Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3629119 A
Publication typeGrant
Publication dateDec 21, 1971
Filing dateDec 22, 1969
Priority dateDec 22, 1969
Also published asDE2062936A1
Publication numberUS 3629119 A, US 3629119A, US-A-3629119, US3629119 A, US3629119A
InventorsJohn J Weaver
Original AssigneeShell Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Water-in-oil emulsions
US 3629119 A
Abstract  available in
Images(3)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,629,119 WATER-IN-OIL EMULSIONS John J. Weaver, Edwardsville, Ill., assignor to Shell Oil Company, New York, NY. No Drawing. Filed Dec. 22, 1969, Ser. No. 887,353 Int. Cl. B01f 17/16; C09k 3/00 US. Cl. 252-77 5 Claims ABSTRACT OF THE DISCLOSURE Dialkylaminoalkanols are elfective as emulsion stabilizers in water-in-oil emulsions formed with a polyalkenyl succinic anhydride emulsifying agent.

This invention relates to improved water-in-oil emulsions. More particularly, the invention relates to emulsions having a high degree of stability over extended periods of storage or use.

Hydraulic fluids based on Water-in-oil emulsions have found widespread application in a number of industries because of their relatively low cost and fire-resistant properties. The effectiveness of these fluids is, of course, dependent on their remaining in an emulsified state. If separation occurs to any large degree, the lubricating and fire-resistant characteristics of the fluids immediately diminish, necessitating their replacement.

In response to this need for more stable emulsions, a number of emulsifying agents and combinations thereof have been proposed, among the most effective of which is the combination of a polyalkenyl succinic anhydride with a polyalkoxylated partial ester of a polyhydric alcohol such as polyoxyethylene sorbitan mono-oleate. While succinic anhydrides have been effectively employed with other emulsifying agents as co-emulsifiers, they generally do not form suitable emulsions when employed as the sole emulsifying agent.

It has now been found that a dialkylaminoalkanol, which does not possess any inherent emulsifying properties, effectively stabilizes water-in-oil emulsions wherein a polyalkenyl succinic anhydride is employed as the emulsifying agent. The combination of an alkenyl succinic anhydride with a dialkylaminoalkanol produces a remarkably stable emulsion, far in excess of the stability which would be expected from the use of these compounds individually in such compositions.

The compositions of the present invention consist essentially of from 20% to about 45% by weight water phase and from 55% to about 80% by weight oil phase, the oil phase being essentially a mineral oil, containing a minor amount of (A) an oil-soluble compound having the formula R-CH-C CH C wherein R is a polyalkene group of from 30 to 500 carbon atoms, and (B) a dialkylaminoalkanol having the formula ice sirable constituents. For hydraulic fluids, lubricating oils are highly desired for the base oil and these include those having a high viscosity index, i.e., a viscosity index (Dean- Davis) of at least 80, preferably between and 100. Mineral oil fractions of this type are derived from paraffinic, naphthenic or mixed base crudes. They should also be in the lubricating oil range and have a viscosity, as determined at F., of from about 75 to 250 SUS, preferably between 100 and 150. A typical mineral oil base of this kind is a high viscosity index refined mineral lubricating oil having the following properties:

Gr., API", 60 32.2 Color, ASTM 1 Pour point, F. 5 Flash, F., COC 370 Fire, F 435 Viscosity, SUS at 100 F. 103 Viscosity index 93 Neutralization No. 0.01

In some emulsions, other lubricating oils, e.g., low viscosity index oils (2045 VI) may be used. These low viscosity index oils have a viscosity in the range from about 40 to 200 SUS at 100 F.

The oil soluble compound which is additive (A) is an alkenyl succinic anhydride. The alkenyl succinic anhydride can be prepared by alkylating maleic anhydride with a polyalkene from which the (R) group is derived and which functions as an oil-solubilizing aid. Examples of such polymers include polyethylene, polypropylene, polybutene, polyisobutylene, copolymers of ethylene/propylene, copolymers of ethylene/isobutylene, copolymers of ethylene/alpha-methyl styrene and the like. Monoalkylation of maleic anhydride with the above type olefinic polymers can be carried out by conventional means known in the art, preferably in the absence of a catalyst and at temperatures ranging from about 300 F. to 600 F., preferably between 350 F. and 450 F. The mole ratio of the polyalkene to maleic anhydride may vary from 1:1 to 1:10, preferably from 1:1 to 1:5, respectively. Particularly useful in the monoalkylation of maleic anhydride are polyisobutylenes in the molecular weight range of 3 00 to 5,000, preferably from 800 to 1,500.

Dialkylaminoalkanols (Additive B) which are contemplated for use in the present compositions as stabilizers, include those having two alike or dissimilar C alkyl groups, and a C alkanol group attached to the nitrogen atom. Preferred aminoalkanols are dialkylaminoethanols, e.g. dimethylaminoethanol, diisopropylaminoethanol and the like. A particularly advantageous stabilizing agent for use in conjunction with succinimide emulsifier is diethylaminoethanol.

The concentrations of additives (A) or (B) can vary from 0.05% to about 10% by weight of the total composition. Emulsions wherein additive (A) is present in the amount of from 1% to about 4% w., and additive (B) is present in the amount of from 0.05% to about 2% W. are preferred. The ratio of additive (A) to additive (B) can be from 40:1 to 1:2, preferably from 25:1 to 5:1.

In addition to the aforementioned compounds, other additives known to the art to perform a particular function or functions may also be incorporated into the waterin-oil emulsions of the present invention.

Excellent emulsion stability, especially under freezethaw conditions is obtained by the further addition of a water soluble alkylene glycol such as the lower alkylene glycols, i.e. C -C alkylene glycols, and particularly ethylene glycol. The alkylene glycol can be used in amounts of up to 25%, preferably from about 1 to 20% by weight based on the aqueous phase. Particularly preferred concentrations of alkylene glycol are in the range of about 5 to 15% by weight based on the aqueous phase.

In addition, it is preferred to use in the composition of the invention small amounts of from about 0.01% to about 2%, preferably from about 0.2% to about 1%, optional additives such as antioxidants, anti-corrosion agents, anti-wear agents, pour point depressants and the like to improve other characteristics of the emulsion. The antioxidants include the phenolic amines and/or metal thiophosphate compounds. The phenolic compounds are illustrated by the alkyl phenols, e.g., diand trialkyl phenols, for instance, 2,4- 2,3- 3,4- 2,6- and 3,5-diamylphenol; 2,4-dimethyl-6-tertiarybutylphenol; 2,6-ditertiarybutyl-4-methylphenol. The amines are illustrated by arylamines such as phenyl-alpha-naphthylarnine or phenylbeta-naphthylamine. The metal thiophosphates are illustrated by alkaline earth metal thiophosphates, e.g., calcium or zinc dimethyl cyclohexyldithiophosphate. Antiwear agents include sulfur-containing compounds such as oil-soluble polychloro hydrocarbyl thiocarbonate esters, e.g. polychloronaphtha methyl xant-hate marketed by Monsanto Chemical Co. under the name Santopoid S and characterized by sp. gr. 1.19 at 60/ 60 F., flash point 250 F., viscosity 63 cs. at 100 F., sulfur 11%, chlorine 31%. Thiocarbonates of this type are prepared by reacting a chlorinated petroleum naphtha with an alkali metal (potassium) alkyl dithiocarbonate. Other anti-wear agents include, for example, organic sulfides such as dibenzyl disulfide or dichlorodibenzyl disulfide, polyvalent metal dithiophosphates such as zinc or lead salts or C alkyl dithiophosphates, and polyvalent metal dithiocarbamates such as the zinc, cadmium or lead salts of N- or N,N- C alkyl substituted dithiocarbamic acid. The butyl or amyl substituted compounds are generally preferred. Suitable anti-corrosion agents, including vapor space inhibitors to protect against corrosion in vapor spaces of storage or other equipment, may be added. Vapor space inhibitors are generally effective in minor amounts, e.g., 01-03% W. and include, for example, volatile amines or C monocarboxylic acids. Exemplary compounds are n-hexylamine, dicyclohexylamine, piperidine, morpholine, 2,6- dimethylmorpholine, octanoic acid, monanoic acid, decanoic acid, and the like. Morpholine is a particularly preferred corrosion inhibitor.

Dyes and anti-foaming agent can be added to compositions of this invention. Oil-soluble dyes include naphthol yellow, Sandoz yellow, methylene blue, alizarin compounds, etc., while anti-foaming agents include silicone polymer (DC-200 fluids ranging in viscosity in centistokes from 100 to 1,000 at 250 C.) of silicone type A fluid made by Dow-Corning Co. and described in US. Pats. 2,563,588 and 2,662,055 and mixtures thereof. Suitable pour point depressants include for example, the polymeric Inethacrylates marketed by Rohm and Haas Co. under the name Acryloid 150.

Methods of preparing emulsions are well known in the art. In a typical procedure suitable for the preparation of the inventive compositions, a measured amount of water is slowly added to a mineral lubricating oil containing the oil soluble succinic anhydride emulsifying agent and the dialkylaminoalkanol stabilizer. The resulting mixture is passed through a colloid mill wherein it is agitated until a homogeneous emulsion is formed. Other means of emulsifying liquids, such as propeller or sonic agitation, are known to the art, and may likewise be employed.

The present compositions and the advantages thereof will be further described by means of the following examples which are given for illustrative purposes only; therefore, the invention in its broader aspects should not be limited thereto.

Composition A: Percent w. Diethylaminoethanol 0.5 Polyisobutenyl succinic anhydride 3.0 Mineral oil 56.0

Water chafin 40.5

In order to demonstrate the elfectiveness of dialkylaminoalkanols as emulsion stabilizing agents, three waterin-oil emulsions were prepared having the compositions shown in Table I. The emulsion stability of each composition was determined by measuring the volume percent of phase separation after storage for the lengths of time shown in Table II.

TABLE I Composition E F G Component:

Diethylaminoethanol, percent W 0.2

Polyisobutenyl succinic anhydride, percent W. Base fluid A, percent W 1 Base fluid A=38% Water blended With HVl mineral oil SUS 100 F.) containing 2.0% w. ethylene glycol. 0.6% zinc dithiophosphate 0.3% w. 2,6-di-t-butyl-4-methyl phenol, 0.1% \v. morpholine. 0.06% W. phenyl-alpha-naphthylamine and 0.018% w. yellow dye.

1 Balance.

TABLE II Phase separation percent V Time Free oil Oil rich Free Water Com osition;

Pi 46 days--. 3 35 FL... 20 minutes 56 29 15 G 104 days 3 0 1 Slight.

From the results shown in Table II it can be seen that Composition F containing diethylaminoethanol without polyisobutenyl succinic anhydride has extremely poor emulsion stability and would not be suitable as a hydraulic fluid. Likewise, the emulsion stability of Composition E is also unsatisfactory, since a considerable oil-rich phase was formed by the end of 46 days storage. In marked contrast Composition G containing both diethylamino ethanol and polyisobutenylsuccinic anhydride has excellent emulsion stability and gave no evidence of an oil-rich layer forming after 104 days of storage. It can, therefore, be seen that although diethylaminoethanol has no in herent emulsifying properties, it is extremely effective as an emulsion stabilizer when employed in combination with a succinic anhydride emulsifying agent.

To further demonstrate the stability of the water and oil emulsions of the invention, Composition G prepared in accordance with the invention was compared to a number of commercially available fire resistant hydraulic fluids by means of a 35-day storage stability test. In this test the samples are placed in an oven maintained at a temperature of F. for a period of 35 days.'At the end of the test period, the degree of separation into phases is reported as volume percent free oil, oil rich, water rich and free water, respectively. Test results are shown in Table III. The emulsifiers employed in Commercial Fluid 1 are identified in the footnote to Table III. The compositions of the remaining commercial fluids are not known.

TABLE III Oven, 35-Day Storage Stability Test at 140 F.

Phase separation,

Emulsion: .percent W. Composition G 3-0-2-1 Commercial Fluid 1 25010-7 Commercial Fluid 2 24-0-04 Commercial Fluid 3 19-0-0-8 Commercial Fluid 4 12032 Commercial Fluid 5 11-0-3-4 (ta) Values indiealte-free oil/oil wick/Water rich/free uii' Commercial Fluid- 1 40% W. Walter blended with HVl mineral oil (100 SUS 100' F.) containing 1.2% w. basic calcium sultonate, 1.2% w. basic calciium 019-22 al kyl silicylate as coemulsifier s.

The above data give a further indication of the improved emulsion stability obtained by practice of the present invention. While the emulsions of the prior art exhibited free oil separation to the extent of 11 to 25% by volume, the inventive composition had a free oil phase of only 3% at the end of the test period.

I claim as my invention:

1. A water-in-oil emulsion constituting from 20% to about 45% by weight water phase and from 55% to about 80% by weight oil phase, said oil phase consisting essentially of a mineral oil containing from 0.05% to 'by total composition weight each of (A) an oil soluble compound having the formula org-0:0

6 where R is a polyalkene of from 30 to 500 carbon atoms and (B) a dialkylaminoal'kanol having the formula wherein R and R are alike or dissimilar C alkyl groups and R is a C alkylene group.

2. The composition of claim 1 wherein R is polyisobutylene and (B) is a dialkylaminoethanol.

3. The composition of claim 2 wherein (A) is present in the amount of from 1% to about 4% w. and (B) is present in the amount of from 0.05 to about 2% w.

4. The composition of claim 3 wherein the (B) is diethylaminoethanol.

5. The composition of claim 1 wherein the water phase additionally contains from 1 to about 20% by weight based on the aqueous phase of a water soluble C C alkylene glycol.

References Cited UNITED STATES PATENTS 3,378,494 4/1968 Berger 25277 3,280,029 10/1966 Waldmann 25249.5

OTHER REFERENCES The Condensed Chemical Dictionary, pp. 330331. 7th ed. (1966), Reinhold Publ. Corp., New York.

LEON D. ROSDOL, Primary Examiner H. A. PITLICK, Assistant Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3981813 *May 12, 1975Sep 21, 1976Standard Oil Company (Indiana)Hydraulic fluid
US4225447 *Jan 8, 1979Sep 30, 1980Mobil Oil CorporationEmulsifiable lubricant compositions
US4259189 *Jan 19, 1978Mar 31, 1981Exxon Research And Engineering Co.Novel liquid membrane formulations
US4329249 *Sep 27, 1978May 11, 1982The Lubrizol CorporationCarboxylic acid derivatives of alkanol tertiary monoamines and lubricants or functional fluids containing the same
US4368133 *Feb 25, 1981Jan 11, 1983The Lubrizol CorporationAqueous systems containing nitrogen-containing, phosphorous-free carboxylic solubilizer/surfactant additives
US4448703 *Mar 4, 1982May 15, 1984The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4471091 *Aug 9, 1982Sep 11, 1984The Lubrizol CorporationCombinations of carboxylic acylating agents substituted with olefin polymers of high and low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4479888 *Jun 4, 1980Oct 30, 1984Agip Petroli S.P.A.Dispersing additives for lubricants, and the method for their preparation
US4483777 *Sep 20, 1982Nov 20, 1984Mobil Oil CorporationStability improvers for water-in-oil emulsion
US4486573 *Aug 9, 1982Dec 4, 1984The Lubrizol CorporationCarboxylic acylating agents substituted with olefin polymers of high molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4489194 *Aug 9, 1982Dec 18, 1984The Lubrizol CorporationCarboxylic acylating agents substituted with olefin polymers of high/low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4564460 *Aug 9, 1982Jan 14, 1986The Lubrizol CorporationHydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4575526 *Mar 12, 1985Mar 11, 1986The Lubrizol CorporationHydrocarbyl substituted carboxylic acylaging agent derivative containing combinations, and fuels containing same
US4596663 *Oct 19, 1984Jun 24, 1986The Lubrizol CorporationCarboxylic acylating agents substituted with olefin polymers of high molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4613342 *Oct 16, 1985Sep 23, 1986The Lubrizol CorporationHydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4623684Oct 16, 1985Nov 18, 1986The Lubrizol CorporationHydrocarbyl substituted carboxylic acylating agent derivative containing combinations, and fuels containing same
US4666620 *Mar 13, 1986May 19, 1987The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4687590 *Nov 1, 1985Aug 18, 1987First Brands CorporationOil-in-alcohol microemulsion containing oil-soluble corrosion inhibitor in antifreeze
US4708753 *Dec 29, 1986Nov 24, 1987The Lubrizol CorporationWater-in-oil emulsions
US4770803 *Jul 3, 1986Sep 13, 1988The Lubrizol CorporationAqueous compositions containing carboxylic salts
US4828633 *Dec 23, 1987May 9, 1989The Lubrizol CorporationSalt compositions for explosives
US4840687 *Nov 14, 1986Jun 20, 1989The Lubrizol CorporationExplosive compositions
US4844756 *Dec 23, 1987Jul 4, 1989The Lubrizol CorporationWater-in-oil emulsions
US4863534 *Dec 23, 1987Sep 5, 1989The Lubrizol CorporationExplosive compositions using a combination of emulsifying salts
US5041622 *Nov 28, 1990Aug 20, 1991The Lubrizol CorporationThree-step process for making substituted carboxylic acids and derivatives thereof
US5047175 *Nov 1, 1988Sep 10, 1991The Lubrizol CorporationSalt composition and explosives using same
US5129972 *Jul 17, 1991Jul 14, 1992The Lubrizol CorporationEmulsifiers and explosive emulsions containing same
US5336439 *Aug 8, 1991Aug 9, 1994The Lubrizol CorporationSalt compositions and concentrates for use in explosive emulsions
US5360458 *Jun 19, 1991Nov 1, 1994The Lubrizol CorporationOil-water emulsions
US5407500 *Dec 6, 1993Apr 18, 1995The Lubrizol CorporationSalt compositions and explosives using same
US5527491 *Sep 29, 1994Jun 18, 1996The Lubrizol CorporationEmulsifiers and explosive emulsions containing same
US7909924Oct 15, 2007Mar 22, 2011Sun Chemical CorporationStable offset emulsion inks containing non-water soluble polymeric surfactants
US7985820Oct 15, 2007Jul 26, 2011Sun Chemical CorporationNon-water soluble polymeric surfactants
US8013033 *Oct 15, 2007Sep 6, 2011Sun Chemical CorporationWater tolerant emulsion stabilizers
US8013034Oct 15, 2007Sep 6, 2011Sun Chemical CorporationStable offset emulsion inks containing water tolerant emulsion stabilizer
US9127210 *Apr 24, 2014Sep 8, 2015Board Of Regents, The University Of Texas SystemShort chain alkylamine alkoxylate compositions
US20080132675 *Oct 15, 2007Jun 5, 2008Sun Chemical CorporationNon-water soluble polymeric surfactants
US20080134932 *Oct 15, 2007Jun 12, 2008Sun Chemical CorporationStable Offset Emulsion Inks Containing Water Tolerant Emulsion Stabilizer
US20080139743 *Oct 15, 2007Jun 12, 2008Sun Chemical CorporationStable offset emulsion inks containing non-water soluble polymeric surfactants
US20080139831 *Oct 15, 2007Jun 12, 2008Sun Chemical CorporationWater Tolerant Emulsion Stabilizers
US20140319026 *Apr 24, 2014Oct 30, 2014Board Of Regents, The University Of Texas SystemShort chain alkylamine alkoxylate compositions
USRE36479 *Oct 4, 1996Jan 4, 2000The Lubrizol CorporationAqueous compositions containing nitrogen-containing salts
EP1917331A2 *Jun 26, 2006May 7, 2008Arkema Inc.Method of reducing fuel corrosiveness
WO2008057721A2 *Oct 15, 2007May 15, 2008Sun Chemical CorporationWater tolerant emulsion stabilizers
WO2008057721A3 *Oct 15, 2007Jul 3, 2008Nobuo HaruiWater tolerant emulsion stabilizers