US3177146A - Fire-resistant hydraulic fluids - Google Patents

Fire-resistant hydraulic fluids Download PDF

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Publication number
US3177146A
US3177146A US145754A US14575461A US3177146A US 3177146 A US3177146 A US 3177146A US 145754 A US145754 A US 145754A US 14575461 A US14575461 A US 14575461A US 3177146 A US3177146 A US 3177146A
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United States
Prior art keywords
water
oil
soluble
composition
emulsion
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Expired - Lifetime
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US145754A
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English (en)
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Charles E Francis
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Shell USA Inc
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Shell Oil Co
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Priority to NL284405D priority Critical patent/NL284405A/xx
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US145754A priority patent/US3177146A/en
Priority to FR912282A priority patent/FR1337607A/fr
Priority to CH1209262A priority patent/CH434533A/de
Priority to GB38997/62A priority patent/GB967785A/en
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Publication of US3177146A publication Critical patent/US3177146A/en
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    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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    • C10M2219/04—Organic 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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    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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    • C10M2223/04—Phosphate esters
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2229/02—Unspecified siloxanes; Silicones
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    • C10M2229/04—Siloxanes with specific structure
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    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/044—Siloxanes with specific structure containing silicon-to-hydrogen bonds
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    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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    • C10N2010/00—Metal present as such or in compounds
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
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    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • fire-resistant fluids are commercially available such as phosphate ester base fluids, but
  • a water-in-oil emulsion which comprises from about to, about 45% of water phase and from about 55% to about80% of oil phase, the emulsion containing three essential additives namelyftw'o particular types of dissimilar non-ionic surface active agents and a water-soluble polymeric derivative of an acrylic acid represented'by the formula:
  • R is hydrogen or. a C 4 alkyl radical
  • R and R" may be hydrogen or lower alkyl radicals of up to 8 carbon atomsor they may be. mixtures of hydrogen and a lower alkyl radical
  • M is a cation such asanalkali metal such as lithium, sodium or potassium, or ammonia or an organic base
  • x is a positive integer
  • y may be zero 3,177,146 I Patented Apr fi, 1965 or a positive integer
  • z may be zero or a positive integer
  • the molecular weight of the polymer varying from at least 1000, up to 500,000, preferably between 25,000 and'300,000.
  • a polymer as represented by (I) a mixture of water-soluble homopolyrner's containing the desired groups :R CH3C O OM (II and I l- R L lg NRRL (III,
  • the two non-ionic surface agents which are added to the mineral oil are (1) a monoester of a long chain fatty acid having at least 8 carbon atoms and an inner'ether of aliphatic polyhydric alcohols such as hexahydric alcohols and (2) a polyalkyleneoxy phenoxy alkanol.
  • Each of these additives must be present in critical amounts of which the monoester (1) is used in amounts ranging from 1% to 4%, preferably from 1.5% to 3% and the polyalkyleneoxy phenoxy alkanol (2) isused in amounts ranging from 0.5% to 3%,preferably from 1% to 2%.
  • the inner ether alcohol is prepared by partially dehydrating polyhydric alcohols whichv results in the conversion of the polyhydric alcohol to inner ether polyhydric compounds having '1 or 2 ethers and 4 to 6 hydroxyl groups in the molecule in the manner described-in US. Patent 2,322,820.
  • Compounds of this type are exemplified by sorbitan, mannitan, xylitan, dulcitan, etc.
  • Fatty acids which are used to form the monoesters of the inner ether polyalcohols are saturated a-nd unsaturated fattyacidshavingat least 8 carbon atoms, preferably from 12 to 18 carbon atoms, such I ;aslauricgstearic,.oleic, linoleic, ricinoleic acids and the '.like.., Monoesters of this type include'sorbitan monolaurate, sorbitan monostearate,.sorbitan monoole'ate, sor- .bitan monoricinoleate, mannitan monolaurate, mannitan monooleate, and mixtures thereof. Compounds of this type are available commercially as Span 20, 60 or from the Atlas Powder Company.
  • the second essential additive is an oil-soluble alkyl phenoxy polyalkylene glycol having the formula propanol, and mixtures thereof.
  • the water-soluble copolymer or mixtures of homopolymer as defined by the above formulas can be prepared by any suitable means well known to the art.
  • the copolymers of Formula I can be prepared by copolymerizing a mixture of acrylic acid and acrylamide and reacting the copolymer with an alkali metal hydroxide to convert wholly or in part the acid groups to alkali metal carboxylate groups or an acrylamide may be polymerized and hydrolyzed inthe presence'ofapolymerization catalyst and alkali metal hydroxide.
  • the catalysts include inorganic or organic peroxides, or per-acids orazo catalysts .suchas V hydrogen peroxide,.. diethyl peroxide, benzoyl peroxide,
  • sodium or. potassium persulfiate, azocatalyst, e.g., alpha! -alphaJ-azodiisobutyronitrite, etc. and the-alka'li metal hydroxide. includes sodium, potassium and lithium hydroxparts o-f water and (b) aqueous mixture of about 400 parts 900 parts water and reacting the two (a) and (b) at about 80 C. in the presence ofan inert atmosphere.
  • water-soluble polymers in the'molecul-ar weight range of 5000-400,000 include sodium polyacrylate, so-
  • water-soluble polymers of the above type are useful as thickeners, as polyelectrolytes, as fluocculants,
  • polymers are dispersed in the waterphase of emulsions of water containing the polymer to] desired degree.
  • antioxidants and antiwear agents from about 0.01% to about 2%,preferably from about 0.2% to about 1% optional'additives which include antioxidants and antiwear agents.
  • The-antioxidants include phenolic, amine and/or metal thiophosphate compounds.
  • the phenolic compounds are illustrated by the "alkyl phenols, e.g., di-and trialkyl'phenols, for instance, 2',4-, 2,3-
  • the amines are illustrated in ar ylamines such as phenyl-alpha-naphthylamine or phenyl-beta-naphthylamine.
  • the metal thio phosphates are illustrated by alkaline earth metal thiophosphates, e.g., calcium or zincdimethyl cycl'ohexyldithiophosphate. The.
  • antiwear agents are sulfur-containing compounds such as oil-soluble polychlo'ro hydrocarbyl thiocarbonate esters, e.g., polychloronaphtha methyl xanthate marketed by Monsanto Chemical Co. under .the
  • Thi'ocarbonates ofithis type are prepared by reacting a chlorinated petroleum I naphtha with an alkali metal (potassium) amyl dithiocarg bonate; organic sulfides such as dibenzyldisulfide' or di- 'chlorodibenzyl disulfide. Dyes and antifoaming agent can Oil-soluble be added. to composition ofv this invention.
  • dyes include naphthol yellow, Sandoz yellow, methylene blue, .aliz'arin compounds, etc.', 'while anti-foaming agents include silicone polymer (DC-200 fluids ranging in vis cosity in centistokes from 100 to 1000 at 250 C.) or-sili cone type A fluidmade by Dow-Corning Co. and described in US. Patents 2,563,588and 2,662,055and mixtures thereof. 7
  • the oil may beentirely a hydrocarbon oil of wide -vis cosity range, e.g'.,from less than SOSUS atlOO F. to 15 0 SUS.at 210 F.
  • Oils of this type can :beobtain'ed from various crudessuch as parafiinic, naphthenicor mixed basecrudes; refined oi-ls in the lubricating oil viscosity range are preferred.
  • the hydrocarbon ing or after it is prepared'is not necessary. If desired, the emulsion canbeput through a homogenizer to insure 7 shipping costs can bereduced.
  • oil may be blended with fixed oils such as castor oil, lard oil and vthe'like and/or with synthetic lubricants suchas polymerized olefins, organic .estersyofi organic and inor- I ganic acids, e.g., di-Z-ethylhexyl sebacate, dioctyl phthal-- ate, trioctylphosphate; polymeric tetrahydrofuran, polyalkyl silicone polymer,- e.g., dimethylsilicone polymer and the like.
  • fixed oils such as castor oil, lard oil and vthe'like and/or with synthetic lubricants suchas polymerized olefins, organic .estersyofi organic and inor- I ganic acids, e.g., di-Z-ethylhexyl sebacate, dioctyl phthal-- ate, trioctylphosphate; polymeric tetra
  • hydrocanbon oil such .as atmineral-lubricatingzoil is always present in the predominant amount such as from 60% to about of the oil :blend.
  • Astraightmineral lubricating oil havingga viscosity index of at least 50. and ranging inviscosity at 1009--F.
  • emulsion can be preparedby adding. the required amount of water containing the polymeric compound as described to an oil,containing theother two essential additives, while constantly stirring the mixture. Heating the; emplsion dura more, stable emulsion-
  • the :oil concentrate, composition can be prepared and .thejre'quired. amount of water containing a polymeric compound as described added whenthe emulsion lubricant is ready .foruse.
  • storage and Illustrative examples of:minera1 oilbases of this invention which are emulsified ,iwith ,from about 20% 'to about 45%, preferably fromaboutt 30% to about 40% of water. containingpolymeric acylo compound to form a stable fire-resistanthydraulic fluid. are presented below.
  • Sorbitan monostearate 2 Diisobutylphenoxy(ethoxyhethanol 1 Mineral oil Balance Composition C:
  • Mannitan monooleate a. 3 Diisobutylphenoxy(ethoxy) ethanol 1 Mineral .oil Balance Composition -D: 7 i
  • Sorbitan monooleate f 2 Diisobutylphenoxy(ethoxy) ethanol 1 2,6-ditert.butyl-4-methylphenol 0.2 'Phenyl-alpha-naphthylamine f 0.1 Mineral oil Balance Composition E1 V V Sorbitan monooleate I 2 Diisobutylphenoxy(ethoxy) ethanol l 2,6-ditert.butyl-4-methylphenol 0.2 Phenyl-alpha-naphthylamine r 0.1
  • Sorbitanrnonooleate 2 Diisobuty1pl1enoxy,(ethoxy) ethanol 1 4,4'-methylene(2,6 ditert.butylphenol) 'Phenyl-alpha-naphthylamine. a 0.1
  • the finished emulsion fluid is prepared by slowly adding to the oil base compositions such as A, B, C, D, E, F, G or H, from 20% to 45 based on the total composition, an aqueous base, such as water which contains 0.1% sodium polyacrylate-polyacrylamide (X) for compositions A, B and F, 0.05% sodium polyacrylate-polyacrylamide (X) for composition D, 0.1% potassium polyacrylate-polyacrylamide (X) for composition C, 0.2%
  • the water base may or may not contain 0.014% of a corrosion or wear inhibitor such as water-soluble inorganic nitrites, nitrates, chromates, phosphates or water soluble low molecular weight salts such as alkali metal or alkaline earth metal (Na, K, Ca, Ba) acetate or propionate.
  • a corrosion or wear inhibitor such as water-soluble inorganic nitrites, nitrates, chromates, phosphates or water soluble low molecular weight salts such as alkali metal or alkaline earth metal (Na, K, Ca, Ba) acetate or propionate.
  • the water-in-oil emulsion can be mixed by any suitable means such as by air agitation, propeller agitation or by passing through a colloid mill until a homogeneous stable water-in-oil emulsion is formed.
  • the water is added to the oil in desired amounts at the 7 time the emulsion is to be used, although a stable waterin-oil emulsion can be prepared and stored for a moderate period.
  • composition-l A'finished water-in-oil emulsion (Composition-l) wasprepared by admixing 60% of composition D with 40% water and the mixture was passed through a colloid mill until a stable homogeneous water-in-oil emulsion was formed.
  • compositions include:
  • a water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45% water: phase consisting essentially of water and from about 0.01% to about 2% of a water-soluble polymeric compound having a molecular weight in the range from 1,000 to 500,000
  • R is a radical selected from the group consisting of hydrogen and a C alkyl radical
  • R and R" are radicals selected from the group consisting of hydrogen and an .alkyl radical of up to 8 carbon atoms
  • M is a cation selected from the group consisting of an alkali metal, ammonium, and an organic base
  • x is a positive integer and y and 2 may be zero and positive integers, and from about 55% to about 80% oil phase, the oil phase being essentially a high viscosity index mineral oil having a viscosity in the range from 50 SUS at 100 F. to 150 SUS at 210 F. containing (1) from about 1%, to about 4% of a monoester of a long chainfatty acid having'at least 8 carbon atoms and an inner ether of an aliphatic polyhydric alcohol having 1-2 ether and 4-6 hydroxyl groups,
  • Water contains the corresponding water-soluble polymeric additive noted above used to blend with Compositions A to H, respectively and in amounts indicated.
  • Compositions I and V were stored in 100 ml. cylinders at 1 t0 F. and observed for phase separatron.
  • Composition W [water-in-oil emulsion comprising 40% plus 60% mineral oil composition containing 2% sorbitan diisobutylphenoxy (ethoxy); ethanol 7 plus 0.2% 2,6-di-tertiary-4-methyl phenol plus 0.1% phenyl alpha naphthylamine] monooleate plus 1% and (2) from about 0.5% to about 3% of an oil-soluble alkyl 'phenoxy polyalkylene glycol having theformula R-phenyl(OR) OR"OI-l where R is an alkyl radical having 4m 20 carbon atoms; and R and R" are alkylene' groups having 2 to 3 carbon atoms; and n is an integer of from 2 to 6.
  • a water-in-oil emulsion lubricant and hydraulic fluid which is from about 20% to about 45% water phase consisting essentially of water and from about 0.01% to about 2% of a water-soluble alkali metal polyacrylate having a molecular weight in the range from 25,000 to 300,000, and from about 55% to about oil phase, the oil phase being essentially a 80-100 V.I. mineral oil having a viscosity in the range from 75 to 400 SUS at F.
  • composition of claim 2 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl phenols, phenyl-alpha-naphthylamine, and mixtures thereof, said alkyl phenols having 2 to 3 alkyl groups having from 1 to 5 carbon atoms.
  • an oil-soluble antioxidant selected from the group consisting of alkyl phenols, phenyl-alpha-naphthylamine, and mixtures thereof, said alkyl phenols having 2 to 3 alkyl groups having from 1 to 5 carbon atoms.
  • a water-in-oil emulsionlubricant and hydraulic fluid which is from about 20% to about 45 water phase consisting essentially of Water and from about 0.01% to about 2% of a water-soluble alkali metal polyacrylatepolyacrylamide having a molecular weight in the range I from 25,000 to 300,000, and from about 55% to about 80% oil phase, the oil phase being essentially a 80-100 V1.
  • mineral oil having a viscosity in the range from 75 to 400 SUS at 100 F.
  • composition of claim 4 containing in the emulsion from 0.01% to 2% of an oil-soluble antioxidant selected from the group consisting of alkyl phenols, phenyl-alpha-naphthylamine, and mixtures thereof, said alkyl phenols having 2 to 3 alkyl groups having from 1 to 5 carbon atoms.
  • an oil-soluble antioxidant selected from the group consisting of alkyl phenols, phenyl-alpha-naphthylamine, and mixtures thereof, said alkyl phenols having 2 to 3 alkyl groups having from 1 to 5 carbon atoms.
  • -6.-A -water-in-oil emulsion lubricant and hydraulic fluid which is fromabout 120% to about 45% water phase consisting. essentially of water and from about'0.0l% to about 2% of a water-soluble alkali metal polyacrylatepolyacrylicvacid having a molecular weight in the range from 25,000 to 300,000, andfrom about 55% to about 80% oil phase, the oil phase beingtessentially a 80- 100 V.I. mineral oilhaving a viscosity in the range from 75 I to 400 SUS at 100% F.
  • mineral lubricating oil having a viscosity in the range from to 400 SUS at 100, F; containing from. about 1.5% to about 3 of a sorbitan monooleate and from about 1% to about 2% of C alkyl substituted mixture of phenoxy- 8.
  • a water-in-oil emulsion lubricant and hydraulic fluid which is fromvabout 20% toabout 45% water phase consisting essentially of water and from about 0.02% to about 1% of' a water-soluble sodium polyacrylate-polyacrylic acid having a molecular weight in the range .from,25,000 to 300,000, and from about-55% to about oil phase, the oil phase being essentially a 80-100 V.-I.imineralllubricating oil having a viscosity in the, range from 75 to 400 SUS at Rcontaining from about 1.5% to about 3% Ma sorbitan monooleate, and
  • composition of'claim 8 containing in the emulsion from about 0.01% to about. 11% each. of 2,6- ditert.b-utyl-4-methylphenol, phenyl-alpha-naphthylamine and zinc diamyldithiocarbamate.
  • a water-inaoil emulsion lubricant and hydraulic fluid which isfrom about 30% to about;40% water phase consisting essentially of water and froinabout 0.02% to about 1% of a water-soluble sodium polyacrylate-polyamide having a molecular weight in the; range from 25,000 to, 300,000, and from'about 70% to about 60% oil phase, the oil phase being essentially a ,80100*V.-I.' mineral lubricatingoil having a viscosity in the range from 75 to 400SUS at 100, Fpcontainingfrorn about 1.5% to 7 about 3% of sorbitanmonooleate, and from about.1% to about 2%, of anroil soluble diisobutylphenoxy(ethoxy) ALBERT T. MEYERS, Primary Examiner.

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US145754A 1961-10-17 1961-10-17 Fire-resistant hydraulic fluids Expired - Lifetime US3177146A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL284405D NL284405A (de) 1961-10-17
US145754A US3177146A (en) 1961-10-17 1961-10-17 Fire-resistant hydraulic fluids
FR912282A FR1337607A (fr) 1961-10-17 1962-10-15 Lubrifiant et fluide hydraulique du type émulsion eau-dans-l'huile
CH1209262A CH434533A (de) 1961-10-17 1962-10-15 Als Schmiermittel und hydraulische Flüssigkeit geeignete Wasser-in-Öl-Emulsion
GB38997/62A GB967785A (en) 1961-10-17 1962-10-15 Water-in-oil emulsion lubricant and hydraulic fluid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US145754A US3177146A (en) 1961-10-17 1961-10-17 Fire-resistant hydraulic fluids

Publications (1)

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US3177146A true US3177146A (en) 1965-04-06

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ID=22514387

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US145754A Expired - Lifetime US3177146A (en) 1961-10-17 1961-10-17 Fire-resistant hydraulic fluids

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US (1) US3177146A (de)
CH (1) CH434533A (de)
GB (1) GB967785A (de)
NL (1) NL284405A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472781A (en) * 1966-06-22 1969-10-14 Union Carbide Corp Hydraulic fluids
US4045363A (en) * 1975-11-07 1977-08-30 The Elco Corporation Invert emulsions of improved extreme pressure properties
US4462920A (en) * 1983-06-06 1984-07-31 The Dow Chemical Company Water-based hydraulic fluids
US4469611A (en) * 1982-11-01 1984-09-04 The Dow Chemical Company Water-based hydraulic fluids
US6673754B1 (en) * 2001-09-07 2004-01-06 Dai-Ichi Kogyo Seiyaku Co., Ltd. Nonflammable water-based cutting fluid composition and nonflammable water-based cutting fluid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB801411A (en) * 1955-06-29 1958-09-10 Basf Ag Improvements in the properties of aqueous emulsions and dispersions
US2868728A (en) * 1955-12-30 1959-01-13 California Research Corp Salts of acrylamide-acrylic acid ester copolymers as greasethickening agents
US3050465A (en) * 1959-05-04 1962-08-21 Shell Oil Co Water-in-oil emulsion hydraulic fluids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB801411A (en) * 1955-06-29 1958-09-10 Basf Ag Improvements in the properties of aqueous emulsions and dispersions
US2868728A (en) * 1955-12-30 1959-01-13 California Research Corp Salts of acrylamide-acrylic acid ester copolymers as greasethickening agents
US3050465A (en) * 1959-05-04 1962-08-21 Shell Oil Co Water-in-oil emulsion hydraulic fluids

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472781A (en) * 1966-06-22 1969-10-14 Union Carbide Corp Hydraulic fluids
US4045363A (en) * 1975-11-07 1977-08-30 The Elco Corporation Invert emulsions of improved extreme pressure properties
US4469611A (en) * 1982-11-01 1984-09-04 The Dow Chemical Company Water-based hydraulic fluids
US4462920A (en) * 1983-06-06 1984-07-31 The Dow Chemical Company Water-based hydraulic fluids
US6673754B1 (en) * 2001-09-07 2004-01-06 Dai-Ichi Kogyo Seiyaku Co., Ltd. Nonflammable water-based cutting fluid composition and nonflammable water-based cutting fluid

Also Published As

Publication number Publication date
NL284405A (de)
GB967785A (en) 1964-08-26
CH434533A (de) 1967-04-30

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