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Патент USA US2411159

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Patented Nov. 19, 1946
2,411,159
UNITED STATES PATENT OFFICE
‘ 2,411,159
LUBRICANT
William Edward Hanford, Easton, Pa., assignor
to E. I. du Pont de Nemours & Company, Wil
mington, Del., a corporation of Delaware
No Drawing. Application July 22, 1943,
1
Serial No. 495,767
13 Claims. (Cl. 252-29)
2
This invention relates to a new class of stable
and the terminal substituents contribute to. their
Lubricating oils, transformer oils and other re
merizable organic compound" designates any or- '
?uorine-containing lubricants.
lubricating properties. The phrase “non-poly
?ned mineral oils suffer a marked deterioration
in use and when exposed to air at elevated tem
ganic compound containing one or more carbon
atoms which is free from ethylenic or acetylenic
unsaturation.
peratures. Generally, such petroleum oils when
in'use darken in color and eventually may be
The preferred stable lubricating compositions
come saturated and deposit a ?nely divided oil
of this invention vary from relatively high boil
insoluble carbonaceous material, commonly
ing liquids to solids melt‘ g below 300 C. which
known as sludge. Under some conditions, the 10 have molecular weights wit _' the range of from
oils deposit an insoluble ?lm on hot metal sur
250 to 2500 and contain from about 60 to '15 per '
faces. Such oils, in addition, develop an acidity
cent of ?uorine.
after some period of use, particularly when used
v
The following examples are given by way of il
under high temperature conditions. In attempts
lustration of the superior lubricating properties
to prevent this deterioration of lubricating or 15 of these lubricants, but since the conditions may
transformer oils, use has been made of oxida
be varied I do not wish to be limited to the exact
tion inhibitors. Such materials are useful for a
aipparatus, machine or other conditions men
short time, but they themselves are soon oxidized
t oned.
and lose their e?ectiveness.
Exmrrr: I
It is an object of the present invention to pro 20
The
?lm
strengths
of a number of reaction
vide very stable, highly ?uorinated lubricants.
products of tetra?uoroethylene with various
A further object is the preparation of very stable,
non-polymerizable compounds were compared
highly ?uorinated non-?ammable lubricants for
with that of a commercial SAE 30 oil by apply
the purpose of lubricating moving parts under ex
ing them directly to the bearing of a Cornell fric
treme conditions such as those imposed at ele
tion tester and noting the jaw load on said tester
vated temperatures, at extreme pressures, or by
at which seizure occurred. The Cornell friction
corrosive chemicals and the like. It is a principal
tester is described in U. S. Patent 2,279,560.
object of the invention, therefore, to provide lu
These materials exhibited ?lm strengths superior
bricating compositions characterized by the
afore-mentioned improvements. Additional ob 30 to the SAE 30 oil as shown in the‘ following table.
iects will become apparent from an examination
Table I
of the following description and claims.
These and other objects and advantages are
accomplished by a lubricant comprising the re
action product of tetra?uoroethylene and a non 35
polymerizable organic compound as more fully
Ap roximate melting or
Reactmt
b0
g point of product
Jag
loadll
me
friction
on
tester at
seizure
described hereinafter.
The ‘reaction products of tetra?uoroethylene
prepared by reacting tetra?uoroethylene at a tem
perature between 50° C. and 350° C. with a sat
'
Dioxane _______________ -_
40
urated non-polymerizable organic compound of
the general formula XY, wherein X is a member
of the group consisting of hydrogen and halogen
and Y is a monovalent saturated organic radical,
have been found to be exceptionally stable, non 45
?ammable lubricants. Said products, which are
preferably prepared in a closed system and in the
- D ____________ __
1,2-d1methoxyethaue
__________ __
Ethyl propionatc.
n-Butyric acid.
_
Pound:
M. P. l70-175° C .......... ..
2,250
.M. P. 75-00° C. (F, 64.6%)__
M. P. 80° 0 ............... -.
1,600
1,250
M. P. 120" O__.--___..._-_-_
2,500
_ Soft low melting solid _____ -_
_ Sticky low melting solid. _ __
l, 375
3, 000,
Cycl0hexane_._
_
___________ ._
1, 750
n-Butane---
_ M. P. 125° C (F, 70.3%)_-__
2,000
chloroform ___________ -.
M. P. 90-120
- P. 290-295
.......... -_
2,000
Control SAE 30 oil .................................. _-
760
Exmrtr II
presence of a catalyst, have the general formula
The reaction products of tetra?uorethylene
X(CF2CF:)»Y in which X is a member of the
with non-polymerizable organic compounds im
group consisting of hydrogen and halogen, n is 50 proved the ?lm strength of an ordinary‘ com
a positive integer greater than 1 and Y is the
mercial SAE 30 oil when added to the oil in
complementary portion of the organic reactant,
the amount of only one per cent as shown by
being a monovalent saturated organic radical.
the following table which records the jaw load
The ?uoro-carbon atom chain present in these
at which seizure occurred when a commercial
products contributes to their extreme stability I55 SAE 30 oil containing 1% by weight of a reaction
2,411,159
3
-
A
Reactmt
4
variety of isomeric products arevobtained in which
product of tetra?uoroethyli ne with a non-poly
merizable reactant was applied directly to the
bearing of a Cornell fristion tester.
Table II
all the tetra?uoroethylene units are not neces
sarily connected together. For example, the
above products may react with more tetra?uoro
ethylene as illustrated below:
Jagorne
loaduon
roximate melting or
brfl‘ing point of product
machine
at seizure ‘
10
DM
an _______________ __
8
C . (F
M. P. 75-90"
However, it will be observed that the sum total of
the atoms other than those in the tetra?uoro
ethylene units is equivalent to one unit of the
7) __ pomldgm
64.6
B. P. 171-19o° 0-1---- " _.
B. P. 211-230“ C _____ -.
B. P. 86—92° 0/42 mm__
11250
1, 125
-
1,250
o ______________ __ B. P. 127-145‘? 0/42 111111....
Control SAE 30 oil __________________________________ --
1,250
800
original \non-p‘olymerizable organic compound
XY.
The saturated non-polymerizable organic com
pounds include acids, esters, anhydrides, nitriles,
amides, imides, ketones, aldehydes, acetals,
ketals, alcohols, glycols, hydrocarbons, ethers,
EXAMPLE III
Considerable di?iculty was encountered on at
tempting to distill or store corrosive chemicals 20 mercaptans, sul?des and disul?des. The com
such as antimony trichloride, antimony penta
pounds mentioned above may be straight or
chloride, and boron tri?uoride in glass apparatus
branched chains or may be cyclic. The preferred
containing ground glass joints or stopcocks due to
type of non-polymerizable organic compounds
the rapid attack of the chemicals on the com
for preparing stable lubricants from tetra?uoro
mercial lubricants causing sticking or freezing 25 ethylene are saturated aliphatic hydrocarbons.
of the joints. A glass apparatus containing
Examples of said hydrocarbons are methane,
numerous ground glass joints and stopcocks
ethane, propane, n-butane, isobutane, cyclohex
which was designed for distilling and storing cor
ane, pentanes, hexanes, saturated petroleum hy
rosive chemicals such as aluminum bromide, boron
drocarbons, and isooctane. These reaction prod
tri?uoride, and antimony halides was found to 30 ucts are exceptionally stable and exhibit ex
be practically inoperable using the highest grade
commercial lubricants due to the rapid sticking
cellent lubricating properties.
The lubricants of this invention have m’any
and freezing of the glass joints which actually oc
curred in a few hours. However, when the‘ joints
were lubricated with a mixture of graphite and
distinct advantages over the commercial mineral
H(CF2CF2) 11C4H9, where n averaged about 7, the
deterioration, or sludge formation even under
extended severe conditions of elevated tempera
tures or pressures, and their relatively low vis
oils including non-?ammability, extreme thermal
and chemical stability, freedom from acidity,
ground glass joints and stopcocks operated
smoothly for over a week while distilling alumi- '
num bromide under high vacuum. This lubricant
was also superior to commercial lubricants in that
co'sity also facilitates their rapid circulation and
40 penetration between metal, glass, or other sur
it was unattacked by the corrosive chemicals and
imparted no color or contamination to the puri?ed
materials. Similar results were obtained when
the stopcocks, present in an apparatus used for
the storage of bromine, were lubricated with this 45
material.
The present invention comprises'the discovery
of a new class of stable lubricants which are
applicable for use on bearing surfaces, e. g. on
faces. Two samples of H(CF2CF2)11C4H9 where n
averaged about 3 and 7 were passed through a 26
inch furnace which was heated to 500-550" C.
and the color and lubricating properties of the
heated samples remained unchanged.
The lubricants vary from liquids to waxy solids
' which makes them applicable as lubricants for
moving parts in a wide variety of different ma
chines and apparatus. The liquid lubricants are
metals, glass, ceramics, plastics, wood, leather, 50 particularly useful as lubricating oils where the
or other materials. The lubricating compounds
lubricant may be subjected to extreme condi
which are the subject of this invention may be
tions such as elevated temperatures, for example
represented by the formula X(CF2CF2)..Y, where
X is hydrogen or halogen, XY constitutes a non
polymerizable organic compound and n is a
in internal combustion. engines of the spark and
compression-ignition types, such as airplane,
positive integer greater than 1 which generally 65 Diesel, marine and automobile engines; as well as
for cutting oils, turbine lubricants, wire-drawing
varies from 2 to about 25. In the preferred prod
ucts, because of the superior results thereby ob
lubricants, etc. They are also applicable as
stable insulating and lubricating oils in trans
formers, switch boxes and the like. The higher
their greater utility, the preferred products are
liquids or solids which melt below 300° C. and 60 molecular weight waxy lubricants may be applied
directly to the bearing surfaces or may be blended
contain at least 60% ?uorine by weight. The
with the high boiling liquid lubricants to give
following examples are given to illustrate the
greases which are particularly adapted for use
preparation of the compounds. ,
tained, n is in the range of 2 to 15. In view of
“
“or, = or, +'xY -_-» xwrzorna
nor, = or, + co]. -_-» cuoricrmcoh
CH:
Cg! CH3
“CF, : CF, + JJH:
C
(I'J‘H:
1
Since the structure of these products has not been
de?nitely determined, it is possible that a large
as lubricants for metal or glass surfaces. A few
65 speci?c examples ‘of uses for which these lu
bricants are especially‘ suited include ammuni
tion lubrication, glass stopcock lubricants, mill
greases, extreme pressure lubricants, cutting oils
and as lubricants for various types of electrical
70 motors. They may be employed as lubricants
' alone or in conjunction with other oils, lu
bricants, or agents added to the oil for various
purposes such as fatty acid esters, organic phos
phites, organic phosphates, halogenated aro
matic compounds, pour point depressants, vis
2,411,109
6
cosity index improving agents, anti-ring sticking
agents ‘and the like.
erai formula. H(CF:CF5) "04H: in which n is a pos
itive integer greater than 1.
_
7. A lubricating composition comprising a sat
As many apparently widely different embodi
urated organic poly?uoro compound of the gen
ments oi’ this invention may be made without
departing from the spirit and scope thereof, it is
to be understood that I do not limit myself to
the speci?c embodiments thereof except as
eral formula H(CF2CFz)nC4Ho in which n is
about ‘I.
.
8. A lubricating composition comprising a lu
bricating oil and a saturated organic poly?uoro
compound of the general formula X(CF:CF2) “Y
defined in the appended claims.
Having described the present invention, the
10 wherein X is a member selected from’the group
following is claimed as new and useful:
1. A lubricating composition comprising the
reaction product of tetrafluoroethylene with a
consisting of hydrogen and halogen, n is :a posi
tive integer greater than 1, ‘and Y is a molovalent
saturated non-polymerizable organic compound
saturated organic radical.
9. A lubricating composition comprising a lubri
selected from the group consisting of hydrogen 15 cating oil and a saturated organic poly?uoro
and halogen and Y is a monovalent saturated
compound which contains from about 60% to 75%
organic radical, said reaction product consisting
of ?uorine, has a melting point of less than 800'
of from two to about 25 tetra?uoroethylene units
C. and a molecular weight within the range 01'
per unit of organic compound. '
from 250 to 2500, and is or the general formula
2. A lubricating composition comprising a sat 20 H(CF2CFI)1IY wherein n is a positive integer
urated organic poly?uoro compound of the gen
within the range of from 2 to 15 and Y is a mono
of the general formula XY where X is a member
eral formula X(CF2CF2) "Y in which X is a mem
valent saturated hydrocarbon radical.
ber selected from the group consisting of hy
drogen and halogen, n is a positive integer greater
10. A lubricating composition comprising a
lubricating oil and a saturated organic poly?uoro
than 1, and Y is a monovalent saturated organic 25 compound of the general formula radical.
I
3. A lubricating composition comprising a. sat-v
urated organic poly?uoro compound containing ~
at least 60% ?uorine and having the general
‘
'
H(CF2CF2) 1043's
wherein n is about "I.
11. A lubricating
composition
comprising
formula X(CF2CFi)nY in which X is a member 30 graphite and a saturated organic poly?uoro com
selected from thagroup consisting of hydrogen
pound of the general formula xicraorai ‘Y
and halogen, n is a positive integer greater than
1, and Y is a monovalent saturated organic rad
ical.
4. A lubricating composition comprising a sat
urated organic poly?uoro compound which con
wherein x is a member selected from the group
consisting of hydrogen and halogen, n is a posi
tive integer greater than 1, and Y is a monovalent
tains at least 60% ?uorine, has a melting point oi’
less than 300° 0., and is of the general formula
saturated organic radical.
12. A lubricating composition comprising
graphite and a saturated organic poly?uoro com
pound which contains from about 60% to 75% of
?uorine, has a melting point of less than 800° C.
xwrscra) nY inv which X is a member selected
from the group consisting 01 hydrogen and halo 40 and a molecular weight within the range of from
250 to 2500, and is of the general formula
gen, n is a positive integer greater than 1, and Y
H(CF'=CF:) ‘Y wherein n is a positive integer
is a monavalent saturated organic radical.
5. A lubricating composition comprising a sat
within the range of from 2 to 15 and Y is a mono
urated organic poly?uoro compound ofthe gen
eral formula H(CF2CF2)1|Y in which n is a posi
tive integer greater than 1 and Y is a monovalent
saturated hydrocarbon radical.
6. A lubricating composition comprising a sat
urated organic poly?uoro compound of the gen
valent saturated hydrocarbon radical.
13. A lubricating composition comprising
graphite and a saturated vorganic poly?uoro com
pound ot the general formula H(CF:CF:) ‘C48:
wherein n is about '7.
WILLIAM EDWARD HANFORD.
'
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