwear additives are:
[0094] Sulfur- and/or phosphorus- and/or halogen-containing
compounds, e.g. sulfurised olefins and vegetable oils, zinc
dialkyldithiophosphates, alkylated triphenyl phosphates, tritolyl
phosphate, tricresyl phosphate, chlorinated paraffins, alkyl and
aryl di- and trisulfides, amine salts of mono- and dialkyl
phosphates, amine salts of methylphosphonic acid,
diethanolaminomethyltolyltriazole,
bis(2-ethylhexyl)aminomethyltolyltriaz- ole, derivatives of
2,5-dimercapto-1,3,4-thiadiazole, ethyl
3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl
thiophosphate (triphenylphosphorothioate), tris(alkylphenyl)
phosphorothioate and mixtures thereof (for example
tris(isononylphenyl) phosphorothioate), diphenyl monononylphenyl
phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the
dodecylamine salt of 3-hydroxy-1,3-thiaphosphetane 3-oxide,
trithiophosphoric acid 5,5,5-tris[isooctyl 2-acetate], derivatives
of 2-mercaptobenzothiazole such as 1-[N,N-bis-(2-ethylhexyl)a-
minomethyl]-2-mercapto-1H- 1,3-benzothiazole, and
ethoxycarbonyl-5-octyldi- thiocarbamate.
[0095] The compounds of this invention are prepared by methods
which are known per se, conveniently in accordance with the
following scheme: 15
[0096] Addition of the dithiophosphoric acid II to acrylic or
methacrylic acid III gives the carboxylic acid IV, which is
esterified by conventional methods, typically by adding
p-toluenesulfonic acid as catalyst, with a dialcohol V to give the
desired bis-compound VI. The synthesis can be carried out in
general accordance with the process described in GB 1 347 845.
[0097] Specific parameters for carrying out the process embraced by
the above reaction scheme can be inferred from the following
working Examples. These Examples and the Use Examples illustrate
the invention in more detail, but without implying any restriction
thereto. Unless otherwise indicated, parts and percentages are by
weight.
EXAMPLE 1
O,O-Diisoamyl-S-2-carboxyethyl dithiophosphate
[0098] With stirring, 23.44 g (0.33 mol) of acrylic acid are added
at 70.degree. C. over 1 hour to 93.24 g (0.3 mol) of diisoamyl
dithiophosphate and the mixture is then stirred for 4 hours at
75.degree. C. The readily volatile constituents are removed under
vacuum (70.degree. C./0.08 mbar/2 h). The liquid is clarified by
filtration by addition of a filter aid.
[0099] Yield: 108.3 g (93%) of a pale yellow liquid,
n.sub.D.sup.20:1.4983,.sup.31P-NMR:94.9 ppm/H.sub.3PO4.
EXAMPLE 2
Bis-3'-(O,O-diisoamyldithiophosphoryl)propionyl-1,4-butanediol
[0100] 70.98 g (0.21 mol) of the dithiophosphate prepared according
to Example 1, 9.01 g (0.1 mol) of 1,4-butanediol, 0.57 g of
p-toluenesulfonic acid and 100 ml of toluene are refluxed for c. 3
h on a water separator until the water of reaction has been
completely removed.
[0101] The resultant product is then washed with 60 ml of a 10%
solution of sodium sulfate and twice with 60 ml of a 10% solution
of sodium sulfate/5% solution of sodium carbonate and dried over
anhydrous sodium sulfate. The solvent is subsequently removed by
distillation on a rotary evaporator and residual solvent is
stripped off under vacuum (60.degree. C./0.05 mbar/2 h).
[0102] Yield: 73.6 g (99%) of a yellow liquid,
n.sub.D.sup.20:1.5008, .sup.31P-NMR:94.7 ppm/H.sub.3PO.sub.4.
[0103] The compounds of Examples 3 to 11 listed in Table 1 are
prepared in general accordance with the procedure described in
Example 2.
1TABLE 1 [(RO).sub.2P(S)--S--CH.sub.2--CH.sub.2--CO-
--O].sub.2R.sup..circle-solid. Yield .sup.31P-NMR Example
R.sup..circle-solid. R (%) n.sub.D.sup.20 ppm/H.sub.3PO.sub.4 3
CH.sub.3N(CH.sub.2CH.sub.2--).sub.2 i-propyl 71 1.5075 91.3 4
O[CH.sub.2--CH(CH.sub.3)--].sub.2 i-Propyl 96 1.5005 91.4 5
O(CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--).sub.2.sup..noteq.)
i-propyl 87 1.5031 91.2 6
O(CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--O--CH.su-
b.2CH.sub.2--).sub.2*.sup.) i-propyl 85 1.4997 91.2 7 16 i-propyl
96 1.5226 91.5 8 (--CH.sub.2--).sub.4 i-butyl 96 1.5036 91.5 9
(--CH.sub.2--).sub.4 n-propyl 97 1.5136 94.9 10 (--CH.sub.2).sub.4
i-propyl 97 1.5087 91.1 11 (--CH.sub.2--).sub.6 i-propyl 96 1.5057
91.5 .sup..noteq.)Average number of ethylene groups: 4, based on
polyethylene glycol 200 as dihydric alcohol *.sup.)average number
of ethylene groups 6, based on polyethylene glycol 300 as dihydric
alcohol
EXAMPLE 12
SRV Test
[0104] To test the antiwear and friction reducing properties, the
novel dithiophosphates are incorporated in an undoped lubricating
oil and the coefficient of friction .mu. is determined at
100.degree. C. and 150.degree. C. using the SRV apparatus
(oscillating friction device supplied by Opitmol GmbH, Munich; q.v.
Lubrication Engineering 39 (11) 1982, Advert. Index cover 3, page
729).
[0105] In this method, an oscillating ball (50 Hz) is pressed with
a force of 200 N against a firmly clamped metal cylinder on which
there is a film of test oil. The horizontal and vertical forces are
measured with a piezoelectrical transducer. The signal so obtained
is transmitted direct to the recorder. At the conclusion of the
test, the cross-section of the wear scar on the metal cylinder is
measured with a profilometer (TALYSURF 10). The test results are
summarised in Table 4.
2TABLE 2 Wear Additive* [mm.sup.210.sup.-5].sup..noteq. Coefficient
of friction .mu. Example No. 100.degree. C. 150.degree. C.
100.degree. C. 150.degree. C. -- 85.2 217.4 0.121 0.122 4 25.5 41.5
0.093 0.075 7 18.5 53.5 0.097 0.080 8 20.5 35.5 0.104 0.081 9 25.0
40.0 0.096 0.075 *Additive concentration 2% in mineral oil,
viscosity 139.3 mm.sup.2s.sup.-1 at 40.degree. C.
.sup..noteq.Cross-section of wear scar on the cylinder
[0106] The low wear index and coefficient of friction relative to
the undoped base oil demonstrate that the compounds have antiwear
properties. What is claimed is:
* * * * *