close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3074900

код для вставки
Jan. 22, 1963
E. ATTWOOD.
3,074,889
UNINF‘LAMMABLE HYDRAULIC FLUIDS
Filed May 20, 1959
U (mm)
F
(kg)
I
F2
350~
300
F3
250 '
200 ‘Q04 6 _
.
/'/
rlpplng
0,03
I00 0,02 ,1
'
50
' f" ,,,"T
,..-4>4‘:":', Total number
- ' ~ 7/"
’
200
,-/'
I50 -
50 _°,o|
Tm)
U
,/-"|000
7"
2000
‘l
of rotations
3000
"
50'
A
200 I400 I600 800 I000 I200 I400 I600 loud (kg)
Almen-Wielond Test
INVEN TOR.
WWIL
Uite ci- ettes
1
,
3,074,889
certain types of pumps.
5
Cimms pnomy’igpgigggsn $822232}??? May 23’ 1958
.
I
_
'
'
_
°
7
Patented Jan. 22, 11%63
cordingly, they cannot be used at high temperatures.
Furthermore, the ?lm strength of these materials is in
suiiicient and therefore they are unsuitable for use in
_
UNINFLANHVJIABLE HYDRAULIC FLUIDS
Edmund Attwood,Winchmore Hill, London, England, as
sig'nor to Labo?na, Brussels, Belgium
,
.
.
.
.. .ESQ-ear.
'
..
,
Filed
May
20,
No.. 814,451
3,674?89
ice
g1.
" atent
The second class of materials suffers from the disad
vantage of great changes in viscosity at low temperatures.
_
Also,
. T1115 ?mvemlon relafes ‘to mlm?'ammabh? hydl'auhe'
?uids Sultable' £01" ‘lee in hydraulic SYStemS,_1n$tT“ments’
the freezing point of these compositions is un
usually high. Furthermore, they are very susceptible
to oxidation although they can be quite easily protected
hydraulic transmissions, etc. More partrcularly, the 10 by the addition of anti_oxidants_
present invention is concerned with hydraulic ?uids based
The Silicones have a PO91- ?lm strength
ell tria'l'yl Phosphates “{hleh ‘exhibit a unique eembme'
{1030fv deslfable pfep'el'tlee- . _
>_
The properties of the chloro derivatives vary depend
.
ing on their chemical structure.
I-Ivdrau11c_?wds_are sl‘lbiepted to partlcularlv high
The majority of these
materials are highly corrosive. Other limitations exist
Pressures dufmg thelf use 111 VleW of the fPnellene whleh 15 where it was possible to reduce the corrosiveness. These
they have '10 Perfefm-_ ‘A5 '21 result, eleek 111 the hydrauhe
System Where these‘ ?uids are used 18 llkely to lead i0 2111
limitations include large changes in viscosity with
changes in temperature, and a high solvent power for
ejection of the hard which may take the form of an 011
rubber parts of the hydraulic system
mlsf- C'e?s'equen?y; fhefe eXlStS the dange? Of an 1nThe organic phosphates or rather a great number of
flammatlon of the oil and even an EXPlOSIOQ haZaI'd 20 individual members of this class were studied exten
Whe? maehlne Perle“ m§tena1_S-_heeled t0 hlgh ten?
sively. As a result, there were found large groups of
Pereltm'eS are 111 ttlfle lmlTledle'ie vlellllty 0f the hydl‘alllle
alkyl phosphates, aryl phosphates, alkyl aryl phosphates
sys'iem- I11 PF?eUeer l-hle ease eeeu‘fs Very frequently,
and mixed phosphates which proved to have some satis
for example 1H steel mills, particularly 1n rolling or
factory properties.
flattening end Shaping op'eretlens as Well as 111 the press- 25
Organic esters of phosphoric acid are the most fre
mg, etemplng and Pullehlf_lg of metal lgleeee Therefore,
quent members of this class but esters of other acids
the Eff-‘Peril’ 0f lJemg unln?ammable 1S hlghly deslrable
of phosphorus, such as the phosp-hites and phosphonates,
fol‘ hydraulle _?1l1d-
.
_
were also proposed for use and applied alone or in mix
The following properties are generally desired of a
tunes,
hydr?lllle ?uid?»
30
Among the phosphates, the tertiary ones are the most
Lubricating properties such as a viscosity adapted to
the application, slight changes in the viscosity with
changes in the temperature and good ?lm strength;
Resistance to ?ames as provided by low vapor pressure
frequently used materials. Theoretically, all these phos
phatcs may be suitable but certain physical properties
‘such as the solidi?cation point, the boiling point and
the volatility, impose limitations on these compounds
‘and a high ilash point;
35 which render it necessary to carefully select the size of
Good chemical qualities such as resistance to deterithe hydrocarbon radicals. The corrosive action of these
oration and chemical inertuess to the components
materials, which is due to a hydrolysis of the esters,
of hydraulic systems; ‘and
varies from compound to compound but places also a
Certain special properties such as a, negligible compractical limitation on these compositions. Of the
pressibility and non-toxicity.
40 various possible substituents, the aromatiosubstituents
Numerous compositions have been proposed for use
"s uniniiammable hydraulic ?uids.
“ Af
L.
.
.
.
prevail-to be title bait Wm; {esp?ct 10 "the ehmmatlon of
aggresdv?ness- OWar S me a s‘
. ~
r0 amps to Oils based on
atroleum b
.
.
Representative examples of trralkyl phosphates include
ter attempting to impart the missing ?re-resistant
.
inco: oration
.
the phosphates whose alkylrad1cals contam 4 to 12 car
p p . ".
. . .
p
.
y
. rp
45 bon atoms, such as trihexyl phosphate, triamyl phosphate,
of
such as drphenyl amine or . lead
.
.
t oxidation inhibitors,
.
.
tridodecyl
phosphate, and the branched isomers
thereof
etra-ethyl or various. ?ame-proo?ng
agents,
. homologues, such as the trrcyclohexyl
.
.
. the Oll 1n.
as well as cyclic
dustry proposed various formulauo-ns which met with
yo 1 ss success
.
These formulations can be divided
phosphate and the m Z'ethyl hexyl phosphate’
gi?ri’?vg 1; e classés
vo
g
J _
Aqueous comPoeltlofls
QIYCOIS and 'denvatlves
511mm?“
‘
50
The group of the aryl and alkyl aryl phosphates is
represented for example, for triphenyl phosphate, tri
cresyl phosphate, trixylenyl phosphate, diphenyl xylenyl
phosphate, and diphenyl cresyl phosphate.
_
Examples of mixed phosphates include the dioctyl
chlonfleted deTlVatlVee
phenyl phosphate, butyl cresyl octyl phosphate and
Ofgame Phesphetes
55 dibtuyl cresyl phosphate.
The ?rst mentioned materials have limited applicability
The properties of some of these phosphates are listed
in view of the low boiling temperature of water. Acin Table I.
TABLE I
.
Name
Viscosity
Structure
Tri-n-butyl-phosphate ............ _-
Molec-
Density
incenti-
F.P.,
ular
at 20° C
poises
at 20° 0.
° 0.
'
Manufacturer
Refer
ences
266
0. 978
3.4
398
1.022
12.2
436
285
0.926
1. 41
14.1
44
(CuH50)3EPO .................. .-
326
1- 268
........ ._
Cresyl~diphenyl-phosphate _______ -.
(CtHsO)z-(CtH4CHs—O)EPO-__-
340
1.208
39.8.
Tri-cresyl-phosphate _____ __
(CHs-CuH4—-O)3EPO
_
368
1.17
90
_
354
1.19
_
_
410
362
1. 14
1.092
230
21,
Do.
O-xenyl-diphenyl-phosphate ______ __ (C5H5—'C0H40)(C6H5O)2EPO____-
402
1.233
30
D0.
Tr‘Kpter-butyl-phenyl) phosphate. (Cl?wCtHrOhEl’O ......... ..
495
Tri(butyl-ee1losolve)phosphate..."
'l‘z-i (Z-ethyl-heryl) phosphate
Tri~chlor-ethyl-pl1osphate_-
(CqC17—O)sEPO
(ClCHzI
Tri-phenyl-phosphate ____ _-
Di-phenyl vylyl-phosphate.
Tri-xylyl-phosp‘nate __________ _2-ethylhexylediphonyl-phosphat
_.
((QnI-IQnCHMCBHcO)
_
CH3) 2- CBHQOBEP O
CsHrrO)(CsI-I5O)zEPO._
._
Comm.Solv Co_____ Kirk.
-
0 ______________ __
Do.
Carbide ___________ __
Hoeehshliayer
O
Do.
‘
Dow, Mon.,
D0.
.
D0.
70
Do.
3,074,889
'
3
Unfortunately, these organic phosphates have a very
unsatisfactory viscosity index. Furthermore, they have
isomers are preferable to ortho cresyl phosphates. The
sometimes a poor ?lm strength, which results in un
usually high wear in certain types of apparatus such as
melting point. if harmful effects due to a low melting
gear pumps.
' It is therefore an object of the present invention to
isomer or the xylyl, xenyl or phenyl derivatives.
provide hydraulic fluids which avoid the shortcomings
of the known hydraulic ?uids.
‘ Another object of the present invention is to provide
ful phosphate because it is not toxic and satisfactory
paracresyl phosphate, however, has a substantially higher
point are to be avoided, one has to use the pure para
The diphenyl xylenyl phosphate is certainly a very use
from the standpoint of its physicochemical characteristics,
hydraulic ?uids having a low volatility (see French 10 which are very close to those of tricresyl phosphate.
The trixylenyl phosphate is like wise non-toxic but
Patent No. 1,104,423 page 2, and Rev. Prod. Chim.,
it has a higher viscosity at 20° C. than TCP. It is also
61(1249), page 207 (31/5/19520).
less known.
A further object of this invention is to provide by
The other phosphates cited above are likewise not
draulic ?uids having maximum fire resistance.
Still another object of the present invention is to 15 available in large quantities and therefore more di?i
provide hydraulic ?uids the viscosities of which meet
cult to utilize. Nevertheless, there exists an interest
in these compounds and our experiments have shown
the usual speci?cations, i.e. 150 to 300 SSU at 100° F.
that they are capable of replacing advantageously the
(see British Patent 671,408).
above-described phosphates.
A further object of the present invention is to provide
hydraulic ?uids having reduced corrosiveness.
The list of phosphates given is not to be considered
20
A further object of the present invention is to provide
as limiting the present invention but intended to show
hydraulic ?uids exhibiting the exceptional combination
some representative members of the class consisting of
of a high viscosity index, a high ?lm strength and a
the triaryl phosphates to which we refer.
viscosity range permitting to meet practically all speci~
?cations, i.e. 150 to 1200 SSU at 100° F. (see British
Patent 712,062, page 2, ?rst column, line 55).
Still further objects will appear hereinafter.
The vinyl polymer used in the practice of this invention
is distinguished by a combination of particular properties.
(1) Its miscibility with the other components and in
particular with the triaryl phosphate generally represent—
I With the above objects in view, the present invention
ing more than 80% of the composition.
provides hydraulic fluids comprising a major proportion
(2) Its pronounced effect on the viscosity-temperature
of an aryl phosphate and minor proportions of a medium 30 curve; more particularly, the important increase in the
molecular weight vinyl copolymer and of a halogenated
viscosity index produced by this material. The viscosity
in accordance with a preferred embodiment of the
index is a measure of the change in viscosity observed
between two standard temperatures, i.e., 100° F. and
alkyl phosphate.
present invention, there is provided a hydraulic ?uid
210° B, using two standard samples of pure mineral oils,
which comprises at least about 80%, preferably about 35 one of these oils showing a minimum variation and
90 to 95 % by weight of a triaryl phosphate, about 5 to
having a viscosity index of 100 and the other oil show
10% by Weight of a chlorinated alkyl phosphate con
taining less than 8 carbon atoms per alkyl group, and
up to about 5% by weight of a vinyl chloride-vinyl acetate
copolyrner, said copolymer having a molecular Weight
Within the range of 5,000 to 25,000 and cantaining about
80 to 90% by weight of chloride and about 10 to 20%
ing a maximum variation and having a viscosity index
of 0, the viscosity at 210° F. being the same for both
oils.
40
(3) Its elevated intrinsic viscosity in the ester phos
phate, i.e. its important thickening effect at low and
medium temperatures, which makes it possible to cover
by weight of acetate.
Any suitable aryl phosphate may be used in the prac
tice of the invention, the term “aryl” designating a radical
polymer.
which contains an aromatic nucleus regardless of the
composition.
a wide range of viscosities by small additions of the
(4) its bene?cial effect on the ?lm strength of the
existence, the position and the nature of side chains.
(5) Its good resistance to mechanical stress.
Experience has shown that it is very di?icult to ?nd
such a polymer which is miscible with the aryl phos
phates and the molecular weight of which is within the
phosphat (T.C.P.), diphenyl xylenyl phosphate, and tri~ 50 range of 5,000 to 25,000, considered to be the optimum
xylenyl phosphate. Other known aryl phosphates which
range by the one skilled in the art.
can be used are: dicresyl phenyl phosphate, diphenyl
‘In order to solve the problem of solubility, some
cresyl phosphate, diphenyl ethyl phenyl phosphate, and
authors have proposed the use of a third solvent (solu
diphenyl ortho xenyl phosphate.
tizer) such as the chlorinated biphenyls and the alkyl
The radicals quoted have the following structures:
phosphates with a lower molecular weight. Other au
Cresyl or tolyl: GHQ-((361415)
thors have defined structural conditions to be met by
Phenyl: (C6H5)—
homo or copolymers of acrylic compounds in order to
obtain a good miscibility without losing the effect on
Xylenyl or xylyl: CH3
Some of the aryl phosphates suitable for formulating
the hydraulic ?uids of the present invention have already
been named and include triphenyl phosphate, tricresyl
(Coils)
the viscosity index.
60 ' In fact, the eifect on the viscosity index is somewhat
in
disagreement with the miscibility because this effect
is, in the ?nal analysis, accounted for by variations in
The tn'phenyl phosphate can normally not be used
because it is solid at ordinary temperature.
The tricresyl phosphate is certainly the best known ester
phosphate. The commercial tricresyl phosphate is a
mixture of tri ortho cresyl phosphate, tri meta cresyl
phosphate, tri para cresyl phosphate, and mixed phos 70
phates in which the tri ortho cresyl phosphate predomi
nates and in which the mixed phosphates are present
in minor quantities. It should be noted that ortho cresyl
phosphate is considered to be somewhat toxic (see British
Patent 681,357) and that the mixtures of the para-meta 75
the solubility with changing temperature. The increase
in solubility with rising temperature is accompanied by
an unwinding (straightening) of the polymer molecules
which in this form exhibit a maximum activity in the
homogenous system; in particular there is obtained a
maximum intrinsic viscosity .or, stated differently, the
strongest thickening effect.
At low temperature the molecule contracts to a point
where it changes from the dissolved state to the dispersed
state, thus giving a reduced viscosity and sometimes even
a very small viscosity. In other words, the thickening
effect is considerably smaller than at high temperatures,
if not zero.
'
3,074,889"
5
Accordingly, there is no superimposition of two in
verse viscosity curves but an increase in the thickening
effect with rising temperature and, as a result, a decrease
in viscosity differences due to an indirect effect.
‘It is by no means surprising in this situation that a
group of well-de?ned polymers must have a particular
structure in order to obtain a thickening effect and a sub
6
relatively short chains containing halogen substituents,
such as for example trichloro ethyl phosphate.
This product does not act as a third solvent (solutizer)
since solubility experiments with the polymer have shown
that compatibility exists also in‘ the absence of this prod
uct. The functionvof this material is an extreme pressure
effect.
.
Very surprisingly, we have found that the combination
stantial improvement of the viscosity index.
of the trichloro ethyl phosphate with the above de?ned
In particular, it is not at all surprising that compounds
vinyl chloride/vinyl acetate copolymer results in an un
used for improving the viscosity index of mineral oils 10 expected increase in the extreme pressure properties of
cannot be utilized for the same purpose with organic
the composition and brings about a remarkable and un
phosphates and, in particular, aryl phosphates.
expected decrease in- wear.
We have indicated hereinabove the optimum range of
In fact, it has. been found in accordance with this inven
5,000 to 25,000 for the molecular weight. It is generally
tion
that, the individual effects of the trichloro ethyl phos
recognized that a molecular weight of 5,000 must be 15 phate and the vinyl chloride/vinyl acetate copolymer are
reached in order for the polymer to exercise a sufficient
rather limited whereas the combination of the two prod
in?uence on the viscosity index of the ?uid base material.
uc'ts makes it possible to considerably exceed the resistance
On the other hand, it is generally accepted that the poly
to seizure (as measured with the 4'-ball EP tester) and
mer must have a molecular weight lower than 25,000 and,
the antiwear properties brought about by the individual
if possible, ‘lower than 15,000 in order to exhibit a good 20 components. This indicates an unexpected synergistic
resistance to breakage, i.e. degradation by mechanical
effect.
actiont
It follows from the above that the vhydraulic ?uid com
Within the above range of molecular weights, certain
position of the present invention exhibits a combination
homologues of some series of polymers give satisfactory
results in the absence of a third solvent with triaryl phos 25 of- properties distinguishing it over the known formula-~
tions.
phate's, such as tricresyl phosphates.
‘ The proportions of the components of the hydraulic
Thus, it was shown that there exists an optimum num—
fluids
of the present invention can be derived quite easily
ber of carbon atoms in the alkyl chains of alkyl poly
from‘.
the
above disclosure.
acrylates (see French Patent 1,138,794) and that outside
As stated above, the triaryl phosphate is the major com
this range the eifect on the viscosity index decreases or 30
ponent. It is preferably present at a concentration of at
complete insolubility of the polymer is observed.
least about 80% by weight and‘ evenv more preferably at a
Numerous other polymers have been described as be
concentration
between about 90 and‘ 95% by weight.
ing- capable of bene?cially acting on the viscosity index
The halogenated alkyl' phosphate is used in an amount
but the experience has shown that these products are
' sufficient to produce the desired extreme pressure effect as‘
elfective only if used with a third solvent (solutizer).
well as a decrease‘ in wear. It has been found inv accord
Thus, an alkylated polystyrene of a molecular weight
ance with this invention that the most preferable concen
of 60,000 can be used with a mixture of TCP and chlo
tration of trichloro ethyl phosphate ranges from about 5
rinated diphenyl, said mixture containing 40% TCP.
to about 10% by weight.
Polyisobutylene was also described as being suitable for
The polymer is added in the amount required to obtain
use in mixtures of organic phosphates containing in addi
the desired viscosity. It is advisable to avoid concentra
tion to a triaryl phosphate 65 to 85% of a trialkyl phos
tions above about 5% by weight which could have an
phate, the alkyl group of which has less than 12 carbon
atoms (see British Patent 692,172).
The polyoctyl methacrylate of the molecular weight
10,000, sold by Rohm & Haas under the designation
adverse effect on the ?re resistance.
If high viscosities are required, copolymers of the high
est molecular weight (within the range specified above)
Acryloid HF 855, can also be used with a mixture of
are used because they produce the greatest thickening
organic phosphates containing in addition to tricresyl
effect.
phosphate 80% of trioctyl phosphate (see British Patent
671,408 and Ind. Eng. Chem. (1951)).
The same product can also be used with a- mixture of 50
Table ‘II lists the viscosities, expressed as degrees Eng'lcr
at 50° C., of mixtures of tricresyl phosphate-with various
quantities of the copolymer.
TCP and chlorinated diphenyl known by the trade name
TABLE II
Aroclor 1248 (Monsanto) containing 48% of diphenyl
(see British Patent 744,544).
However, it has been found that all these products
when combined with tricresyl phosphate without a third 55
solvent are incompatible with the latter and therefore
inoperative.
The same is true of polyvinyl chloride, polyvinyl ace
fate and polyvinyl buty'ral when using materials having a
60
molecular weight within the range of 5,000 to 15,000.
Very surprisingly, it has now been found in accord
ance with the present invention that copolymers of vinyl
chloride and vinyl acetate containing about 80 to 90%
by weight of the chloride and about 10 to 20% by weight
Amount of
polymer
in percent
by weight
Polymer:
Polymer:
Polymer:
Polymer:
87 Cl
13 ac,
mol.
87 0-1»
13 ac,
mol.
90 O1
10 ac,
mol.
90 Cl
10 ac,
11101.
weight
n eight
weight
Weight
6,000
10,000
16,000
24,000
0‘
1
2
2.8
3. 4
4. 4
2. 8
4. 2
6. 5
3
5. 4
10. 5
,
_
2. 8
4. 5
7. 3
13
2. 8'
5_. 4
l1
1,8. 6
Norn.-C1=chloride, ac=.acetate.
To the basic formulation of the present invention known
of the acetate are completely compatible with tricresyl 65 additives, such as corrosion inhibitors, may be added, if
desired. These additives confer their Known properties to
phosphate without the aid of a third solvent (solutizer)
the novel formulation without in any way charging the’
and that these copolymers ‘are at the same time very
character of this invention.
'
'
effective as viscosity index improvers and thickening
The present invention contemplates also the presence
agents, Furthermore, these copolymers confer extreme
70 of minor amounts of functional groups, of substituents in
pressure properties to hydraulic ?uid compositions.
the copolymer, such as maleic anhydride and dibasic acid
The halogenated alkyl phosphates used in the practice
radicals. Such compounds are sometimes added in small
of the instant invention are characterized by the presence
amounts to the copolymer of vinyl chloride and vinyl
of a su?iciently labile halogen atom, preferably chlorine.
acetate in order to improve the adhesiveness of the resins
Representative examples of such compounds’ are alkyl
phosphates, the alkyl groups of which are formed by 75 in cases where they are used in protective coatings.
C42)
7
!_ ?
The following examples are additionally illustrative of
53
‘
the present invention but are not to be construed as limit
ing the scope thereof.
'
TABLE IV
ProdnctslGlHJI’J'K’L
Example 1
Tricresyl phosphate,
A series of mixtures of a vinyl chloride/vinyl acetate
copolymer with tricresyl phosphate was prepared.
The copolymer was a “Bakelite” resin of Union Carbide
known under the designation VYHH-l and possessed the
following characteristics:
Weight percent of vinyl chloride ____________ __
Weight percent of vinyl acetate _____________ __
percent _________ __
Trichlorethyl phos
phate, percent____
Viscosity:
96
9O
80
50
0
0
4
10
20
5O
100
SSU at 100° F__
192 ______ __
SSUat210°F__
10 Visc0sityindex_____
Neg. ______ ..
87
13
42
168
________ __
148
109
73
41
40
37.9
35.5
Neg.
Neg.
Neg.
Neg.
Example 3
Compositions containing 85 to 90% by weight of tri
cresyl phosphate, 10% by weight of trichloro ethyl phos
phate and rising amounts of vinyl chloride/ vinyl acetate
copolymer were prepared following the procedure de
scribed in Example 1.
The products used had the following characteristics:
Tricresyl phosphate “ABRAC” of Boake Roberts 8; Co.
Molecular weight _________________________ __ 10,000
Density at 15° C _________________________ __
1.36 15
. The tricresyl phosphate was a commercial product of
Boake Roberts and Co. (London) designated “ABRAC.”
it consisted of a mixture of the three cresyl isomers and
had the following characteristics.
Density at 15° C ___________________________ __ 1.13
(London)—-—
Viscosity:
SSU at 100° F _________________________ __
SSU at 210° F _________________________ __
10D
156
40>
Density _______________________________ __ 1.15
Viscosity:
Viscosity index __________________________ __ Negative
SSU at 100° F ______________________ __ 193
SSU at 210° F. ______________________ __ 42
The mixtures were prepared by dissolving increasing
amounts of the polymer in about 100 grams of tricresyl
phosphate. The relative proportions of the two compo
Viscosity index ____________________ __ Negative
Trichloro ethyl phosphate of Hoechst
nents are expressed as percent by weight based on the 30
weight of the mixture.
The polymer was introduced into the phosphate heated
Density _______________________________ __ 1.41
>
Viscosity:
to a temperature of 60° C. The mixture was agitated for
SSU at 100° F. ______________________ __ 76
5 to 10 minutes and allowed to cool down to ambient
temperature over a period of 2 to 3 hours.
The cold mixture was examined as to homogeny and
‘Viscosity index __________________________ __ 37
SSU at 210° F. ______________________ __ 36
physicochemical measurements were made if the sample
was homogenous.
The characteristics of the mixtures obtained were tabu
lated in Table III.
Vinyl
A
‘acetate
copolymer
“Bakelite
Density _______________________________ __ 1.36
Molecular weight _____________________ __ 10,000
40
TABLE 111
Products
chloride/vinyl
VYHH-l” of Union Carbide
Weight percent of vinyl chloride ____________ __ 87
Weight percent of vinyl acetate _____________ .._ 13
B I C I D ‘ E I F
The properties of the compositions obtained are tabu
Percent T.C.P___ __
100
99. 30
98. 45
97. 80
97. 40
96. 80
Percent polyrnernn
Engler at 50° C_._._
Engler at 100° C____
0
2. 69
1. 33
0.70
3. 59
1. 46
1.55
5. 17
1. 61
2. 20
0. 63
1.78
2. 60
7. 99
1.90
3. 20
10.28
2.13
SSU at 100° F ____ ._
156
216
317
440
544
717
45 lated in Table V.
TABLE V
SSU at 210° F__ __
Viscosity index. .___
41
Neg.
47
85
52
85
58
85
63
88
Density at 15° C____
solidi?cation point:
1.14
1.15
1.15
1.15
1.15
1.15 50
73
91
° C ___________ __
° F ___________ -_
—26
—15
—-23
—9
—-23
—9
-—23
—9
——23
—9
—23
Example 2
Binary mixtures of tricresyl phosphate with trichloro
Products
J
M
Trichloro ethyl phosphate of Hoechst
Density _______________________________ __ 1.41
Viscosity:
SSU at 100° F _______________________ __ 76
SSU at 210° F _______________________ __ 36
Viscosity index __________________________ __ 37
The compositions obtained had the characteristics listed
in Table IV.
P
Q,
R
S
90
89.2
89
88
87.7
87.3
87
phate, percent_...
10
10
10
10
10
1O
10
10
percent _________ __
0
1
2
2.3
2.7
3
3.4
1.13
1.18
1.18
1.18
SSU at 100° F_.
168
219
222
344
436
566
597
717
ssU at 210° F_.
41
45
4s
53
59
68
as
75
Viscosity index.-." Neg.
57
G1
83
89
101
95
99
0.8
55 Density at 15° O___ 1.18 1.18 1.18 1.18
Viscosity:
'
(London)
SSU at 100° F ______________________ __ 193
SSU at 210° F. _____________________ __ 42
Viscosity index _____________________ __ Negative
O
Tricresyl phos
phate, percent____
Trichlorethyl phos
Polymer VYEZl-Ll,
ethyl phosphate were prepared at different concentrations.
The products utilized had the following characteristics:
Tricresyl phosphate “ABRAC” of Boake Roberts & Co. 60
Density _______________________________ __ 1.15
Viscosity:
'
N
86 o
Example 4
The lubricating power of the compositions described in
Examples 1, 2 and 3 under conditions of extreme pressure
65 were tested in the frictometer by Boerlage, also referred
to as 4-ball EP tester.
A description of this machine and a discussion of the
results obtainable therewith can be found in the work by
Gro? “L’A B C du Graissage,” Ed. Institut Prangais du
70 Petrole, and in greater detail in papers published in “Gel
and Kohle,” vol. 40, number 1/2 of January 1944, pages
19 to 23, and in “Engineering,” number 136 (1933).
The Boeriage frictometer gives data on the wear at dif
ierent loads and a load limit at which seizure occurs.
The values obtained are listed in Table VI.
ante-e89
101
Example 6
TABLE VI
_
._
. _
Mtn-
,
Various aryl phosphates and vinyl copolymers can be
Ohlo-
TC]? plus:
TGP plus
TOP plus1
ri-
polymer
TGEP
TGEP plus
nated
'
used in place of the tricresyl phosphate and the‘ copolymer
represented by Bakel'iteVYI-lH-l as employed in the
preceding examples. Thus, compositions‘ made up of
the following products'were prepared:
polymer
Product leral diphen
oil
ylPy
Trixylyl phosphate
draulA~GBDFHILNOR
F0
Diphenyl xylyl
1
Vinyl chloride/vinyl acetate copolyrrrers containing 87%
chlorine and 1-3 % acetate
Molecular weight 6,000 such‘asBakelite VYLF
____ ____ -__- 1,28 0.80 -7.-- 0. 65 0.60 0.60
____ _»___
8 2,32 -___
2.00
S
S
0.
____ _,.__
.
Molecular weight 10,000 such as Bakelite VYI-lI-I-l
Molecular- weight 16,000- such as Bakelite VYNS-3
.__
1.10
2
-_._
____
Copolyrner from» 85% vinyl chloride, 13% vinyl acetate
and 1% maleic acid anhydride
2.00
Molecular weight 10,000 such as‘ Bakelite VMCH
The properties of some of these compositions are tabu
latediin Table VIII.
1' Complete‘wear.
TABLE VIII
Trichlorethyl phosphate,
percentnu, ______________ _
Tricresyl phosphate, percent
Trixylyl phosphate, percent.
Diphenyl xylyl phosphate,
percent _______ __v_p_l__-__
Bakelite VYLF, percent
Bakelite VYHHH,
Bakelite VYNS-3, perc'en _
Bakelite VMCH, percent..."
Density at 15° C __________ ..
Viscosity SSU:
10
21
F
Viscosity index. _ _
solidigl‘cation poin
Example 7
Example 5
Compositions containing:
Some compositions accordingv to the present invention
were compared to various known hydraulic ?uids.
The hydraulic compositions of the instant invention
differ markedly from the known compositions in some
particular and unexpected properties.
(a) 89% of tricresyl phosphate, 10% of trichloro ethyl
phosphate and 1% of a vinyl acetate/vinyl chloride co
polym'er (13/ 87 ) and
(b) 84% of diphenyl xylenyl phosphate, 15% of trichloro
ethyl phosphate and 1% of the above copolyrner,
Ta'ole V11 lists the comparative date obtained.
respectively
TABLE VII
Product:
Trioresyl phosphate, percent ..................... __
Trichlorethyl phosphate, percent...
._
Chlorinated diphenyl, percent_____
_
89
10
0
88,
10
0
86
10
0
480
48
01
0
8
92
0
8
Q0
0
10 ,
0
1
2
4
4
1
0
0
3
0
0
0
0
0
0
0
Insol.
Insol.
InsoL
Sol.
Insol.
89
10
0
88
10
0
10
._
0
0
Vinyl copolymer, percent ________________________ ._
1
2
S01.
S01.
S01.
222
374
597
Methacrylate, percent _______ __
Characteristics:
Solubility __________________ _.
Viscosity: SSU at 100° F.
Viscosity index _____ __, _____ __
Seizure load: Measured with n tomete
0
61
86
95
350
400
450
Composition based on other vinyl polymers such as:
Polyvinyl chloride homopolymer, mo
lecular weights _______________ __ 16,000 and 24,000
Polyvinyl acetate ho-mopolynier, mo
lecular weights _______________ __ 16,000 and 24,000
Polyvinyl butyral homopolymer, mo
lecular weights _______________ _._ 16,000 and 24,000
_
~
7
251
150
0
Sol.
_ i
4-4
_
0
0
100
_
156
157
i cg.
Neg.
150
150
275
’
,
200
were subjected to a series of. tests designed to demonstrate
their hydraulic ?uid quantities. The components were
those described in the preceding experiments.
(A) FIRE RESISTANCE Test‘
The two compositions gave very similar resultsv in these
tests.
We used a little oven heated by gas, the crucible of
are insoluble in tricresyl phosphate, diphenyl xylyl ph0s~
had a diameter of 20 cm. and contained 25 kg. of
phate, trixylyl phosphate, and in mixtures of these phos 75 which
an aluminum alloy in the molten state. The temperature
phates with trichloro ethyl phosphate
ans/dean
l l“
12
was measured with the aid of a thermocouple immersed
at a short distance below the surface of the molten metal.
small ?ame localized in the immediate surroundings of the
torch and assuming the form of the latter.
It must be emphasized that the ?ame formed by the
fluid is immediately stopped after the ejection of the ?uid
A hydraulic multiple-piston pump conveyed the ?uid
under pressure to a point 75 cm. from the spout of the
crucible. The maximum e?iciency of the pump was ‘1.4
liter per hour at a pressure of 140 kg./cm.2.
was turned o?. In contrast thereto, a known hydraulic
?uid continued to burn until the product was completely
consumed.
In each of the following tests the temperature at the
surface of the alloy was 630° C.
(B) DETERMINATION OF FILM-STRENGTH TESTS
TEST NO. 1
TEST ON THE BOERLAGE FRICTOMETER
This test was designed to reproduce the conditions re
sulting from a rupture of a conduit of a hydraulic system.
Seizure:
Composition a,* 300 kg.
Composition b,* 350 kg.
The test consisted in having a sudden ejection of ?uid
under a pressure of 140 kg./crn.2 pass through an ori?ce
of a diameter of 1 mm., the jet being directed towards the
spout or" the crucible.
The jet of ?uid did not ignite at ori?ce pressures lower
After Example 7 .
FZG TEST ON THE NIEMANN MACHINE
This test involves subjecting a pair of gear wheels to
than 35 kg./cm.'~’.
At pressures above 35 kg./cm.2 the ?uid ignites im
increasing loads, said gear wheels being immersed in the
oil to be studied and rotating at a de?ned speed. The
mediately upon contact with the molten metal and the 20 test is continued until gripping of the gear wheels occurs.
?uid remaining in the crucible continues to burn after
A description of this test can be found in Erdtil und
shutting o? the jet. Although the ?ame was very in
Kohle, vol. 7, No. 7, pages 640 to 642 (October 1954).
tense in the immediate vicinity of the crucible, i.e. up to
The test was conducted under the following conditions
a distance of about one meter, the ?ame did not tend to
(Test A/8, 3/90):
spread out by following the direction of the jet or by going
back on the jet.
A considerable amount of vapor and smoke was evolved,
in particular at the maximum pressure of 140 kg./cm.2
when the e?iciency of the pump was 1.4 liter per minute.
Speed of rotation-2,175 rotations per minute,
Peripheral speed—V=8.3 m./scc.,
Sliding speed at the top of the teeth
30
TEST NO 2
-In order to reproduce a complete rupture of a tube of i
a hydraulic system, the total amount of liquid conveyed
|by the pump was suddenly directed towards the spout
of the crucible using a tube of a diameter of 9.5 mm.
Being under a small pressure, the jet did not stir up very
Vg=0.675, V=5.6 m./sec.
0.675-constant for the test A/8, 3/90,
Temperature of the oil at the beginning of the test: 90° C.
The results of this test are contained in Table IX.
Table IX also contains test results obtained with some
conventional oils.
TABLE IX
much the surface of the molten metal.
The ?uid did not ignite spontaneously but gave rise to
Gripping load
a considerable amount of thick vapor.
Level
Mo
of mentum
load (Rams)
A large proportion of the ?uid ?ew from the top of 40
the oven to the ?oor but did not ignite.
When we
Wear
Load
Spec.
factor
wear
(kg/sec.) (mg./Cvh.)
Wear
poured some molten aluminum in the puddle of liquid
Pure mineral oil..-
formed on the ?oor, no ?ame was formed.
The vapors formed could be ignited by a match thrown
m E p. A
into the crucible; the ?ames which rose were not as in
tense as in Test No. 1 and resembled the combustion of
vs
9. 84X10 5
mceowm
.‘a:
I
I l I
I
Oil for hypoid
I l I
I
1
gears (E .P.) .
such a material as paper or straw.
TEST NO. 3
13. 36x10 5
0. 22-0. 67
0. 08-0. 44
. 226-0. 66
0. 078—0. 43
0. 1
0. l
0. 08-1. 0
* After Example 7.
About one-quarter of a liter of ?uid was thrown by 50
hand on the molten metal in order to reproduce the con
ditions of an accidental spilling of hydraulic ?uid. The
fluid ignited and burned slowly.
We found that the ?uid burned when brought to a high
temperature but that the ?ame did not tend to go away
from the source of the heat (in this case the crucible
?lled with molten metal). We also found that liquid
ALMEN/WIELAND TEST
The Almen-Wieland machine consists of a steel pin
rotating between two bearing halves. The machine is
lubricated with the oil to be studied.
The steel pin is rotated at a constant speed by means
of an electric motor, suspended like a pendulum. The
bearing halves are subjected to loads increasing by 50 kg.
The rotary moment exercised on the driving motor by
the increasing loads gives a measure of the friction coef
?cient, which can easily be read from a dial (expressed
?owing down from the upper portion of the oven ex
tinguished immediately. At no time did the ?ame spread
over more than one meter from the crucible. Even the 60
as “friction force”).
most intense ?ame was of such a nature that an individual
A more detailed description of this test can be found
standing at a distance of 1.5 meter from the crucible
could endure it. In other words, the ?ame did not pre
vent the operator from approaching up to this distance
in “Schweiz. Arch. Angew. Wise,” vol. 21 (1955), pages
251-257, and 392-404.
in order to stop the pump or shut off the broken tube.
oil by the following factors.
This test characterizes the lubricating properties of an
In contrast thereto, the ?ames of a jet of hydraulic oil
derived from petroleum were, under the same conditions,
extremely intense and of an explosive character. Such
?ames could not be endured at a distance of 3.5 meters
from their center.
TEST NO. 4
This test consisted in ejecting the ?uid under pressure
onto the ?ame of an acetylene torch having a mean tem
The load at which failure of the pin occurs (gripping
or seizure). For a pure mineral oil this load is about
350 kg. The fluid (a)* did not give rise to failure even
at a load of 1700 kg. (maximum capacity of the ma
70
chine).
The friction coe?lcient or the friction load is expressed
in kg. The accompanying diagram shows the variations
in the friction coe?icient as a function of the load for
perature of 1800° C. (measured with an optic pyrometer).
various oils including the hydraulic ?uid (a)""'. It will
‘The ejection of liquid resulted in ‘the formation of a 75 be observed'that the latter is represented by a curve (F2)
3,074,889
located between that of a pure mineral oil (F1) and that
TABLE XII
of an extreme pressure oil of hypoid gears (F3);
.
The wear cause by the friction is expressed by the (16-
I
crease in the diameter of the pin, said decrease being ex-
.
Copper Irony Alumi
Fluid (1))‘
mm‘
81°“
C“ " Fe " A‘
pressed in mm. In the accompanying diagram curve U 5
'
.
'
'
‘
v
'
tit
represents the behavior of fluid (a) . '
g
(1)
(1)
The temperature of one of the bearing halves 18111635“
ured with a thermocouple. For the ?uid (a)‘* this tem-
Change in weight of
Inmates vewsne- 4-48
.
°~°3
0‘ 13
perature amounted to 177
Inization iigdgrr?y?
0.50
0.56 ______ __
'
.
L
d
.
_
‘ 1
.
corrosiomgrrum? Light. /
.
V
.
.
_
4
C. after 3,400 rotations and
‘
‘
at a load of 1700 kg. (curve T).
_
crease in neutral-
‘
crease
10
use
.ng er
BEHAVIOR TOWARDS SEALS
Dgglgiigfgiéég?i-tg-
Nil
0-13
“~43 '
°~°4
1.36 ...... _
‘
I
V
‘16's
(1)
.
.
yiscosity at 50., Q
The behavior of hydraulic ?uids (a)* and- (-b)* to-
'
‘5‘6
"6'7
""" "
19 6 ;
'
'
"""" “
032% ggglis?iégg
wards various materials used in seals and gaskets were
studied.
The results of these tests are contained in‘ Table X.
,_
Light
#1011) ____
______
o >
0-
0V ______ __
o ...... ..
15
‘Atte'r‘Exa‘niple
lVeryllght. 7'.»
* After" Example‘ 7.
TABLE x
,
Y
Test
Manufacturer
and designation
Nature of seal
Swelling
..
.
‘ Length,
hrs.
Temp.,
° 0.
Size,
percent
Vol.,
percent-
Weight,
percent
Natural-rubber ____________ ._ Dowty AMGO ........ ._
17b
70
27.8
Do ________ _.
Ronald 'I‘rist AR 32/13
Neoprene .................. _. Dowty AM 35_-_-._
170
170
70
70 ,
19'
57.
,
.
Butyl _____________________ ..
170
170
70
70 ‘
Ronald Trist R 1319...“
Thiokol ___________________ ._ Ronald Trist R850 ____ ._
170
170
70
70
Nitrile _______ _. ____________ __
170
70
‘
Ronald Trist R942
Dowty AM 40..-.
.
.
g
.
V
-
Ronald Trist L 01/13....
I
1.4
—2.3
,
,
-5. 0' a
91
.
91V
_
V
Butadiene acrylonitrile rub-
Dowty C 1000 ......... ._
her.
170
________ __
________ __
70
________ __
.
.
Conditionot
seal after test
,
once.
Do.”
‘
weakening
of abra
sionresistance.
142
1.07
Good;
_
Abrasion'r'eslstance
not a?ected.
1. 84
278
Good.
Conistiderable
87
t
8.5 -_ _______ __
SO
enlng.
weakening of abra
v
_
,sion resistance;
67.8
v
1 Generally
tendencygood
to ?ake.
Hardness
Before
Pei-buns. .................. ._
Freudenberg 21 P0/716__ '
100
100
as7
117
100
Silicone ____________________ _. Freudenberg 29 Si/519.-..
Te?on _____________________ ..
_
Freudenberg4Til520.;--
_
After
80
so
so‘
75
as
36
100
100
0.6
1.3 ~_
81
81
80
so
100
2. o' _
31
so
100
100
0.1
0.2 __
98
as
98'
98
100
6.2
9s
98
........ __
Experience hasvv shown that after three years of use
there was no trace of a‘ deterioration of the product or
(C) INSPECTION OF OXIDATION RESISTANCE
We examined the resistance of ?uids (11)“ ‘and (b)*
to oxidation and corrosion using standard procedure
5308-3 of the US. Speci?cation VV-L-791e (oxidation
test for oil). The test in question consists in heating 110
the material.
(D) CoMPREssmrLrrY
ccm. of the oil to be studied for 168 hours at a tempera
55
ture of 250° F. (121° C.) in the presence of various
metals while bubbling dry air through the oil (5 liters
per hour).
The variations in the compressibility coe?icient of hy-'
draulic ?uids (a) and (b) were studied as compared
with those of some conventional oils for hydraulic trans
missions. This test was conducted within a pressure
The results of this test are tabulated in Tables XI and
range of 0 to 1,000 lag/cm.2 and at temperatures of 10,
XII.
60 65 and 100° C.
‘After Example 7.
At each of these three temperatures the changes in the
volume of the sample were measured at rising and then at
TABLE XI
falling pressures.
Fluid (41)"
Copper
Iron
Alumi
alone
alone
num
‘These measurements led to the determination of a com
65 pressibility factor B de?ned by the equation
Cu -- Fe -- Al
alone
Corrosion ........ __
(1)
Nil
Nil
Change
in weight of
'
0.07
0
0
0.16
0.17
0.18
0. S
0.8
0
0
ti
Increase in Engler viscos
ity at 50° C. in percent__
(1)
0.05
____ __
0.8 .... ._
Nil
Nil
0
0
0.17
.... -_
-—1 do
tr? a).
0.8 .... _.
Deposits, precipitation,
gums, lacquers (resini-v
?cation) ______________ __
0
____ ._
0
____ ._
Table XIII contains the variation of the compressibility
factor as a function of the pressure at the three tempera
*After Example 7.
1 Very light.
75 tures in question.
aovaese
16
TABLE XIII
Pressure
kgJem.’ rel.
to>95% by-weight of tricresyl phosphate; about 5 to
10% by weight of trichloroethyl phosphate; and about
,1 to 5% by weight of a vinyl chloride-vinyl acetate
copolymer, said copolymer having a molecular weight
within the range of about 5,000 to about 15,000 and
containing about 80, to 90% by Weight of chloride and
about 10 to 20% by weight of acetate.
Isotherm
10° C.
Isothcr
65° 0.
Isotherm
100° C
4.57X10'5
4. 35X10‘5
at. 12><10—5
3.89><10-5
5. 50><10'5
5. 32Xl0-5
5.13X10"5
4. 93><10-5
6
0
5
5
400
3. 73><10-5
4. 7l><10-5
5 34><10"5
500
3. 5e><i0—5
4.43><10—5
5 05><1o—5
95% by Weight of diphenyl Xylyl phosphate; about 5 to
10 10% by Weight of trichloroethyl phosphate; and 1 to
0
100
200
300
49><10-5
20x10-5
91x10-5
63><10-Ls
000
3. 41><10-a
4. 25><l0~~5
4 name-5
700
800
900
1, 000
3. 28><10‘5
3.17X10-5
3. 07><10~5
3. 00X10"5
4.00X10-5
3. 75><10-5
3. 48X10-5
3. 21X10'5
4 47>(10-5
4 18x10‘5
3. 90><10—5
3. 69(10-‘5
6. A hydraulic ?uid consisting essentially of about 90 to
about 5% by weight of a vinyl chloride-vinyl acetate
copolymer, said copolymer having a molecular weight
Within the range of about 5,000 to about 15,000 and con
taining about 80 to 90% by weight of chloride and
about 10 to 20% by weight of acetate.
While the invention has been described with reference
to speci?c embodiments, it will be apparent to those
skilled in the art that various modi?cations may be made
7. A hydraulic ?uid consisting essentially of about 90
to 95% by weight of trixylyl phosphate; about 5 to 10%
by Weight of trichloroethyl phosphate; and about 1 to
‘5% by weight of a vinyl chloride-vinyl acetate copolymer,
said copolymer having a molecular weight within the
range of about 5,000‘ to about 15,000 and containing
about 80 to 90% by weight of chloride and about 10 to
and equivalents substituted therefor without departing
from the principles and true nature of the present inven
tion.
What is claimed by Letters Patent is:
1. A hydraulic ?uid consisting essentially of about
5-10% by weight of trichloroethyl phosphate, about 1
20% by weight of acetate. '
25,000 and containing about 80-90% by weight of vinyl
chloride and about 10-20% by Weight of vinyl acetate,
by weight of trichloro ethyl phosphate; and about 1 to
5% by Weight of a vinyl chloride-vinyl acetate copolymer,
said copolymer having a molecular weight within the
range of about 5,000 to about 15,000 and containing
about 80 to 90% by Weight of chloride and about 10
8. A hydraulic fluid consisting essentially at about 90
to 5% by weight of a vinyl chloride-vinyl acetate co 25
to
95% by weight of a triaryl phosphate; about 5 to 10%
polymer having a molecular weight of about 5000 to
and the balance of a triaryl phosphate.
2. A hydraulic fluid consisting essentially of about 30
5-10% by weight of trichloroethyl phosphate, about 1
to 20% by weight of acetate.
to 5% by weight of a vinyl chloride-vinyl acetate co
copolymer having a molecular ‘weight of about 5000 to
25,000 and containing about 80-90% by weight of vinyl
chloride and about 10-20% by weight or" vinyl acetate,
and the balance of tricresyl phosphate.
3. A hydraulic ?uid consisting essentially of about
5-10% by weight of trichloroethy-l phosphate, _‘about 1
I
9. A hydraulic ?uid consisting essentially of 89% of
.tricresyl phosphate; 10% of trichloro ethyl phosphate;
and 1% of a vinyl chloride-vinyl acetate copolyrner hav
35 ing an average molecular Weight of about 10,000 and
containing about 87% of chloride and 13% of acetate.
10. A hydraulic ?uid consisting essentially of about
84% of diphenyl Xylenyl phosphate; about 15% of tri
to 5% by Weight of a vinyl chloride-vinyl acetate co
chloro
ethyl phosphate; and about 1% of a vinyl chlo
polymer having a molecular weight of about 5000 to 40 ride-vinyl
acetate copolymer having an average molecu
25,000 and containing about 80-90% by weight of vinyl
chloride and about 10-20% by weight of vinyl acetate,
and the balance of a diphenyl Xylyl phosphate.
4. A hydraulic ?uid consisting essentially of about
5—10% by Weight of trichloroethyl phosphate, about
lar weight of about 10,000 and containing 87% of chlo
. ride and 13% of acetate.
45
1 to 5% by Weight of a vinyl chloride-vinyl acetate
copolymer having a molecular weight of about 5000 to
2,636,862
2,866,755
15,000 and containing about 80-90% by‘ weight of vinyl
chloride and about 10-20% by weight of vinyl acetate,
and the balance of a triaryl phosphate.
5. A hydraulic ?uid consisting essentially of about 90
References Cited in the file of this patent
UNITED STATES PATENTS
50
Watson _____________ __ Apr. 28, 1953
Tierney _____________ __ Dec. 30, 1958
OTHER REFERENCES
The Condensed Chem. Dict., 5th ed., Reinhold Pub.
C0., 1956, page 124.
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 258 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа