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United ate'nt tates ice 1 2 for bacteria inhibition of soluble oils and soluble oil emulsions is Z-nitro-l-butanol. 3,033,735 BACTERIA INHIBITED SOLUBLE OIL ' 3,033,785 ‘Patented May ,8, ‘l 962 The nitro-butanols are effective bactericides in soluble oil emulsions in amounts ranging from about 25 to 2500 ppm. The amount of these bactericides placed in solu ble oils in order to obtain the proper concentration in the formed emulsions ranges from 0.1 to about 6 percent by COMPGSITION Edward 0. Bennett, Houston, Tex., assignor to Texaco Inc., a corporation of Delaware No Drawing. Filed June 2, 1958, Ser. No. 738,990 5 Claims. (Cl. 252-—33.3) weight based on the oil. This invention relates to a soluble oil inhibited against The soluble oil mainly comprises a minerallubricat bacterial action. More particularly, it relates to a bac 10 ing oil and an emulsifying agent. The mineral oil is pref tericide-containing soluble oil particularly useful in the erably a naphthene base distillate oil although mixed form of an emulsion as a metal working lubricant. paraf?n-naphthene base distillate oils are at times effec tively employed. . Naphthene base distillate fractions are mixtures of mineral and vegetable oils, and an emulsify desirable because of their better emulsi?cation properties ing agent to lower the interfacial tension between the oil 15 and stability. In general, re?ned base oil fractions hav and large volumes of water whereby emulsions of the oil_ ing an SUS viscosity at 100° F. between 70 and 800 are in-water type may be easily formed. The emulsifying used in the formulation of the soluble oils of this inven agents commonly used include soaps of petroleum sul :tion. Soluble oils generally are composed of mineral oil or fonic acids, naphthenic acids, fatty acids, rosin and tall The emulsifying agents useful in the present invention oil. Soluble oils usually contain coupling agents and 20 are those known ‘in the ant. Examples of these emulsi small amounts of water to stabilize the composition prior ?ers include oil soluble metal petroleum sulfonates, alkali to emulsi?cation. Various lubricant additives are also metal naphthenates, and resinates, salts of fatty and car used to correct or improve certain characteristics of the boxylic acids, such as guanidine salts of high molecular . soluble oil or soluble oil emulsion. The oil-in-water emulsions are formed with water-to oil ratios ranging from 5:1 to 100:1. The more dilute Weight ‘fatty acids and alkylolamine salts of carboxylic which it was intended. employed. acids containing at least 10 carbon atoms, alkali metal salts of tall oil, etc. These soaps or salts are usually. emulsions, from 25:1 to 100:1 are preferred for cutting formed with sodium because of the lower cost and avail oils which are used as lubricants and coolants in high ability, but potassium is also used. Mixtures of emulsi» speed metal turning operations. ?ers, for example a mixture of sodium naphthenate and The soluble oil itself is shipped to the user, in a sub 30 sodium petroleum sulfonate, a mixture of sodium resinate, stantially sterile condition. However, bacteria can be sodium naphthenate and sodium petroleum sulfonate, and. introduced in an emulsi?ed soluble oil either through the a mixture of guanidine stearate and triethanolamine water used in the preparation thereof or through contami stearate have been found extremely useful. nation by the workers or from the air during use. The The total emulsi?er concentration is between 10 and bacteria, if allowed to grow unchecked, will eventually 20 percent, by weight of the total soluble oil composition cause breakdown of the emulsion and curtail the use for with concentrations between 12 and 16 percent usually ' In addition to the above occurrence, a serious odor Minor amounts of coupling agents are also advan problem is created by certain bacterial growth in the cut tageously employed in the soluble oil composition to im ting ?uid. It is believed that initially the growth of 40 prove the texture and stability thereof. Those coupling aerobic bacteria takes place with a resulting slight break agents useful in this invention include mono and polyhy down of the emulsion. During shutdown periods of the droxy alcohols, ether-alcohols, and phenols. Examples cutting machinery, as on weekends and holidays, an of these compounds include ethyl, isopropyl, n-propyl, aerobic sulfate-reducing bacteria grow quickly in ‘the used cutting ?uid due to inadequate aeration in the quiescent 4.5 system and to the conditions or material provided by the prior growth of aerobic bacteria in the ?uid. The isobutyl, n-butyl and n-amyl alcohols; ethylene glycol, di ethylene glycol and propylene ‘glycol; ethylene glycol monoethylether (Cellosolve), ethylene glycol monoiso propylether, ethylene glycol monobu-tylether, ethylene glycol mono-n-pentylether, ethylene glycol mono-n hexylether, diethylene glycol monoethylether (Carbitol), presence of large amounts of sulfate-reducing bacteria causes severe odor problems due to the formation of sul~ ?des, and the odor is particularly noticeable on Monday 50 diethylene glycol monobutylether and cresol. The con mornings after weekend shutdown periods. ,The growth centration of the coupling agents in the soluble oils is of anaerobic bacteria also causes a quicker and more usually between 0.1 and 1.5 percent by weight. A pre severe emulsion breakdown than is caused by aerobic ferred coupling agent is ethylene glycol monobutylether bacteria necessitating draining and cleaning of the cut at a concentration of about 0.6-1.0 percent by weight. ting ?uid system and the addition of new cutting ?uid. 55 In preparing the soluble oil of this invention a small ' The problem of ?nding a satisfactory bacterial in amount of Water is preferably used to make the soluble hibitor for a soluble oil is made di?icult by a number of oil ?uid and to prevent oil separation, or Strati?cation of factors which must be considered. These factors include the emulsion, upon mixing the soluble oil with much toxicity, oil solubility, storage stability, emulsion degra larger amounts of Water. The water content, to stabilize dation, additive compatibility and growth inhibition of 60 the oil, usually falls between 1 and 4 weight'percent. HA: harmful bacteria for a sufficient period during the life water content of about 2 percent has been found to be of the oil. In accordance with the present invention a soluble oil particularly effective in the soluble oil composition. composition which will meet the above requirements con taius a bacteria-inhibiting amount of a hydroxy substi tuted nitrobutane. Examples of the bactericide com pounds of this invention include 2-nitro—1-butanol, 3 nitro-l-butanol, 4-nitro-1-butanol, l-nitro-2-butanol, l nitro-3-butanol, 2-nitro-2-butanol, 2-nitro-3-butanol, and ' Other useful lubricant additives, to improve certain characteristics of the solublev oil, are at times used in the 65 composition. These include, for example, rust preventa tives such as tn'ethanolamine, extreme pressure and oil - iness agents, and settling agents. In order to determine the value of compounds, known or expected to have bacteria destroying properties in wa the hydroxy substituted nitro-isobutanes such as Z-nitro 70 ter solutions, as bactericides in soluble oil emulsions, a Z-methyl-l-propanol, 3~nitro-2-methyl-2-propanol and 3~ screening test was used. This test'consisted of preparing nitro-2-rnethyl-1-propanol. The preferred nitrop-butanol the cutting ?uids or soluble oil emulsions and adding 100, a 3,033,785 q . g 4 > 500, and 1000 p.p_.m. of each bactericide to 20 m1. of Table I——Continued the emulsion in test tubes.‘ The tubes were then auto claved at 15 pounds, steam pressure for 15 minutes} After the tubes had cooled to atmospheric temperature, ‘ 0.5 ml; of a composite used cutting oil samples or inocu No. of Eliective Days of Inhibition 100 p.p.m. lum was ‘prepared by mixing the “spoiled” cutting oil sam , ples of several users. .The bacterial content of the in 500 p.p.m. 1,000 p.p.m. 27 10% Phenylmercuric acetate .... __ Organic mercurial (Exact; chemi oculum was determined and‘in every case the tubes were inoculated with a standard known number of viable bac cal composition not known) _ - _ ; 1,2 - Dichlorohexa?uorocyolopen - teneal teria. Tubes of sterile uninhibited. uninoculated emul 10 sions and uninhibited inoculated emulsions were em Oyelohexyl chloride. _ 2-Arnino-L4 naphthoquinone____. Propyl-p-hydroxyhenzoate__.____ ployed as controls. All tubes were placed on a shaking Butyl-p-hydroxybenzoate.--- machine making 209 oscillations per minute. Immedi ately after inoculation of the emulsions and at 24 hour --. ...................... __ p-Ohloro-m-xylenol _____________ __ 3 6 agro Lauryl isoquinolinium bromide__ Phenylmereuric monoethauol-am intervals for a period of 7 days, each tube was tested for 15 monium acetate ______________ ._ Zinc salt of dimethyl dithiooarha the presence of viable bacteria by inoculating nutrient mic racid broth with a small standard volume of emulsion. The 3,5-Dibromo-2-phe'nyl Inercurloxy benzoic acid ____ _. broth tubes were incubated for 48 hours and then ex Sodium salt of dibromohydro‘xy amined for bacterial growth. Those bactericides which ' mercuri, ?uoreseein (mercuro caused the inoculated emulsions to become sterile within 20 Phenyl mercuric salicylate_.._-_-_ the seven day test period were considered promising and 1-Hydroxy-2-(1H)-pyrid.ine'thi0ne (zinc salt) _ __ were subjected to further testing. Of over 250 known l-Hydroxy- -(1H)-pyridine thlone bactericides tested in- the above manner less than a third (copper salt) _____ Morpholine 511i co?uoride _______ _ _ were considered promising for bacteria inhibition of sol Rosine amine si1ic0?uor1de.__ ‘ uble oils. ’ chrome) ___________ __'_________ - n>o—‘: O QcKaGOnNUo-gw4: Trls(hydroxymethyl)amiuo meth 7 "mp Effective materials found with the above test procedure Tris(hydroxymethy1 (nitro-meth- RT] P were further tested in an Open System Test. The pro Nitromethane. _ cedure consisted of placing 3.0 grns. of powdered iron Nitroethane- _ 1-nitropropane_-___ and 3000 ml. of a 25:1 soluble oil emulsion containing the experimental ‘bactericide in a one gallon jar and in 30 2-nitropromne l-Ohloro-lanitro-propane ________ __ 2-Ohloro—2-nitro-propane“_ oculating with a known quantity of bacteria. The solu 1,l-Dichloro-l-nitro-propane ..... _. ble oil consisted of a naphthene base distillate oil having 2-Amino-2-ethyl-L3 propane-din! an SUS viscosity at 100°5 F. of about 72, 7.5 percent so 1,4~diehlorobufane ' dium resinate, 12.0 percent sodium petroleum sulfonate, 1.0 percent ethylene glycol monobutylether, 0.5 percent " WOG 2-Nitro-l-butano1 _______________ _. triethanolamine and 2.0 percent water. The system was then aerated for 5 days and allowed to stand quiescent for 2 days each week. Immediately after inoculation and twice a week, thereafter duplicate standard plate In the aboverdata, l00‘p.p.m., 500 ppm. and 1000‘ ppm. correspond respectively to about 0.25, 1.25 and 2.50 percent by weightof the potential bactericides in the counts were made. The inhibitors were considered ef 40 soluble oil before the formation of the 25:1 dilution emul-. fective as long as bacteria counts remained less than IOOO/ml. sion. The following table shows the results of the Open Sys tern Test on the potential bactericides: , , In addition to the above ?ndings, 3-nitro-2-pentanol ’ was found ineii‘ective in the previously described screening ' ' test. From the above data it can easily be concluded that 45 the compounds of the invention are exceptional aerobic ' Table I bacteria inhibitors in soluble oil emulsions. Some of the compounds listed in the foregoing Table I No. of Effective Days of Inhibition 100 ppm. 500 p.p.m. 1,000 p.p.m. o-Phenyl phenol ........ -. Resorcino1 ____________ .. Resoreinol dibenzoate ______ .- _ ______________________ __ ' Mercuric naphthenate __________ __ 0 0 0 the solution turned clear. The solution was then able to be added to the soluble oil.’ Obviously, many modi?cations and variations of the invention, as hereinbefore set forth, may be made without Zinc salt of alkyl-N-propylene diamine-pentachloronheunl Pentachloronbeuol - Tetradecylamine salt of o-phenyl nhpnnl ’ v Dichlornphene ' Copper naphthenate, 8% _______ __ H Azochloramide _________________ __ Mixture of 4 and 6 chloro-2-phenyl ‘ exco henol ________________________ __ 1N ethylene bis-phenoL. _ Tetrachlorophenol ........... _..__ Mixture of o and p-dimethyL onO030 aminomethyl phenol __________ __ 2,4,6- ri(dimethylarninomethyl) H phenol ________________________ __ Beta-propio1actone-_ _. Diethyl acid pyrophosphate m-CresoL. 2 ‘ 3 Malonio arid 1,2-Dlbromo-1, dichloroethaue__-_ Hydroxylamlne H01 sol. _______ -_ Mixture of 2,8-diamiuo-10-methyl acridinium chloride and 2,8 diamino am-idinp Ditto, H01, sol Dtchloro-m-xy1erm1 M mHwe: g5o:m20gcazomwr 60 departing from the spirit and, scope thereof, and there fore only such limitations should be imposed as are indi cated in the appended claims. I claim: g , 1. An improved soluble oil consisting essentially of a 65 major portion of an emulsi?able mineral lubricating oil, from 10 to 20 percent by weight of an oil-in-water emulsi fying agent, and a bacteria inhibiting amount of Z-nitro-l butanol. 2-Methyl-lA-naphthoquinone ___________________________ __ 2-Phenyl ethylamine 50 se, decomposed in the soluble oil in storage, degraded. soluble oil emulsion properties, or could only be incorpo rated in the soluble oil by utilizing a special technique which entailed adding the potential bactericide to ethylene glycol monobutylether, which is usually incorporated as 55 a coupling agent, heating this solution to 130° F. until Sodium o-phenylphenate. Alkylamine o-phenyl phenol ____ __ were eifective in this test. However they were objec tionable as either completely insoluble in soluble oil per ‘ . 2. An improved soluble oil consisting essentially of a 70 majorv portion of an emulsi?able mineral lubricating oil, from 10 to 20 percent by weight of an oil-in-water emulsi tying agent, and from 0.1 to about 6 percent by weight Z-nitro-l-butanol. 3. An improved soluble oil emulsion consisting essen~ 3“ 75 tially of about 5 to 100 ‘parts of‘water, about one part of 3,033,785 6 an emulsi?able hydrocarbon oil composition consisting es of water; and from about 100 to 1000 parts per million sentially of a major portion of a mineral lubricating oil, of Z-nitro-I-butanol. from 10 to 20 percent by weight of an oil-in-water emulsi References Cited in the ?le of this patent fying agent, and from 25 to 2500 parts per million of 2-nitro-1-butanol. UNITED STATES PATENTS 4. An improved soluble oil emulsion as described in 2,402,487 Batchelder et a1 ________ __ June 18, 1946 claim 3 containing from about 100 to 1000 parts per 2,653,909 Frazier ______________ __ Sept. 29, 1953 million of Z-nitroJ-butanol. 2,668,146 Cafcas et a1 ____________ _.. Feb. 2, 1954 5. An improved soluble oil emulsion consisting essen tially of about 25 to 100 parts of water; about one part of FOREIGN PATENTS an emulsi?able hydrocarbon oil composition consisting 421,189 Italy ________________ __ Mar. 19, 1947 essentially of a major portion of a naphthene base distil 107,419 Australia ____________ _.’_ May 25, 1939 late oil having an SUS viscosity range at 100° F. of from 70 to 800, 12 to 16 percent by weight of a sodium salt of OTHER REFERENCES a compound selected from the group consisting of naph- 15 Pivnick et al.: “Disinfection of Soluble Oil Emulsions,” thenic acid, sulfonic acid, rosin and mixtures thereof, Journal of the American Society of Lubrication Engineers, from 0.1 to 1.5 percent by weight of a coupling agent March 1957 (pages 151—153). selected from the group consisting of monhydroxy alco “Fundamentals of Microbiology," by Frobisher, 5th ed., hols, polyhydroxy alcohols, ether-alcohols, phenols and mixtures thereof, and from about 1 to 4 percent by weight 20 1953, by W. B. Saunders Company, page 3.