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Патент USA US3036024

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iv ' v United States
0i
atent
_, 3,000.00
'
Patented May 22! 196
1
2
mixtures are used may range in chain length from 2 ‘
3 036,005
12 carbon atoms. Normal acids are preferred, althoug
‘ HIGH TEMPERATURE’LUBRICANT ‘COMPOSITION
John E. Koch, Jr., Bayonne, N.J., assignor to Celanese
branched alkanoic acids may also be used, particular
those with no more than two carbon atoms in side chain
The polyol esters are prepared by the esteri?cation t
the polyol in the'presence of a slight excess of alkano
No Drawing. Filed Apr. 23, 1959, Ser. No. 808,325
acid, either in the presence or in-the absence of an acid
. 17 Claims. (Cl. 252-4945) . _
catalyst. For optimum heat stability, it is‘ preferred ‘
This invention relates to synthetic‘ lubricants and more
carry out the reaction in the absence of a catalyst. Whe:
particularly to ester lubricant compositions which are 10 a catalyst is used, it is generally used in an amount b
particularly resistant to high temperature oxidative deg
tween about 0.05 and about 1.0 percent, based on tl
radation in the lubrication of jet turbines used in air‘
weight of the reactants. The preferred catalysts are 1
Corporation of America, New York, N.Y., a corpora
tion of Delaware,
craft.
a
‘
toluene sulfonic acid, benzene sulfonic acid, zinc salt
lead salts, and related materials.
.
Jet turbines are turbines actuated by‘the energy of a
burning fuel and are-used to drive compressors which 15 The 'esteri?cation temperature .is preferably betwee
provide large amounts of air for the burningv of the fuel.
about 180° and about 240° C. and the reaction peric
The combustion of the fuel provides the energy for
may suitably range from about ‘6 to about 18 hour
driving the compressors which serve it with the remainder
Water is‘remov'ed by volatilization, preferably in ti
v of the useful energy going into the propulsion of the
' presence of an azeotroping agent, such as a liquid hydrt
aircraft Jetturbine bearings are lubricated by pumping 20
a lubricant to .the ‘bearings from a reservoir in a closed.
carbon.
‘
v
The diaromatic secondary amines include diaryl amine
system- The design of__more, powerful jet. turbines has
aryl-alkaryl amines and dialkaryl. amines, with the arj
groups preferably having no more than 5 benzene ring
and to greater difficulty. in maintaining lubricant stability
and the alkyl substituents, when present, having no mo:
under the more severe conditions._ For example, a lubri 25 than 24 carbon atoms. Among the speci?c diaromat
cant which will'operate satisfactorily at a reservoir-tern
secondary amines which may be used are phenyl a nap]
led to an increase in' the‘, lubricant reservoir temperature
‘
perature of 250° F. will sludge badly, build up viscosity, .
develop high acidity and corrode metals at a reservoir‘ ,
temperature of ‘400° F.
thylamine, p,p' dioctyldiphenylamine and phenyl B napl
vthylamine.
' _
The diaromatic secondary amine is suitably used i
Carboxylic acidesterafsuch as esters' of polyols with 30 amounts between about 0.25 and about 3% by weigh
alkanoic acidsare useful as lubricants and esters of poly~v "
. based on the polyol ester and most preferably in amoun
ols, such as- trii‘nethylolpropane, trimethylolethane and
between about 0.5 and about.2% by weight.
The phenosilazine compound, having the structure (it
‘ pentaerythritol," which have at least two methylol groups
bonded to a quaternary carbon atom are particularly use- ,
?ned above, ‘preferably has a hydrogen atom or a low:
ful for good oxidative. and. thermal stability. However, 35 alkyl group bonded to its‘ nitrogen valence and preferabl
even‘ these compounds are not" stable under oxidative con
has aromatic rings bonded to its silicon valences.
ditions in a system ,wherelthe reservoir temperature isj'of
The preferred silicon~containing compound is N-ethy
the order of 400°,F. and the local temperature at the
phenodiphenyl 'silazine which has the structure:
bearings ‘may be as high as600° to 700° F..
'
C211!
It is an object of this‘ invention to provide a lubricant 40
11:
composition whichwill withstand oxidative conditions
at temperatures of the‘ order‘of 425° F. and higher, for
‘ extended periods witho'utY-substantial degradation.
It is a further object ‘of this invention to provide at
additive composition; which can enhance the oxidative
stability 'of'polyol esters to, the. desired degree.
’
Sl
The objects of this invention are achieved by provid- .
ing a high ‘temperature [lubricant comprising a major
proportion of an alkanoic acid ester of a polyol having
at least two methylol groups on a‘quaternary carbon atom, 50
said alkanoic acid having an average of at least 5 carbon
oxidative degradation by‘ a minor proportion of a di-.
aromatic ‘secondary amine and a minor proportion of a
compound‘ having at phen'osilazine ring,
This compound may be prepared from N~ethyl diphen;
amine by ?rst reacting one mol of the latter with tw
moles of butyl lithium (at 100° C. with a nitrogen purg
to sweep out the butane by-product) to produce 2,2‘
atoms, said ester being-stablized against high temperature
dilithium-N-ethyl diphenylamine and then reacting th
last named compound (at 180°-220° C.) with an eqtr
molar proportion of diphenyl dichlorosilane to produc
the desired compound.
Another method of preparationinvolves the reactio.
60 of N-ethyl phenothiazine with diphenylsilane in equimola
proportions to produce the desired compound with hydrc
55
gen sul?de as a by-product.
The polyol esters are esteri?cationproducts of single
alkanoic acids, or mixtures of alkanoic, acids, with a
‘ polyol having atleast two, and preferably three, methylol 65
groups one. quaternary carbon atom.‘ Among the polyols
which may be used are trimethylolpropane, trimethylol- '
ethane, neopentyl glycol, pentaerythritol, 2»butyl-2-ethyl
1,3-propanedio'l ‘and 2,2,4-trimethyl-1,3-pentanediol.
Other phenosilazine derivatives which may be use
include phenodiphenyl silazine, N-methyl-phenodipheny
silazine, N-isopropyl-phenodiphenyl silazine, N-ethyl
phenoditolyl silazine and N-ethyl-phenodinaphthyl sila
zine, bis-N-ethyl‘ phenosilazine, and his compounds 0
the other derivatives mentioned above.
The phenosilazine derivative is suitably used in amount
The alkanoic acids used to make the polyol esters have 70 between about 0.25 and about 3% by weight, based 0:
the pol'yolesterand most preferably in amounts betweei
about 0.5 and about 2% by weight.
average chains of at least 5 carbon atoms and preferably
from 5 to 8 carbon atoms. The individual acids, where
3,036,005
3
4
.It has been found that a-combination of the-two com; ’
Examples 11 to’ VIII
The Itrihept'anoate esters of Examples Ia and lb, were
aundsprodudes substantiallylbetter inhibition of vis
>sity“buildup‘4and of acidity development than either
blended with~N-ethyl-phenodipheny1 silazine and phenyl
rmpound'a-lone, even when'used in equivalent amounts. .
a-naphthylamine in the proportions shown in the table
qtrirnetholpropane triheptanoate, for example, stabilized '
below.’ vThe'Nfethyl-phei'iodiphenyl‘silazine was‘dissolved,
ith_'=-'1% each' of N-ethyl-phenodiphenyl silazinev and ' . with
‘stirring, after heatingthe ester to 200° F. and the
ienyluinaphthylamine' can-withstand 100 hours in a-jetv " phenylpz-napht-hylamine
was dissolved while. cooling __the
lrbineengine at a reservoirj‘temperature,of' 400° F.
ester back to room temperature. Each rblend. in a 1100
ithout ‘excessive viscosity buildup‘. orjthe development
10 ml. sample,'was.'heated in a glass tube to the temperature
shown‘in .thetable while dried ‘air ‘at, a rate of 5 1./hr.
_Whi1e his not desired to be bound by any particular
was
blown‘through the sample. One inch square metal
teory," it is believed that each of the compounds comple- ‘
platelets'labout0.032
inch thick) were suspended in the
rents the ‘action of the'othei'. to provide’; the‘ desired
blends and weighed before and after exposure to determine
E'excessive acidity.
I.
-
-
.
V
‘A
_
'otection. 1 It is believed; that the‘phe'nosilazine lderiva-_
. corrosion‘. iPlat'eletsiof' steel, copper, aluminum, titanium
V8 full?tidns as an anti-lilidanfo?-lyilat ,tlhiefhirgh iempera- 1” and ‘silver were-i used except in they case of ‘Example II
[res referred to ‘above, andris incapable of retarding‘
Where onlysteel ‘was used. The tests were run for 20
tidation at low and intermediate*temperatures.
Example N0‘______
_____
It _;
is .......hours.
_'_.‘ ______ _.
'Estero'fExaniplé---;.' ____ -.';_--;_'.; .....
It; ~ ' '
____
.Pero'ent N-ethyl-phenodiphenyl silazine
,hang'ei
_.
_.-
~~
-
'
'
-_.-
'
-7
. 'Ib
I11
1.1
1.0‘ '
1.0
1.0
‘ 0.5
1. 0
1.0
1. 0
g -.500_
12.7
21.57
~
n.
'
VI
.'1.5’
.
-
_,
V
1-,‘0
+0.09
'
-
1.0
500
9.48
22.63
weight of metal specimens, rugs/cm):
Steel.
IV
' r..-
-
Percent P-henyl a-naphthylamine
.TempeI8tiIreS,j93F ............ -Acidity, _Mgs. KOH per gm
Visgosity'rcs. @ 100° F ........
III '
500‘
400
7.4 ' 0.39
21. 8516.69
VII
lb
VIII
Ia.
1.0
1.0
1.0
1.0
400
450
0. 23 ' 3. 39
16.57
17.14
450
2. 49
18. 02
_
’
+0.10
+0.19
+0.81
-0. 54
+0.-12 +0. 14
+0. 11 +0. 09
_ +0.09‘ +0.12
+0.04
+0.03’
-0. 09
-0. 0e
-0. 45
—0. 23
+0. 05 +0. 01
+0. 06 +0. 03
+0.05 ‘+0.03
+0. 03
+0.02
+0.05
+0.08
-0. 01
N.O.
-0.02
N.C.
so believed that the phenosilazine derivatives: .are xrela-. ~3'5' It is to beuriderstood that;the-foregoing 'detailed'de
t'ely ineffective even at high temperatures ‘once acidity
vscription is merelygive'n'by wayof illustration and that
LS started to'build up. The secondary: amine; which‘, _ many variations may helm‘a‘dé therein without departing
' itself is incapable of retarding oxidation‘at high tern; ' '
‘from the spirit of my invention.
matures, Serves to retard. oxidation ‘and-acidity buildup 1;
icing the warming and cooling periods and permits the" 40
‘Having described my invention, what I desire to secure ~
by.‘ Letters Patent is:
i'enojsilazine derivative‘to operate at its iulljeffectiveness '
the higher temperature.-
-
The 'phenosilazine derivatives and the‘se'condary amines -'
oportion to produce a. combinatio'n’addi'ti'y'el] Or each
' carbon atom. said-galkanoic ‘acid having an average of at
45 least 5 carbon atonsandfthe individual acids of which
‘contain 2 to 12- carbonv atoms, ‘said ester being stabilized
lenosilazine' derivative generallyfbeing dissolved-‘at a _
against high temperature oxidatilve degradation by a minor
:nperatureof about 200° F. and the secondary amine
a temperature of about 100-200"v F.
.
proportion of a diaro'matic secondary amine selected from
>
' so.
I
'
.
Example
I
‘
.
I
All-f‘parts" in this and‘
eight unless otherwise designated.
-
.
examples 'are by
_ _
_~f
.
.
‘
(a)fA¢reaction mixture was prepared by mixing 1063;
‘ valence satis?ed by‘a member of the groupconsisting of
_ hydrogen and lower alkyl radicals and its silicon valences
bonded to aromatic rings. ‘A
parts ‘of tolu'enesulfonic acid and ‘395'parts offnaphtha. , _'
re mixture'was': heated in a reactionv still-‘fora. total of
».5.h'ours with the-maximum temperature in the-‘reaction lui'd‘rising ,to 242° C. At the end .o'f'the- heating" period '
e naphtha was ?ashed off. The mixture-was-then dis 60
Hg‘v and the vfr'ac- _ -- -,
Pl'l coming'o? at a vapor temperature of 255-2819 C.
lS- collected. vThe collected materialwas giveriian alka
le wash and a water wash and then
The ?nishedvv
the group consisting-of diaryl amines, aryl alkaryl amines
and diaalkaryl ar'ninesand aininor proportion of acom~
' pound‘ ‘having a phenosilazine ring. having its nitrogen
rts‘of'eheptanoic acid, 350j;pa_rts of trimethylolpropane,
led at an'absolu'te pressure of
.
polyol having two to four methylol groups on a quaternary
ay be advantageously blended together, in the desired
aynbe'se'parately dissolved injthe ,polyohester with ‘the
_
4 .j l. A vhigh ‘temperature lubricant comprising. a major
proportion of a normally liquid'alkanoic acid ester of a
,
I
-
-'2.‘A high temperature lubricant comprising a major
proportion of a normallyiliquid- alkanoic acid ester of a
polyol having three methylol groups on a quaternary car
bon atom. said alkanoic acid having an average of at least
5 carbon atoms and the individual acids of which contain
2 to 12 carbon atoms, said‘ ester being stabilized against
high temperature oxidative degradation by a minor pro~
lportion of a diaromatic secondary amine selected from the
group consisting of diarylj amines, aryl alkaryl amines
and di-alkaryl amines and a minor proportion of "a com—
nie'thylolpropane triheptanoate had .a speci?c gravity 65 pound having a phenosilazine ring having its nitrogen
0/20) of 0.963, an acid number (mg, KOH/g.) of 0.04,
hydroxyl content of 0.20 weight-percent and a water
main- of 0.0] weight percent,
(b) Another batch of trimethylolpropane_triheptanoate v -
valence satis?ed by a member of the group consisting of
*hydrogen and lower alkyl radicals and its silicon valences
- 'bondedto aromatic rings.
.3; A high temperature-lubricant comprising a major
lS- prepared by‘ ‘a procedure essentially similar to that 70 proportion of an alkanoic acid ester of trimethylolpropane,
scribed above except that the toluenesulfonic acid was
said alkanoic acid having an average of from 5 to 8 car
iitted‘in the reaction and that the distillation‘ step was
bon atoms, said ester beingstabiliz'ed against high tem
iitted. The product had a speci?c gravity‘ (20/20) of
perature oxidative degradation by a vminor proportion of
964, an acid number (mg. KOH/g.) of 0.01 and a water - a diaromatic secondary amine selected from the group
ntent of 0.01 weight percent.
75 ‘consisting of diaryl amines, aryl alkaryl amines and di
5
1
3,036,005
‘7 alkaryl amines and a minor proportion of‘ a compound
i said alkanoic acid having an average of from 5 to 8 c
having a phenosilazine ring having its nitrogen valence sat‘~
is?ed by a member of the group consisting of hydrogen
bon atoms, said ester being stabilized against high te
perature oxidative degradation by from 0.25 to 3 weii
and lower alkyl radicals and its silicon valences bonded
to aromatic rings.
percent of phenyl ot-naphthylamine and from 0.25 tc
weight percent of N-ethyl-phenodiphenyl silazine.
4. A high temperature lubricant comprising a major
11. The lubricant of claim 1, wherein said diaromz
Q ‘ proportion of trimethylolpropane triheptanoate, said tri
secondary amine is present in an amount between abt
0.25 and 3 weight percent and said phenosilazine co
methylolpropane triheptanoate being stabilized against‘ _
high temperature oxidative degradation by a minor pro- '
pound is present in an amount between ‘about 0.25 and
portion of .a diaromatic secondary amine selected from
weight percent.
the group consistinggof diary-l amines, aryl alkaryl amines
12. A high temperature lubricant comprising a ma;
and di-alkaryl-amin'esand a minor proportion of a com
proportion of trimethylolpropane triheptanoate, said 1
pound having a. phenosilazine ring having its nitrogen
methylolpropane triheptanoate being stabilized agaii
valence satis?edibya member of the group consisting of.
high temperature oxidative‘ degradation by from abc
hydrogen and‘ lower alkyl radicals and its silicon valences _ 15 0.5 to about 2 weight percent of phenyl e-naphthylami
bonded to aromatic rings.
and from about 0.5 to about 2 weight percent of N-ethj
v. 5. A vhigh temperature lubricant-comprising a major "
‘ pheno'diphenyl silazine.
* e
13. An‘ anti-oxidant composition consisting essential
proportion of_.:a normally liquid, alkanoic acid ester of , a _
polyol having two tofour methylol groups on a quaternary’
‘ of a diaromatic secondary amine selected from the grow
. carbon atom,ls'aid‘alkanoic ,acid'havingan average of at
consistingod diaryl amines, aryl alkaryl amines and (
alkaryl amines and a compound having a phenosilazi
ring having its nitrogen valence satis?ed by a member
least 5 carbonjat'oms land the individual acids of which
contain 2. ‘to 121ca1ihon atoms, said ester being stabilized
against high temperature oxidative degradation by a minor‘
the group consisting of hydrogen and lower alkyl radica
and it's' silicon valences bonded to aromatic rings, sa
components being present in a weight ratio of 0.25
‘e. proportion of adiar‘omatic secondary amine selected from
the group consisting of diaryl‘arnines, aryl alkaryl amines
and di~alkaryl amines and aminor proportion of an N'
alkyl-phenodiphenyl silazine.
‘
Y
to 3:0.25.
'
14.‘ An anti-oxidant composition consisting essential
'
6.‘ A high. temperature‘ lubricant comprising a' major
of a diaromatic secondary amine selected from the grot
proportion ofajnormally liquid alkanoic acid ester ot‘tr‘i- I ' eonsistingpof diaryl amines, aryl alkaryl amines and c
methylolpropan'e, ‘said alkan'oic'acidhaving an average of :30
i at least 5 carbon atoms and the individual acids of which? .
contain 2 to 12 carbon atoms, said ester being stabilized
alkaryl-amines and a phenosilazine compound having tl
structure
against high temperature oxidative, degradation by a;
I
it
minor proportion, of a diarom'atic secondary amine selected I
from'the groupconsisting of diaryl amines, aryl alkaryl
amines and di-alkaryl amines and a minor proportion of
s5
.
‘an N-alkyl—phenodiphenyl silazine.‘ , .
s1
'
,7. A high‘ temperature lubricant comprising a major
/
\
-
proportion of a normally liquid alkanoic acid ester of a;
polyol having two tofour' methylol groups on a quaternary 40 wherein the nitrogen valence is satis?ed by a member (
the group consisting of hydrogen and lower alkyl radica
carbon atom, said alkanoic acid having an average of at.
and the silicon valences are bonded to aromatic ring
least 5 carbon atomsand the individual acids of which 3 said
components being present in a weight ratio of 0.25:
contain 2 to 12 carbon atoms, said ester being stabilized‘ \to 320.25..
against high temperature oxidativefdegradation by a minor '
proportion of a diaromatic secondary amine selected from 45 4 15. An anti-oxidant composition consisting essential]
the group consistingof diaryl amines, aryl alkaryl amines‘ - v‘of phenyl a-naphthylamine and a compound having
and di-alkar'yl' amines and a minor'proportion of N-ethyl- . 'phenosilazine ring having its nitrogen valence satis?e
.by a member of the group consisting of hydrogen an
phenodiphenyl sila'z'ine.‘
lower alkyl radicals and its silicon valences bonded t
8. A high temperature lubricant comprising a major.‘
proportion of an‘alkanoic acid ester. of a polyol having
two to four methylol‘groups on a quaternary carbon atom,.. ‘ '
said alkanoic acid having an average of from 5 to 8 carbon
atoms, saidester being stabilized against high tempera
aromatic-rings, said components being present in a weigl
ratio of 0.25:3 to 3:025.
16. An anti-oxidant composition consisting essential]
‘of a diaromatic secondary amine and N-ethyl-phenod
phenyl s'ilazine in a weight ratio of 0.25:3 to 3:025.
ture ‘oxidative degradation by a minor proportion of
17. An anti-oxidant composition for carboxylic este
phenyl a-naphthylamine and a minor proportion of a
compound havinga phenosilazine ring having its nitrogen ' > lubricants consisting essentially of phenyl a-naphthylamin
and N-ethylphenodiphenyl silazine in a weight ratio fror
valence satis?ed by a member of the group'consisting of - ' 0.25:3 to 3:025.
55'
.
.
.
.
.
hydrogen and lower alkyl radicals and its silicon valences
bonded to aromatic rings.
9. A high temperature lubricant comprising a major
proportion‘ of an alkanoic acid ester of a polyol having
two to four methylol groups on a quaternary carbon atom,
said alkanoic acid having an average of from 5 to 8 carbon
References Cited in the ?le of this patent
FOREIGN PATENTS
600,325
v
Great Britain _________ __ Apr. 6, 194
atoms, said ester being ‘stabilized against high tempera
OTHER REFERENCES
ture oxidative degradation by a minor proportion of phenyl 65. , Atkins et al.: “Development of Additives and Lubricai
a-naphthylamine and a minor proportion of N-ethyl- - ing Oil Compositions,” I. & E. Chem., vol. 39, No. 4, p;
phenodiphenyl silazine. _
491-7, April 1947.
10. A high temperature lubricant comprising a-major
Barnes et>al.: “Synthetic Ester Lubricants,” Lubricatio
proportion of an alkanoic acid ester of trimethylolpropane,
Engineering, pp. 454—8, August 1957.
In Interference N 0. 93,833
ion in Interference
. 3,036,005 J. E. Koch’, J12,
involvingiPatent
N0
NT coMPoslTléN,
?nal ]udg
BRIG
endered
Dec.
20, 1965, as to claims 9, 10,
HIGH TEMPERATURE LU
ment adverse to the patentee was r
12 and 17
[bf?cial Gazette June %8, 1.966.]
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