Note: Descriptions are shown in the official language in which they were submitted.
- 1 _
A-17655/+
Lubricant composition
The present invention relates to lubricant compositions which are
stabilized against oxidative degradation. Stabilization is effected by
the incorporation of at least two specific additives.
It is known and conventional to incorporate additives into lubricants
based on mineral oils or synthetic oils in order to improve their general
use properties. Additives for stabilizing lubricants against oxidative
degradation, known as antioxidants, are especially important. The oxi-
dative degradation of lubricants is particularly significant in the case
of engine oils, because high temperatures prevail in the combustion
chamber of engines and, as well as oxygen, nitrogen oxides (NO ) are
x
present and act as oxidation catalysts.
The antioxidants used for lubricants are, in particular, organic sulfur
and phosphorus compounds and also aromatic amines and phenols, especially
sterically hindered phenols (see e.g. Ullmanns Encyklopadie der techni-
schen Chemie (Ullmann's Encyclopaedia of Chemical Technology),
4th edition, Verlag Chemie, volume 20 (1981), page 541-43).
Sterically hindered amines have also already been proposed as
stabilizers for lubricating oils, e.g, in US 4 069 199 or JP-A-85128496.
EP-A-356 677 has proposed mixtures of aromatic amines and sterically
hindered amines as antioxidants for lubricants, it also being possible
for phenolic antioxidants to be added to these mixtures.
It has been found that combinations of phenolic antioxidants with
sterically hindered amines are outstandingly suitable for the stabiliza-
tion of lubricants, even without the addition of aromatic amines.
~~~~'~~?
The present invention relates to a lubricant composition comprising
(A) a mineral or synthetic oil or a mixture of such oils,
(B) at least one sterically hindered amine and
(C) at least one phenol of formula I
A\
HO-.\._.~._X I
B/.-.
wherein A is hydrogen, C1-Cz4 alkyl, CS-Clz cycloalkyl, C~-C9 phenyl-
alkyl, phenyl or a group -CHz-S-Ri or
~H
-CHz-~~~~\ ~-B
.\~/.
X
B is C1-Cz4 alkyl, C5-Clz cycloalkyl, C~-C9 phenylalkyl, phenyl or a
group -CHz-S-R1, ?C is hydrogen, C1-C18 alkyl or one of the groups
CaH2a Sq-Rz' CbH2b-CO-OR3, -CbH2b-CO-N(RS)(R6), -CHzN(R1°)(Rii) and
_Cgz_.\. ~j.-pH
Rl is Cl-Cla alkyl, phenyl or a group -(CHz)c-CO-OR4 or -CHZCHzOR~, Rz is
hydrogen, C1-C1° alkyl, phenyl, benzyl or a group
-~\._.~.-OH or -(CHz)c-C0-OR'' or -CHzCHzOR9,
.-.~
R3 is C1-C5° alkyl or one of the groups -~H-CHz-S-RS
-Q-0-~-CbH2b ~~~ ~/~-OH
and
- g _
-CHz-C CHz-0-C-CbH2b_~\'_~~~-OH
3
wherein Q is Cz-CB alkylene, C4-C6 thiaalkylene.or a group
-CHzCHz(OCHzCHz)d-, R'' is Cl-Cz4 alkyl, RS is hydrogen, C1-C18 alkyl or
cyclohexyl, R6 is C1-C18 alkyl, cyclohexyl, phenyl, C1-C18 alkyl-substi-
tuted phenyl or one of the groups
-(CHz)f-NH-~-CbH2b .\°_.~~-OH
-(CHz)i.-0-~-CbH2b ~\~_~~._OH
-C (CHz)_0_~-CbH2~ ~\° ~%~-OH
or RS and Rs together are C4-Ce alkylene which can be interrupted by -0-
or -NH-, R~ is hydrogen, C1-C4 alkyl or phenyl, R8 is C1-Cze alkyl, R9 is
hydrogen, C1-Cz4 alkyl, phenyl, Cz-C18 alkanoyl or benzoyl, R1° is C1-
ClB
alkyl, cyclohexyl, phenyl, C1-C18 alkyl-substituted phenyl or a group
-(CHz)f NH -CHz_,\._.~~vOH
R11 is hydrogen, C1-C18 alkyl, cyclohexyl or a group
_CHz_,\._~~._OH
._.
~B
CA 02020558 2000-06-23
29276-316
4
or R1° and R11 together are C4-Ca alkylene which can be
interrupted by -O- or -Nl3-, a is 0, l, 2 or 3, b is 0, 1, 2 or
3, c is 1 or 2, d ._s 1 to 5, f is 2 to 8 and q is 1, 2, 3 or 4,
or, as component (C:), a mixture of polyphenols formed by
reacting at least one phf=_nol of the formula
qH QH
~_ i'y ~\ i's ~
il i or n i
.\,~.
with at least one phenol of the formula
TH 1H
/'\
E II i or II I
.\ %. .\ /.
and with formaldeh~rde or paraformaldehyde, wherein C, D and E
independently of the others are C1-Cz4 alkyl, cyclohexyl or
phenyl, the composition containing no aromatic amine.
The present invention further relates to a method for
stabilising a lubricant against oxidative degeneration, which
comprises incorporating .into the lubricant a combination of
component s ( B ) and ( C ) .
In this composition, the weight ratio of (B) to (C)
is preferably 1:1 to 1:100, especially 1:3 to 1:20. The sum of
(B) and (C) is preferably 0.05 to 5% by weight, especially 0.1
to 3% by weight, of: (A).
A and B as C1-C'z4 alkyl can be linear or branched
alkyl, e.g. methyl, ethyl, i-propyl, t-butyl, s-butyl,
s-pentyl, t-pentyl, n-heayl, i-hexyl, t-hexyl, i-heptyl,
n-octyl, t-octyl, :;-decyl, s-dodecyl, n-dodecyl, s-tetradecyl,
n-hexadecyl, n-octadecyl,, s-octadecyl or n-eicosyl.
CA 02020558 2000-06-23
29276-316
4a
A and B as cyc:loalkyl can be e.g. cyclopentyl,
cyclohexyl or cyclooctyl, especially cyclohexyl. A and B as
phenylalkyl can be e.g. benzyl, phenylethyl, phenylpropyl or
a,a-dimethylbenzyl.
RS and R6 as C1-C1z alkyl can be a . g . methyl , ethyl ,
propyl , butyl , pent:yl , h~~xyl , octyl , decyl or dodecyl . Rl , Rz ,
R3 and RB as C1-C18 alkyl can also be e.g. tetradecyl, hexadecyl
or octadecyl . R4 a.s C1-C'24 alkyl can also be a . g . eicosyl or
tetraeicosyl.
~~~~~~~
The subscript a is preferably 0, 1 or 2, especially 0 or 1; b is prefer-
ably 0, 1 or 2, especially 1 or 2; q is preferably 1 or 2, especially 1.
Component (A) is a mineral or synthetic base oil of the kind conven-
tionally used for the preparation of lubricants. Synthetic oils can be
e.g. esters of polycarboxylic acids or of polyols, aliphatic polyesters
or poly-a-olefins, silicones, phosphoric acid esters or polyalkylene
glycols. The lubricant can also be a grease based on an oil and a
thickener. Such lubricants are described e.g. in D. Klamann "Schmier-
stoffe and artverwandte Produkte" ("Lubricants and Generically Related
Products"), Verlag Chemie, Weinheim 1982.
Component (B) can be any cyclic or non-cyclic, preferably cyclic,
sterically hindered amine. (B) is preferably a compound containing at
least one group of formula II
RC~ ~CH~
II
RCHz~ \CH3
wherein R is hydrogen or methyl. R is preferably hydrogen. Said compounds
are derivatives of polyalkylpiperidines, especially of 2,2,6,6-tetra-
methylpiperidine. These compounds preferably carry one or two polar sub-
stituents or a polar spiro ring system in the 4-position of the piper-
idine ring. They can be low-molecular, oligomeric or polymeric compounds.
The following classes of polyalkylpiperidines are of particular
importance:
~~~~:~~3
- 6 -
a) Compounds of formula III
RCHz~ ~CHa/R
Ri i_~.~~~._0- Ri z III
RCHz~~~CH3
n
wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or
methyl, R11 is hydrogen, oxyl, hydroxyl, Cl-Clz alkyl, C3-Ce alkenyl,
C3-Ce alkynyl, C~-Clz aralkyl, C1-Cla alkoxy, CS-Cs cycloalkoxy, C~-C9
phenylalkoxy, Cz-Ce alkanoyl, Ca-CS alkenoyl, C1-C18 alkanoyloxy, benzyl-
oxy, glycidyl or a group -CHzCH(OH)-Z, wherein Z is hydrogen, methyl or
phenyl, R11 preferably being H, C1-C4 alkyl, allyl, benzyl, acetyl or
acryloyl, and R1z when n is 1 is hydrogen, Ci-C18 alkyl which may be
interrupted by one or more oxygen atoms, cyanoethyl, banzyl, glycidyl, a
monovalent radical of an aliphatic, cycloaliphatic, araliphatic, un-
saturated or aromatic carboxylic acid, carbamic acid or phosphorus-
containing acid, or a monovalent si.lyl radical, preferably a radical of
an aliphatic carboxylic acid having 2 to 18 C atoms, of a cycloaliphatic
carboxylic acid having 7 to 15 C atoms, of an ec,f3-unsaturated carboxylic
acid having 3 to 5 C atoms or of an aromatic carboxylic acid having 7 to
15 C atoms, Rlz when n is 2 is C1-Clz alkylene, C4-Clz alkenylene,
xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic
or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing
acid, or a divalent silyl radical, preferably a radical of an aliphatic
dicarboxylic acid having 2 to 36 C atoms, of a cycloaliphatic ar aromatic
dicarboxylic acid having 8 - 14 C atoms or of an aliphatic; cycloali-
phatic or aromatic dicarbamic acid having 8 - 14 C atoms, Rlz when n is 3
is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tri-
carboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-
containing acid, or a trivalent silyl radical, and Rlz when n i.s 4 is a
tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetra-
carboxylic acid.
,", ". P.
_
Any C1-C1z alkyl substituents are e.g. methyl, ethyl, n-propyl, n-butyl,
sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl,
n-undecyl or n-dodecyl.
R11 or R12 as Cl-C18 alkyl can be e.g. the groups listed above and
additionally n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, for
example.
Riz as C3-Ce alkenyl can be e.g. prop-1-enyl, allyl, methallyl, but-2-
enyl, pent-2-enyl, hex-2-enyl, oct-2-enyl or 4-tent-butylbut-2-enyl.
R11 as C3-C8 alkynyl is preferably propargyl.
Rls as C~-Clz aralkyl is especially phenethyl and in particular benzyl.
R11 as C1-Ca alkanoyl is, for example, formyl, propionyl, butyryl or
octanoyl, but preferably acetyl, and R11 as C3-CS alkenoyl is especially
acryloyl.
RlZ as a monovalent radical of a carboxylic acid is, for example, an
acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid,
benzoic acid or (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid
radical.
R12 as a divalent radical of a dicarboxylic acid is, for example, a
malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid,
sebacic acid, malefic acid, itaconic acid, phthalic acid, dibutylmalonic
acid, dibenzylmalonic acid, butyl(3,5-di-tert-butyl-4-hydroxybeinzyl)-
malonic acid or bicycloheptenedicarboxylic acid radical.
R1z as a trivalent radical of a tricarboxylic acid is e.g. a t=imellitic
acid, citric acid or nitrilotriacetic acid radical.
R12 as a tetravalent radical of a tetracarboxyiic acid is e.g. the tetra-
valent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic
acid.
_ g _
R12 as a divalent radical of a dicarbamic acid is, for example, a hexa-
methylenedicarbamic acid or 2,4-toluylenedicarbamic acid radical.
Preferred compounds of formula III are those in which R is hydrogen, R11
is hydrogen or methyl, n is 1 and R1z is C1-C1a alkyl or n is 2 and R12
is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C
atoms.
The following compounds are examples of polyalkylpiperidine compounds of
this class:
1) 4-hydroxy-2,2,6,6-tetramethylpiperidine
2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
4) 1-(4-tent-butylbut-2-enyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine
5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
8) 1,2,2,6,6-pentamethylpiperidin-4-yl a-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate
9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate
10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate
11) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate
12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate
13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate
14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
15) di(1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate
16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate
17) 1-hydroxy-4-a-cyanoethoxy-2,2,6,6-tetramethylpiperidine
18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
19) tri(2,2,6,6,-tetramethylpiperidin-4-yl) trimellitate
20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate
22) di(1,2,2,6,6-pentamethylpiper.idin-4-yl) dibutylmalonate
- 9 -
23) di(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl(3,5-di-tert-butyl-4-
hydroxybenzyl)malonate
24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
26) hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethyl
piperidine)
27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethyl-
piperidine)
28) dimethyl-bis(2,2,6,6-tetramethylpiperidin-4-oxy)silane
29) phenyl-tris(2,2,6,6-tetramethylpiperidin-4-oxy)silane
30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate
32) phenyl(bis(1,2,2,6,6-pentamethylpiperidin-4-yl)) phosphonate
33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine
34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine
36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
b) Compounds of formula IV
RCHz\ /CH3/-
13
R1 1 _~ \.-~ Rl'~ IV
\ /
.--.
RCHz/ \CH3
n
wherein n is the number 1 or 2, R and R11 are as defined under a), R13 is
hydrogen, C1-Clz alkyl, Cz-C~ hydroxyalkyl, C~-C~ cycloalkyl, C7-Cg
aralkyl, Cz-C1$ alkanoyl, C3-CS alkenoyl, benzoyl or a group of the
formula
RCHz\ /CH3~t
Rl 1 _~ \
\ _ /
RCHz/~\CH3
and R1'' when n is 1 is hydrogen, C1-C18 alkyl, C3-Cg alkenyl, CS-C~
cycloalkyl, C1-C4 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl
or carbamide group, glycidyl or a group of the formula -CHz-CH(OH)-Z or
~~~r.~
- l0 -
of the formula -CONH-Z, whezein Z is hydrogen, methyl or phenyl, Rl.'' when
n is 2 is Cz-Clz alkylene, C6-Clz arylene, xylylene, a group
-CHz-CH(OH)-CHz- or a group -CHz-CH(OH)-CHz-0-D-0-, wherein D is Cz-Clo
alkylene, C6-C15 arylene or C6-Clz cycloalkylene, or, provided that Rls
is not alkanoyl, alkenoyl or benzoyl, Rr'' can also be a divalent radical
of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or di-
carbamic acid or the group -CO-, or R13 and Rr'" together, when n is 1,
can be the divalent radical of an aliphatic, cycloaliphatic or aromatic
1,2- or 1,3-dicarboxylic acid.
Any C1-Clz or C1-C1g alkyl substituents are as already defined under a).
Any CS-C~ cycloalkyl substituents are especially cyclohexyl.
R13 as C~-CB aralkyl is especially phenylethyl or in particular benzyl.
R1j as Cz-CS hydroxyalkyl is especially 2-hydroxyethyl or 2-hydroxy-
propyl.
R13 as Cz-C18 alkanoyl is, for example, propionyl, butyryl, octanoyl,
dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and R13
as C3-CS alkenoyl is especially acryloyl.
R1'' as Cz-CB alkenyl is e.g. allyl, methallyl, but-2-erryl, pent-2-enyl,
hex-2-enyl or oct-2-enyl.
Ri'' as C1-C4 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or
~arbamide group can be e.g. 2-hydroxyethyl, 2-hydroxypropyl, 2-cyano-
ethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonyl-
propyl or 2-(dimethylaminocarbonyl)ethyl.
Any Cz-Clz alkylene substituents are e.g. ethylene, propylene, 2,2-di-
methylpropylene, tetramethylene, hexamethylene, octamethylene, deca-
methylene or dodecamethylene.
Any C6-C15 arylene substituents are e.g: o-, m- or p-phenylene, 1,4-naph-
thylene or 4,4'-diphenylene.
- 11 -
D as C6-Clz cycloalkylene is especially cyclohexylene.
Preferred compounds of formula IV are those in which n ~s 1 or 2, R is
hydrogen, R11 is hydrogen or methyl, R13 is hydrogen, C1-Clz alkyl or a
group of the formula
RCHz\ ~CH3/t?
Rz i -~.-. \
RCFIZ~~\CH 3
and Rl'' in the case where n = 1 is hydrogen or C1-Clz alkyl and in the
case where n = 2 is Cz-Ce alkylene.
The following compounds are examples of polyalkylpiperidine compounds of
this class:
37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diamine
38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacet-
amide
39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine
40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine
41) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N, N'-dibutyladipamide
42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-
hydroxypropylene-1,3-diamine
43) N,N'-bis(2,2,6,6-tetraraethylpiperidin-4-y1)-p-xylylenediamine
44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)succindiamide '
45) di(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tetramethyl--
piperidin-4-yl)-a-aminodipropionate
46) the compound of the formula
- 12 -
CHa\ /CH3 aHe
CH3-N\~~~j~-~-CHz-CH(OH)-CHz-
CH3/~\CH3 /~\.
II I
CH3-~-CH3
/.\.
II I
CH3\ /CHa ~\~~.
CH3_?~~-~~._ _CHz_CH(OH)-CHz-
CH3/~\CH3 ~°H9
47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine
48) 4-(3-methyl-4~-hydroxy-5-tart-butylbenzamido)-2,2,6,6-tetramethyl-
piperidine
49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine
c) Compounds of formula V
RCHz\ /CH3/R 0
Ri i _~.-.\ ~ I R1 s V
\ _ /~~
RCHz/~\CH3 0 n
wherein n is the number 1 or 2, R and R11 are as defined under a) and Rls
when n is 1 is Cz-Ce alkylene, Cz-Ce hydroxyalkylene or C4-Czz acyloxy-
alkylene and when n as 2 is the group (-CHz)zC(CHz-)2~
Rls as Cz-G$ alkylene or Cz-C8 hydroxyalkylene as, for example, ethylene,
1-methylethylene, propylene, 2-ethylpxopylene or 2-ethyl-2-hydroxymethyl-
propylene.
Rls as C4-Czz acyloxyalkylene is e.g. 2-ethyl-2-acetoxymethylpropylene.
The following compounds are examples of polyalkylpiperidine compounds of
this class:
2~~~,~~~r~
- 13 -
50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro(5.5]undecane
51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro(5.5]undecane
52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro(4.5]decane
53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro-
[5.5]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-
dioxaspiro(5.5]undecane
55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-
5"-( 1 " , 3"-dioxane)-2 "-spiro-4" ' -( 2 " ' , 2 " ' , 6" ' , 6" ' -tetra-
methylpiperidine)
d) Compounds of formulae VIA, VIB and VIC
_i s
RCHz\ /CHa/R
-0
Ri i _~ VIA
\ _ R1~
RCHz~~\CH3 n
RCHz\ /CH3/R i
- p.._ -T z
Rl_~ VIB
\ , ~- -0
RCHz~~\CH3
RCHz\ /CH3/R i
- 0- -Tz
Ri 1_~ VIC
\ _, - Rm
RCHz~A\CH3 n
wherein n is the number 1 or 2, R and Rll are as defined under a), Rls is
hydrogen, C1-Czz alkyl, allyl, benzyl, glycidyl or Cz-Cs alkoxyalkyl, R1'
when n is 1 is hydrogen, C1-Clz alkyl, C3-CS alkenyl, C~-C9 aralkyl,
CS-C~ cycloalkyl, Cz-C', hydroxyalkyl, Cz-Cs alkoxyalkyl, Cs-Clo aryl,
glycidyl or a group of the formula -(CHz)p C00-Q or of the formula
-(CHz)p-0-C0-Q, wherein p is 1 or 2 and Q is Cl-C4 alkyl or phenyl, and
R1~ when n is 2 is Cz-Czz alkylene, C4-Clz alkenylene, Cs-Clz arylene, a
group -CHz-CH(OH)-CHz-0-D-0-CHz-CH(OH)-CHz°, wherein D is Cz-Clo alkyl-
- 14 -
ene, C6-C15 arylene or C6-Clz cycloalkylene, os a group
-CHZCH(OZ')CHz-(OCHz-CH(OZ')CHz)z-, wherein Z' is hydrogen, C1-C~,e alkyl,
allyl, benzyl, Cz-Clz alkanoyl or benzoyl, and T1 and Tz independently of
the other are hydrogen, C1-C18 alkyl or C6-Clo aryl or C~-C9 aralkyl
which is unsubstituted or substituted by halogen or C~-C4 alkyl, or T1
and Tz form a C5-C~z cycloalkane ring together with the C atom to which
they are bonded.
Any C1-Clz alkyl substituents are e.g. methyl, ethyl, n-propyl, n-butyl,
sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl,
n-undecyl or n-dodecyl.
Any C1-C18 alkyl substituents can be e,g. the groups listed above and
additionally n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, for
examgle.
Any Cz-C6 alkoxyalkyl substituents are e.g. methoxymethyl, ethoxymethyl,
propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoXy-
ethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
R1' as C3-GS alkenyl is e.g. prop-1-enyl, allyl, methallyl, but-2-enyl or
pent-2-enyl.
R1', T1 and Tz as C~-C9 aralkyl are especially phenethyl or in particular
benzyl. If T1 and Tz form a cycloalkane ring together with the C atom,
said ring can be e.g. a cyclopentane, cyclohexane, cyclooctane or cyclo-
dodecane ring.
R1~ as Cz-C4 hydroxyalkyl is e.g. 2-hydroxyethyl, 2-hydroxypropyl,
2-hydroxybutyl or 4-hydroxybutyl.
R17, T1 and Tz as C6-C1o aryl are especially phenyl or a- or Q-naphthyl
which are unsubstituted or substituted by halogen or C1-C4 alkyl.
- is -
R1~ as Cz-Clz alkylene is e.g. ethylene, propylene, 2,2-dimethylpropyl-
ene, tetramethylene, hexamethylene, octamethylene, decamethylene or
dodecamethylene.
R1~ as C4-Clz alkenylene is especially but-2-enylene, pent-2-enylene or
hex-3-enylene.
R17 as C6-Clz arylene is, for example, o-, m- or p-phenylene, 1,4-naph-
thylene or 4,4'-diphenylene.
Z' as Cz-Clz alkanoyl is, for example, propionyl, butyryl, octanoyl or
dodecanoyl, but preferably acetyl.
D as Cz-Clo alkylene, C6-C15 arylene or C6-Clz cycloalkylene is as
defined under b).
The following compounds are examples of polyalkylpiperidine compounds of
this class:
56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro(4.5]decane-2,4-dione
57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiso(4.5]decane-2,4-dione
59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro(4.5]decane-2,4-
dione
60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione
61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro(4:5]decane
62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]-
heneicosane
64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane
65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.'S]decane-
2,4-dione
or the compounds of the following formulae:
m
x
m U m
x I x
W~i
x~ ~x
U . . U
m m
x x x
~ v%'~i
\x
N U ~ ~ V
x m
v x
v
° W%
x ~ ,\x
x U~ ~U //\
U ~ ~
O i II
N
\\
( N
N
v U-~ x U
x ~ ~ i' ~ o
o N .. v
~/ /'~ / \ N N
U, ~ ~ II V v
x ~ \\ / x
m ~ m m ~ m m a m m s m
\ / \ / \ / \ /
/ \m m '/. m m / \m U ~~.,/ m
~ ( U U M U U ~' U x x U
x x
V U
n r~ n rw
~D r. op rn
W O vD v0
_. 2~~~'
-m-
e) Compounds of formula VII
~~e
~\
\~I~ Rz ° VI I
Ri s /.~/.
n
wherein n is the number I or 2, R~& is a group of the formula
I~CH3\ /CHzR
-E-(A)X ~~~~~~1-Rli
CHa/~\CHzR
wherein R and R11 are as defined under a), E is -0- or -NRzl-, A is Cz-Cs
alkylene or -(CHz)3-0- and x is the number 0 or 1, R19 is the same as R18
or is one of the groups -NRzlRzz; _ORz3, -NHCHzORz3 and -N(CHzORz3)z,
Rz°
when n = 1 is the same as R18 or R19 and when n = 2 is a group -E-B-E-,
wherein B is Cz-C6 alkylene which may be interrupted by -N(Rzl)-, Rzl is
C1-Clz alkyl, cyclohexyl, benzyl, C1-C4 hydroxyalkyl or a group of the
formula
I~CH3\ /CHZR
~-~ Ri i
_.\
CH3/~\CHZR
Rzz is C1-Clz alkyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl and Rz3 is
hydrogen, Ci-Clz alkyl or phenyl, or Rzl and Rzz together are C4-CS
-CHZCHz\
alkylene or Cu-C5 oxaalkylene, for example /0 or a group of
-CHZCHz -CHZCHz
the formula ~1-R11 or Rzl and R22 are each a group of the
-CHZCHz
formula
- 18 -
CH3\ /CH3 aHs
HN .-.\._~_.~~.-gH-A-.
\.-./
CH3/ \CH3 \ /
CpH9-
.
CHs\I/ \I/CH3
CH3/~~~\CH3
Any C1-C12 alkyl substituents are, for example, methyl, ethyl, n-propyl,
n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,
n-decyl, n-undecyl or n-dodecyl.
Any C1-C4 hydroxyalkyl substituents are e.g. 2-hydroxyethyl, 2-hydroxy-
propyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
A as CZ-C6 alkylene is, for example, ethylene, propylene, 2,2-dimethyl-
propylene, tetramethylene or hexamethylene.
If R21 and Rzz together are C4-Cs alkylene or C4-Cs oxaalkylene, this i.s
e.g. tetramethylene, pentamethylene or 3-oxapentamethylene.
The compounds of the following formulae are examples of polyalkylpiper-
idine compounds of this class:
H3
H3C~ ~\ /CH3
HaC/I\ /I\CHa
70) ~-CbH9
(CH3CH2 ) z~~~/~~~CHzCH3 ) Z
~~C4H9)2
CHa\ /CHa /~ CHa\ /CHs
71) CgHs ~~ ~/._ ~.\~._ ~.\~
~yC2Hs
CH3/~\CH3 ~ZHs ~zHs CH3/~\CH3
- 19 -
~t H3C~ /CH3
N~~~~ where R = -NH-CHZCHzCHz-0-~~~ ~~1-CH3
R~~\N'~~ H3C~~~CFIa
0
N
m
M
x
x
x
v/~%
i
I\
.
U
m
\
/
r.~
m
x
U-
~
-
/
\
M
n7
x
x
U
U
M 07
x x
x
\_
x x x z
vl~% x
\
_
N
/
\
M M
m m
xxUU U x U
~~/\\
U
\ N M
N7
x
N
U \ / U N x
/
~ ~
\
_
i o, \
N ~ x
/
x x s M
M U
U
U
x x ~~ v\
U-J~
M
M
x
W%
z
x ii
, W
r'-'~
..~.
~ \
~
e
.
x .~
i
U
%
\
x
V
~
/'\ /\
n ro
a
'n
m a ~
\ / \ /
r~ ~/ \eo
\m ~
~/.
x x
v
.y
r. r~
~~~~ ~ a
- 21 -
75) R-NH-(CHz)s-~-(CHz)z-~-~(CHz)j-NH-R
CHs\ /CHs
where R - ~N\ ~''H9 /~ ~~H
\ _
C~3~CH3
CaH9-
CHa\~/~\I/GH3
GHs/~\N/~\GHs
H
76) R-NH-(CHz)a-~-(GHz)z-~-(CHz)a-NH-R
CHs\ /CHs
where R - _ ~N\ ~kH9 /~ ~~-GH
\ _
~~~ CHs\GHs
CaH9-
CHs\I/~\I/CHs
GH3/~~~\CHs
Hs
H3 H3
77) R-~-(CHz)s-~-(CHz)z-~-(CHz)a-~-R
CHs\_ /CHs
where R - ~N\ ~4H9 /~ ~~-GHs
~\ _
G~3\CHs
CaH9°~
GHs\I/~\I/GH3
CH3/~~~\CHs
H3
- 22 -
CfIa\ /CH
CBH1'-~-°\.-.~H
°\~I CI~Ia/~\CH
78) CeHl~-l~~~~~~H(CHz)s
CHa\I/~\I/CHa
CHa/. H .\CHa
HzCHzOH
CHa\ ~\ /CHa
CHa/~\ /I\CHa
79) ~-CaH9
CHa\ /CHa \~ CHa\ /CHa
HO-CHZCHz-?\° ° j~- ~~ -~\°-°~-CH2CHz-0H
/°~° 4H9 4H9
CHa CHa CH3 CH3
Hz-CH=CHz
HaC\ ~\ /CHa
HaC/i\ /i\CHa
-C4H9
Ha
80) HaC\ /CHa \ ~/CH3
s
HzC=HC-HzC-~~_.~°-~~~~ ~-,\°_°~-CHz-CH-CHz
/°~° C4H9 4H9
H3C CHa CHa CHa
f) Oligomeric or polymeric compounds whose repeat structural unit
contains a 2,2,6,6-tetraalkylpiperidine radical of formula (I),
especially polyesters, polyethers, polyamides, polyamines, polyurethanes,
polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylarnides
and copolymers thereof which contain such radicals.
- 23 -
The compounds of the following formulae are examples of 2,2,6,6-poly-
alkylpiperidine light stabilizers of this class, m being a number from 2
to about 200:
81) CH3\ /CH3
-~~-CHz-CHz-C-0-CHz-CHz-~. .\ -
\ _ /~ m
CH3/~\CH3
82) CH~\ /CHa CHs\ /CH3
--~-CHz-CHz-~. '~~-0-~-(CHz)a-C-O-.\. .yCHz-CHz-0-~-(CHz)o-~~
_ m
CH3/~\CH3 CHa/~\CH3
83) CH3\ /CzHs CH3\_ /CzHs
-~-NH-(CHz)3-~~-.~._NH_~-II/~\j ~-NH-~\. '~-(CHz)a-NH-~-j/~\II
/ . \CHa .\./. CHa/ . \ .\./.
CH3 CzHs CHa CzHs
84) H3 H3
~IH-~-CH z-~-CH a
H3 H3
-~ ( CH z ) s ~"~ m
CHa\!/~\I/CH3 CHa\I/~\I/CH3
CH3/~~~\CHa CH3/o~e\CH3
85)
-~--~T CHz-CH(0H)-CHz
CH3\i/~\I/CHs
CH3/~~~\CH3
86) CHa\ /CHa CH3\ /CH3
/.- -~~ ~\ -~~-~4H
0-~\ ~~I-CHz-CH=CH-CHz \ /~ m
4Hy
CHa/~\CHa CH3/~\CH3
- 24 -
87)
(CH2)s ~_~__~~
N ~m
CH3 ,/~\ CHa CHa ~/~\I/CH3
,t,_C4H9 \I I/ \~
CH3/~~~\CH3 CH3/ ~/~\CH3
CHa\I/~\I/CH3
CH3/~~/~\CH3
88) CH3\ /CH3 CHa\ /CH3
~e\._.~-CHz_~\._.~._CHz_~. ~~._~~_(CHz)4-
CH3/ \CH3 ~_. CH3/.~CH3
m
89) CHs\ /CH3
_~2Hs _.\
-p-CHz_CHz_~~ /..-
zHs '
CH3/e\CH3
90) Ha ~~__~1_
--CHz
CH3\ /CH3
~ /.-.
.\ eCHa
CH3/~~CH3
91) Ha _~I-
--CHz
CHa\ /CH3
.-.
C6H13-_ -~\ CH3
s-.
CH3/ \CH3
- 25 -
92)
/o\
I I
/.
(CHz)s N~
CH3\I/~\I/CH3 CH3\I/~\I/CH3
CH3/'~~\CH3 CH3/~\~~\CH3
93)
-~~ (CHz)s Jj CHz-CHz
m
CH3\I/'\I/CHs CH3\I/o\I/CH3
CH3/e~'\CH3 CH3/~~~\CH3
94)
( CH z ) s ~~~-CH z-~~
m
CHa\I/~\I/CH3 CH3\I/~\I/CHs
CH3/~~~\CH3 CHa/~~~\CH3
g) Compounds of formula VIII
RCHz\ /CH3/R
Ri i_~~.-~~.=p VIII
RCHz/s\CH3
wherein R and R11 are as defined under a).
Preferred compounds of formula VIII are those in which R is hydrogen or
methyl and Rll is hydrogen or methyl.
Examples of such compounds are:
95) 2,2,6,6-tetramethylpiperidin-4-one (triacetonamine)
96) 1,2,2,6,6-pentamethylpiperidin-4-one
97) 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one
9$) 2,3,6-trimethyl-2,6-diethylpiperidin-4-one
- 26 -
Polyalkylpiperidines are known compounds and are used as light
stabilizers for organic materials. Some of them are commercially
available.
Component (C) is a phenolic antioxidant. (C) is preferably a compound of
formula I in which A is hydrogen, C1-C° alkyl, cyclohexyl, phenyl or a
group
qH
-CHz-~~~~~~-B
X
B is C1-C° alkyl, cyclohexyl or phenyl, X is C1-C8 alkyl or one of
the
groups -CaH2a-S-Rz, -CbH2b-COORS, -CHZN(R1°)(Rii) and
_CHz_.\. "%._OH
Rz is C1-Clz alkyl, phenyl or a group -(CHz)c-COOR'', R3 is Ci-C1g alkyl
or a group
-Q-OOC-CbH2b ~~~ ~j~-OH
.-~,\ B
in which Q is Cz-C6 alkylene, -CHZCHzSCHZCHz- or -CHZCHz(OCHZCHz)d , R''
is C1-C18 alkyl, R1° and Ril independently of the other are Cl-Clz
alkyl
or R1° and R11 together are pentamethylene or 3-oxapentamethylene, a is
i
or 2, b is 1 or 2, c is 1 or 2 and d is 1 to 3,
or (C) is a reaction mixture of a phenol of the formula
Fd ~.., ~' ,
! .' a~ ~~
_ 27 _
QH QH
_ /~\ C\ /~\
C II I or II I
.\~/. .\./.
with a phenol of the Formula
QH QH
_ /.~ /
E II i or II I
. . .\
and (para)formaldehyde, in which formulae C, D and E independently of the
others are C1-CB alkyl.
One class which is particularly suitable as component (C) consists of the
compounds of formula I in which A and B independently of the other are
C1-C4 alkyl, X is a group -CaH2a-S -Rz, a is 0 or 1, g is 1 or 2, Rz is
9
Ca-C18 alkyl, phenyl or -CHz-CO-OR4 and R'' is C1-Cle alkyl, especially
the compounds of formula I in which A and B independently of the other
are C1-C4 alkyl, X is -CHz-S-Rz, Rz is C8-Clz-alkyl or -CHz-CO-OR'' and R''
is Ce-Cl$ alkyl. In this class, especially preferred compounds of formula
I are those in which A and B are tert-butyl and X is -CHzSCH2C00(CB-C13
alkyl).
Another class which is particularly suitable as component (C) consists of
the compounds of formula I in which A and B independently of the other
are C1-C4 alkyl, X is a group -CbH2b-CO-~R3, b is 1 or 2 and R3 is one of
the groups
-(CHz)z-S-(CHz)z-0-G-CbH2b-~\. ~~._OH
_ 28 -
-(CHz)s-0-~-CbH2b ~\'_~~._OH
and
-CHz-C CHzO-~-CbH2b ~\°_~~._OH
especially the compounds of formula I in which X is a group
-(CHz)z-CO-OR3 and R3 is a group
-(CHz)z-S-(CHz)z-0-~°(CHz)_,\._.~~-OH
Another class which is particularly suitable as component (C) consists of
the methylenebisphenols of the formula
~H 1H
_ /.\ /
B II j-CHz II I-B and
'~~/° '~~/°
HO-'~e_,~.~CHz-~~. ~~~-OH ,
B/~_ -
wherein A, B and X independently of the others are C1-C4 alkyl.
Another class which is particularly suitable as component (C) consists of
mixtures of polyphenols obtained by reacting at least one dialkylated
phenol o~ the formula
.,,
- 29 -
QH QH
_ /~\ C\ /~~
C II I or II I
.\./. .\ /.
with at least one monoalkylated phenol of the formula
QH qH
_ /~\ /
E II I or II I
. \ / . o \ , / a
and formaldehyde or paraformaldehyde, G, D and E independently of the
others being C1-C~, alkyl.
The mixtures formed by this reaction contain predominantly diphenols and
triphenols.
Examples of compounds of formula I are: tridecyl 4-(4-hydroxy-3,5-di-
tert-butylphenyl)-3-thiabutyrate, 3-thiapenta-1,5-diol di(3-(4-hydroxy-
3,5-di-tart-butylphenyl)]propionate, di(3-thiapentadecyl) di(4-hydroxy-
3,5-di-tart-butylphenyl)malonate, octadecyl 4-(4-hydroxy-3,5-di-tert-
butylphenyl)-3-thiabutyrate, 4-(2-thiapropyl)-2,6-di-tart-butylphenol,
octadecyl 3-(4-hydroxy-3,S-di-tart-butylphenyl)propionate, 3-thiapenta-
decyl 3-(4-hydroxy-3,5-di-tart-butylphenyl)propionate, di(4-hydroxy-3,5-
di-tart-butylphenyl) sulfide, di(4-hydroxy-3,5-di-tart-butylphenyl)
disulfide, 2,4-di(octylthiomethyl)-6-methylphenol, N-octadecyl-3-(4-
hydroxy-3,5-di-tart-butylphenyl)propionamide, N,N'-(3-(4-hydroxy-3,5-di-
tert-butylphenyl)propionyl]hexamethylenediamine, 4,4'-methylene-bis(2,6-
di-tart-butylphenol), 2,2'-methylene-bis(2-tart-butyl-4-methylphenol),
2,4-di(4-hydroxy-3,5-di-tart-butylbenzyl)-6-tart-butylphenol, 4,4'-
methylene-bis(2-tart-butyl-4-(4-hydroxy-3,5-di-tart-butylbenzyl)phenol],
4-dimethylaminomethy2-2,6-di-tart-butylphenol, 4-dibutylaminomethyl-2-
methyl-6-tart-butylphenol and N-di(4-hydroxy-3,5-di-tart-butylbenzyl)-
octylamine.
~~~"~Cs~~
- 30 -
Especially preferred lubricant compositions are those in which (B) is a
compound of formula IX or X
C~13/CH 3 C~13/CH 3
_. _~
Ri i_~~ \ Y R~ i_~~ \.-p
\ _ /~ \ _ /
C~3\CH a Cti s\CH 3
n
IX X
in which n is 1 or 2, R11 is hydrogen or methyl and Y when n is 1 is
-0(C°-Cis alkyl) and when n is 2 is a group -NH-(CHz)s-NH- or
-0-CO-(CHz) -CO-0- in which m is 2-8, and (C) is a compound of formula I
m
in which A is hydrogen, Cr-C4 alkyl or a group
A
-CHz-~~/~\ ~-B
.\~/.
?~
B is C1-C4 alkyl, X is C1-C4 alkyl or one of the groups -CHz-S-Rz,
-CHzCH2C00R3, -CHzN(R1°)(Rii) and
~,A
_CHz_~\._.~._OH
._.~
Rz is Ci-C1° alkyl or -(CHz)z-COOR'", R3 is Cl-Crg alkyl or
-CHzCHz-S-CHzCHz-0-~-CHzCHz-~~~ ~j~-OH
._.
R'' is C1-Cls alkyl and R1° and R11 are C1-Cg alkyl, or (C) is a
reaction
mixture of 2-tent-butylphenol, 2,6-di-tert-butylphenol and (para)formal-
dehyde.
~5 ~' ,~ j ',~ t
°tJ~~ tys:9Cl
- 31 -
Components (B) and (C) can be added direct to the base oil or (B) and (C)
are first dissolved in a small amount of base oil, with heating if
necessary, and the solution is mixed with the remainder of the oil. As a
further possibility, a concentrated solution of (B) and (C) in a solvent
is mixed with the oil.
The addition of (B) and (C) to the base oil stabilizes the oil against
oxidative degradation and reduces the formation of sludge in engine oils.
The lubricant composition can additionally contain other additives, e.g.
phosphorus(III) esters, metal passivators, rust inhibitors, agents for
improving the viscosity index, pour point depressors, daspersants,
surfactants and/or wearing protection additives.
Examples of phosphorus(III) esters are: traphenyl phosphate, decyl-
diphenyl phosphate, phenyldidecyl phosphate, tris(nonylphenyl) phosphate,
tralauryl phosphate, trioctadecyl phosphate, distearylpentaerythritol
diphosphite, tris(2,4-di-tert-butylphenyl) phosphate, diasodecylpenta-
erythratol diphosphite, bas(2,4-da-tert-butylphenyl)pentaerythritol di-
phosphite, tristearylsorbitol triphosphite, tetrakas(2,4-di-tert-butyl-
phenyl)-4,4'-biphenylene daphosphonite and bis(2,6-da-tert-butyl-4-
methylphenyl)pentaerythratol diphosphite.
Examples of metal passavators, e.g. for copper, are: triazoles, benzo-
triazoles and derivatives thereof, tolutriazoles and derivatives thereof,
2-mercaptobenzothiazole, 2-mercaptobenzotraazole, 2,5-dimercaptobenzo-
triazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylene-bas-benzo-
triazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidenepropylenediamane,
salacylaminoguanidane and salts thereof.
Examples of rust inhibitors are:
a) Organic acids and their esters, metal salts and anhydrides, e.g..:
N-oleoylsarcosane, sorbitan monooleate, lead naphthenate, an alkenyl-
succinic anhydride, e.g. dodecenylsuccinic anhydride, alkenylsuccanic
acid partial esters and partial amides, 4-nonylphenoxyacetic acid.
- 32 -
b) Nitrogen-containing compounds, e.g.:
I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines
and amine salts of organic and inorganic acids, e.g. oil-soluble
alkylammonium carboxylates.
II. Heterocyclic compounds, e.g.:
substituted imidazolines and oxazolines.
c) Phosphorus-containing compounds, e.g.:
amine salts of phosphoric acid partial asters or phosphonic acid
partial esters, zinc dialkyldithiophosphates.
d) Sulfur-containing compounds, e.g.:
barium dinonylnaphthalenesulfonates, calcium petroleumsulfonates.
Examples of agents for improving the viscosity index are: polyacrylates,
polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinyl-
pyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copoly-
mers, polyethers.
Examples of pour paint depressors are: polymethacrylate, alkylated naph-
thalene derivatives.
Examples of dispersants/surfactants are: polybutenylsuccinamides or poly-
butenylsuccinimides, polybutenylphosphonic acid derivatives, basic mag-
nesium, calcium and barium sulfonates and phenates.
Examples of wearing protection additives are: compounds containing sulfur
and/or phosphorus and/or halogen, such as sulfurized vegetable oils, zznc
dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl
and aryl disulfides and trisvlfides, triphenyl.phosphorothionates, di-
ethanolaminomethyltolyltriazole, di(2-ethylhexyl)aminomethyltolyl-
triazole.
an
- 33 -
The lubricant can also contain solid lubricants such as graphite or
molybdenum sulfide.
The following Examples illustrate the invention in greater detail.
Percentages are by weight.
Example 1: The oxidation behaviour of lubricating oils stabilized
according to the invention is tested by the TOST (turbine oxidation
stability test) method according to ASTM D-943.
This is performed by adding 60 rnl of water to 300 ml of a mineral oil
(Mobil STOCK 305) containing 0.05% of a corrosion inhibitor (Reocor~ 12)
and heating the mixture at 95°C for 1000 hours, in the presence of iron
and copper wire, while oxygen is passed through. The formation of acids
is measured by determining the neutralization number TAN (mg KOH/g oil)
and the amount of sludge formed (= SLUDGE) is also measured.
The Following stabilizers are used;
(CH3)aC\
P-1 HO-°\ /~ CHz S,-CHz-COOCI3Hz~
(CH3)3C~~=v
C~ /CH 3
H-1 HN~\~/a~~ -OCi zHz s
CH3' \CH3
The total amount of stabilizers is 0.25%, based on the oil. The.composi-
tion of the stabilizer mixture is varied. The results are listed in
Table 1.
n~
- ~ ~ r.~ 'ti
- 34 -
Table 1
Proportion TOST
P-1 H-1 TAN SLUDGE
100 % - 0,19 64
mg
95 % 5 % 0 17
mg
90 % 10 % 0 8
mg
75 % 25 % 0 26
mg
Example 2: Testing is carried out as in Example 1, using the following
stabilizers:
~CH3)3G~ /C(CHa)s
a . .
P-2 HO-~~~ ~j~-CH2CHzC00CHzGHzSCHzCHz00CCHzCHz-~~ j~-OH
- . s = .
~CH3)3C/~ \CtCHs)a
C~ /CH 3 C~ /CH 3
H-2 CHs-N~\~/-~~ -00G-(CHz)e-C00-~~~ / -CH3
CH3~ \CH3 oCH3A \CH3
The total concentration is 0.25%, based on the oil.
Table 2
Proportion TOST
P-2 H-2 TAN SLUDGE
100 % >2 >1000 mg
95 % 5 % 0,26 219 mg
90 % 10 % 0,24 190 mg
- 35 -
Example 3: Testing is carried out as in Example 1, using the following
stabilizers:
(CH3)3C~ ~C(CH3)3
P-2 HO-~~~ ~j~-CHzCH2C00CHzCHzSCiizCHz00CCHzCHz-'~~-~~°-OH
(CH3)3C~~= ~~C(CH3)3
C~ /CH 3 C~ /CH 3
\ /- \ /.
H-3 HN/ ~ ~ -NH-(CHz)s-NH-~~~~ H
C~.~CH 3 . C~.~CH 3
The total concentration is 0.25%. The results are listed in Table 3.
Table 3
Proportion TOST
P-2 H-3 TAN SLUDGE
100 % - >2 >1000 mg
95 % 5 % 0,24 180 m~
Example 4: Testing is carried out as in Example 1, using the following
stabilizers:
(CH3)3C~ /C(CH3)3
P-2 HO-~~~_'j~_CHzCHZC00CHzCHzSCHzCHz00CCHzCHz_;\~_.~~-off
.-. .
(CH3)3~ -e\C(CH3)3
C~ /CH 3
H-1 HN~~/~~~ -OC1 zHz s
CH3~ \CH3
- 36 -
The total concentration is 0.25%. The results are listed in Table 4.
Table 4
Proportion TOST
P-2 H-1 TAN SLUDGE
100 % - >2 1000
mg
95 % 5 % 0 86
mg
85 % 15 % 0,10 44
mg
75 % 25 % 0,03 75
mg
Example 5: Testing is carried out as in Example 1, using the following
stabilizers:
~CH3~3C~ ~C~CH3~3
P-2 HO-~~~-~j~-CHzCHzC00CHzCHzSCHzCHz00CCHaCHz-~~~ ~j~-OH
~CH3)3C~~=~ .-~~C~GH3)3
C~ /CH 3
H-4 HN~\~/ ~~ =o
CH3~ \CH3
The total concentration is 0,25%. The results are listed in Table 5.
Table 5
Proportion TOST
P-2 H-4 TAN SLUDGE
100 % - >2 >1000 mg
95 % 5 % 0,18 91 mg
90 % 10 % 0.16 161 mQ
- 37 -
E:cample 6: The oxidation resistance of the oils stabilized according to
the invention is measured in a differential scanning calorimeter. To do
this, a base oil is mixed in a small A1 dish with 0.025% of iron(III)
acetylacetonate (as oxidation catalyst) and 0.55% o.f a stabilizer and the
mixture is heated isothermally at 160°C in a calorimeter under 10 bar
of
oxygen. The time at which the exothermic reaction begins, TB (induction
time), and the time at which the exothermic reaction ends, T~, are
measured: the longer the induction time, the higher the oxidation
resistance. The stabilizers used are the phenolic antioxidants P-1 and
P-2 and also:
P-3: the reaction pzoduct of 160 g of 2,6-di-tert-butylphenol, 40 g of
2-tert-butylphenol, 5.8 g of KOH, 50 ml of ethanol and 24 g of paraform-
aldehyde at 80°C, containing the following main components:
(CH3)3C\ /C(CH3)3
HO-.\._.~.-CHz-.\> ,j._OH
(CH3)3L./.=. .c~\C(CH3)3
(CH3)3C\ /C(CH3)3
HO-~~. .~~ CHz /~~~ CHz ~~. ~~._pH
\ / II I \ /
/.
(CH3)3C/~-. ~\ / \0H ~-~\C(CHa)a
4(CH3)3
(CHs)aC\ /C(CHa)a
HO-.\._.~.~CHz~~I/~~ i-.CHz-il/~~ i-CHz.~,\~_.~~-OH
(CFi3)3C/~-. ~\ /~\OH ~\ ~~\0H ~=~\C(CH3)3
4(CH3)3 ~(CH3)3
QH QH
P-4: (CHa)aC-~/~\~I CHz ~I/~\~-C(CH3)a
/. .\~~.
I I
C('CHa)s C(CHs)a
~~.~~~~3 3~
- 38 -
P-5: a 1:1 mixture of
QH QH
(CHa)aCy/e\~yC(CHa)a and ~/~~~~-C(Ctla)a
.
4(CH3)3 ~(CH3)3
The following sterically hindered amine is used:
CF~I3/CH a C~I a/CH a
H-5 H~~_o~._pOC-(CHz)a-C00-~~~_~~IH
C~3~CH3 C~3~CHa
The results are listed in Table 6.
Table 6
Stabilizer TB(min) TE (min)
0,55 % P-1 1,47 9,12
0,55 % H-5 17,16 22,97
0,45 % P-i
+ 0,10 % H-5 14,02 27,71
0,55 % P-2 16,08 26,07
0,55 % H-5 17,16 22,97
0, 45 % P-2
+0,10 % H-5 32,27 47,90
0,55 % P-3 7,21 14,20
0,55 % H-5 17,16 22,97
0,45 % P-3
+0,10 % H-5 50,55 67.97
>. ,r~
~~Gsi~ ~>,.3(:~
- 39 -
0,55 % P-4 3,00 9,67
0,55 % H-5 17,16 22,97
0,45 % P-4
+0,10 % H-5 12,02 20,37
0,55 % P-5 4,46 16,44
0,55 % H-5 17,16 22,97
0,45 % P-5
+0,10 % H-5 14,10 23,23
It can be seen from this Table that when using stabilizer mixtures of
0.10% of component A and 0.45% of component B, the oxidation resistance
of the oil is higher than would be expected from the data for the
individual components.
Example 7: The oxidation resistance is tested in a differential scanning
calorimeter as in Example 6, except that the measurements are made under
8 bar o~ air with which 380 ppm of (NO) have been mixed, rather than
x
under oxygen, and the isothermal temperature is 170°C. Only the
beginning
of the exotherms is measured.
Stabilizer TB(min)
0,55 % P-2 11,2
0,55 % H-5 <2
0,45 % P-2 + 0,10 % H-5 20,7
- 40 -
0,55 % P-6 3,8
0,55 % H-S <2
0,45 % P-6 + 0,10 % H-5 10,8
P-6 HO-~~~ ~j~-CHZN(C4H9)z
