Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/24—Polyethers
  • C10M145/26—Polyoxyalkylenes
  • C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
  • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

• the invention relates to a process for preventing the dissemination of a hydrocarbon liquid having a free surface into a dispersion of fine liquid droplets under conditions of shock or stress. It is often desirable to control the extent of misting or dispersion-in-air of hydrocarbon liquids having rather low flash points. More particularly, hydrocarbon fuels such as are employed in aircraft are desirably protected from misting under conditions of shock or stress as produced, for example, during an aircraft crash, or whenever such fuels are subjected to shock or stress while exposed to an ignition source. Additionally it is also desirable to control mist formation in hydrocarbon-based metal cutting fluids employed in metal cutting, grinding and machining operations.
• Preferred compounds include non-crystalline polymers substantially devoid of polar groups, especially polymers of ethylenically unsaturated hydrocarbons such as ethylene, propylene, isobutylene, and butadiene. Polymers formed by the addition polymerization of alkylene oxides are briefly discussed.
• U.S. Patent 3,557,017 ultra high molecular weight oxyalkylene polymers are taught as demulsifiers and thickeners for hydrocarbon systems used in oil well fracturing.
• Preferred oxyalkylene oxide polymers were those derived from propylene oxide.
• catalyst systems are known for preparation of high molecular weight alkylene oxides.
• Illustrative are a combination of ferric halide salts and propylene oxide disclosed in U.S. Patent 2,706,181, or organoaluminum, organozinc and organomagnesium compounds taught in U.S. Patent 2,870,100.
• Improved coordination anionic polymerization systems include chelated forms of organoaluminum such as disclosed in U.S.Patents 3,219,591; 3,186,958; 3,301,796; and 3,135,705.
• Such elongational deformation properties are in fact particularly relevant in imparting improved performance to anti-misting agents. Because the tensile or elongational viscosity of various materials appears to be affected by molecular weight considerations, particularly the average molecular weight and the distribution thereof, as well as by molecular geometry, the elongation properties of polymeric compounds and therefore the anti-misting properties thereof are not necessarily predictable on the basis of shear viscosity considerations.
• shear stability Another important property of an anti-misting agent is the shear stability of the material. Application of relatively mild shear should not significantly degrade the polymer and thereby destroy the polymer's ability to prevent the dispersion of the hydrocarbon liquid. For example, normal pumping and handling procedures used in transporting a jet fuel should not cause deterioration of the anti-misting properties of the polymer. Shear stability is particularly desired in cutting fluids due to repeated use under conditions of relatively high shear.
• an improved process for preventing the dispersion of a hydrocarbon liquid having a free surface upon application of shock or stress comprising adding to the hydrocarbon liquid an effective amount to prevent the dispersion thereof of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane.
• a composition comprising a hydrocarbon liquid and an effective amount to prevent the formation of a dispersion thereof upon application of shock or stress thereto of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane.
• Addition polymers comprising polybutylene oxide e.g., addition polymers of 1,2-epoxybutane, useful herein may be prepared by any technique suited to the preparation of extremely high molecular weight polymers. Examples include the anionic polymerization of U.S. Patents, 2,870,100 and 3,219,591.
• a preferred catalyst for polymerizing 1,2-epoxybutane to extremely high molecular weight polybutylene oxide comprises a composition prepared by contacting:
• Component A is a compound represented by the formula RR'AlX wherein R and R' each independently represent an alkyl group of 1 to 4 carbon atoms, and X represents hydrogen or an alkyl or alkoxy group of 1 to 4 carbon atoms.
• X represents an alkyl group.
• R, R' and X all represent the same alkyl group and most preferably, the compound is triethylaluminum.
• suitable compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, diethylaluminum hydride, dipropyl- aluminum hydride, diisobutylaluminum hydride, diethyl ethoxy aluminum, and diisobutyl ethoxy aluminum.
• Component A is normally supplied in a solution of a hydrocarbon or other solvent.
• Component B is an organic nitrogen base compound selected from secondary nitrogen-containing compounds having basicity about equal to or less than the basicity of dimethylamine and having no active hydrogen atoms other than those of the secondary nitrogen.
• active hydrogen atoms are meant Zerewitinoff hydrogen atoms (see J. Am. Chem. Soc., 49:3181 (1928)) which initiate alkylene oxide polymerization as are found on hydroxyl, thio or primary and secondary amine functional groups.
• Such secondary amines are commonly those bearing electron-withdrawing groups in close proximity to the nitrogen atom such as carbonyl groups, phenyl rings, cyano groups, halo groups, carboxylic acids or ester groups, and other such groups that have strong electron-withdrawing effects on the secondary amine.
• such compounds are N-alkyl or -aryl amides, arylalkylamines, diarylamines, and other weak bases.
• Secondary amines having a pK b of greater than 4 are suitable and those having pK b of greater than 6 are preferred.
• suitable secondary amines are dimethylamine, diethylamine, N-methylaniline, N-methyl--p-nitroaniline, N-alkylacetamide, N-arylacetamide, succinimide, diphenylamine, phenothiazines, and phen- oxazines.
• phenoxazine, phenothiazine and N-acetamide are especially preferred.
• One simple method for determining whether a secondary amine is less basic than dimethylamine is to employ both in side-by-side preparation of the catalyst, use the resulting catalyst in polymerization of a monomer such as propylene oxide, and then determine the intrinsic viscosities of the resulting polypropylene oxide products. If the intrinsic viscosity of the product derived from the catalyst prepared with dimethylamine is lower than the one from the other amine, then the other amine may be considered less basic than dimethylamine.
• the amount of Component B to be employed may be expressed in the molar ratio of Component B per mole of Component A.
• the lower amount is suitably about 0.01, preferably 0.05 and most preferably 0.1.
• the upper amount is suitably 2.5, preferably 1 and most preferably 0.5.
• the optimum molar ratio of B:A for producing very high molecular weight polyethers is about 0.25:1.
• Component C is selected from ⁇ -diketones or the tautomeric enol form thereof. Suitable, for example, are 2,4-pentanedione, 2,4-hexanedione, 3,5-heptanedione, 1-phenyl-1,3-butanedione, ethylacetylacetate, and similar materials. Examples of numerous suitable p-diketones are described in U.S. Patent 2,866,761. Preferred for use as Component C is 2,4-pentanedione because of its relative availability.
• a lower amount is suitably 0.1 and preferably 0.2.
• the ratio is suitably 1.5 and preferably 0.8.
• the optimum molar ratio of C:A is about 0.5:1.
• Component D is water and is suitably employed in a lower amount of about 0.1, preferably 0.3 and more preferably 0.4, mole of D per mole of A.
• the upper amount is suitably 1.5, preferably 1.1 and more preferably 1.0, mole of D per mole of A.
• the optimum ratio of D:A is 0.5 to 0.8:1.
• the above components are employed such that when the molar ratio sum of (C + 2D):A is greater than 3:1, then the B:A molar ratio is at least 1:1. Preferably the components are combined in the ratio where (B + C + 2D):A is less than or equal to 3:1 and more preferably less than 2:1.
• the following molar ratios are employed to form a catalyst which when contacted with a vicinal alkylene oxide produces a polyether of a very high intrinsic viscosity: B:A - about 0.25:1; C:A - about 0.5:1; and D:A - about 0.6:1.
• a catalyst is prepared which will give moderately high intrinsic viscosity polyethers when contacted with vicinal alkylene oxides according to the process described herein.
• the molar ratios in this second embodiment are: B:A - about 2.5:1; C:A -about 0.5:1; and D:A - about 0.5:1.
• the most preferred species of the catalyst are prepared in the form where B is phenothiazine or N-methylacetamide or C is 2,4-pentanedione.
• a small but effective amount of a Lewis base such as a tertiary amine or an aliphatic ether capable of forming a complex with Component A may be added to the catalyst mixture.
• a Lewis base compound such as a tertiary amine or an aliphatic ether capable of forming a complex with Component A
• Preferred Lewis base compounds are the aliphatic ethers, most suitably cyclic aliphatic ethers such as tetrahydrofuran or dioxane. These compounds are employed in minor amounts sufficient to form a complex with Component A in the presence of the remaining components of the catalyst.
• the aliphatic ether is present in molar amounts from 1 to 6 for each mole of Component A.
• ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, and lower alkyl monoethers of diethylene glycol or dipropylene glycol may be added to the catalyst in purified form as an aid in rendering the catalyst soluble in various solvents.
• the catalyst formation and polymerization are carried out according to known techniques such as those of U.S. Patents 3,186,958 and 3,219,591.
• the catalyst is prepared by contacting the components in the desired ratios in any of the common hydrocarbon or chlorinated hydrocarbon diluents employed for organic reactions so long as they do not bear Zerewitinoff hydrogen atoms.
• Suitable diluents for example, are hexane, toluene, benzene, styrene, decane, chlorobenzene, trichloroethane, perchloroethylene and the like.
• a preferred diluent is the hydrocarbon fluid, e.g., fuel or cutting oil, to which the polymer will be later added.
• the catalyst components may be combined in any order desired, because it has been found most effective to employ polymers of relatively high intrinsic viscosity in the present invention, it is preferable, particularly where the catalyst consists essentially of only Components A, B, C and D, that Components B, C and D be first combined by mixing them well and thereafter adding Component A to the mixture of the other three components. It is also convenient to prepare the catalyst in situ in the butylene oxide monomer to be polymerized. This is most preferably done by combining Components B, C and D in a solvent with the desired quantity of butylene oxide monomer and thereafter adding Component A to the mixture after which the polymerization is allowed to proceed.
• butylene oxide monomer acts as a cosolvent for the catalyst prior to initiation of the polymerization.
• Butylene oxide for polymerization and use herein may first be purified as by the technique described in U.S. Patent 3,987,065.
• the catalyst may be "killed” or deactivated by addition of a reactive hydroxyl compound such as water, alcohols or organic acids.
• a reactive hydroxyl compound such as water, alcohols or organic acids.
• the catalyst may be effectively “killed” by exposure to the atmosphere for a short time. It is believed that water vapor present in the air is sufficient to deactivate the catalyst.
• the polymer employed in the instant process comprises polybutylene oxide.
• the hydrocarbon liquid is a fuel, for example, a jet fuel for gas turbines
• the polymeric anti-misting additive not detrimentally form a precipitate or colloidal state, particularly at low temperatures.
• the temperature at which such formation occurs e.g., the theta temperature of the solution, is desirably less than -50°C. Further discussion of theta temperature as well as a more detailed description of suitable components of fuels for gas turbines is contained in U.S. Patent 3,996,023.
• the hydrocarbon liquid is a cutting fluid
• extremely low theta temperatures are not as necessary. Accordingly, a theta temperature of greater than -50°C may be suitable.
• certain hydrocarbon liquids, especially cutting fluids may contain substantial amounts of a non-hydrocarbon component, such as an alkylene glycol, an alkylene glycol ether or even water. Therefore under conditions where an extremely low theta temperature is not requisite or the hydrocarbon liquid additionally comprises non-hydrocarbon components, the polybutylene oxide anti-misting agent may include comonomers of additional alkylene oxides.
• Higher vicinal alkylene oxides such as l,2-epoxypentane, 1,2-epoxyhexane, etc., or glycidyl ethers such as n-butyl glycidyl ether, tertiarybutyl glycidyl ether, n-octyl glycidyl ether, etc., may be employed as comonomers without as significant a detrimental effect on compatibility with the hydrocarbon fluid.
• the preferred anti-misting agent for use in hydrocarbon fuels consists essentially of polymerized 1,2-epoxybutane.
• the catalyst residue may be left in the polymer solution without disadvantageous results, it is also possible to remove catalyst residue.
• the aluminum compound which exists as a hydroxide or oxide after deactivation is only sparingly soluble in hydrocarbon liquids, particularly at low temperatures and may be removed by filtration. This process may be particularly desired where the polymer solution is employed as a jet fuel.
• Intrinsic viscosity [n] is related to molecular weight by the equation: wherein K is a constant, M is molecular weight and a is another constant (correlated to the degree of configurational coiling in the architecture of an involved polymer).
• [q] The value of [q] is determined by plotting the measured specific viscosity divided by concentration of polymer in solution ( ⁇ sp /conc.) vs. conc. and extrapolating to zero concentration. It is dependent upon the solvent and temperature used during measurements. Toluene is a good solvent for the purpose. And, 100°F (38° C ) is an apt temperature at which to measure ⁇ sp , per the equation: wherein t is the efflux time of solution and t is the efflux time of solvent.
• Concentration for each diluted solution is simply calculable from the concentration of the stock solution. Three samples of this stock solution are then ordinarily weighed into aluminum dishes from which they are devolatilized in a vacuum oven at 100°C overnight (under a normal line vacuum). The aluminum dishes are then reweighed to determine the weight of pure polymer remaining. Concentration is then calculated as weight percent. This method of determining concentration is quite convenient since concentration normally associated with measuring [q] is reported in the literature as "grams/deciliter". Therefore, values for concentration so determined are higher by a factor corresponding to the density of toluene (0.8502 g/cc at 38°C). Values forx ⁇ sp /conc. and [ ⁇ ] are correspondingly, therefore, lower by this factor also. Consistent with this, the herein given [q] values are corrected for the density factor, with [ ⁇ ] being herein reported in units of dl/g.
• polymerized 1,2-epoxybutanes having relatively high intrinsic viscosity, e.g., intrinsic viscosities in toluene at 38°C of at least and preferably 2 and up to 30. Because of the greater effectiveness toward preventing misting of higher molecular weight polybutylene oxide polymers, such polymers of higher molecular weight may be employed in reduced concentrations thereby resulting in more economical operation. Preferred are concentrations by weight from 0.05 percent to 1 percent, and preferably from 0.1 percent to 0.5 percent by weight.
• polybutylene oxide polymers of reduced molecular weight and therefore intrinsic viscosity may be more suitably employed in order to avoid the necessary reduction in polymer effectiveness due to shear degradation of the polymer under long-life service conditions.
• increased levels of polymer may be employed in order to offset the loss in effectiveness due to decreased molecular chain length.
• Preferred for use in cutting fluids are amounts of polymer by weight from 0.1 percent to 5.0 percent, most preferably from 0.2 percent to 1.0 percent.
• cutting oil containing polymerized 1,2-butylene oxide is tested for mist formation.
• a solution of Mobilmet 308 cutting oil containing 0.25 percent by weight of the above polymer is prepared by rapidly stirring a portion of the above product in the cutting oil. Viscosity of the solution as determined by the cone-plate method is 0.055 Pa-S (55 cps). Unmodified oil has a viscosity of 0.051 Pa ' S (51 cps).
• Mist control is tested.by comparing mist formation upon injecting air (0.38 MPa; 40 psig) through a drop tube immersed in the fluid to be tested. Mist formation is noted by visual reference and assigned values of no-mist, low-mist or fail.
• the fluid is then exposed to high shear in a laboratory blender for one hour and retested for anti-mist properties.
• the cutting oil containing 0.25 weight percent polybutylene oxide showed no mist formation even after blending for one hour.
• Untreated Mobilmet 308 produced large amounts of mist under all testing conditions.
• An additional quantity of polymerized 1,2-butylene oxide is prepared in hexane solvent.
• the catalyst employed is prepared by combining in a dry box under nitrogen atmosphere at ambient temperature with stirring, hexane solutions of triisobutylaluminum (0.015 mole) and phenothiazine (0.004 mole) (total hexane is about 40 ml). Tetrahydrofuran (0.090 mole) is added dropwise with stirring over a period of about 10 minutes at reduced temperature of 0°C-10°C. Next, water (enough to provide 0.006 mole total) is added dropwise over a period of 10 minutes, followed by acetylacetone (0.006 mole) which is added dropwise over a period of 5 minutes.
• reaction mixture is stirred for 1 hour and transferred to a Parr bomb reactor and diluted with hexane (100 g) and toluene (30 g). After aging by heating and stirring under nitrogen for one hour at 95°C, catalyst preparation is complete.
• the polymer is formed by adding about one mole of 1,2-butylene oxide to the Paar bomb in increments at 75°C over a one-hour period. The reaction mixture is stirred at 75°C for 5 hours and then cooled. Evaporation of solvent leaves the desired polymer, a light amber colored rubbery solid.
• Jet fuel containing 0.2 percent by weight of polymerized 1,2-butylene oxide prepared employing the catalyst prepared according to the above process is tested for anti-misting properties by means of the Flammability Comparison Test Apparatus (FCTA).
• FCTA Flammability Comparison Test Apparatus
• the testing device consists of a compressed air source connected to a sonic orifice and a diffuser cone. Fuel is supplied through a metal tube terminating in the airstream at a point selected to produce high shear to the fuel entering the airstream. The air fuel mist thereby prepared is passed over a propane torch flame.
• Mist ignition is determined by fuel type (including the presence or absence of an anti-misting agent), the fuel flow rate and the air velocity.
• Passing, marginal and fail grades are assigned according to visual examination of the flame propagation. No propagation ahead of the torch constitutes a passing grade. Propagation ahead of the torch but not to the diffuser cone constitutes a marginal grade. Propagation ahead of the torch all the way to the diffuser cone constitutes a failing grade.
• Jet A fuel at 27°C which is not treated with an anti-misting agent consistently fails under all conditions of air velocity above 40 m/sec at fuel flow rates above 10 ml/sec. To the contrary, when modified by addition of 0.2 weight percent of polymerized 1,2-butylene oxide, no consistent failure is observed at fuel flow rates less than 16 ml/sec at air velocities less than 70 m/sec.
• polymerized 1,2-butylene oxide is an effective anti-misting agent which demonstrates surprisingly good effectiveness at preventing the formation of a hydrocarbon fuel/air dispersion even at extremely low concentrations.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Engineering & Computer Science (AREA)
• Polyethers (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Colloid Chemistry (AREA)
• Lubricants (AREA)

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Cited By (5)

Citations (4)

• 1983
  • 1983-02-18 CA CA000421896A patent/CA1180186A/fr not_active Expired
  • 1983-02-18 AU AU11668/83A patent/AU1166883A/en not_active Abandoned
  • 1983-02-18 EP EP83101525A patent/EP0110003A3/fr not_active Withdrawn
  • 1983-02-18 JP JP58024967A patent/JPS59105087A/ja active Pending

Patent Citations (4)

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