US 2692859 A
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Patented Oct. 26, 1954 2,692,859 METAL-WORKING LUBRICANT Samuel K. Talley, Berkeley, and Stewart J. Beaubien and Leonard P. Calii'., assignors to Sh pany, Emeryville, Calif.
Richardson, Oakland, ell Development Coma corporation ofDela- No Drawing. Application July 18, 1951, Serial No. 237,472
13 Claims. (0]. 25.2-49.3)
This invention relates to improved lubricating compositions and more particularly to lubricating compositions adapted for cooling and lubricating of surfaces subjected to high speeds, high temperatures, extreme pressures and the like, such as encountered in various metal cutting and fabrication operations.
Lubricants suitable for use in metal fabrication such as in lathe work, cutting, drilling, reaming,
broaching, drawing and the like, must effectively cool and lubricate both the tool and worked metal. During such operations an enormous amount of heat is generated at the tool and work piece interface which mustbe quickly dissipated therefrom in order to prevent damage to either the tool or work piece or both. This can only be accomplished by flooding the tool and work piece with a fluid having a high capacity for heat adsorption. The second function of such fluids, that of lubrication, is essential in reducing friction between contacting metals, thus preventing wear, scoring and even welding of contacting metal parts. Effective lubrication of the tool and work piece during metal cutting and the like reduces the tendency of build-up formations on the tools which generally account for rough surface finishes, inaccurate cutting dimension and even tool failure. Cutting fluids which adequately perform the functions discussed, increase tool life, increase the useful speed of such operations, improve the surface finish of the work piece, de-
crease power consumption and the like.
Countless compositions have been compounded for aiding in cooling and lubricating during metal fabrication such as cutting and the like. Where a cooling effect is most desired, water is most suitable because of its high capacity to adsorb heat. However, water has a serious drawback in that it causes corrosion and is an exceedingly poor lubricant. Although addition of corrosion inhibitors to water can aid in overcoming its corrosion tendencies, the composition still remains a poor lubricant, thus rendering it substantially useless as a cutting fluid especially under stringent operation conditions. Straight hydrocarbon oils, although they aid lubrication to some extent, are relatively poor coolants and are incapable of acting as efiective lubricants under extreme pressure conditions and hightemperatures. To some extent the addition to straight hydrocarbon oils of fixed fatty oils or sulfurized and/or halogenated fatty oils or other such treated materials, aids lubrication under cutting conditions, by increasing the oiliness and film strength of the lubricant. However, the presence of such materials in a hydrocarbon oil does not improve its cooling properties and frequently is the cause of corrosion and staining of the work piece. Fixed oils also have a tendency of becoming rancid, developing obnoxious odors, thereby rendering them useless. Highly halogenated additives as Well as some other additives frequently cause skin irritation resulting at times in serious cases of dermatitis.
It is an object of this invention to produce a cutting fluid having excellent cooling and lubrieating properties. Another object of this inventionis to produce a non-corrosive aqueous cutting solution. Still another object of this invention is to produce a stable, non-corrosive, aqueous cutting composition free of ingredients of an infectious nature. Furthermore, it is an object of this invention to produce a multi-functional metal working lubricant suitable for use at high speeds, pressures and temperatures. The above and other objects can be attained,
, in accordance with the present invention, by adding to water or any aqueous medium, a combination'of three essential additives in specific concentrations and ratios which exert a synergistic zefiect resulting in an aqueous metal working lubricant of outstanding quality. The three additives in question are: (l) a particular type of water-solublenon-ionic surface active agent, (2) a nitrite, preferably an inorganic nitrite, and (3) a phosphate, preferably an inorganic phosphate.
The non-ionic surface active agent, which can be liquid or solid, is selected from the group con sisting of alkaryl polyoxyalkylene oxyalkonols, which compounds can be equivalently named as being alkaryloxypolyoxyalkylene alkanols and the same holds true for the other class of compounds, such as, polyEalkaryl polyoxyalkylene oxyalkanoll alkanes, polylalkaryl polyoxyalkylene oxyalkanollsulfides, polyEalkaryl polyoxyalkylene oxyalkanollethers and the sulfur, selenium and tellurium analogues of the polyoxy (polyoxa) compounds and their alkanolates 'ethers, sulfuric acid estersand phosphorus acid esters, which compounds can be represented by the general formula:
it" JG l t (I) cal of at least four and preferably nine carbon atoms; R is an alkylene group, preferably ethylene or propylene (1,2 or 1,3); X is an element selected from the chalcogen family of which those with atomic numbers of from 8 to 16, namely oxygen and sulfur, are preferred; Y is a divalent non-metal radical selected from the chalcogen family and the alkylene group a is a whole number from zero to 10, b and e have values of 1 to 21 inclusive, d is a whole number from zero to 1; Z can be hydrogen, a hydrocarbon radical, a cation, or a sulfur or phosphorus-containing acid radical such that XaZ is, for example, XSOsA, SOsA, POsA or XPOsAz wherein A is hydrogen or a hydrogen equivalent of a cation, preferably an alkali metal, such as Na, K, Li, or an alkaline earth metal such as Ca, Ba, Mg or Sr.
A preferred class of compounds for use in the practice of the invention, and coming within the broader class defined before, is the class which is representable by the general formula:
l R .L R wherein the symbols R, R, Z, a, b and c are the same as in Formula I and R." is an alkylene radical of the same class from which the R's are selected, preferably being methylene. A preferred sub-class of substances coming within this class is the group wherein all of the Rs are ethylene, the Rs are octyl (Ex. l,l,3,3-tetramethyl butyl) or nonyl (Ex. 3,5,5-trimethyl hexyl), R" is methylene, a is from 0 to 4 and b and c are each from 6 to 10, preferably about 8, with B being paraand B," being orthoto the (XR)bXdZ group.
The starting materials for the preparation of surface active compounds of this invention are alkylene oxides and/or sulfides or analogues thereof and phenolic compounds.
The alkylene oxides can be exemplified by ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, amylene oxide, epichlorhydrin, glycidyl compounds (e. g., glycidyl isopropyl ether) ethylene sulfide, propylene sulfide and the like are representative alkylene sulfides. The phenolic compounds can be exemplified by 2,4-diisobutyl'phenol; 2,4-diamyl phenol; 2- or 4-octyl phenol (e. g. 1,l,3,3-tetramethyl butyl phenol); 2- or 4-nonyl phenol (e. g. 3,5,5-trimethyl hexyl phenol); paraffin wax phenol; 2- or 4-cyclohexyl phenol; alkyl phenol-formaldehyde condensation product, e. g., p-octyl phenol-formaldehyde condensation product containing from 2 to about 6 phenol units; 2,2- methylene bis(4 methyl 6 tertiary butyl phenol); octyl thiophenol; nonyl thiophenol; ortho(p-octyl phenol) sulfide; chloroalkyl phenol; chloroalkane phenol, e. g., chlorowax phenol and the like.
The surface active agents of this invention are prepared by reacting an excess, preferably an excess of at least three moles of an alkylene oxide and/or sulfide with a suitable phenolic material so that the final product contains at least 4 ether groups and preferably between 8 and 10 ether reaction is carried out preferably in the presence groups per phenyl radical in the molecule. The
of a base such as sodium hydroxide. Specifically, products of this invention can be formed by reacting about one mole of phenolic material such as nonyl phenol with from 4 to 30 or more moles of alkylene oxide (ethylene oxide) at a temperature of from to 200 C. and preferably at a temperature ranging from to C. and the reaction continued until the desired amount of alkylene oxide has reacted with the phenolic material.
Derivatives of alkaryl polyoxy alkylene oxyalkanols of this invention which can be also used as essential additive components in metal working lubricants of this invention are the sulfuric Example I.-Reactz'on product of ethylene oxide and nonyl phenol In a suitable solvent such as toluene, a mixture of pnonyl phenol and ethylene oxide in a mole ratio of about 1 to 10, respectively, can be reacted, preferably in the presence of an alkaline catalyst (NaOH) at an elevated temperature ranging from 120 to 160 C. until about 8 to 10 moles of said ethylene oxide have been adsorbed. The solvent can then be removed by any suitable means, such as by steam distillation. The final water-soluble product is representable by the formula:
wherein m, or mixtures thereof, has an average integral value of 8 to 10.
Example I I .Reaction product of ethylene oxide and bis(p-octyl phenohmethahe Following the general procedure, of Example I, a mixture of bis(p-octyl phenol) methane and ethylene oxide can be reacted in the mole ratio of l to 16-20, respectively, and at a temperature of around 160 C.- C. in the presence of an alkaline catalyst (NaOH) for at least four hours to produce a product which is water soluble and is representable by the formula:
wherein the total of both 50's is an average integral value of 16 to 20; actually each a: has an average integral value of 8 to 10.
Example III.-Reactioh product of ethylene owide and bis(4-methyl-6-tert-butyl phenol) methane This reaction product can be prepared in the and fully describedmn page 3 in their aeeaece manner set forth in Example II and the resultant product is water-soluble and can be represented C(CHa):
p-Cyclohexyl phenol ethylene oxide reaction product p-Cyclohexyl phenol product p-Dodecyl phenol propylene oxide reaction product propylene oxide reaction .2,6-ditert-butyl-4-methyl phenolxethylene oxide reaction product 2,4-ditert-butyl-S-methyl phenol ethylene oxide .10 reaction product m CH3 p-Octyl phenol propylene oxide reaction product wherein is an integer of fromg to p-Nonyl phenol propylene oxide reaction product i. Bis me h l ert-b t l henol) ethane Example IV.-Reaction product of ethylene oxide (4 t y 6 t u y p m I h propylene oxide reaction product fl'" octyl h l-M d6 We condematwn l p-Octyl thiophenol ethylene sulfide reaction product p t This reaction product can be prepared by rep-Nonyl thiophenol ethylene sulfide reaction acting, at a temperature of from 120 to 160 C. (the product other conditions) Pemg substantially the same as Products of this invention which are partic m Exlample ethylene oxiqe and ularly preferred are sold commercially by Antara phieno 'forma deihyde condensatlon product m Products, a division of General Aniline and Film su table proportions to form a product WhlCh can Corporation under the trade name of e represented by the formula" of which Antarox A-400 is particularly pre- (OC2H4O)::H O(C2H4O)2H a ferred and is a water-soluble liquid representable 1 by the general formula:
CHE J ()(C2H4O-/\TH 8H" 1: CaHrl I R wherein y is an integer of at least 4 and a: is an integer of 8 to 12. l l 1 wherein R is a p-nonyl radical and a: is an integer Dmmple v' sulfongte if of the product of 8 to 10. Another class of commercial ethylene of e V oxide reaction products coming within the scope To prepare the sulfonate derivative of the of this invention are sold by Wyandotte Chemproduct of Example IV, this product can be reical Corporation under the trade name acted with a halogenating agent such as phos- Pluronics, which compounds have the followphorus chloride or thionyl chloride so as to con- 40 ing properties:
Pluronic L44 Pluronic L62 Pluronic L64 Iluronlc F68 Appearance Pale yellow, opaque Paleyellow,1iquid Pale yellow, opaque Free flowing, liquid. 1 uid White flakes.
Percent Active Agent Specific Gravity at 25/25 C.
Viscosity (cps): at 25 C at 40 C. Pour Point, C Melting Point, C pH of 0.25% solution at 25 slight.
51 minimum. 6.5-7.5.
vert the terminal hydroxyl group of the product of Example IV to a chloride. The chloride derivative can then be dispersed in water and treated withisodiumsulfite at a temperature of above 150 C. to form a sulfonate producthaving the formula:
()(CzH40 CzH4SOzN8. O C2H40\ CaHiSQaNB above and which represent working examples of this invention are:
2,4-diamyl phenol ethylene oxide reaction product E. g. Amberol ST-137, produced by Rlghm illd tflilaztis, 00 on yn e 1e Resins for Coating.
The above surface active agents and mixtures thereof can be used in metal working compositions of this invention in amounts varying from 0.01 to about'10% and preferably from.0.1 to 5% by Weight.
The other two essential additives which constitute essential components of this invention are inorganic and organic nitrites and organic or inorganic phosphates; said materials, when combination with a non-ionic surface active agent or agents as described above, exert a synergistic eifect both with regard to metal working efficiency and corrosion inhibiting properties of compositions of this invention.
The nitrites include the metal nitrites such as Na, K, Li, Ca and Ba nitrites, of which the alkali preferred and/or organic base tritessuch as benzyltrimethylammonium nitrite, morpholinium nitrite, dibenzylammonium nitrite, 3,3,5-trimethylcyclohexylammonium nitrite, cyclohexylammonium nitrite, betaphenylethylammonium nitrite, 2,4,4,6-tetramethyl tetrahydro 1,3-0xazonium nitrite, methyl isobutyl carbammonium nitrite, piperidinium nitrite, dicyclohexylammonium nitrite, dicycloisopropylammonium nitrite, etc.
The inorganic phosphates include the alkaline earth metal and alkali metal phosphates of which the mono-, diand tri-sodium phosphates are preferred. However, potassium phosphates,
' tetra-sodium pyrophosphate, sodium tripolyphosphate and sodium borophosphate, as Well as calcium phosphates and ammonium phosphates, can be used or organic phosphates, e. g. tributyl phosphate, trioctyl phosphate, tricresyl phosphate and the like.
The nitrites and phosphates are each used in approximately equal amounts and in concentrations based upon the final composition of from 0.01 to 10% and preferably from 0.1 to by weight.
If desired, minor amounts of anti-foaming, masking or/ and perfuming agents may be added to improve the composition. Among such materials may be included: Anti-foaming agents, e. g., organic silicone compounds (dimethyl silicone polymer), organic phosphates (tributylphosphate), polyglycidylisopropyl ether (mol. wt. 500-1200, preferably 600-800); masking agents, e. g., low molecular weight aldehydes (acetaldehyde) oil of nines. oil of mirbane and the like.
The additive combination of this invention is preferably used with water as the base, however, the combination may be used with any substantially inert polar liquid cutting oil emulsion particularly for use under extreme pressure conditions. In cases where an emulsion is used a coupling agent may be used, suitable illustrative agents being the soluble salts of petroleum sulfonic acids such as sodium petroleum sulfonate; alkali soaps of fatty acids, of rosin acids, of petroleum acids; alkali salts of sulfonated alcohols, e. g., sodium oleyl sulfate, sodium lauryl sulfate, sodium ocenol sulfate; alkali salts of monoand polyalkyl esters of sulfo-dicarboxylic acid (sodium dioctyl sulfosuccinate).
Effective metal working lubricants, in accordance with the present invention, are preparable according to the following formulations:
Broad Preferred Range, Range, Percent Percent Wt. Wt.
. Essential Additives:
Non,ionic agent, e. g., alkyl phenolethylene oxide reaction product (Antarox A-400) 0. 01-10 0. 1-5 Inorganic and/or organi nitrite 0. 01-10 0.1-5 Inorganic phosphate 0. 01-10 0.15 Optional Additives: Anti-foaming agents, coupling agents, etc., e. g., silicone pol ers 0. 0001-1 0.0010.5 Base: Water or aqueous emulsion Balance Balance Illustrative examples of compositions of this invention which can be used, neat or diluted with from 1 to 100 parts of water as metal working lubricants such as for cutting, drilling, breaching, reaming, and the like, are:
Per cent Antarox A-400 0.5 Disodium acid (hydrogen) phosphate 0.5 sodium nitrite 0.5 Water Balance 8 Composition B:
Antarox A400 0.5 Trisodium phosphate 0.5 Sodium nitrite 0.5 Water Balance Composition C:
Antarox A-400 0.5 Disodium acid phosphate 0.5 Dicyclohexylammonium nitrite 0.3 Water Balance Composition D:
Antarox A-400 0.5 Disodium acid phosphate 0.5 Diisopropylammonium nitrite 0.3 Water Balance Composition E:
Pluronics F-68 0.5 Disodium acid phosphate 0.1 Sodium nitrite 0.1 Water Balance Composition F:
Antarox A-400 0.3 Disodium acid phosphate 0.5 Sodium nitrite 0.5 Organic silicone (made by General Electric and identified as 81066 Silicone) 0.05 Water Balance Composition G:
Antarox A-400 1.0 Trisodium phosphate 0.5 Sodium nitrite 0.5 Organic silicone (made by General Electric and identified as 81066 Silicone) 0.05 Water Balance Composition H:
Antarox A400 0.5 Disodium acid phosphate 0.5 Sodium nitrite 0.5 Tributyl phosphate 0.5 Water Balance Composition I:
Antarox A-400 0.5 Disodium acid phosphate 0.5 Sodium nitrite 0.5 Polyglycidylisopropyl ether (mol. wt.
7'70) 0.5 Water Balance Composition J:
Pluronics F-68 1.0 Disodium acid phosphate 0.1 Sodium nitrite 0.1 Tributyl phosphate 0.05 Water Balance Composition K:
Pluronics F-68 1.0 Disodium acid phosphate 0.5 Sodium nitrite 0.5 Organic silicone (made by General Electric and identified as 81066 Silicone) 0.01 Water Balance Composition L:
Antarox A-400 1.0 Disodium acid phosphate 0.5 Sodium nitrite 0.5 Mineral oil 10 Na petroleum sulfonate 1 Water Balance Disodium acid phosphate 0.3 Sodium nitrite 0.3 Water Balance Composition N:
Reaction product of Example II 1.0
Disodium acid phosphate 0.5 Sodium nitrite 0.5 Water Balance CompositionO:
Reaction product of Example In 2.0 Disodium acid phosphate .5 Sodium nitrite 0.5 Water Balance Composition P:
Reaction product of Example IV 0.5 Disodium acid phosphate Sodium nitrite 0.5 Water Balance Composition Q:
Reaction product of Example V Disodium acid phosphate 0.5 Sodium nitrite 0.5 Water Balance Composition R:
Pluronics F-6'8 2.0 Disodium acid phosphate 1.0 Lithium nitrite 0.5 Organic silicone (made by General Electric and identified as 81066 Silicone) .0 Water Balance Composition S:
"Pluronics F-68 0.5 Disodium acid phosphate 0.5 Dicyclohexylammonium nitrite 0.5 Organic silicone (made by General Electric and identified as 81066 Silicone) 0.05 .Water Balance Composition T:
Reaction product 01 Example II 1 Disodium acid phosphate Sodium nitrite 1 Water Balance Composition U:
"Antarox A-400 0.5 Disodium acid phosphate Sodium nitrite 0.5 Mineral oil 1 Water Balance Composition V:
Antarox A-400 0.5 Disodium acid phosphate 0.5 Sodium nitrite 0. Hexadecane succinic acid 0.01 Mineral oil 10 Water Balance In order to illustrate the outstanding properties which compositions of this invention possess, they were subjected to the following tests:
I. TOOL LIFE TEST Compositions as identified hereinbelow were used as lubricants in a drilling operation in which AISI 4340 steel was drilled at a speed 01' 1240 R. P. M. and feed of .006"/rev. with drill to a 10 depth of 1" and the number of holes drilled with each lubricant tested was noted.
Drill life Composition F 58 Composition G- 62 Composition H 72 Commercial cutting fluids:
Cimcool 1 29 "Lns0l 2 29 Composition as described in Br. Patent 644,
1% n-butanol 0.1% NaNOz 0.1% NasPO4 8 0.2% K ricinoleate Water-balance Composition I 21 Composition II 32 Mineral oil 8 Water 8 II. RUST TEST Compositions: Rust Rating Compositions A through S l0 Composition III 1 6 Composition IV 3 Composition V 4 Composition VI 3 Composition VII 3 Composition VIII 6 Composition IX 6 Coinposition III.-Water containing 0.5% Antarox A.--}UU," 0.0% Na i-1.150 and 0.5% Na niercaptobenzocontaining 0.5
thxllZOl. Composition IV.Water Antarox 11-400,? 0.5% Na HP0 and 0.5% thiourea. COHlpOSItlOD. V.wate1' containing 0.5% Antarox 11-400 and 0.5% NagHPU Composition VI.Water containing 0.5% Antarox A-IUO'j and 0.5% NaNO Composition VlI.-Water containing 0.5 Antarox A IOOQ 0.o% NaH0 and 0.5% thiourea. Composition VIIL-Water containing 0.5 Antarox A-LUU 8.116. 0.5% Nflgfiom 7 Composition 1X.w ater containing 0.5% Antarox A400, 0.5% NaHPO; and 0.5% lauryl pyridinium chloride.
m. AIR FLOW FOAMING TEST Foaming tendencies of compositions were evaluated by measuring the amount of foam developed when air is bulbed through the composi tion to be tested. The conditions of the test are:
Measurements- Foam-height at 1,2, 5, 10, 15min.
11 (loniposition: Foam rating after 15 min. F throughK III 950 IV 800 V 800 VI 850 VII 800 VIII 950 IX 950 Percent by weight Nonyl phenol-ethylene oxide reaction product 0.5 Sodium nitrite 0.5 Disodium phosphate 0.5 Water .1 Balance 2. A metal working lubricating composition consisting essentially of the following constituents in the following proportions:
Percent by weight Nonyl phenol-ethylene oxide reaction product 0.5 Sodium nitrite 0.5 Disodium phosphate 0.5 Tributyl phosphate 0.5 Water Balance 3. A metal working lubricating composition consisting essentially of the following constituents in the following proportions:
Percent by Weight Nonyl phenol-ethylene oxide reaction product 0.5 Sodium nitrite 0.5 Disodiumphosphate 0.5 Polyglycidylisopropyl ether 0.5 Water Balance 4. A metal working lubricating composition consisting essentially of the following constituents in the following proportions:
Percent by Weight Nonyl phenol-ethylene oxide reaction product 0.5 Sodium nitrite 0.5 Disodium phosphate 0.5 Dimethylsilicone polymer 0.05 Water Balance 5. A metal working lubricating composition comprising a major amount of water and a minor amount of from 0.01 to each of alkyl phenol-ethylene oxide reaction product, a nitrite selected from the group consisting of an alkali metal nitrite and an organic nitrogen base nitrite and an inorganic alkali metalphosphate.
6. A metal Working lubricating composition comprising a major amount of water and a minor amount of from 0.01 to 10% each of alkyl phenolalkylene oxide reaction product said alkylene oxide being selected from the class consisting of ethylene oxide and propylene oxide, alkali metal nitrite and an inorganic alkali metal phosphate.
. Div. 64.
12 '7. A metal working lubricating composition comprising a major. amount of water and a minor amount'of from 0.01 to 10% each of an alkylphenoxypolyoxyalkylene alkanol, wherein the alklene radical is of 2 to 3 carbon atoms, a nitrite selected from the group consisting of an alkali metal nitrite and an organic nitrogen base nitrite and an inorganic alkali metal phosphate.
8. A metal working lubricating composition comprising a major amount of water and a minor amount of from 0.01 to 10% each of a polyalkylphenoxypolyoxyethylene alkanol, a nitrite selected from the group consisting of an alkali metal nitrite and an organic nitrogen base nitrite and an inorganic alkali metal phosphate.
9. A metal Working lubricating composition comprising a major amount of water and minor amounts of from 0.01 to 10% each of a non-ionic material having the general formula:
A ohm} wherein R and R." are alkylene radicals of from 2 to 3 carbon atoms, R is a hydrocarbon radical, Z is selected from the group consisting of hydrogen, hydrocarbon radical and a -SO3A and --PO3A radicals wherein Ais selected from the group consisting of hydrogen and a cation, the symbol a is a whole number of from 0 to 10 and b is an integer of from 1 to 21; a nitrite selected from the group consisting of alkali metal nitrite and or anic nitrogen basenitrite and an inorganic alkali metal phosphate.
10. A. metal working lubricant composition comprising a major amount of water. and minor but substantially equal amounts of from 0.01% to 10% each of alkyl phenolethylene oxide reaction product, sodium nitrite and disodium phosphate.
11..A metal working lubricant composition comprising a major amount of water and minor but substantially equal amounts each of from 0.01% to 10% of alkyl phenol-ethylene oxide reaction product, disodium phosphate and dicyclohexylammonium nitrite.
12. A metal working lubricant composition comprising a major amount of water and minor but substantially equal amounts each of from 0.01% to 10% of alkyl phenol-ethylene oxide reaction product, disodium phosphate and diisopropylammonium nitrite.
13. A metal working lubricating composition comprising a major amount of water and a minor amount of from 0.01 to 10% each of alkylphenolalkylene oxide reaction product, said alkylene oxide being selected from the class consisting of ethylene oxide and propylene oxide, an organic nitrogen base nitrite and an inorganic alkali metal phosphate.
References Cited in the file of this patent FOREIGN PATENTS Country Date Number Great Britain Oct. 4, 1950 OTHER REFERENCES Synthetic Detergents-Antara Products-Gen. Aniline and Film Corp, March 3, 1950. Copy in