CA1114394A

CA1114394A - Phosphoric acid esters of poly (2-10) ethyleneoxy n-butane 1,4 diols in synthetic aquous based metal working fluid compositions

Info

Publication number: CA1114394A
Application number: CA320,517A
Authority: CA
Inventors: Paritosh M. Chakrabarti; Mohammed M. Hashem
Original assignee: GAF Corp
Current assignee: GAF Corp
Priority date: 1978-06-05
Filing date: 1979-01-30
Publication date: 1981-12-15
Also published as: FR2428046A1; DE2921572A1; AU4407779A; GB2023606B; FR2428046B1; AU523114B2; DE2921572C2; GB2023606A; CH650512A5

Abstract

Abstract Phosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diols are water soluble compounds which may be used in formulating light to heavy duty water-based metal working fluid compositions.

Description

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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.

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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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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 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

(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 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:

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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 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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3'~ -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.

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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

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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

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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.

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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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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds and mixtures of phosphoric acid esters poly(2-10) ethyleneoxy n butane 1,4-diol.

2. Compounds and mixtures of phosphoric acid esters of poly(2-10)-ethyleneoxy n butane 1,4-diol of the formula:

wherein X represents hydrogen, or a group of the formula ;

and n are positive integers equal to 1 or higher, and when greater than 1 are similar to the degree of polymerization occurring in polyphosphoric acid;
p and q are positive integers the total of which is from 2 to 10 inclusive;
and z is an integer having a value of 1 or higher.

3. Compounds and mixtures of phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol as set forth in Claim 1 or 2 wherein the com-pounds may be the mono-, di- or triester and the mixtures.

4. Compounds and mixtures of phosphoric acid esters of poly(2-10) ethyleneoxy n butane diol as set forth in Claim 1 or 2 wherein the monoester is present in a major amount.

5. Compounds and mixtures of phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol as set forth in Claim 1 or 2 wherein the di-ester is present in a major amount.

6. Compounds and mixtures produced by reacting about 1 mole of n 1,4 butane diol with about 2-10 moles of ethylene oxide, then phosphating the ethoxylated n 1,4 butane diols produced with polyphosphoric acid.

7. Compounds and mixtures produced by reacting about 1 mole of n 1,4 butane diol with about 2-10 moles of ethylene oxide, then phosphating the ethoxylated n 1,4 butane diols produced with P205.

8. The compounds and mixtures produced as set forth in Claim 6 where-in about 6 moles of ethylene oxide are reacted.

9. The compounds and mixtures produced as set forth in Claim 7 where-in about 6 moles of ethylene oxide are reacted.

10. Synthetic metal working composition concentrates comprising phos-phoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols in aqueous solution having the pH of the composition adjusted to the alkaline side.

11. Synthetic metal working concentrates comprising phosphoric acid esters of poly(2,10) ethyleneoxy n butane 1,4-diol of the formula wherein X represents hydrogen, or a group of the formula ;

m and n are positive integers equal to 1 or higher, and when greater than 1 are similar to the degree of polymerization occurring in polyphosphoric acid;
p and q are positive integers the total of which is from 2 to 10 inclusive;
and z is an integer having a value of 1 or higher, in aqueous solution having the pH of the composition adjusted to the alkaline side.

12. Synthetic metal working composition concentrates as set forth in Claim 10 or 11 wherein the pH of the composition is adjusted to at least 7.5.

13. Synthetic metal working composition concentrates as set forth in Claim 10 or 11 wherein the pH is adjusted by reacting the phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols with an alkaline material.

14. Synthetic metal working concentrate as set forth in claim 10 or 11 wherein the pH is adjusted by reacting the phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol with an alkaline material which pro-duces salts selected from the group consisting of ammonium, substituted ammon-ium, alkali metal and alkaline earth metal salts of phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols.

15. Synthetic metal working concentrate as set forth in claim 10 or 11 wherein the pH is adjusted by reacting the phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol with triethanolamine.

16. Synthetic metal working composition concentrates as set forth in Claim 10 or 11 wherein there is also present an auxiliary anti-foaming agent and a rust inhibitor.

17. A synthetic metal working composition comprising phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols being present in aqueous solution in an amount by weight from 0.1 to 1.2%, the pH of the composition being adjusted to the alkaline side.

18. Synthetic metal working concentrates comprising phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol of the formula wherein X represents hydrogen, or a group of the formula ;

m and n are positive integers equal to 1 or higher, and when greater than 1 are similar to the degree of polymerization occurring in polyphosphoric acid;
p and q are positive integers the total of which is from 2 to 10 inclusive;
and z is an integer having a value of 1 or higher, present in aqueous solu-tion in an amount by weight from 0.1 to 1.2%, the pH of the composition being adjusted to the alkaline side.

19. A synthetic metal working composition as set forth in Claim 17 or 18 wherein the pH of the composition is adjusted to at least 7.5.

20. A synthetic metal working composition as set forth in Claim 17 or 18 wherein the pH is adjusted by reacting the phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols with an alkaline material.

21. A synthetic metal working composition as set forth in claim 17 or 18 wherein the pH is adjusted by reacting the phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diol with an alkaline material which produces salts selected from the group consisting of ammonium, substituted ammonium, alkali metal and alkaline earth metal salts of phosphoric acid esters of poly(2-10) ethyleneoxy n butane 1,4-diols.

22. A synthetic metal working composition as set forth in Claim 17 or 18 wherein there is also present an auxiliary anti-foaming agent and a rust inhibitor.