Note: Descriptions are shown in the official language in which they were submitted.
1045634
This invention relates to certain alkyl silane
derivatives which are useful as components of hydraulic fluids
and to hydraulic fluids containing such derivatives particular-
ly hydraulic fluids having high boiling point and vapour lock
temperatures.
Hyraulic fluids based on glycol ethers have been used
in, for example, vehicle brake and clutch systems for many years
and still remain the most commonly used type of fluid. However,
specifications of required quality standards laid down by
hydraulic systems manufacturers and non-commercial organisations
such as the Society of Automotive Engineers and the U.S.
Department of Transportation have become progressively more
severe. In particular, a need has arisen for fluids having
higher boiling points and, more importantly, higher vapour lock
temperatures both for the fluid as formulated by the manufacturers
and also for the fluid in the presence of water. Glycol ether
based fluids are known to be deficient in this respect due to
the hygroscopicity of the fluid which results in the absorption
of water from the atmosphere. This in turn reduces the boiling
point and vapour lock temperature of the fluid and with extended
use the water content of the fluid can build up to a level at
which the boiling point and vapour lock temperatures are reduced
to a dangerous extent. When subjected to heat, e.g. generated
by heavy braking, the fluid may boil or vaporise to a sufficient
extent to cause a serious brake malfunction.
Hydraulic fluids having low hygroscopicity have been
developed, based on glycol esters, to deal with this problem.
Such fluids are relatively insensitive to the effec$ of
atmospheric moisture, but are more expensive than glycol ether
based fluids and have certain technical disadvantages, e.g.
their viscosity properties are inferior to those of glycol ether
based fluids. Consequently, use of these low hygroscopicity
-2-
, .
1045634
fluids has been mainly limited to where the desirable properties
s~lch as high boiling point and vapour loc~ temperatures are
deemed to outweigh their disadvarltages. Other types of water
insensitive fluids have also been developed. Nevertheless,
manufacturers are still seeking new fluids which combine as
many as possible of the desirable properties of both glycol
ether based and low hygroscopicity fluids and, desirably, have
even higher boiling points and/or vapour lock temperatures than
the low hygroscopicity fluids.
Recently, there has emerged a growing tendency in
vehicle design to use a single hydraulic system to operate
equipment, such as power-steering, shock absorbers and krakes,
which hitherto were provided with separate hydraulic systems.
This has created serious problems in the formulation of
1C~ suitable fluids. The mineral oil based fluids hitherto used
in power-steering systems and shock absorbers are satisfactory
with respect to the nitrile and chloroprene rubber used for the
seals and gaskets in such s~stems but are highly detrimental to
the natural and styrene/butadiene rubbers used in the construction
2~ of hydraulic brake and clutch systems. This results in
excessive swelling of the latter seals which can lead tc a
- serious malfunction of the brake or clutch system. Conversely,
the fluids hitherto used in brake and clutch systems, which are
normally based on glycols, glycol ethers and/or glycol ether
esters, and which have operated satisfactorily in such systems,
have a detrimental effect on the nitrile and chloroprene r~bber
gaskets used in power-steering systems and shock absorbers
which can also lead to malfunctioning. In the case of vehicle
operation the characteristic of reliability in operation, which
is generally desirable in all mechanical devices, is increased
in importance to an absolutely essentir.l re~uirement by virtue
of safety considerations. The need has therefore arisen for a
1045634
fluid which can be used satisfactorily in a central system
controlling the operation of a number of different items of
equipment.
We have now found certain novel silicon derivatives
which are useful as components of hydraulic fluids, for hydraulic
brake and clutch systems and also for central hydraulic systems.
These derivatives exhibit improved rubber swell properties with
- respect to a variety of natural and synthetic rubbers used in
the construction of hydraulic systems and they are also relatively
water insensitive.
Accordingly the present invention provides alkyl silane
derivatives prepared by a process which comprises reacting a di-
or tri-chlorosilane of the formula:
fl
~ R - Si - Cl
X
; with a hydroxy compound of the formula HO-R -OH and a glycol mono-
ether of the formula:
HO ~ CH-CH -O ~ R
R
wherein:
(a) R is an alkyl group;
~b) R2 is a hydrogen atom or a methyl or ethy} group, and where
n is greater than one, each R2 may be the same as or different from
any other group R2;
(c) R is an alkyl group;
(d) R4 is the residue of a diol or polyol;
(e) n is an integer of from 1 to 10; and
(f) X is a chlorine atom or an alkyl group.
- 4 -
1045634
In another aspect of the present invention there is
provided a hydraulic fluid containing one or more alkyl silane
derivatives prepared by the aforesaid process.
In the case of alkyl silane derivatives for use
in hydraulic brake and clutch systems it is preferable for
the groups R and R to be relatively short chain alkyl groups,
e.g. containing from 1 to 4, more preferably 1 or 2, carbon
atoms, in order to minimise the rubber swelling effect
on the seals and gaskets used in such systems. However
when used in a central system it may be more desirable to effect
a compromise between the requirements, often conflicting, for
5-
, . ~ , . . .
1045634
each of the various seal and gasket materials. In this case some,
or all, of the groups R and R3 may be longer chain alkyl groups,
e.g. up to 6, or even 8, carbon atoms.
In yet another aspect of the present invention there is
provided the process for the preparation of alkyl silane derivatives
which comprises reacting a di- or tri-chlorosilane of the formula:
Cl
X
with a hydroxy compound of the formula Ho-R4-oH and a glycol mono-
ether of the formula:
10HO ( CH-CH2-O ) R3
R
wherein:
~a) R is an alkyl group;
~b) R2 is a hydrogen atom or a methyl or ethyl group, and where
n is greater than one, each R2 may be the same as or different from
any other group R ;
~c) R is an alkyl group;
~d) R4 is the residue of a diol or polyol;
(e) n is an integer of from 1 to 10; and
(f) X is a chlorine atom or an alkyl group.
A dialkyl dichlorosilane may be reacted with a glycol
of the formula:
H-O ( fH-CH2-0 )n H
R
and the glycol monoether. Alternatively an alkyl trichlorosilane
may be reacted with a glycol of the formula:
H0 ( C~12 2 ~ H
and the glycol monoether. Reaction of the glycol and glycol mono-
ether with the alkyl chlorosilane may be carried out simult-
B
-- 6 --
iO45634
aneously in a single stage reaction. Such a single stage
reaction may be more convenient but is more difficult to
control and therefore sequential reaction is preferred, most
preferably employing the glycol in the first stage.
In place of the glycol, a dihydroxy benzene, such as
p-hydroxyphenol, or other diols such as neopentyl glycol, or
a polyol such as trimethylol propane, pentaerythritol,
dipentaerythritol, or a trihydroxy benzene may be used. In
this case the product may bear one or more residual
hydroxyl groups. Alternatively, sufficient chlorosilane may
be used to react with all the hydroxyl groups of the polyol.
In the preparation of the hydraulic fluid components
of the pTesent invention, the reaction of a chlorosilane with
a hydroxyl group may be carried out in the presence of an acid
acceptor to neutralise liberated hydrogen chloride. Especially
preferred acid acceptors are tertiary bases such as pyridine.
To ensure substantially complete conversion it is usually pre-
ferred to use a slight, e.g. 10%, excess of the glycol monoether
starting material.
The alkyl silane hydraulic fluid components may be
used as an additive, as a base stock or as a component of a
blend of base stocks. The proportions employed may therefore
vary over a very wide range. When used as a base stock the
alkyl silane derivatives will constitute the bulk of the
hydraulic fluid, for example from 75% or 80% to 99%
by weight, based on the total weight of the hydraulic
fluid. The remainder of the hydraulic fluid may be composed
-7-
1045634
of conventional hydraulic fluid additives, as more fully
described hereinafter, and/or small quantities of other
hydraulic fluid base-stocks, as also more fully described
hereinafter.
When used as a component of a blend of base stocks
the total blend of base stocks will likewise constitute the
bulk of the hydraulic fluid. In this case, the base stocks
may be predominantly one or more alkyl silane derivatives
blended with a lesser quantity of one or more other base
stocks, of the type hereinafter described, so as to modify
the properties of the alkyl silane derivatives. Thus
the hydraulic fluid may contain, for example 55% to 70% by
weight of one or more alkyl silane derivatives based on
the total weight of the hydraulic fluid. Alternatively,
one or more other base stocks may be modified by blending with
a lesser quantity of alkyl silane derivatives so that the
hydraulic fluid contains, e.g. from 20% to 40% by weight
alkyl silane derivative. In addition, a compromise between
the properties of the alkyl silane derivatives and the other
fluids may be effected by blending in approximately equal
quantities to provide fluids containing from 40% to 55%
alkyl silane derivative.
When used to suppress the sensitivity of hydraulic
fluids, and in particular the boiling point and vapour lock
temperatures of the fluids, to water the alkyl silane
derivatives are preferably used in amounts in the range of 20%
to 55%, more preferably 20% to 40%. Alternatively but less
preferably, an improvement can also be obtained using lower
amounts of the alkyl silane derivatives, e.g. from 0.5% to
15% or 20% by weight based on the total weight of the hydraulic
fluids. The bulk of such fluids will be constituted by one or
more base stocks as hereinafter described.
8-
1045634
When the alkyl silane derivatives are used as
a component of a blend of base stocks the resulting hydraulic
fluids may contain conventional hydraulic fluid additives in
like manner as when the base stock substantially consists of
the alkyl silane derivatives. Similarly, when used as an
additive the alkyl silane derivatives may, if desired, be used
in conjunction with conventional hydraulic fluid additives.
Base stocks with which the alkyl silane derivatives
may be blended, or with which they may be used as additives,
include glycols, glycol ethers, glycol esters, glycol
orthoesters and borate esters. Glycol ether base stocks are
well known and suitable examples thereof are those commonly
used in hydraulic fluids. The preferred glycol ester base
stocks are those having the general formula:-
~ COOR ~ OR ~ OR
R6 and/or R9-C-O~ R10O) C-R9
O O ~ .. Y .,
- COOR ~ OR 3XOR O O
I II
wherein R6 is a straight or branched chain alkylene group
containing at least 2, preferably 2 to 8, carbon atoms each R7
is the same or different and is an alkyl radical containing
from 1 to 4 carbon atoms or a phenyl radical, each R8 is the
same or different and is an ethylene, propylene or butylene
group, each x is the same or different and is 0 or an integer
of from 1 to 3, each R9 is the same or different and is an
ethyl or methyl group, each R10 is the same or different and
is an ethylene or propylene group and y is an integer, preferably
an integer such that the total number of carbon atoms in the
~R10O3 y group is from 4 to 12, more preferably 4 to 9.
The dicarboxylic acid esters of formula I are described
in British Patent Specification No. 1083324. Esters which may
g
1045634
suitably be used in the present invention are the succin~tes,
glutarates, adipates, azelates, sebacates, isosebacates and
- nylonates of methyl, ethyl, propyl and butyl monoethers of mono,
di- and tri-ethylene glycols described in ~ritish Patent
Specification ~o. 1083324, the nylonates, especially di mono
methyl ether o~ diethylene glycol nylonates, being particularly
- preferred.
The glycol di-esters of formula II are known compounds
and the preferred glycol di-esters are the glycol dipropionates
described in British Patent Specification ~o. 1249803. It
is preferred that the hydraulic fluids comprise not more than
50~ by weight of the glycol di-esters; the remainer, if any,
of the carboxylic acid ester component being the esters of
formula I.
~umerous varieties of borate ester base stocks are
known and these may be depicted by the following general formula:-
B~ rOR11 ~ oR12)3 III
R120--~R110)p . (OR11 ~ oR12
~0 ' \. /
B ~ 0 - B
j . \ . ..
R120 _~_ R1 1 o ) p \ (oR1 1~ '
R120 ~R1 10~p . . .
B - - R13
~ ~Q~ o~p / ~ q
R14
~ / x1~ VI
- ~~ \ R14 /
10.
~045634
R ~ ~ R14 ~ ~ 14 VII
,.... .~ ~
wherein each R 1 is the same or different and is a straight
or branched chain alkylene group, each R12 is the sams or
different and is an alkyl group, each p is the same Ol` different
and is an integer, q is an integer of from 2 to 6, R13 is the
residue of a di- or poly-hydro2y organic compound having a
number of reactive hydroxy groups equal to q, and each R14 is
the same or different and is the residue of a di-hydroxy
organic compound which residue is attached to each boron atom
via an 02ygen atom.
~hese borate esters are more fully described in
~ritish Patent Specification ~o. 1341901 to which reference may
be made for further details.
Further base stocks which may be used are the glycol
- orthoesters described in ~ritish Patent Specification No.
13~0468 having the general formula:-
oR 6 ~ o~R16 o,R.6 , ; !
~15 ~ - or~1 6 ~15 C -- R17 _ C - R15
o l 16 . o* 6 1R16
. . ~II . . - IX i
wherein R15 is a hydrogen atom, an alkyl radical containing
from 1 to 5 carbon atoms, or the same as OR16; each R16 is the
~ame or different ~nd each is an alkyl radlcal containing from
1 to 4 carbon atoms, an 02yalkylene glgcol monoether radical,
or a polyo2yalkylene glycol monoether radical containing from
2 to 20 alkylene 02y units, provided that at lea~t one R16 is
an 02yalkylene glycol monoether radical or a polyoxyalkylene
glycol monoether radical; and R17 is an alkylene radical
~0 contai ing from 1 to 12 carbon atoms, provided that R15 is then
the same as CR16 or R17 is the group ~0-R180~z, wherein each
R18 is the ~amc or different and ea~h i~ an alkylene radical
11. , ... .~. `
1045634
containing from 2 to 8 carbon atoms and z is an integer from
1 to 6. Reference may be made to British Patent Specification
No. 1330468 for further details of such glycol orthoesters.
In a particularly preferred embodiment of the present
invention the alkyl silane derivatives are used, as a base
stock, in hydraulic fluids also comprising a small amount,
e.g. 1% to 10% by weight, of a rubber swell modifier such as
an ethylene glycol.
In another particularly preferred embodiment of the
present invention the alkyl silane derivatives are used,
either as an additive or as a component of a blend of base
stocks, in hydraulic fluids comprising one or more glycol
esters of foregoing formulae I and/or II or comprising a
mixture of one or more glycol esters of foregoing formula I
and/or II with one or more borate esters of foregoing formulae
III to VII especially borate esters of formula III.
Typical additives which may be used in, or in
conjunction with, the alkyl silane derivatives are lubricity
additives selected from castor oil or castor oil treated in
various ways, for example:-
Firsts Castor Oil,
Castor Oil to Specification DTD72
Blown castor oil, i.e. castor oil blown with air
or oxygen while being heated.
Special Pale Blown Castor Oil, i.e. a similarly
blown castor oil.
"Hydricin 4" i.e. a commercially available ethylene/
oxide/propylene oxide treated castor oil.
Other lubricity additives which may be incorporated
in hydraulic fluids in accordance with the present invention
include borate esters e.g. tricresyl borate and phosphorus-
containing esters, especially phosphates e.g. tricresyl phosphate.
-12-
,~".,
1045634
The hydraulic fluids of the present invention may
also include minor proportions of polyoxyalkylene glycols or
ethers thereof e.g. those sold by Union Carbide Corporation
under the Registered Trade Mark "Ucon", particularly those
of the ~ and HB series. Suitable examples of these poly-
oxyalkylene glycols and their ethers and esters are given in
~ritish Patent Specification ~o. 1055641. Other suitable
lubricity agents are orthophosphate or sulphate salts of
primary or secondary aliphatic amines having a total of from
4 to 24 carbon atoms, dialkyl citrates having an average o
from 3~ to 13 carbon atoms in the alkyl groups, aliphatic
dicarboxylic acids and esters thereof, specific examples being
Diamylamine orthophosphate
Dinonylamine orthophosphate
t~ Diamylamine sulphate
Dinonyl citrate
Di(2-ethyl hexyl)citrate
Polyoxyethy]ene sebacate derived from a polyoxyethylene
glycol of M.W. 200
Polyoxyethylene azelate derived from a polyo~yethylene
glycol of M.W.200
Polyoxyethylene adipate derived from a polyoxyethylene
glycol of M.W. 200
Polyoxyethylene/polyo~ypropylene glutarate derived
from mixed polyoxyglycols of average M.W. of about 200
Glutaric acid
Azelaic acid
Sebacic acid
Succinic acid
~0 Di ethyl sebacate
Di 2-ethyl hexyl sebacate
Di iso octyl azelate
13-
1045634
Unsaturated aliphatic acids or their salts may also
be used e.g. oleic acid or potassium ricinoleate.
Corrosion inhibitors which may be used in the
present invention may be selected from heterocyclic nitrogen
containing compounds, e.g. benzotriazole and benzotriazole
derivati~.res such as those described in ~ritish Patent
Specification No. 1061904 or mercapto benzothiazole. MaLy
amines or derivatives thereof are also suitable as corrosion
inhibitors, for e~ample
di n-butylamine
di n-amylamine
cyclohexy-lamine
morpholine
triethanolamine
and soluble salts thereof e.g. cyclohexyl~mine carbonate.
Phosphites are also good corrosion inhibitors e.g.
Tri phenyl phosphite
Di isopropyl ph~sphite
and certain inorganic salts may be incorporated e.g. sodium
nitrate,
Other additives which may be included are antioxidants
- æuch as diaryl~mines e.g. diphenylamine, p,p'-dioctyl-
diphenylamine, phenyl-~-naphthylamine or phenyl-~-napht~yl-
amine, Other suitable antioxidants are th~se commonly known
as hindered phenols which are e~emplified by
2,4-dimethyl-6-t-butyl phenol
2,6-di-t-butyl-4-methyl phenol
2,6-di-t-butyl phenol
1,1-bis (3,5-di-t-butyl-4-hydroxyphenyl)-methane
3,3',5,5'-tetra-t-butyl - 4 - 4' - dihydroxydiphenyl
3-~ethyi-4,6-di-t-butyl phenol
4-methyl-2-t-butyl phenol
14-
.... . .. . . ... . . .. . . .. . ... _ . .
1045634
Yet further additives which may be used are phenothiazine
and its derivatives, for example those hav_ng alkyl, or aryl,
groups attached to the nitrogen atom or to the aryl groups of
the molecule.
Other additives which may be used include alkylene
o~ide/ammonia condensation products as corrosion inhibitors,
- for egample the propylene oxide/ammonia condensation product
described in ~ritish Patent Specification ~o. 1249803. ~urther
lubricity additives which may be used are complex esters~ such
as that sold under the trade name Reople~ 641 and also described
- in ~ritish Patent Specification ~o. 1249803. Moreover, long
chain (e.g. C10 18)~primary amine corrosion inhibitors and
polymerised quinoline resin antioxidants, as described in
Specification No. 1249803, may be used, e~amples of such amines
and resins being the commercially available materials Armeen
12D and Agerite resin D respectively.
Conventional additives such as those hereinbefore
described are normally employed in small amounts such as 0.05%
to 10%, for e~ample, 0.1% to 2% by weight.
We have found that tertiary amines have advantages
- over primary and secondary amines as corrosion inhibitors such
that hydraulic fluids in accordance with the present invention
containing tertiary amines show less tendency to gel, especially
in the case of hydraulic fluids wherein R5 is as the group R1.
~hus, a particularly preferred aspect of the present invention
-provides hydraulic fluids containing one or more tertiary amines,
or derivatives thereof, having the general formula:-
R1 9
R19 - ~ - R19
wherein each R19 is the same or different and is an alkyl
group, preferably containing from 1 to 6 carbon atoms, an aryl,
alkaryl or aralkyl group, preferably containing from 6 to 12
15. ~ _
1045634
carbon atoms or a group having the general formula:-
~R200~ R21
wherein the, or each, group R20 s a straight or branched
chain alkylene group, preferably an ethylene, propylene or
b~ltylene roup, R21 is a hydrogen atom or an alkyl group
preferably containing from l to 6 carbon atoms and m is an
Integer of from 1 to 6, or any two groups R19 may be taken
together to form a cyclic system provided that if the nitrogen
atom is thereby rendered tertiary the third group R19 is absent.
When two of the groups R19 in the above general
formula are taken together, the cyclic system so formed
preferably contains 4 to 6 carbon atoms in the ring. ~urther
hetero atoms such as oxygen and nitrogen may also be contained
in the ring as, for example, in tertiary amines derived from
morpholine and piperazine respectively; it is desirable however
that any further nitrogen hetero atoms should also be tertiary
as in 1,4-dimethyl piperazine. ~xamples of tertiary ~m1nes
in accordance with the above general formula wherein the two
groups R19 taken together render the nitrogen atom tertiary,
~0 the third group R19 thus being absent, are pyridine and
quinoline.
~specially preferred tertiary amines for use in the
hydraulic fluids of the present invention are triethylamine,
triethanolamine, triphenylamine and amines having the formula:-
CH3
~ (CH2.~H-0 ~m 3
amines of s ~id formula being commercially available under the
trade name PROPY~AN A 350
~he tertiary amines may be employed in an amount of
from 0.05 to 3.00 percent by weight ba3ed on the total weight
of the hydraulic fluid.
16.
1045634
Regardless of precise composition it is highly
desirable that the hydraulic fluids of the present invention
have a kinematic viscosity at -40C. of not more than 5,000 cSt,
especially not more than 2,000 cSt. It is also desirable that
the hydraulic fluids have a boiling point of at least 260C.
In a particular aspect of the present invention there
is provided a hydraulic system which contains, as the functional
fluid, a hydraulic fluid as hereinbefore described.
In a further particular aspect of the present invention
there is provided a method of operating a hydraulic system
which comprises introducing into the hydraulic system a
hydraulic fluid as hereinbefore described and transmitting
power by applying pressure to the hydraulic fluid.
The present invention will now be illustrated with
reference to the following Examples:-
EXAMPLE 1
Triethylene glycol (150g., l.Om) and pyridine
(158g., 2.0m), were mixed and the resulting mixture added to
dimethyl dichloro silane (258g., 2.0m) dissolved in toluene
(3.01) over a period of 12 minutes. During the addition a
dense white precipitate was formed and an exotherm was noted.
The temperature of the reaction mixture was kept below 42C.
during the addition.
The reaction mixture was then heated to about 100C
for 4 hours and then allowed to cool. To the resulting first
stage product was added a mixture of triethylene glycol
monomethyl ether (361g., 2.2m) and pyridine (174g., 2.2m)
over a period of 20 minutes during which an exotherm was noted.
i ~ ~ -17-
" ~
. ",
lUg~SW4
During the exotherm the temperature was kept below 35C.,
but thereafter the reaction mixture was heated to about 100C"
for 4 hours, The resulting product was allowed to cool and
was then filtered, the filter cake being wa~hed with I~rtner
toluene, The solvent (toluene) was removed from ths filtrate
using a rotary evaporator and the product stripped to 180C,/
0,05 torr, The final product (yield 333,0g,) was a clear,
very pale yellow liquid containing 11,1% by weight Si and 0,03%
by weight Cl (theory 9.5% and 0 respectively),
~XAMP~ES 2 to 25
~urther preparations were carried out in a
similar manner as in Example 1, salient differences being
summarlsed in the following Table 1.
18,
~045634
z a ~o c~ ~ ' o o 0~ ~t _
Z ~ _, u, + I~ _ a) + I~ u~ + ~
O ~: ~ _1 l t~ ~0 _1 _1
C~ .
~ a ~
O Z ~1 N ~_1 N
~0
L~
a~z ~0 ~ l ~g ~ ~ ~
~ ~ O CO .~ O O ~ 0 00
~_1 H ~ U~ _ .~ ~ H 11~
~ .~ l !~ 1 .E~
¢ .
~n
z
H ~1> O ~ Q> O O a) O ~
V~ ~ 1 g~: ~ g~ 4 ~ gr~ ~o
_I H ~ ~S _I _1 ~1 l .S ~ .~ ~
O ~ O ~`D ~ O ~.--I ~ O :.
Z ~ ~ .C ~ _ a~ ~ .C a>
~ O ~O~.,~ ~ ~ ~1 ~ ~ .,
¢ . ;~;h _I ~ l /~ _I ~ h H
O ~ ~ i ~WE! .
C¢,
~: ~ oo¢o ~o ~ ~ I o m
!~! _1 0 0~ 00 ~ O O -I
:~ _I ,s: H n h t~ 4 N 11
a~ ~D ~ ~
r~ h r-l ~ ~ C-~
~ ~0.0 _1
_
~ ~ : _ ~
~!~ -19-
104S634
a D~ ~ ~ .~ ~ _ _ ~o ~0 1~ ,~
H ~_ t~+ ~0 L~l + t~ 1~) + ~_ _I + ~ t'~ + ~0
~Ll ~ ~ t~l ~ _1 _1 ~ _ 1~ 10 ~`1 1~1
z a ~ ~ ~ l ~ ~ ~
~ ~ O L~ U~ : L~ O + O
:~ ~ ~ ~ ~ l ~ _,
X V~
~: .__
o
H cr ~
¢ O ~ ~ O _I O _I O _I O --I O
~Ll 1_1 Z ~: h ~ h ~ ~ h ~ , ~ h b4 ~ h l~o
~: :~ ¢ ~ O ~ ~ O Ot~ ~:: O 00 ~:: O ~D ~ O ~
~> ~ I~ ~ ~ U~ ~ ~ _ ~ ~ ~ ~ oo
H ~ ,~ CO Ei t~ E3 ~ ~ ~i ~ ~ ~
~ ~:1 ~ ~ ~:1 ~ ~ ~ ~ ~S ~
~:
O O 11> ~ ~ I h a~ O ~
4 ~ o
o~ ~ ~ ~ ~ ~ l ~ _,
~ ~ ~ ~ _I ~ ~ ~ _I ~4--I ~ ~ ~ .c ~ ~
_I ~ zO S O .~ ~ O h 8 s h 8 s ~ o
ul ~ ~ . ~ Q) ~ O.~ _I Q> l .~ ~ > h O
¢ ~ t~O ~ ~ ~ t~4 ~3 ~a b4 Ei ~ ~
h N
C~ ¢ c~ ¢ ~ ~ h _
X ~ O t1l\ O ~ O ~ N t~l 00 ~ O --I
O O ~ I~ ~ 00 ~ O ~ L~ _I O
a ~ c~ N ~ ~1 ~ N N ~ ~ S
5~ ~ U.l lLl ~ 1~ ~
~,a - 20-
1045634
~ -- ~ ~ ~ ~ ~ _~ ~ r_ ~ ~_ ~ ~ N _~ _~ ~ _ ~
~ 00 _10 00 00 00 00 00 ~10 ~0 _~0 _~0
' o\ O O O O O O O O O O
~ O~ r~ ~ Ot~ ~ ~ L~ 00 ~ ~I I~ 00 t~l t~ _~ ~_
~n ~ ~I t~ I~ o~ t~ ot) -I ~;t ~ ~O O O ~ a) I~ oo o a- `D
o\ ~ O 1~ 00 00 O~ O!) O L~ ~ O O ~ 00 ~ 1~ ~ L~ O 00 0
~__~ ~_ `_ _~ ~_
_ __
_~ ~ U~ ~ 00 U~ ~ ~ O
~_ _~ ~ 00 C~ 1` ~ ~ ~ O U~ `O
U~~ ~ ~t O 0~ 1~ 1~ ~ ~ 0~ ~ O
H~_ t~ t~ 11~ t~ ~ C t~ ~ 11~ ~ ~D
~Z _ . _ _
U~ U~ In ~ L~
h o o t~ _I ,~ o o _I ~ ~ ,~
_~ ~ o o o o o o o o o o o
~ ~Z
~ ZO _
U~ ~ ~ o o ~ _ I ~I o o ~ ~
~ _
o O ~ ~ ~ oO o~ ~D ~ oo
~ I~
~ ~ ~ ~ ~ ~ ~ ~ ~ f ~ ~
Z U~ o , l o l o l l l l o
o ~ o o o o
C~ ~ el ~1 _ _ _~ _ _~ _ _ _ _ ~
OOZ WE- ~ l l ~ l ~ l l l l ~
~ H ,
~Z I~
. E- ~ o l l o l o l l l l o
U) U~ C~ O O O O
~ ~ j~ ~ _ _ _1 _ ~1 _ _ _ _ _1
~U~ ~t l l e~ l ~ l l l l ~
~Ll
~3 ~ ~ U~ ~O I~ 00
U~
_ _ _
~045634
Z~ ~ ~ 10 , CO
a ~o _, + ~ .~ + ,~ u~ + ~ ~ + ~ _ _
C/:) H ~_ tt) t~ H H _I _I ~ l l
E-i
~: a ~ _
O E~ u~ u~ o u~ o ~ u~
~ C> ~ N 1~ i _ N ~`i
Z
H ~
O ~ h 1~0~ h ~0 l .5: h
.s o ~~ o o
1_1 H ~ H H ~ H 1/~ _ E3 .~
~ u~ E3 .S Lr~~ l ~ `I _
et ~ h _ _~
,_ O h O ~
a I h l ~ bO a>
O ~.Ll ~ ~ O h ~ :~ ~.s:
:~ ~ _~ ~ U ~ ~ ~ _l ~ _ _
O E~ ~--I _I oo ~ ~ ~ ~ ~~ ~ oo _ _
~ o ~ 8 ~ ~ .,: o _, ~ a> o ~ .c ~o ~ l l
,. a~ ~ ~1 ~ a~ ~
O ~1 _I ~ .,1 H ~ h O ,1 0
~: _
E~ O
~a ~ ~ O
~ 2 ~ N O 00 171) a~ ~4 _~ l l
~ W)
a ~: ~ o o _1 o ~: N ~ ~t ~o4 ~
C~ ~ N 1 ~ a~ ~ 1: 0 _ ~ O
Z ~.Ll '~g O l N
~L 1~ 1"' 1`' - ~
2 2 -
1045634
-- _ A ~ 00 -- Z 00 ~ O~D ___
Z H ~_ _I + ~ _ ~ 11~ Lt~ + 1~ Z N 11~
~ ~ _
o a u~ ~
~ E- ~ u~~ ~ n ~+~
K O N N N N _I _I N
H _
~ O _l
:~ h t~i :~ h ~0 ~ h ~1 S h ~o
H S O ~ _ _ ~ ~ S O `D
~ ~ l l ~ ~ O h
~1 _~
~ ~ ~ h ~ O ~ ~> V O
~S . ~S ~S ~ ~ ~S
zo ~: ~ ' ' ~ ~ ~ ~ ~ ~ ~
~ ~ ~ ~ ~ N _ _ ~ ,S ~ ~ S~ e~ _I ,C O ~
~ E~ s~ 8 ~ l l s~ o~ ~ -' s ~ oo ~ ~ ~
~ O O O ~ O h O ~ O ~ O
_1 ~1z '~ ~ E~ ~ '~1 ~ :1 ~
O O ~0~4
00 u~ . G~- . ~ S~
~ O~4 ~ ~0 ~0 ~ ~0
P ~ ~ ~e~ ~ O ~ O ~ O .,1
i~ CL, C!~`J ~tO ~ Ol ~ h
h O ` h
~ ~ _ ~,
. _
~ O _l ~ ~ ~ L~
~ ~ ~ r~l ~ ~ ~
A~- -23-
1045634
. o . o . o . o . o . o . o~ ~ o~ ~ o~ ~-- ~ ~ ~ ~ ~ --
o ~_ o ~ o ~ o ~ o ~ o ~_ o ~ o ~_ o ~ o ~ o ~ o ~ o ~
o\ V V V V V V V V
¢
~ ~ ,~
~n t~ t~ I NO O117 ~ ~ ~ `.D 00 _I Ln ~` _I 00 ~ ~ ~ n LO
o\ oo ~ u~) oc~ c)~I~ oo oo oocn oc~ o ~ o ~
~ _~ oO ~ ~ t~ oo o ~
U~ 04 ~ ~ _~ O 00 0 ~ ~ Lr~ 0000 ~ O '
~ ~ e~e~ ~t ~ ~ ~ ~t `D ~ ~` ~oo
a
E- _ _
o
h
O O ~ o ~ `O ~ _~
tO ~ ooooooooo ooo
U.l H H O
- E-- CL, H
~ O ~ ~Ln 0 00 0 ~ ~O ~ O C:~ O O
U~ C~ o Ir~`D 00 0~ cn r~ Ll~ ~D r ~ ~ I~ C1~
_
a
O U~ g O O I ' ' ' o g o o
~ E~ ~ - - - - - oo ~
cn ~ ~ ~ ~ ~ ~ I I I I I e~ et ~ ~t
~ o o
H H _._
~ Z
~: E~ ~ O 1 8 g ' ' ' ' ~ o o ~ o
_~ _ ~ ~ _ _ _ -- _ 00 ~ _ ~t
~: r ~ U ) ~ I ~
rLl
~ O ~ ~ Ul ~ ~ 00 C~ O _I ~ ~ ~ U~
,_ U.l
- 24 -
~045
5_ ,
;,,,~ ,
~ ~ l
~ ~o q~
cd ~ 6q ~H O
~ a) . . a)
a) d ~ u~ a) c) ,
O h o rl rl c) ~ .
E3 ~ ~o ~ ~ l
E3 ~ ,~ d s:l I
tl5 ~ . ~ ~o do ~ ~ a) I
a) ~ Pi E
.. ~ hd E3 E , .
p~N U~ j h
E3 ,~ h h rl co ~ ~ ,, o
t ~ d
g m ~q~ ,~, h
S~ ~ d ~ q~ c) ~
~ ~ o ~ ~ o Q) ~ ~ d
~ o a m ~ ~ o~ a~ d a)
~ Y h v~ d d
;" a) s~~I zi h h ~ ~
1 ~ o ~ q~ o c3 ~ o V,
m ~ t~ ~ oq~v 2;
a) a) a) .
d o
~ h a ~ ~ ~N ~
O ~ O~ ~ C~ ~ 4D
h~ ~ h ~ P, ~~1 h c~ bO d ~ o . ~ h
h ~ h ~I q~ h P~q, ~ h ~ h h
9 ~~ 3~a ~ 9~ ~~
m v
1045634
IR Speotra of the products of the foregoing
examples were all found to be consistent with the expected
product being obtained.
To determine the suitability of the products of the
foregoing examples for use n hydraulic fluids the following
tests were carried out.
(a) Kinematic viscosities at -40 , in centistokes, were
measured in the manner set forth in the SAE J1703c specification.
(b) Samples were subjected to the D.O.T. Humidity test
according to the procedure set forth in the ~MVSS 116
specification and the vapour lock temperatures of the samples
were measured. The vapour lock temperatures were determined
in the manner described in ~ritish Patent Specification No.
1341901.
- 15 (c) Rubber Swell propertles were measured by placing 1"
~quare by 3 mm. thick rubber specimens in 60 ml jars each
containin~ 50 ml test fluid for a period of 3 days during which
the temperature was maintained at 70C. for the nitrile and
natural rubber specimens and at 120C. for the styrene/butadiens
rubber specimens. After the test, the percentage vo_ume
increase of each of the rubber specimens was measured.
~ The results of these tests are set out in the
following Table 2. In addition, the hydrolytic stability of
- a number of products were tested in accordance with the Water
Tolerance tests as set out in the SAE J1703c specification, all
products so tested satisfying the stability standards
required by this test.
26.
~045634
~r~
h N N N I~ N I~ N N N
h ~ _I oo o oo o t~ oo o 1~ o `.D o ~ ~ Lr
c~ t~) ~ CO ~ ~ ~ ~D u~ U~ t~ ~ Ot~ _~ N
~ t~ _~ _l 10 _ _ _ _ l _ t~ t~ _1 tO
_~ ~: _~
v~ ~ ~ h N co ~ o t-) Lr~ _~ It~ Lr~ o _~ ~0 1~ ~` ~
h h cd ~ N N 1~ 1~ 00 N N N _I ~ ~ ~ --I t~)
;~ ~ ~ ~ _ __ _ _~ _ _ _ _ _ _ _
cd h
h~ ~ u~ N _l 0~ ~t Ot~ t~ ~ _~ ~ t` 00 U~ 0~ t~)
Z~ _ __ _ N X _ _ `D 1~ ~ N 11~ O 11~
u~ ~ _ cn _I 1~ L~ 3 N N O~ N O~ N t/~ 1/) Lt~ ~1
O O N N a~ `D O 1~ 00 ~t _~ ~ ~ _I r` O N
~ .
Z _~ N t~ el~ 1~ ~D 1~ 00 O~ O _~ N _
h X
C~LU _ _ _ _ _ _ _ _ _ _ _ _
10~
r ~r~
~ . ~ ~ ~ O O
~ ~ +~
~ ~ 0 ~ ~ ~ 0 ~ ~D ~
t ~ ~ ~ ~ ~ ~o
_ ~1 rrl r
.,~ .'; . O. .. ~ .~ . O. ~ ~ .~
. i ~ ~ ~ ~ ~ ~ ~ ~ ~
: - ~ L LL L LL LLLI
~ N -
~ ,'.~ ~ t~ Is~ 0 ~o ~ ~ Ir~ 1~ 1~
¦ ~ ¦ N ¦ I I o
I I I I 1~11~
0 C~l 0 CJ~ N 0 0
~, ,~1 . .
L~ L ~ L L~ L ~ ~ ~
28.
