close

Вход

Забыли?

вход по аккаунту

?

код для вставки
Patented Jan. 1, 1941 '
v
. OFFICE
2,413,718~
' UNITED STATE sv _ PATENT
2,413,118
LUBRICANT
Bert 11. Lincoln, Ponca City, Okla... and Gordon D.
Byrkit, Niagara Falls, N. Y., assignors to Con
tinental Oil Company, Ponca City, Okla” a
' corporation of Delaware
' No Drawing. Application November
’
.
._
a, 1942,
8erialNo.4
. j ._..c1.1m.. (crass-49.1)
. 2
_
This invention relates to addition (agents and *trating or adsorbing on the metal, andleaving a
film of lubricant with high oiliness character
which remains on the metal surface irrespective
01' the length of time the machine is idle.
This high oiliness ?lm is very even and results
in smooth operation which‘may be easily discemed by the experienced operator and lubricat-v
lubricating compositions containing the same and
is a continuation-in-part of our'copending appli
cation, Serial No. 330,950, ?led April 22, 1940.
, Present-day mechanical devices require lubri-.
eating oils of high ?lm strength and of high oil
iness characteristics. It-has been found that the
ing engineer.
, present-day hydrocarbon lubricants of the very
-
When the hydrocarbon lubricants are diluted
important characteristics. These two properties 10 with unburned fuel or with other light hydrocar
highest quality are de?cient in these two very
are of vital‘ importance under conditions of thin
?lm lubrication where the lubricant ‘has been
bonsj, the'small degree of oiliness of the original
should tend to keep the coe?‘lcient of friction as
low as possible and must have a very high ?lm
bricating composition having improved ?lm‘
hydrocarbon lubricant is greatly decreased. We
have found that the addition of the product of_
‘squeezed from between‘thefri'ction surfaces due
our invention, to hydrocarbon ‘lubricants more
to high pressures, slow speeds, and other causes.
It is readily seen that the viscosity or the body 15 than compensates for the loss in oiliness and load
carrying ability by dilution.
‘
of the lubricant plays no part in this. type of
' One object of our invention is to provide a lu
lubrication and that the remaining ?lm ofv oil
strength and extreme pressure characteristics.
strength and be of high oiliness value to prevent 20 Other and further objects of our invention will
appear from the following description.
rupture of the ?lm‘of the lubricant, which would
We have found that certain compounds are
Mechanical‘ devices are being designed for
adsorbed or absorbed by metals forming a plural
cause
seizure.
'
‘
-'
’
>
"
'
higher pressure operation, and the ?lm strength ‘
ity of layers or ?lms on the surface 01 the metal, .
of the best quality straight hydrocarbon lubri 25 which ?lms are very tenacious (they have a high
?lm strengthTa'nd have thevproperty of reducing
1 ‘cents has been found to be too low and not sum
the coe?icient of friction to a greater extent than
means of improving the ?lm strength of these
any known lubricant. The compounds which most
lubricants is of great importance to the art of
readily are adsorbed by metals are ones‘ consist
lubricant manufacture and'to the designer and 30 ing of polar molecules, that is, molecules of un
symmetrical electrical character which contain
fabricator of mechanical devices.
an atom or group'of atoms eihibiting a secondary
Substantially, all machines operate in part or
or residual valence. Thesepolar compounds tend
at times totally under conditions of boundary
to produce regimentation of the molecules of
or thin ?lm lubrication, under which conditions
cient; therefore an invention which provides the
hydrocarbon oil when added thereto. If a metal ,
is immersed in a‘ stronglypolar compound, a
the oiliness or unctuosity of the lubricant is the -
?rst and primary requisite of e?icient operation.
Those skilled in the. art of lubricant manufac
- regimentation or cybotaxis oi.’ the ‘molecules will
take place in the adsorbed ?lm, the molecules be
, ture or machine manufacture will readily appre
ciate the value of an invention that will improve
ing oriented with'respect to ‘the surface of, the '
the oiliness of these otherwise high-quality lubri 40 metal bywhichthey are adsorbed. The ?lms of
polar compounds, adsorbed by 1a metal, (can be"
cants. Under some circumstances, a very small
plainly seen and ‘the orientationof the polar '
amount of an addition agent will stabilize a hy
drocarbon oil against formation of corrosive oxi
molecules on the ‘metal surface ascertained by '
dation ‘compounds or sludge-forming compounds,
X-ray.di?iractionfmethods, :in which a mono
andv as littleas 0.001%is often su?icient. . '
45 chromatic JX=ray beam is passed ‘through the ‘ad
instarting idle mechanical-equipment which
is lubricated-"from a sump‘ by pumping-or cir- ,
culating’ the, lubricant, there is always a short
I‘acts
sorbed'
as ?lm's
a diffraction
at ‘an angle.
grating,
_ The
and
series‘
a diiifractcdv
of. ?lms
beam will be re?ected from the planes of_the
period of time during which the ‘rubbing surfaces
must operate'under conditionsof dry'friction if
' :?lms and can be recorded photographically. The
50 X-ray photographs will clearly show the orienta
' ordinary hydrocarbon lubricants are used- With - tion of the molecules by cl .aracteristic pictures.
.dry friction, "the wear on‘friction surfaces is ex- f
treme; and during cold weather when the lubrié
' - cant is sluggish or during periodswhen thelubri
X-ray investigation has shown vthat strongly,
polar molecules form adsorbed ?lms of unusual
thickness'and regularity of'arrangement. Thick
eating system is'not-functioning properly for one 55 nesses oi’ ?lms of 9,000 Angstrom units have been
reason or another, rubbing surfaces may not only
'suiler considerable, wear but may be damagedto
the point where they must'be replaced. The prod
uct 01'. our invention has the very important prop-'
obtained, which are of enormous magnitude when
compared with molecular dimensions.
Broadly stated, our invention comprises the
making available for use as addition agents in
erty oi reacting with; the metal surfaces, pene; 60 lubricatingcompositions of halogen bearing or- "
2,418,718
3
4
gano-boron esters of the type which contain the
ency of the lubricant to drain from the bearing
surfaces, etc., all as previously explained.
>B-OR group (in which R is an organic radi
cle) and improved lubricating compositionscon
taining minor amounts of such addition agents.
The use of organo-boron compounds broadly in
lubricating compositions is not new. Their
principal use in lubricating compositions is dis‘
closed in Patent No. 2,234,581, wherein acidic or
gano-boron compounds are disclosed for the pur
pose of preventing oxidation of lubricants, espe
cially when the same are subjected to high tem
peratures and gases which tend to promote oxi
A second and equally important effect of the '
increased polarity ‘ of our improved‘ addition
agents is the increased ?lm strength of the lubri
cant containing the same, attributable to the
functionlof the cooperative eifect of the halogen
and the R>BOR"group present in the molecule
as a ?lmstrength improver.
10
»
The presence of halogen in the molecule has
an additional advantage in that it renders ‘the
compound much less volatile so that it will not
be so readily evaporated from the lubricating
compositions during use at high temperatures.
for use are in all cases “minute.” While organic 15 At this point it may be well to note that for most
purposes the addition agents should have a vapor
‘substituted boric acids, that is, compounds having
dation. That patent, as indicated, relates to the
use'of acidic materials, and the amounts speci?ed
pressure less than atmospheric at a temperatur
the >B-OH group, are disclosed therein, these
are described as being of low solubility and less
desirable,‘
of 140° C. and preferably at'l70° C.
.
‘
Whenoneof the desired. effects of the presence
'
In addition to the disadvantage of low oil 20 of the addition agent is an increase in the film
strength of the lubricant, the ester materials of ,,
solubility, the acidic organo-boron compounds
this invention are particularly advantageous be-.
are corrosive to sensitive bearing metals, such as
cause their higher solubility, as‘ compared with
are commonly used in modern internal combus-v
the acidic materials of the prior art, makes it
tion engines.
We have found, however, that a much more 25 possibleto incorporate amounts which are much
more ~“e?'ective for that purpose; that is, in
satisfactory sub-generic class of organo-boron
amounts higher than‘ .75% or preferably above
compounds .for the foregoing uses are those of
the ester type and which are additionally char
acterized by the presence of combined halogen
in the molecule. '
‘
The upper limit of the concentration of
1.0%.
addition agents is determined by factors such as
30 the limit of their solubility; reasons of economy,
..
The ester type material is preferable for use
I in that it does not have the objectionable high
reactivity above pointed out which is possessed by
the acidic material. In the same ‘concentrations
as suggested by the prior art for the acidic type
_material, our ester type material is quite e?ective
from the standpoint of inhibiting oxidation with
out, however, possessing the undesirable proper
_
-etc. Our invention, therefore, contemplates that
these addition agents may be used in lubricating,
compositions such as those which comprise a
mineral oil base in effective amounts up to the
limits of their solubility in the oil, there being
generally no reason, however, for including more
than about 20%.
-
-
The broad class of~organo-boron esters con
templated for use by this invention contains two
ties of the acidic material. The additional char 40 important sub-divisions respectively represented
'acteristic of our improved addition agent, name
by the following formulas:
'
ly, that it contains halogen, gives rise to further
a
O-—R'
‘advantages, the most important of which may
\ /
B
I
be enumerated as follows:
The presence of halogen in the molecule ren
ders the compounds much more strongly polar,
and accordingly they are attracted to the metal
lic surfaces with which the lubricant comes in
x
in which R and R’ are organic radicles and X is
a radicle of the class ‘consisting of —R" and
--O—R"' where R" and R’” are organic radi
contact and which the lubricant is designed to
protect from scu?ing and scoring, due to over 50 cles; and
' load and the like.
’l‘his strongly polar nature of '
the compounds makes it possible to achieve ef
fects on the metal surfaces, such as the bearings,
which are not only impossible by the prior art
uses of the acidic materials, but which the prior 55
art deliberately sought to avoid by keeping down
'
R4=B-—0R
. in which Rd is a divalent organic radicle, and R
is an organic radicle.
Other sub-divisions of the broad class of esters
contemplated hereby are the following;
RzBOR’, in which R and R’ are organic radi
cles, at least one or which contains four or more‘
carbon atoms. An example of this type is chlor
The addition agents of our invention are de- ‘
, sirably strongly polar 'for the reason that one of 60 diethyl boric acid lauryl ester.
RB (OR'Yz, in which R and R’ are organic radi
the principal purposes for which they are pres
cles, at least one of which contains four or more
ent in the lubricating compositions of our in
carbon atoms. An example of this type is chlor
vention is dependent upon their ability to react
phenyl boric acid dilauryl ester.
in a chemical or physico-chemical fashion with
These two types of organo-boron esters have
the ‘bearing surfaces being lubricated. This
the general formula RnB(OR’)3—-n where n is an
chemical or physico-chemical action by which
integer less than 3, the valence of boron. They
the addition agents of our invention improves
to as low as possible the concentrations within
which such acidic materials were employed.
the lubricating compositions containing the same
contain at least one carbon-boron bond, and at ,
least one organic radicle is removable by saponi
is two-fold, and the e?ects thereof are likewise
70 ?cation. R and‘ R’ are usually hydrocarbon radi
two-fold.
cles but are not necessarily hydrocarbon radicles,
In the ?rst place, the strongly polar nature
and they may contain besides carbon and hy
of the addition agents causes the ‘same to be
drogen also other elements including oxygen, sul
oriented as an adsorbed film on the bearing sur
phur, halogen, phosphorus, or metals.v Other ex
faces sought to- be lubricated with the attended
advantages, such as higher “oiliness”; less tend 75 amples of our compounds are chlorophenylboric
2,418,718
C. Sulphur-containing organic radicalPContinued.
Speci?c examples—-Continued.
B. Oxygen-containing organic radicles--Continued~.
2. Of the ketone type-Continued.
'
Adipyl~
Thio-acetyl-benzyl ,
Mercapto-ggenyl
Mercapto- nzl
.
Benzoylene
'
Butyry
Isobutyryl
Carbothoxy
Cresotyl
Desyl
~
Mcrcapto-ethy
Mercapto-butyl
Mercapto-benzoyl
Mercapto-stcaroyl
_
Mercapto-thio-benzoyl
Mercapto-thic-atearoyl
Mcrcapto~thio~stearoyl~phenyl
Glutaryl
Glycolyl
Melonyl
Oxalyl
Phthalyl
Succinyl
Mercafito-thio-benzoyl-phenyl
Laury mercapto- henyl
Lauryl mercapto~ enzyl
Thlenyl
10'
3. 0f the ester type, i. e.
1
Derived from hydroxy-esters b the removal of the
hydroxyl group, as for examp e, by the removal of
Thiazyl
ganic radicles may have one or more atoms of
_
Esters formed by substitution or any oi the
“R” grougs listed above for one or more of
halcgen, and more speci?cally of chlorine, sub
thedacid ydrogen atoms of the following
801
S!
_
It is to be understood that‘the foregoing or
thehydroxyl group from the following esters?
a. Esters of ydroxy acids, a. a.
I
stituted for one or more hydrogen atoms in the
.
preparation of the halogen bearing esters which
comprise the addition agents of this invention.
Esters of the type RR’BOR'_', or-RzBOR” may
Lactic acid
Hydracrylic acid
Citric acid
Tartaric acid
Ricinoleic acid
Hydroxy-stearic acid
Hydroxy-chlorstearic acid
Cyclohcxanol carboxylic acids
Hydroxybcnzoic acids
Salicylic acid
Hydroxy-phthalic acids
Hydroxy phenyl-bcnzoic acids
20 be made by replacing one ester group of a tri
ester by reacting the ester with only enough
Grignard reagent of the formula RMgBr to carry
the reaction just one step. The second step may
then be carried out with the same Grignard re
agent, or a di?erent one, R'MgBr, depending on
Esters of polyhydroxy alcohols and phenols in 25 whether R and R.’ are to be the same or di?erent.
which at least .one hydroxyl group remains
The esters of type RB(OR')2 may-be prepared
unsubstituted, for example-esters iormed by
esteriiyirg the iollowirg so that at least one
as follows:
hydroxyl group remains in the resulting ester:
Ethylere glycol
.Diethylene glycol
3R’OH + BC]; _-> B—0R' (the triester)
30
Propylere gylcols
Butyler'a glycols >
0R’
Poly-hydroxy benzenes
Dihydruxy-benzenes
The
triester
is
reacted
with
RMgBr»
Resorclrol
Naphthol carboxylic acids I
/OR'
Catechol
R
Hgdroqulrone
Tri- ydroxybenzenes
Pyiogallol
'
Hydroxy-ethyl
Hydroxy-butyl
Hydroxy-amyl
4. Hydroxy radicles
. \OR’
Hydroxy-cyclohexyl
Amy] hydroxy-phenyl
Laur lhydroxy- henyl
Cety hydroxy-p enyl
Di-amyl hydroxy-phenyl
Lauryl hydroxy-ben zyl,
Amyl hydroxy-cyclohexyl
Phenyl hydroxy-phenyl
Phenyl hydroxy-benzyl
Hydroxyphenyl- henyl
the same.
\
nzyl-phenyl
Salicylal
_
_
‘
-
It is possible to use phenyl, chlorphenyl, naphyl,
45. aliphatic, aliphatic substituted aromatic, and aro
matic substituted aliphatic radicles to form the
Hydroxy henyl- enzyl
triester. It is preferable to have the chlorine in
the radicles prior to the reaction.
By varying the alcohol and the Grignard re
agent it would be possible to obtain a great variety
~
Hydroxybenzoyl-phenyl
Hydroxy-benzoyl
Hydroxy-stearoyl
.
R and R’ may be any organic radicles, for ex
ample ethyl and CH2CH2CH2CH2—C1 respectively.
The above ‘type reaction makes use of the
40
Grignard reagent and reaction. The above reac
tion would give a product in which the R's are
Hydroxy-ghenyl
Hydroxy- enzyl
Hydroxy
on’
\B/
85
,
C. Sulphur-containing organic radicals.
of esters.
An aromatic radicle may be placed in the ester
linkage in the following way:
Exam les are any of the radicles listed under B in which a
Sltllp ur atom has been substituted for one or more oxygen
a oms, e. g.,
H
s
ll
R-C
s
where R is an aliphatic radicle (e. g., methyl, ethyl, butyl,
lauryl), a cyclo-aliphatic radicle (e. g., cyclohexyl, methyl
cyclohexyl) or an aromatic radicle (e. g., phenyl, benzyl, 60
tolyl, xenyl, naphthyl), and R’ is a divalent organic
rad1c1e,_e. g., methylene, ethylene, amylene, phenylene,
—CeH|-’CH:—, —CeH4-—CeH4
65
Thin-stearoyl-phenyl
'l‘hlc-acetyl-phenyl
.
75
H
01
-—>
H
B
\
\
0
C]
H
H
\
70
.
H
H
Na-O
H
Thio-benzoyl-benzyl
C]
H
BC]: + 3
Thio-stearoyl-benzyl
0
.
0
Cl
H
H
2,413,71;
v This t'riestencan bei‘eacted with any Grignard
reagent to obtain the ester containing a carbon»
to boron-linkage.
‘
I
,
_
Specific examples of the organo-boron esters of
this invention are:
ooinnoi
claws
»
"
.
'
OCcHuCl
H
1-
,
.ooinnciz_
01'
' where M is a divalent metal, e, g., the alkaline‘
earth metals;
I
_
'
a
,
7
It is sometimes advantageous to combinemore
than one'ot these compounds in a blend to ob-;
tain particular ‘properties. 'We accomplish this
by mixing two or ‘more of these compounds to-"'
25
gether' and blending the mixture with hydrocar-.
bon oil, or by blending one in the hydrocarbon oil,
blending the second into this mixture, and ‘so on
until the composition is complete.
' '
We have found that the organic boron c0m-'
30 pounds above se't'forth may be more effective in
.‘some compositions if. a comparatively small
amount ‘of halogengfree, oxygen-containing can
j --.-1 ' vbon'"conm’o'und
The oxygen-containing
is included
carbon
invthe
compound
composition.
may be
35 of, aliphatic, aromatic, or hetero-cyclic nature and
may be blended withthe organic boron compound
in amounts ranging from 5 to 50 percent.
It will be understood that certain‘ features
sub-combinations are or utility and may be em
ployed withoutreferencev .to- other features and
sub-combinations; ,Thisis contemplated ‘by and
is within the scopevof-ourclaims. It is‘further
1. obvious that variouschanges may be made in de
tails within the scopefof ourfclaims vwithout; de
parting from the spirit of our'invention." Itis, ' '
,irxtherefore, to be understood that our ‘invention '
, 4.5.,
is ‘not to be limited to the speci?c details shown
and described.
'
'
Other modes oi" applying the principle of the '
50
invention may be employed, change being made
as‘ regards the’ details described, provided the
features stated in any of the following claims or
theequivalent or such be employed;
.
i Wetherefore- particularly point out and‘ dis
" ' " tinctly
as our invention:
1._ {A "Plubricantgcomprising in} combination a.
niai; pl'?wl‘?qhfbtahydrocarbon'oil and'rmm“
- ' -
-
0011 vto?‘about.20%1oi’ anxolil-soluble halogen- , '
I ter containingat least one carbon-u-boronv _
li'ibricant*'coniprisins,,1n - combinationia
a .
.. *Pl'?pdi‘tion-iofa hydrocarbon oil and from
001%
{20% of an: oiles'olubley halogen
bearingY‘organo-boron ‘ester containing at least
‘.one carboneboron bond and having the formula:
' ii
- in which Bandit-ii’; are organicradicles, x is a
> radicljej
consisting ‘of — "
here‘ R",_ and R1"
Y78 ' " “3.
and
organic radiclles.
‘comprising vin“combination ,af 7
'
2,418,718
11
-
.001% to about 20% of an oil-soluble halogen
bearing organo-boron ester containing at least one
carbon-boron bond and having the formula:
boron ester containing at least ‘one carbon-boron
. bond andrhavinlg the formula RzB.OR' in which
R and R’ are organic radicles.
,
7. A lubricant comprising in combination a
major proportion of a-hydrocarbon oil and a
minor proportion of an oil-soluble halogen-bear
ing organo-boron ester containing at least one
carbon-boron bond and containing an alkaline
earth metal in the molecule.
8. A lubricant comprising in combination a
major proportion of lubricating oil and from
.001% to about 20% of chlorphenylboric acid di
in which Ft‘l is a divalent organic radicle and R
is an organic radicle.
4. A lubricant comprising in combination a
major proportion of a hydrocarbon oil and from
.001% to about 20% of a halogen-bearing organo
boron ester containing at least one carbon-boron
bond and having the formula RnB(OR')3-n in
iéutiél ester'containing- at_1east one carbon-boron
which R and R’ represent organic radicles and n
is an integer less than 3. .
12
.001% to about 20% of\a halogen-bearing organo
major proportion of a hydrocarbon oil and from"
15
9. An extreme pressure lubricating composition
5. A lubricant comprising in combination a
comprising a major proportion of a lubricating
major proportion of a hydrocarbon oil and from
oil and from .'75% to about 20% of a halogen
.001% to about 20% of a halogen-bearing organo
bearing organo-boron ester containing at least
boron ester containing at least one carbon-boron
bond and having the formula-RB(OR')-z in which 20 one carbon-boron bond. '
R and R’ are organic radicles.
‘ 6. A lubricant comprising in combination a
major proportion of a hydrocarbon oil and from
BERT H. LINCOLN.
GORDON D. BYRKIT.
Документ
Категория
Без категории
Просмотров
0
Размер файла
711 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа