Note: Descriptions are shown in the official language in which they were submitted.
3~
Background of the Invention
.. : ,:. .
The use of synthetic cutting fluid compositions has
grown rapidly. The oil-free ccmpositions are designed to impart
lubricity at high temperatures, inhibik rust, reduce surEace ten-
~ion, produce low foam and be compatible with conentrated electro-
lyte solutions Eor hard water.
Examples of synthetic metal working fluid ccmpositions
which may be both oil and water soluble are those formed frcm oon- ~;
ventional non-ionic surfactants which consist of a hydrophobe which
has been polyoxyethylated. Such non-ionic surfactants ha~e been
provided with a phosphate radical which improves several of the
sought for characteristics including increasing the hydrophilic
characteristic o such surfactants. Examples of such metal work-
ing fluids are the ANTAR~ R lubricant comEositions which are sold
by the GAF Corporation. These metal working fluid compositions i~ ~
are based on aliphatic and aromatic hydrophobic moieties which are - --
fur~her alkoxylated and phosphated. ~ ~
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The present invention provides ccmpounds particularly suitable for
use in formulating synthetic aqueous based metal w~rking fluids. The ccm~
pounds are phosphated, polyethoxylated (2-10 EO) n butane 1,4 diols. They
are completely hydrophilic in nature. They do not contain any hydrophobic
moiety. The particularly novel aspect of the present invention resides in
phosphoric acid esters of the condensation prcducts of one mole of butane-
1,4-diol with from 2 to 10 moles of ethylene oxide. mese esters are useful
in a variety of applications such as synthetic aqueous based metal working
fluids. Other uses are as lubricating ~dditives, corrosion inhibitors,
hydraulic fluids, flame retardant additives, plasticizers and the like. me
phosphate esters of the present invention may ~e represented as follows:
X~- P~ 0 ~2CH2~ n-C4H8 {C82C~H -- {P - ~X
m p q z n
~herein X is a member selected from the group consisting of H and polyoxy-
ethylbutanol having the general forn~la:
CP2 ~ n C4H8 ~ CH2 ~ ~
such that the compound can be either a mono-, di- or tri-ester of phosphoric
or polyphosphoric acid, or mL~tures of the three, m and n are positive
integers of 1 or higher. In the case where m and n are greater than 1,
~hP;r values are similar to the degree of polymeri~ation occurring in poly-
phosphoric acid; q and p are positive integers the total of which is from 2to 10 and wherein z is also an integer having a value of 1 or higher.
3;~
An examlnatian of the general formula set forth above
discloses a straight chain molecule which contains no branched
chains. The component mDieties of the compound are individually
hydrophilic and in cambination remain hydrophilic. m is is be-
lieved to particularly distinguish the co~,pounds of the present
invention fram those found generally available which are based on
combinations of hydrophobic and hydrophilic moieties. The
straight chain nature o~ the present compounds indicates a further
characteristic that is particularly desirable that of being
biodegradable. me compounds of the present invention may be
further madified by forming ammonium, substituted ammonium, alkali
metal or alkaline earth metal salts thereof.
The preparative methods for synthesizing the rather cam
plex compounds and ~ixtures thereof of the invention follow well
known synthetic procedures. The ethyoxylation is carried out by
adding a pre-determined number of moles of ethylene oxide to the
term m al hydroxyl groups of the butanediol. It is understood that
this addition results in a well kncwn random distributian of
oxyethylene graups on either side of the butanediol moiety. The
phosphation is also carried out by well known methods. The
phosphating agent preferred in the present invention is poly-
phosphoric acid although PzO5 may also be used. The choice be-
tween the tWD phosphating agents depends upon whether a proponder-
ance of diester or monoester is preferred. Polyphosphoric acid
produoe s more monoester while P205 produces more diester.
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3~9L
I~pical p~eparative methods used in the present invention were as
follows:
_ Butanediol is ch æged into a pressure vessel such as an auto-
clave. 0.05% NaO~ catalyst based on the diol is added. A predetermined
amount of ethylene oxide is charged into a cylinder which is coupled to the
pressure vessel by means of a valved pipe. The valve is opened to permit the
reaction to proceed at a pressure of 30 to 33 psig with the temperature con-
trolled to 130 to 140C. me reaction continues until the pressure drop
indicates no unreacted ethylene oxide remains.
Phosphation of ethoxylated n butanediols may be c æ ried out using
P2O5 or polyphosphoric acid (PPA) of 115~ strength. me phosphation was
carried out in a four-necked flask which is equipped wi-th a mechanical
stirrer, a thermometer, an N2 inlet (or CaC12 tube) and a vent tube (or a
condenser). Prior to phosphation a color stc~bilizer may be added to the diol
ethoxylate in amounts of 0.5 to lg. The stabilizer is hypophosphorous acid
when P205 is used and sodium hypophosphite when PPA is used.
P205 is added in portions while holding the tem~erature to about
50-60C. Upon completion of the addition the reactants are heated for about
five hours at go-gs&.
PPA in a predeterm med amount is placed in a dropping funnel which
was provided to one neck of the flask. The PPA was added dropwise maintain-
ing the temperature at 40 to 45 &. Upon completion of the addition the
reactants are heated for about two hours at 9S to 100C.
The products of either phosphation may be bleached using 1 to 3 ml
of 30~ H2O2.
Typical preparations are shcwn below.
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me compounds of the present invention are all based on butanediol
which for convenience sake will be indicated as BLD. The moles of ethylene
oxide with which one mole BlD is ethyoxylated will be indicated as a number
of EO and the phosphating agent will be indicated as P2O5 or PPA for poly-
phosporic acid. The ratio shown following the butanediol, ethylene oxide
and phosphating agent indicates the ratio between 1 mole of the ethoxylated
butanediol and the moles of phosphating agent with which it has been reacted.
The compounds of the present invention are all based on BlD. The
degree of ethoxylation varies between 2 EO to 10 EO, and the phosphation may
be of varying degrees with either PPA or P205. The compounds falling within
those described by such ratios are all suitable for use in synthetic metal
working fluid compositions sometimes called coolants. When the compounds are
dil~lted with water, they form true solutions. The compounds further produce
little or no Eoam and such Eoam as may be produced is oE a quick breaking
character. The o~mpounds of the invention further provide corrosion protec-
tion to most metals. They further stand up well under extreme pressure and
ele~ated heat.
The desirable qualities of the ethoxylated phosphated butanediols
of the present invention are demonstrated by comparison with two commerci-
ally available compounds used in preparing metal working fluid compositions.ANrA~A LP-700 is a phosphate ester of phenol plus 6 EO reacted with one
mole of P205 for each 2.7 moles of the ethoxy]ated phenol. ~NTAR~ R LK-500
is the phosphate ester of n C6H13OH -~ 3.4 EO and phosphated using 1 mole of
P2O5 for each 2.7 moles of the ethoxylated alcohol.
'"'
The following tests are designed to demonstrate the foam ;
characteristics of the compounds of the present invention and
those of the ~o compounds used in commercial metal working fluids.
A typical concentrate of aqueous based metal ~orking Eluid co~,posi-
tion is the following:
Con oentrate
Compound
Phosphate ester 10 Parts by Weigh-t
Triethanol amine 20 Parts by Weight
Water 70 Parts by Weight
The triethanol amine is used in the composition as an
alkaline adjuster for the phosphate esters which are acidic. The
comm~rcially available metal working fluid co~,positions are also
adjusted to alkaline in the same type of concentrate composition
as the compounds oE the pre æ nt invention. In each of the runs
shc~ later in Table I, 15 grams of the concentrate is diluted to
250 ml with distilled water resulting in approximately a 0.6 per-
cent concentration of phosphate ester compound.
A mixer such as a Waring Blender is provided with a tape
marked off in millimeters on the side of the mixing bowl. The
ruled tape was adjusted so that the 0 mark coincided with the
height of the unagitated dilute composition of metal w3r]cLng fluid.
The solutions were stirred with the blender set at high speed for
cne minute. Readings of foam height were taken at the time the
agitation was discontinued and at each sucoeeding minute until
five minutes had elapsed.
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It is to be noted that all of -the above metal working
fluid compositions are biodegradable with the exception of
ANTARA LP-700. Biodegradability is a most desirable feature in
metal working fluid compositions particularly with the raised
awareness with respect to sa~eguarding the envir~nment from
unnecessarily oontaminated effluents.
It is to be noted that all of the metal working fluid
c~mpositions based on ethoxylated, phosphated butanediols produce
less foam than biodegradable alkoxylated phosphated alcohols, a
foam which breaks more rapidly than either ccmmercial product.
The decrease in foam production and the relatively quick breaking
of that produced, increases with the degree of ethoxylation. The
compositions are further improved when the phosphating agent is
PPA whi.ch produces a prepanderance of monoe ster. The outstanding
compound with respect to low foam is BlD.6EO:PPA (1:1). It was
incorporated in compositions having væious ratios with respect to
triethanolamine and water and the p~I noted. The compositions are
set forth in Tc~ble II. The parts shown there æe by weight.
Cbmpositions A, B and C are shown in Table II.
TAE~E II
Composition A Composition B Composition C
BlD. OEO:PPA (1:1) 10 Parts 10 P æ ts 5 Parts
Triethanolamine 20 Parts 33.5 Parts 20 P æ ts
Water 70 Parts 56.5 Parts 75 Parts
p~ 8.25 8.6 8.5
3'~4
The ccmpositions were diluted in water to a concentra-
tion of 0.6 percen-t phosp~ate ester. This required formulation C
to be added in twi oe the amount as A and B to 250 ml. The results
of the foam test are shown in Table III.
TABLE III
BLENDER F3AM TEST
(Co~positions of Table II, Diluted to 0.6% Phosphate Ester Conc.
with Distilled Water)
.
F02~1 HEIGHT IN MM
.
CCMPO6ITICNS 0 ~5in 1 Min 2 Min 3 Min 4 Min 5 Min
A 70 25 8 0 0 0
B 70 35 14 0 0 0
C 70 27 3 0 0 0
The resul-ts indicate that the phosphate esters of -the
current invention have fast breaking foam irrespective o the
degree of neutralization. It is noted that no foam remained at
the end of three minutes. ~ -
Further redu~tions in foam and increase in the speed of
breaking thereof were obtained by adding to 99~ by weight of com
position C L% by weight of Surfynol 104E (tetramethyl decynediol
in ethylene glycol 50~ concentration). The compositions C and C
plus Surfynol 104E were agitated in the blender at a 0.6 percent
phosphate ester concentration with the ollowing results:
-10- ~,
3~
TABLE IV
BLENDER FO~ TEST
(Cbmpositions Diluted with Distilled Water to 250 ml and 0.6
FOAM XEIGHT IN MM
CCMPOSITICNS0 Min 1 Min 2 Min 3 ~in 4 Min 5 Min ~ '
C 70 27 3 o 0 0 '~ -'
C with Surfy,nal 25 l 0 0 0 0
104E
rme lubricating properties of compounds of the presen-t
invention were measured in aqueous solution for wear protection be
means of a standcard Four Ball test and by the extreme pressure
lubricating properties as measured'by the Falex text.
'~e Four Ball t~st is carried out with a test load of
lO0 kg at 1500 rpm at an initial temperature of 100 E' for five
minutes. One half inch diameter chrome alloy steel balls were
used. Three balls are held stationar~r abutting one another below
the fourth ball which is urged against the others at the load
indicc~ted, turning at the indicated speed while immersed in the
various aqueous based metal w~rking fluid ccmpositions to be
tested. rrhe test was run for five minutes after which the balls
were retrieved and examined for wear. The smaller the scar, the
more effective compound tested.
~rhe metal working oomposition for the purposes of carYy-
ing out the Four Ball wear test was prepared by diluting 121/2
grams of the stock compositions into sufficient water to 250 ml of
solution. me resultant composition has a phosphate ester compound
concentration of O.S~. An adjustment was made in the total am~unt
of triethanolanune present in the test solution in that the pH of
~ .
3~4
each sample was adjusted to a consistent 8.3 ~ 0.1. The results
of the test is shown in Table V. It will be seen that the com-
pounds of the present invention give results oo~parable to the
leading ccmmercial product.
TABLE V
SHELL FOUR BALL WE~R TEST
t0.5% Phosphate Ester - pH to 8.3 ~ 0.1 with TEA)
:
PHOSPH~TE ESTER WEAR SCAR DIAMETER
Water only to pFi 8.3 with TEA Failure (1) ~ ;
Antara LP-700 0.77
BL~.2EO:P20 (1:0.74) 0.74
B3D.2Eo:P2o55 (1:0.74) 0.79
BlD.4EO:P2O5 (1:0.74) 0.85
B2D.4EO:P2O ~1:0.74) 0.76
B3D.4EO:P2O5 (1:0.74) 0 79
BlV.6EO:P O ~1:0.74) 0.78
B2D.6EO:P2O5 ~1:0.74) 0.76
B3D.6Eo:P2055 ~1:0.74) 0.74
BlD.6EO:PPA (2) (1:0.5) 0.77
BlD.6EO:PPA (2) (1:2) 0.76
(1) Failure means, the rpm could not be maintained and the
test had to be abandoned before the required 5 minutes
were over. A typical scar diameter at failure (Less
than 5 min.) is well ovex 3 mm.
(2) 115% PPA.
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A Four Ball wear test was carried out ccmparing the pre~
ferred comFound of the present invention BlD.6EO:PPA (1:1) was com~
pared with a 0.5% solution of triethanolamine and the leading
commercially available product ANTARA LP-700. The other variable
included in this particular test was the diluting of succeeding
compositions by a half from the preceeding one in order to deter-
mine at what point the composition was no longer sufficiently
effective to prevent undue wear. The results of this test are set
forth in Table VI which follows.
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Some of ~he composi-tions described in Table I are
diluted to give a 0.15~ of -the phosphate ester compound in test
solution. No adjustment of the pH after dilution was attemped.
The results of the load bearing capacity tests are shown in Table
VII below.
TABLE VII
FALEX LOAD-BEARING QPACII~ TEST
(Cc~positions Diluted to Give 0.15% Phosphate Ester Compound)
CQMPOUND r~ESTEDJAW LOAD MAX = rr~RQUE
(0.15% Concentration)FAILURE PRESSUgE LBS/INCH
(lbs.)
Water alone
Antara LP-700 2200 66
BlD.2EO:P2O5 ~1:0.74) 1900 70
BlD.~EO:P2O5 (1:0.74) 2000 70
B2D.4EO:P2O5 (1:0.74) 2000 70
B3~.4EO:P2O5 (1:0.74) 1800 70
BlD.6EO:P2O5 (1:0.74) 2000 72
B2D.6EO:P20 (1:0.74) 1800 72
B3D.6EO:P2O5 (1:0-74) 1800 72
BlD.6EO:PPA* (1:0.5) 1900 74
BlD.6EO:PPA (1:1) 2500 74
* 115% PPA
A second series of laad bearing capacity tests were
carried out comparing the preferred compound oE the present inven- ,-
tion, BlD.6EO:PPA (1:1) with a leading commercial compound
ANTARA R LP-700. The comparisons are made at three different con-
centrations of the metal working fluid composition. The results
are shown in Table VIII.
-15-
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~ABLE VIII
FALEX LQAD C~R~YING CAPACII~ TEST
(pH of Test Solutions 8.3 + 1)
. . ~
CCNCENTRA~ION/ JA~ LOAD, MAX = IORQUE
CCMPCUND FAILURE PRESSURE LBS/INCH
(lbs.)
0.15~
Antara LP~700 2400 63
BlD.6EO:PPA* (1:1) 2500 73
0.075%
Antara LP-700 1500 60
BlD.6EO:PPA* (1:1) 1800 65
0.037%
Antara LP-700 800 --
BLD. OE O:PPA (1:1) 1800 65
* 115% PP~
Ccmparison of results between the commercial product and
the preferred ccmpound of the present invention show ne æ equival-
ence at 0.15~ concentration but a longer continued effectiveness
at diminishing concentrations by the pre~erred compound of the pre-
sent invention.
The same two co~pounds, the preferred phosphate ester of
the present invention and ANTARA LP-700 were tested for rust ;
inhibition. The materials used were cast iron blocks, 2-1/2 x 5 x
3/~". The~ were freshly polished with aluminum oxide paper of 240
grit to remDve any oxides from the surface. The blocks were
further cleaned with m m eral spirits or hexane and wiped with a
clean cloth till no black oxide appeared on the clothO
-16-
3.~
Test solu-tions were applied as relatively uniform drops
usually in a row oE five across the face of the block. me test
blocks were left undistur~ed for 24 hours at amblent temperature.
During this time all the water in the metal work:ing fluid evapor-
ates. men the block may be examined for rust. m e outlines of
the dried sol~tion are visible and an estimate o~E rust inhibition
is made by averaging the areas of each spot which show rust.
ANTARA LP-700 was compared with water alone and the
preferred compound of the present invention. The test solutions
were adjusted to a pH of 8.3 ~ 0.1 with triethanolamune. me re-
sults were rated on a scale of A through E. A equals no rust. B
less than 10~ oE the æea on which the compositions were allcwed
to dry are covered ~y rust. C between 10 to 50% æe covered by
rust. D between 50 and 99% are covered by rust. E 100% covered
by rust.
rr~e ccmpositions æe shcwn at either 0.1 or 0.3 con oen-
tration. One set of runs included 0.02% sodium nitrite and an-
other 0.06% sodium nitrite as a supplementary rust inhibitor. Re-
sults are shcwn in Table XI.
TABLE IX
RUST INHIBITION TEST
(Test Solution ~djusted to pH 8.3 -~ 0.1 with TEA)
CONCENTR~TION IN r~EST SOL'N AVER~OE
aCMPOUND % Cbmpound % NaN02 RUST R~TING*
Water Alone -- None E
Antara LP-700 0.1 None B
BID.6EO:PPA (1:1) 0.1 None B
Antara LP-700 0.3 None A
BlD.6EO:PPA (1:1) 0.3 None A
Antara LP-700 0.1 0.02 A
BLD.6EO:PPA (1:1) 0.1 0.02 A
Antara LP-700 0.1 0.06 A
BlD.6EO:PPA (1:1) 0.1 0.06 A
-17-
: .
3~ :
Tne results show tnat the preferred compound of present
invention itself exhibits rust inhibitory properties and that
these properties can be enhanced by the addition of a suppl~men-
tary rust inhibitor.
The compounds of the present invention have been shown
to have rust inhibiting properties. They are co~patible witn ~
electrolyte corrosion inhibitors commonly added to metal working ;~ :
fluid compositions such as sodium nitrite. Load bearing tests
were run oomparing the preferred com~ound of the present invention
and a leading commercial product ANTARA R LP-700 in compositions
aontaining NaN02. The results are shown in Table X.
-18-
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There is some loss in load bearing capacity by both but
those of the present invention are affected to a lesser dbgree
than the commercial product.
The various compounds and mixtures described above will
be understood to be by way of exemplification ancl not by way of
limitation.
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