US3167511A - Metal working lubricant - Google Patents

Metal working lubricant Download PDF

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Publication number
US3167511A
US3167511A US102675A US10267561A US3167511A US 3167511 A US3167511 A US 3167511A US 102675 A US102675 A US 102675A US 10267561 A US10267561 A US 10267561A US 3167511 A US3167511 A US 3167511A
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chlorinated
oil
weight
sulphurized
wax
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US102675A
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Crawford William
Wood James Arthur Herbert
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ExxonMobil Oil Corp
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Socony Mobil Oil Co Inc
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    • C10M173/00Lubricating compositions containing more than 10% water
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C10M2207/20Rosin acids
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    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/22Metal working with essential removal of material, e.g. cutting, grinding or drilling
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/242Hot working
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    • C10N2040/243Cold working
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01Emulsions, colloids, or micelles

Definitions

  • the present invention is concerned with lubricants, especially those intended for metal working applications of all kinds and particularly metal cutting, rolling and drawing.
  • the invention is particularly concerned with an additive for such lubricants which will provide greater eificiency than those hitherto used.
  • the lubricant medium envisaged in the present application is generally a petroleum oil or an emulsion thereof in water.
  • Additives for securing particular properties in such lubricants have already been applied in the prior art in great variety.
  • Such additives include compounds added to minimize metal-to-metal contact and the resulting damage to the metal under extreme conditions of pressure.
  • Representative types of such compounds include sulphur compounds, halogen compounds and phosphorus compounds and substances in which these elements are combined, for instance organic sulphides and polysulphides and phospho-sulphurized compounds.
  • Fur ther examples are chlorinated kerosenes and chlorinated waxes.
  • Another class of such additives includes sulphurized fats, fatty acids, esters and higher alcohols.
  • a high proportion of additive is found to be necessary and may, for instance in the case of chlorinated wax, exceed 50 percent of the lubricant.
  • Such a high proportion of additive material is inconvenient, costly and not alway satisfactory from the point of view of the lubricant properties as such.
  • the sulphur frequently used in extreme pressure lubricants to impart anti-welding characteristics may be required in a proportion or degree of activity sufiicient to introduce corrosion of lubricated metal.
  • Fatty oils and sulphurized fats in particular are unstable of themselves and lead to thickening of the oils and the development of unpleasant odour.
  • this and other objects of the invention are achieved compounding a highly chlorinated polyolefine and particularly a chlorinated polyolefine of a molecular weight range of about 50100() and a degree of chlorination of '20'-60% by weight with a suitable base petroleum oil.
  • the preferred molecular weight range of the polypropylene is 126 to 210 and the preferred chlorine content is 30 to 50% by Weight of the product.
  • a compounded lubricating oil particularly useful for broaching, cutting and rolling is formed by adding to a lubricating oil of viscosity range 50350 at 100 F. (S.U.S.) a small amount of a chlorinated polypropylene, such as Anchor N55 (trade name for polypropylene having a molecular weight of about 126 to 2.10 which is chlorinated to a chlorine content of about 30-60% by weight), wherein the polypropylene has a molecular Weight of about 126-210 and is chlorinated to a chlorine content of about 30-50% by weight, manufactured and sold in Great Britain by the Anchor Chemical Company.
  • a chlorinated polypropylene such as Anchor N55 (trade name for polypropylene having a molecular weight of about 126 to 2.10 which is chlorinated to a chlorine content of about 30-60% by weight)
  • Anchor N55 trade name for polypropylene having a molecular weight of about 126 to 2.10 which is chlorinated to a chlorine content of about
  • a sulphurized mineral oil or sulphurized fatty oil may also be present and, if desired, an emulsifier.
  • the preferred lubricating compound also contains a chlorinated wax, such as a chlorinated petroleum Wax, either of the paraffin or microcrystalline type.
  • the chlorinated Wax may vary quite widely provided it has a minimum chlorine content of 40% by weight. Such a Wax is marketed in Great Britain by L.C.I. Limited under the trade name Cereclor 42.
  • the total amount of chlorinated additives including the chlorinated olefine and the chlorinated wax should amount to between 0.5% and 50% by Weight of the total composition, preferably between 2% and 15%.
  • the ulphurized mineral oil is of the type already known for the purpose and may contain about 1% reactive sulphur as measured by the Institute of Petroleum test l/58T Sulphur (reactive to copper) in Cutting Oils.
  • the proportion of sulphurized mineral oil is preferably less than "50% by weight of the total composition.
  • the sulphurized fatty oil is also of the type known in the art andmay be an animal or Vegetable oil containing after sulphurization up to 20% sulphur in such a manner that the sulphur is largely unreactive to copper.
  • the proportion of sulphurized fatty oil should preferably be limited to not more than 15% by weight of the composition.
  • the components other than the chlorinated polyolefine are of types generally known in the art and they may be varied in a manner known in principle to suit the severity of the lubricating operation for which they are intended. For instance, in the lubrication of heavy machinery, an oil of a suitable viscosity will be chosen and the propertions and selection of additive components made to suit the severity encountered, to provide, say, a straight cutting oil. In rolling or the machining of light metals on'the other hand, where cooling is an important factor, an aqueous emulsion may be preferred.
  • the emulsifiers are of a conventional type, such as alkali metal petroleum sulphonates, alkali metal or alkaline earth metal soaps of naphthenic or rosin acids, and also so-called non-ionic emulsifiers.
  • lubricating oil such as fatty oils, fatty acids, esters, alcohols, polyglycols and their esters, antioxidants, anticorrosives, foam suppressors and bactericides.
  • Coupling agents such as phenolic compounds and polyhydric alcohols may also be necessary.
  • the chlorinated polyolefine under the conditions of the test hereinafter described is more effective in preventing wear than the chlorinated wax at equal concentration. It has surprisingly been found, furthermore, that there is a synergetic effect between these additives in that part of the chlorinated olefine can be replaced by a similar amount of the chlorinated wax, the effectiveness of the combination being maintained at a higher level than is to be expected from proportionality, so long as the ratio of chlorinated polyolefine to chlorinated wax is not less than about 1:1, preferably 221. This is important economically at the higher additive concentrations where a considerable cost reduction can be effected by this means.
  • the sulphonates are sodium petroleum mahogany sulphonates of molecular weight about 420.
  • the Renex and Ethylan materials are condensation products of nonyl-phenol with ethylene oxide.
  • the nonyl-phenol used in the preparation of these materials is a mixture of orthoand para-nonyl phenol in which the para-isomer predominates in the proportion of about parts to 15 parts of the ortho.
  • Renex 688, Renex 697, and Ethylan BCP one mol. of the nonyl-phe'nol is condensed with 8, 6 and 9 mols respectively of ethylene oxide.
  • the polyethylene glycol (300) di-oleate is the di-oleate ester of a polyethylene glycol of molecular Weight approximately 300.
  • a lubricating composition comprising (1) a major proportion of a petroleum lubricating oil having a viscosity in the range of 50-350 S.U.V. at F, (2) a minor proportion of a sulphurized mineral oil, (3) about 2l5% by Weight of a chlorinated petroleum Wax having a chlorine content of at least 40% by Weight, and (4) about 2-15% by weight of a chlorinated polypropylene, the
  • polypropylene having a molecular Weight of about 126 210 and being chlorinated to a chlorine content of about 30-50% by weight, said composition being further characterized in that the ratio of the chlorinated polypropylene to the chlorinated petroleum Wax is at least 2: 1.

Description

United States Patent 3,167,511 METAL WORKHNG LUBRICANT William Crawford, Leigh-on-Sea, and James Arthur Herbert Wood, Fobbing, Essex, England, assignors, by mesne assignments, to Socony Mobil i] Company, Inc., New York, N.Y., a corporation of New York No Drawing. Filed Apr. 13, 1961, er. No. 102,675
1 Claim. (Cl. 252-483) The present invention is concerned with lubricants, especially those intended for metal working applications of all kinds and particularly metal cutting, rolling and drawing. The invention is particularly concerned with an additive for such lubricants which will provide greater eificiency than those hitherto used.
The lubricant medium envisaged in the present application is generally a petroleum oil or an emulsion thereof in water. Additives for securing particular properties in such lubricants have already been applied in the prior art in great variety. Such additives include compounds added to minimize metal-to-metal contact and the resulting damage to the metal under extreme conditions of pressure. Representative types of such compounds include sulphur compounds, halogen compounds and phosphorus compounds and substances in which these elements are combined, for instance organic sulphides and polysulphides and phospho-sulphurized compounds. Fur ther examples are chlorinated kerosenes and chlorinated waxes. Another class of such additives includes sulphurized fats, fatty acids, esters and higher alcohols.
In very severe operations in which lubricants are used, for example breaching, a high proportion of additive is found to be necessary and may, for instance in the case of chlorinated wax, exceed 50 percent of the lubricant. Such a high proportion of additive material is inconvenient, costly and not alway satisfactory from the point of view of the lubricant properties as such. Again, the sulphur frequently used in extreme pressure lubricants to impart anti-welding characteristics, may be required in a proportion or degree of activity sufiicient to introduce corrosion of lubricated metal. Fatty oils and sulphurized fats in particular are unstable of themselves and lead to thickening of the oils and the development of unpleasant odour.
It is an object of the present invention to provide a compounded lubricating oil having unusual properties for metal cutting, metal rolling and particularly for cold rolling aluminum.
We have found that this and other objects of the invention are achieved compounding a highly chlorinated polyolefine and particularly a chlorinated polyolefine of a molecular weight range of about 50100() and a degree of chlorination of '20'-60% by weight with a suitable base petroleum oil. The preferred molecular weight range of the polypropylene is 126 to 210 and the preferred chlorine content is 30 to 50% by Weight of the product.
According to the present invention a compounded lubricating oil particularly useful for broaching, cutting and rolling is formed by adding to a lubricating oil of viscosity range 50350 at 100 F. (S.U.S.) a small amount of a chlorinated polypropylene, such as Anchor N55 (trade name for polypropylene having a molecular weight of about 126 to 2.10 which is chlorinated to a chlorine content of about 30-60% by weight), wherein the polypropylene has a molecular Weight of about 126-210 and is chlorinated to a chlorine content of about 30-50% by weight, manufactured and sold in Great Britain by the Anchor Chemical Company. A sulphurized mineral oil or sulphurized fatty oil may also be present and, if desired, an emulsifier. The preferred lubricating compound also contains a chlorinated wax, such as a chlorinated petroleum Wax, either of the paraffin or microcrystalline type. The chlorinated Wax, however, may vary quite widely provided it has a minimum chlorine content of 40% by weight. Such a Wax is marketed in Great Britain by L.C.I. Limited under the trade name Cereclor 42. The total amount of chlorinated additives including the chlorinated olefine and the chlorinated wax should amount to between 0.5% and 50% by Weight of the total composition, preferably between 2% and 15%.
The ulphurized mineral oil is of the type already known for the purpose and may contain about 1% reactive sulphur as measured by the Institute of Petroleum test l/58T Sulphur (reactive to copper) in Cutting Oils. The proportion of sulphurized mineral oil is preferably less than "50% by weight of the total composition. The sulphurized fatty oil is also of the type known in the art andmay be an animal or Vegetable oil containing after sulphurization up to 20% sulphur in such a manner that the sulphur is largely unreactive to copper. The proportion of sulphurized fatty oil should preferably be limited to not more than 15% by weight of the composition.
The components other than the chlorinated polyolefine are of types generally known in the art and they may be varied in a manner known in principle to suit the severity of the lubricating operation for which they are intended. For instance, in the lubrication of heavy machinery, an oil of a suitable viscosity will be chosen and the propertions and selection of additive components made to suit the severity encountered, to provide, say, a straight cutting oil. In rolling or the machining of light metals on'the other hand, where cooling is an important factor, an aqueous emulsion may be preferred.
The emulsifiers are of a conventional type, such as alkali metal petroleum sulphonates, alkali metal or alkaline earth metal soaps of naphthenic or rosin acids, and also so-called non-ionic emulsifiers.
Further additions may be made as desired, to modify the properties of the lubricating oil, such as fatty oils, fatty acids, esters, alcohols, polyglycols and their esters, antioxidants, anticorrosives, foam suppressors and bactericides. Coupling agents such as phenolic compounds and polyhydric alcohols may also be necessary.
The chlorinated polyolefine under the conditions of the test hereinafter described is more effective in preventing wear than the chlorinated wax at equal concentration. It has surprisingly been found, furthermore, that there is a synergetic effect between these additives in that part of the chlorinated olefine can be replaced by a similar amount of the chlorinated wax, the effectiveness of the combination being maintained at a higher level than is to be expected from proportionality, so long as the ratio of chlorinated polyolefine to chlorinated wax is not less than about 1:1, preferably 221. This is important economically at the higher additive concentrations where a considerable cost reduction can be effected by this means.
The interaction between the two chlorinated additives Was indicated by statistical analysis of the results of Falex and 4-ball Wear tests on a set of experimental composil 4-ball tests in these cases were made on emulsions containing 10% of the oil and 99% of water by volume:
tions designed on the fractional re licate principle. The mteraction was seen to hold for the chlorinated additives D E F G H alone and also in the presence of the sulphurized additives 5 and a synergetic interaction was also indicated between Chlorinated PmypmpyL Perm Perm" Perm Perm Pmcm the chlorinated additives and the sulphnrized additives. ens (Anchor N55) 2.0 5.0 5.0 These eilects are illustrated in the accompanying tables gf gga f 5 0 5 0 "showing the anti-Wear properties of various compositions (annex cssj iisc'fibd a a 1 h L oe 0W 5.0 4.75 as m asured by the 4 call machine. In this tvS'L three (Reflex 697) Described steel calls are rigidly clamped in contact with eacn other A al n-F and pressed by means of a loading lever against a rotating l fi 6 0 .fourth steel ball which makes contact With all three staz figg g glycomoo) 5 0 r 0 L A L o. tionary balls, the POllltS of contact being lubricated by Rapeseed on- 5.0 5.0 o I I! the composition under test. At fixed load, speed and Q U 730 6&0 time of rotation the average diameter of the scars left on the three stationary balls is a measure of the Wear 'perad, kg; Ssar dia. (aim) mitted by the lubricant and therefore the smaller the scar diameter the better the wear-preventing properties 7 0 of the lubricant. The relative effects hold for a range il; 8: ssi igg seii ti of loads and can be illustrated by the results at one load.
Table l letroleum Sulphurizcd Sulphurized 011, Percent, Mineral Oil, Fatty Oil, Scar Diameter (cm.) Chlorinated Chlorinated Refined Percent, Percent; at load Polyolcfinc, Wax, naphthenic Sulphu'rized (Sulphurized Percent, Percent, oil of the fatty oil of lard oil up to Anchor N 55 Cercclor 42 Saybolt; minimum 1% reactive S,
Universal Sulphur content 100 seconds Viscosity 100 9% by weight viscosity) 150 kg. 300 kg sec. at100 F.
97 Seized The following table gives examples of straight metal Working 0115 showing the corresponding 4-ball Wear test results (S.U.V. refers to second Saybolt Universal 100" an at 100 11 220" S.U.V. at 100 F Load, kg: Scar dla. (1pm.)
0.91 1. 1. 17 1. 58 1. 42 1. 68 1. 46 1. 94 1. (i0 Seized 1. 73
The following table gives examples, of soluble oils.
The sulphonates are sodium petroleum mahogany sulphonates of molecular weight about 420.
The Renex and Ethylan materials are condensation products of nonyl-phenol with ethylene oxide. The nonyl-phenol used in the preparation of these materials is a mixture of orthoand para-nonyl phenol in which the para-isomer predominates in the proportion of about parts to 15 parts of the ortho. In Renex 688, Renex 697, and Ethylan BCP one mol. of the nonyl-phe'nol is condensed with 8, 6 and 9 mols respectively of ethylene oxide.
The polyethylene glycol (300) di-oleate is the di-oleate ester of a polyethylene glycol of molecular Weight approximately 300.
The examples given hereinabove are suppliedto illustrate the invention without in any way limiting the scope of the invention. The only limitations intended are those found in the attached claim.
We claim:
A lubricating composition comprising (1) a major proportion of a petroleum lubricating oil having a viscosity in the range of 50-350 S.U.V. at F, (2) a minor proportion of a sulphurized mineral oil, (3) about 2l5% by Weight of a chlorinated petroleum Wax having a chlorine content of at least 40% by Weight, and (4) about 2-15% by weight of a chlorinated polypropylene, the
polypropylene having a molecular Weight of about 126 210 and being chlorinated to a chlorine content of about 30-50% by weight, said composition being further characterized in that the ratio of the chlorinated polypropylene to the chlorinated petroleum Wax is at least 2: 1.
References Cited in the file of this patent 5 UNITED STATES PATENTS 2,126,590 Valentine Aug. 9, 1938 2,225,318 Morway et al. Dec. 17, 1940 2,296,037 Kaufman Sept. 15, 1942 2,298,833 Muessig Oct. 13, 1942 10 6 Hull et al7 July 2, 1946 Perry et a1. Dec. 9, 1952 Talley et a1 June 29, 1954 Gililland et a1 Aug. 19, 1958 Hughes et a1 Sept. 16, 1958 Beretvas Jan. 19, 1960 Sudholz July 25, 1961 FOREIGN PATENTS Great Britain May 18, 1945
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