MXPA96006514A - Friction modifier for fluids of oil-based wells (reverse) and methods for used - Google Patents

Abstract

The present invention relates to a drilling fluid composition comprising a water-in-oil emulsion formed from a brine, a liquid oil, an emulsifier (A), a friction modifier (B) of the following formula: where X = 1 to 4, z = 1 to 6, Q = 0 to 2, R1 and R2 are, independently, H or an aliphatic group containing 1 to approximately 16 carbon atoms, provided that the sum of R1 and R2 is between 0 and about 16, R 'is an aliphatic group containing an average of about 8 to about 24 carbon atoms and R "is selected from the group consisting of H, an aliphatic group containing between 1 and an average of about 18 carbons , and where Q, X, z, R1, R2, R 'and R "are as defined above, and Y is 0 a

Description

FRICTION MODIFIER FOR FLUIDS OF PERFORATION OF OIL-BASED WELLS (REVERSE) AND METHODS FOR YOUR / USE INDUSTRIAL FIELD This invention relates to a friction modifier that is useful in drilling fluid compositions that serves to reduce the coefficient of friction of the well drilling fluid. The decrease in the coefficient of , friction reduces the force required to rotate the drilling bit in the hole. The force of gravity increases the coefficient of friction in rich horizontal and extensive deviated wells. This is the type of application where the invention finds greater utility.

BACKGROUND OF THE INVENTION The main functions of a fluid or drilling mud are: dragging the chips and cutting fragments produced by the drilling to the surface; lubricate and cool the drilling bit and the drill string; forming a filter cake that obstructs the invasion of the filtrate in the formation; keep the walls of the bore hole; control training pressures and avoid losses by return; suspend cutting fragments during train station stops; and protect the training for a later completed and production successfully. Friction between the apparatus and the drilling hole is a problem. The greater the friction, the greater the force required in the drilling process. The higher the friction, the more likely it is that other problems will appear such as seizing the drilling bit. In addition, in non-vertically drilled wells, for example wells drilled horizontally, a reduction in friction coefficient facilitates the non-vertical drilling operation. Accordingly, it is desirable to use a friction modifying agent that reduces the friction of the drilling process and thus decreases the likelihood of trepan seizure, thus reducing drilling energy costs and facilitating drilling. It is an object of this invention to provide this friction modifying agent.The useful fluids or drilling muds must maintain their rheological and viscosity properties under normal operating conditions. Suspend cutting fragments and loading materials when drilling fluid circulation is stopped It is desirable to have drilling fluids or muds that maintain their thixotropy and rheology even when the solids are increased.

I load and organophilic clays to provide a higher viscosity and density to the sludge. Today, two main types of fluids or drilling muds are used. In addition, a foam drilling fluid is sometimes used that is somewhat different. The fluids are oil-based or water-based. Oil-based fluids are usually water-in-oil emulsions containing water in the form of a discontinuous emulsified phase. The oil is the continuous phase. The other main type of drilling fluid is the "" 'of water-based drilling fluids. These water-based compositions may contain an oil phase. If the oil is present, it exists as a discontinuous emulsified phase. According to this, water-based oil-containing fluids are oil-in-water emulsions. Since the external properties of the emulsions, such as dispersibility, wetting characteristics, and feel to the touch, are determined by the continuous phase, the oil-based fluids are more of the oil type, although they contain water, and the water-based fluids they are more of the water type, although they may contain oil. The drilling muds of the present invention are water-in-oil emulsions. Optional charge agents and organophilic clays are usually in the oil phase of the sludge. If these materials are moistened with water (for example present in the brine phase of the emulsion), then the emulsion weakens. If the emulsion weakens sufficiently, the emulsion can be rapidly reversed, for example, passing from a water-in-oil emulsion (for example inverse) to an oil-in-water (normal) emulsion. When the emulsion is inverted it becomes useless for well drilling applications. U.S. Patent No. 3,236,769 describes drilling fluids containing water and clay to which is added a defoamer and a water-soluble non-i compound having surface active properties and characterized by the formula: R- (x [( CH2-CH2-0) nH] m) and. The non-i compound functions as a flocculation or agglomeration agent for clay. US Patent 4,031,023 discloses lubricating compositions having oxidative stability and anti-wear properties to which certain hydroxy-thiocerers contribute. These t-ioletters include molecules such as 2-hydroxy ethyl n-decyl sulfide US Patent 4,172,800 discloses aqueous drilling fluids containing a mixture of polyethoxylated sulfurized fatty acid and polyalkylene glycol These fluids are especially useful when Reduced torque drilling fluids are required.

US Pat. No. 4,181,617 discloses an aqueous piercing fluid having a lubricant consisting essentially of a reaction product of a fatty vegetable oil with 4, '-thiodiphenol.

COMPENDIUM OF THE INVENTION This invention relates to a composition comprising an oil-in-water emulsion formed from a brine, > "" "" -a liquid oil, an emulsifier (7-0, a friction modifier (B) of the following formula: R'S- 'C HH' ((CCHH)), - "C CHH1 O O + - R" z where X = 1 to 4 z = 1 to 6 Q = 0 to 2, R? and R2 are, independently, H or an aliphatic group containing from 1 to about 16 carbon atoms, provided that the sum of Ri and R2 is between 0 and about 16, R 'is an aliphatic group containing an average of about 8. to about 24 carbon atoms, and R "is selected from the group consisting of on H, an aliphatic group containing between 1 and about 18 carbons, and where Q, X, z, Ri, R, R 'and R "are as defined above, and Y is 0 to 5. In a preferred embodiment z is 1. In the most preferred embodiment, Q = 0, Rt and R2 are both H, X and z are equal to 1, R 'is n-dodecyl and R "is H.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The term "emulsion", as used in the specification, claims to cover water-in-oil emulsions. It is also intended to cover with this term compositions derived, or formulated, from water-in-oil emulsions which are gelatinous or semi-gelatinous compositions. The term "hydrocarbyl" includes both hydrocarbon and "substantially hydrocarbon groups" Substantially hydrocarbon refers to groups containing non-hydrocarbon substituents that do not alter the predominantly hydrocarbon nature of the group Examples of hydrocarbyl groups include the following: (1) hydrocarbon substituents, i.e. substituents aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl), aromatic-substituted aliphatic substituents or aromatic-substituted alicyclic substituents, or aliphatic- and alicyclic-substituted aromatic substituents and the like, as well as cyclic substituents where the ring is completed through another portion of the molecule (i.e., for example, any two of the indicated substituents can together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is, those substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; those skilled in the art will readily recognize the groups concerned (for example, halo (especially chlorine and fluorine), hydroxy, alkoxy, mercapto, a] quiltium, nitro, nitroso, sulfoxy, etc.) ~ (3 ) hetero-substituents, that is, substituents which, although having a predominantly hydrocarbon character within the context of this invention, contain an atom other than carbon present in a ring or chain composed of another part of carbon atoms. The specialists will soon realize which are the right heteroatoms, including, for example, sulfur, oxygen, nitrogen and substituents such as, for example, pyridyl, furyl, thienyl, imidazolyl, etc. In general, no more than about 2, preferably not more than, one of the non-hydrocarbon substituents per ten carbon atoms in the hydrocarbyl group will be present. Typically, there will not be this type of non-hydrocarbon substituents in the hydrocarbyl group. The hydrocarbyl group can be purely hydrocarbon. As used in the specification and claims, a "barrel" is 42 gallons U.S. (158.7 liters). As described above, the present invention relates to a composition comprising a water-in-oil emulsion formed from a brine, a liguid oil, an emulsifier (A), a friction modifier (B) of the following formula : R 'S? - CH - (CH - CH -' O "T - R" where X = 1 to 4 z = 1 to 6 Q = 0 to 2 Ri and R2 are, independently, H or an aliphatic group containing from 1 to about 16 carbon atoms, provided that the sum of Ri and R- is between 0 and approximately 16, R1 is an aliphatic group containing an average of about 8 to about 24 carbon atoms, and R "is selected from the group consisting of H, an aliphatic group containing between 1. and an average of about 18 carbons, and ' where Q, X, z, Ri, R2, R 'and R "are as defined above, and Y is 0 to 5. In a preferred embodiment z is 1. In the most preferred embodiment, Q = 0, Ri and R2 are both H, X and z are equal to 1, R 'is n-dodecyl and R "is H. Friction modifiers can be prepared by condensation reactions. For example, n-dodecyl (2-hydroxyethyl) sulfide can be prepared by condensation of 1- dodecene with mercaptoethanol. The corresponding bis ether, ether-$, 2 '-di- (n-dodecylthio) -diethyl, can be prepared by condensation of the alcohol in the presence of an acid catalyst. The group R "can be a hydrogen, in which case the molecule is an ether, R" can also be an aliphatic group containing between 1 and an average of about 18 carbon atoms. If R "is an aliphatic group, the molecules can be prepared by condensation of a mixture of thio-ether alcohol with alcohol desired aliphatic r. This synthesis will probably result in the formation of some di-aliphatic ether that probably does not represent any problem in drilling mud applications. R "can be a thio-ether radical as shown in the above structure, Different thio-ether radicals can be coupled to create asymmetric ethers Finally, R" can be a mixture of thioether radicals, aliphatic radicals, and hydrogen. These ethers and mixtures of ethers can be prepared by condensation of combinations * of appropriate alcohols. If it is desired to prepare a mixture in which some R "are hydrogen and others are thio-ether radicals or aliphatic radicals, this can be achieved by carrying out the condensation reaction so that it does not come to completion and, therefore, remains of unreacted thio-ether alcohol. they can be prepared by reaction of an epoxide with a suitable mercaptan. The reaction can be carried out in the presence of sulfur if the desired product is a polysulfide (X = 2 to 4 in the above formula). The epoxide can be terminal epoxide or epoxide formed from non-terminal olefin. Preferred epoxides are ethylene oxide and propylene oxide. These : reactions are carried out in the presence of an alkaline catalyst such as sodium or potassium methoxide at temperatures of 100-200 ° C. With the lower epoxies, such as ethylene oxide, the reactions are carried out under pressure. The resulting structures with a terminal hydroxyl group can also be condensed with themselves or with other aliphatic alcohols to form the subsequent ether structures. These reactions are carried out with strong acid catalysts such as sulfuric acid or methane sulphonic acid at a temperature of 100-200C. The water formed during the reaction is separated under these conditions. Some of the molecules can be prepared by reaction of alpha-olefins with thioglycols. These reactions are usually carried out in the presence of free radical catalysts at temperatures of 75-100 ° C.

^ * E > MULTI-CHANGERS The friction modr of the present invention operates in water-in-oil emulsion drilling fluids or slurries. Any suitable emulsr such as a water-in-oil emulsr can be used to prepare the drilling fluids. These emulsrs preferably have a hydrophilic-lipophilic balance (HLB) less than 10 and more preferably in the range of 4 to 8. These emulsrs ,. they are well known in the art and lists thereof as well as emulsion preparation methods are found in sources such as Kir Othmer's "Encyclopedia of Chemical Technology", 3rd Edition, Volume 8, pages 900-930, Interscience Publishers, New York (1979). Frequently, similar types of chemical emulsrs are used to prepare water-in-oil and oil-in-water emulsions. However, within the given chemical type, it is important to select emulsrs having the appropriate HLB for the preparation of water-in-oil emulsion. The following are examples of useful emulsrs.

AMINO DERIVATIVE OF CARBOXYLIC ACILATING AGENTS The reaction products of carboxylic acylating agents with polyalkylene polyamines and hydroxylamines are especially useful emulsrs. Carboxylic acylating agents include mono, di, tri and succinic acylating agents.

CARBOXYLIC ACILATING AGENTS Carboxylic acylating agents are carboxylic acylating agents having from 1 to about 4 carboxyl groups, preferably 2 or 3. The term acylating agents embraces acids, anhydrides, stere.-; inferiors (esters of C? _7), halides, etc. Preferably, the acylating agents are acidic or anhydrides. The carboxylic acylating agents may be monocarboxylic or polycarboxylic acylating agents. Acylating monocarboxylic agents include fatty carboxylic acylating agents including fatty acids and monocarboxylic reaction products of Diels-Alder. The fatty acids generally contain about 8, preferably about 10, more preferably about 12 to about 30, more preferably about 24 carbon atoms. Examples of fatty acids include stearic, oleic, lauric, linoleic, abietic, palmitic, sebacic, linolenic, behenic, tall oil and rosin acids. The polycarboxylic acylating agents of the present invention include dicarboxylic acylating agents such as succinic acylating agents, dimer acylating agents and dicarboxylic acylating agents of Diels-Alder. The tricarboxylic acylating agents include acrylating agents, dimers and tricarboxylic acylating agents of Diels-Alder. The dimer acylating agents include products derived from the dissolution of unsaturated fatty acids, for example, the fatty acids described above. In general, the dimer acids have a mean of about 18, preferably from about 28 to about 44, preferably about 40 carbon atoms. The The dimer acids preferably have about 36 carbon atoms. The dimer acids are preferably prepared from C "fatty acids, such as oleic acids. Dimer acids are described in US Patents 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468, 3,157,681 and 3,256,304, the complete descriptions of which are incorporated herein by reference. Examples of dimer acids include Acid Dimer Empol® 1014, 1016 and 1018, from Emcry Industries, Inc. and HystreneR-3675, 3680, 3687 and 3695 dimer acids, from Humko Chemical. The polycarboxylic acylating agents can be dicarboxylic acylating agents which are the Diels-Alder type reaction products of an unsaturated fatty acid (for example, the fatty acids described above, preferably tall oil acids and oleic acids) with alpha carboxylic acylating agent, beta-ethylenically unsaturated, (for example acrylic or methacrylic acylating agents) as set forth in US Pat. No. 2,444,328, the disclosure of which is incorporated herein by reference. These Diels-Alder acylating agents include Diácido Westvaco® H-240, 1525 and 1550, which are commercial products of Estvaco Corporation. The polycarboxylic acids or anhydrides can be hydrocarbyl substituted succinic acylating agents, preferably acids or anhydrides, more preferably anhydrides. The hydrocarbyl group generally contains an average of about 8, preferably about 14, more preferably from about 16 to about 40, preferably to about 30, more preferably to about 24, even more preferably to about 18 carbon atoms. Preferably, the hydrocarbyl group is an alkenyl group. The alkenyl group can be derived from one or more of the defines described above. The succinic acylating agents are prepared by reacting the olefins described above or olefins isomerized with unsaturated carboxylic acids such as fumaric acids or maleic acid or anhydride at a temperature of about 160 ° C to about 240 ° C, preferably from about 185 ° C to about 210 ° C. Free radical initiators (for example t-butyl catechol) can be employed to reduce or prevent the formation of polymeric by-products. The processes for preparing the acylating agents are well known to those skilled in the art and are described, for example, in U.S. Patent 3,412,111; and Ben et al., "The Ene Reaction of Maleic Anhydride With Alkenes" (The eno-reaction of maleic anhydride with alkenes), J.C.S. Perkin II (1977), pages 535-537. These citations are incorporated by reference for their description of procedures to obtain the previous acylating agents.

The polycarboxylic acylating agent can also be a tricarboxylic acylating agent. Examples of tricarboxylic acylating agents include Diels-Alder tricarboxylic acylating agents and trimers. These acylating agents generally contain an average of about 18, preferably about 30, more preferably from about 36 to about 66, preferably to about 60, carbon atoms. The trimer acids are prepared by trimerization of the fatty acids described above. The Diels-Alder tricarboxylic acylating agents are prepared by reaction of an unsaturated monocarboxylic acid with alpha, beta-ethylenically unsaturated dicarboxylic acid (for example fumaric acid or maleic acid or anhydride). The Diels-Alder acylating agent may contain an average of about 12, preferably from about 18 to about 40, preferably about 30, carbon atoms. Examples of these tricarboxylic acids include Empol® 1040, commercial product of Eryth Industries, Hystrenok 5460, commercial product of Humko Chemical, and Unidyme® 60, commercial product of Union Camp Corporation. The carboxylic acylating agent can be a mixture containing at least 10% by weight of a carboxylic acylating agent having at least three carboxylic groups. The < The mixture preferably contains at least 50% by weight, preferably 80% by weight, preferably 90% by weight, of tricarboxylic acylating agent. The carboxylic acylating agents can be mixtures of the above-identified tricarboxylic acylating agents with monocarboxylic acylating agents and the above-identified dicarboxylic acylating agents. The mixture may contain mono-, di- or tri-carboxylic acids. The monocarboxylic acids can have from 2, preferably from about 8, more preferably from "" "" - about 12 to about 30, preferably to about 24 carbon atoms, Examples of monocarboxylic acids include acetic, propionic, butyric and fatty carboxylic acids such as oleic, stearic, linoleic, dodecanoic or tall oil acids Throughout this specification and the appended claims, the term "succinic acylating agent" is meant to include carboxylic acids as well as - derivatives which produce the corresponding acids such as anhydrides, esters, acyl halides and mixtures thereof, unless specifically stated otherwise.The hydrocarbyl substituted succinic acylating agents can be represented by the following formulas: ?and where R is hydrocarbyl group of C-. to approximately C500. As will be pointed out in more detail below, when two succinic acylating agents are combined in a coupled molecule, the R group can be a C: a hydrocarbyl group of about C5 (preferably R is an aliphatic or alicyclic hydrocarbyl group being unsaturated less about 10% of its carbon-carbon bonds As noted in more detail * below, R can be derived from epine polymers R can also derive from unpolymerized olefins from 10 to about 18 carbon atoms, the alpha-olefins For species with bridges, olefins containing 2 to 18 carbons may be used Examples of these olefins include ethylene, propene, 1-butene, 1-penne, 1-hexene, 1-heptene, 1 -octene, 1-noneno, 1- •• Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, etc. In particular commercial alpha-olefin fractions are useful such as Ci5- alpha-olefins, C12-16 alpha-olefins, C? 4-?? Alfa alpha-olefins, C14-18 alpha-olefins, alpha-olefins, olefins of Ciéis, etc .; these commercial alpha-olefin fractions also usually include minor amounts of alpha-olefins that are outside the given ranges. The group R can also be derived from olefinic compounds containing up to about 500 carbon atoms. Preferably, the R group contains about 60 carbon atoms to about 140 carbon atoms and may contain polar substituents, oil-solubilizing side groups, and be unsaturated within the general limitations explained above. The production of hydrocarbon-substituted succinic derivatives is well known to those skilled in the art and it is not necessary to discuss it here. detail. In general, this process involves the reaction of (1) an ethylenically unsaturated carboxylic acid reagent, acid halide, anhydride or ester, such as maleic anhydride, with (2) an ethylenically unsaturated hydrocarbon (procedure without chlorine) or a chlorinated hydrocarbon ( chlorine process) at a temperature within the range of about 100-300 ° C, preferably, about 100 ° C to about 200 ° C. The product of this reaction is a succinic anhydride substituted with hydrocarbyl where the substituent is derived from the olefin or the chlorinated hydrocarbon. The present invention works equally well with products produced by both a chlorine process and a chlorine-free process. If desired, the reaction product of the halide or olefin can be hydrogenated with the unsaturated acid in order to remove all or part of the covalent ethylenically unsaturated bonds by conventional hydrogenation processes. The ethylenically unsaturated hydrocarbon reagent, used in a chlorine-free process, can be derived from olefin streams. The chlorinated hydrocarbon reagent used in a chlorine process can be derived from substantially saturated petroleum fractions or substantially saturated olefinic polymers. Chlorinated polymers and polymers derived from mono-olefins having from 2 to about 30 carbon atoms are preferred. Particularly useful polymers are 1-mono-olefin polymers such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and -methyl-5-propyl-l-hexene. Polymers of medial olefins, ie, olefins in which the olefinic bond is not in the terminal position, are also useful. Examples of these are 2-butene, 3-pentene and , ¿? 4-octene. The interpolymers of 1-mono-olefins such as those illustrated above with one another and the interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins, and polyolefins are also useful sources of the ethylenically unsaturated reagent. These interpolymers include, for example, those prepared by polymerization of isobutene with styrene, isobutene with butadiene, propene with isoprene, propene with isobutene, ethylene with piperylene, r "'" isobutene with chloroprene, isobutene with p-methylstyrene, 1-hexene with 1, 3 -hexadiene, 1-octene with 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with 1-octene, 3, 3-dimethyl-1-pentene with 1-hexene, isobutene with styrene and piperylene , etc. For reasons of hydrocarbon solubility, the interpolymers employed in the preparation of acylating agents of this invention are preferably substantially aliphatic and substantially saturated, ie they should be containing at least about 80% and preferably about 95%, by weight, of units derived from aliphatic mono-olefins. Preferably, they will not contain more than about 5% olefinic bonds based on the total number of carbon-carbon covalent bonds present. Chlorinated polymers and polymers can be obtained by polymerization of a C4 refinery stream with a The butene content of about 35% to about 75% by weight and an isobutene content of about 30% to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (i.e., more than about 80% of the repeating units in total) repeated isobutene units of the formula: CH3 -H.C- C-I CH, The polymeric materials that can be used to prepare the succinic acylating agents can be characterized, as before, by the average number of carbon atoms they contain. The polymeric materials are not uniform, and contain a diversity of molecules of different chain lengths. These polymers are also characterized by their Mn (number average molecular weight). The average number of carbon atoms corresponds to the Mn of the polymer. For example, if a polymer having an average of 100 carbon atoms is reacted with maleic anhydride, the substituted succinic anhydride produced has an Mn of about 1500. Likewise, for a polymer containing an average of 500 "< carbon atoms, the substituted succinic anhydride produced will have an Mn of about 7100. These polymers are also characterized by their Mw (weight average molecular weight) Since the chain lengths of a polymeric material do not always have a distribution regular, Mw and Mn are not always identical Polymeric materials useful in the preparation of hydrocarbyl substituted succinic acylating agents have Mw / Mn ratios of from about 1.5 to about 4.5. about 1.5 to about 3.6 or 3.2, materials having ratios of about 1.8, or about 2, to about 2.5, about 3.2, or about 3.6 are useful. using gel permeation chromatography to determine the Mw and Mn values as well as the Mw / Mn ratio A useful method is found in U.S. Patent 4,234,435. In order to ionize an excess of maleic acid with the polymeric material to form the substituted succinic acylating agent, more than one succinic group can be added to an individual polymer chain. The amount of this poly-substitution can be expressed in terms of the number of succinic groups for each equivalent weight of substituent group (derived from the polymer material).

The equivalent weight of polyalkene is its Mn. The equivalents of substituent groups in the succinic acylating agent are determined by dividing the total weight of substituents by the Mn of the polyalkene. The number of succinic groups per equivalent weight of substituents present in the succinic acylating agent can be found by comparison of the equivalents of succinic groups in the molecule to equivalents of substituents. This is described in US Pat. No. 4,234,435, which is hereby incorporated as reference by its description of the methods that determine the number of succinic groups per equivalent of substituents and by their description of methods of measuring values of Mw and Mn. The substituted succinic acylating agents useful in the present invention have from about 1.0 to about 4.5 succinic groups for each equivalent weight of substituent group. The number of preferred succinic groups for each equivalent weight of substituent group is from about 1.0 to about 2.5 and the most preferred range is from about 1.0 to 2.0. If the acids are the desired starting material, the hydrocarbyl substituted succinic anhydrides can be hydrolyzed by treatment with water or steam to the corresponding acid. Acid halides of acids / - ,. Succinate hydrocarbyl substituted can be used as acylating agents of this invention. They can be prepared by reaction of these acids or their anhydrides with halogenating agents such as phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride.

ALCANOL-AMINES Hydroxyamines can be primary, secondary and tertiary. The terms "hydroxyamine", "alkanol amine" and "amino alcohol" describe the same class of compounds and, therefore, are interchangeable. The hydroxyamines may be alkanol primary, secondary or tertiary amines or mixtures thereof. These amines can be represented, respectively, by the formulas: H \ H2-R'-OH,? N-R '-OH N-R' -OH / wherein each R is, independently, a hydrocarbyl group of one to about eight carbon atoms or a hydroxyl-substituted hydrocarbyl group of two to about eight carbon atoms and R 'is a divalent hydrocarbon group of about two to about 18 carbon atoms . He > The group -R'-OH of such formulas represents the hydroxyl-substituted hydrocarbyl group. R1 can be an acyclic, alicyclic or aromatic group. Typically, R 'is a linear or branched acyclic alkylene group such as ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. When there are two R groups in the same molecule, these can be linked by a carbon-carbon direct bond or through a heteroatom (for example, oxygen, nitrogen or sulfur) to form a 5-, 6- ring structure. 7- or 8 links. Typically, however, * each R is a lower alkyl group of up to seven carbon atoms. Examples of useful N- (hydrocarbyl hydroxyl substituted) amines are ethanolamine, diethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, di- (3-hydroxylpropyl) amine, N- (3-hydroxylbutyl) amine, N- (4-hydroxylbutyl) amine , N, N-di- (2-hydroxylpropyl) amine, N- (2-hydroxyethyl) morpholine, its thio-analogue, N- (2-hydroxyl ethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, N- ( hydroxyl ethyl) piperazine, and the like. The tertiary alkanolamines can be reacted under condensing conditions such that any salt that forms between the carboxyl groups and the tertiary amine moiety of the alkanol amine molecule becomes a condensed product such as ester. In a typical reaction, the ring of r - Anhydride is opened by alcohol to form an ester. The remaining carboxyl group reacts with a second molecule of the alkanolamine to form a second ester. The tertiary alkanolamines can be reacted under non-condensing conditions to form a salt ester product which acts as an emulsifier. The reaction is carried out under conditions such that condensation reactions are unlikely to occur. Under these non-condensing reaction conditions, the product of the reaction between a hydrocarbyl substituted succinic anhydride acylating agent and a tertiary amine alkanol is a salt ester. Other hydroxyamines are the hydroxy-substituted primary amines described in U.S. Patent 3,576,743 by the general formula R, -NH where Ra is a monovalent organic group containing at least one alcoholic hydroxyl group. The total number of carbon atoms in R does not preferably exceed about 20. The hydroxy-substituted aliphatic primary amines containing a total of up to about 10 carbon atoms are useful. The polyhydroxy-substituted primary alkanols are useful in which there is only one amino group (i.e. primary amino group) having an alkyl substituent containing up to about 10 carbon atoms and up to about 6 hydroxyl groups. These primary alkanol amines correspond to R-j-NH where Ra is a mono- or polyhydroxy-substituted alkyl group. Specific examples of hydroxy-substituted primary amines include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p (beta-hydroxyethyl) -aniline, 2-amino-1-propanol, -amino-l-propanol, 2-amino-methyl-1,3-propanediol, 2-amino-2-ethyl-l, 3-propanediol, N- (beta- >); 'hydroxypropyl) -N' - (beta-aminoethyl) piperazine, tris- (hydroxymethyl) aminomethane (also known as trimethylolamino methane), 2-amino-1-butanol, ethanolamine, beta- (beta-hydroxyl-Letoxy) -ethylamine, glucamine , 4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according to methods known in the art by reaction of isoprenoxide with ammonia), N-3- (aminopropyl) -4- (2-hydroxyethyl) piperidine , 2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N- (beta-n-hydroxyethyl) -1,3-diamino propane, 1,3-diamino-2-hydroxypropane, N- (beta-) hydroxy ethoxyethyl) ethylenediamine, trismethylolaminomethane and the like. U.S. Patent 3,576,743 is incorporated herein by reference. Also useful are hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms. Among the hydroxyalkyl alkylene polyamines "<" substituted useful ones include those in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms. Examples of these hydroxyalkyl substituted polyamines include N- (2-hydroxyethyl) ethylene diamine, N, -bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) -piperazine, diethylene triamine monohydroxypropyl substituted, tetraethylene pentamine dihydroxypropyl substituted, N- (3-hydroxybutyl) tetramethylene diamine, etc. Higher homologs obtained by condensation of the hydroxy alkylene polyamines whose examples have been given above through amino groups or through hydroxyl groups are also useful. Condensation through amino groups results in a higher amine accompanied by separation of ammonia and condensation through hydroxy groups results in products containing ether linkages accompanied by water separation. The hydroxyamines may also be N- (hydrocarbyl hydroxy substituted) amines. These consist of hydroxyl-substituted poly (hydro-carbyloxy) analogs of the hydroxyamines described above (these analogs also include the hydroxyalkylene-hydroxyl-substituted analogs). These N- (hydrocarbyl hydroxyl substituted) amines can be conveniently prepared by reaction of epoxides with the amines described above and can be represented by the formulas: HN2- (R'0) x-H, N- (R'0) x-H where x is a number from about 2 to about 15, each R is independently a hydrocarbyl group of one to about eight carbon atoms or hydroxyl-substituted hydrocarbyl group of two to about eight carbon atoms and R 1 is a divalent hydrocarbyl group of about two to about 18 carbon atoms. Polyamine analogues of these hydroxy amines, particularly alkoxylated alkylene polyanamines, can also be used. (for example, N, N- (diethanol) -ethylene diamine). These polyamines can be obtained by the reaction of alkylene amines (e.g., ethylene diamine) with one or more alkylene oxides (e.g., ethylene oxide, octadecene oxide) of from 2 to about 20 carbons. Similar alkylene oxide-alkanolamine reaction products can also be used, such as the products obtained by reaction of the primary or secondary alkanol amines described above with ethylene, propylene or higher epoxides in a 1: 1 or 1: 2 molar ratio. The ratios of reactants and temperatures to carry out these reactions are known to those skilled in the art.

Specific examples of alkylated alkoxylated polyamines include N- (2-hydroxyethyl) ethylene diamine, N, N-bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) piperazine, diethylene triamine mono (hydroxypropyl) -substituted , tetraethylene pentamine di (hydroxypropyl) -substituted, N- (3-hydroxybutyl) -tetramethylene diamine, etc. Higher homologs obtained by condensation of the hydroxy alkylene polyamines illustrated above through amino groups or through hydroxy groups are also useful. Condensation through amino groups results in a higher amine accompanied by separation of ammonia while condensation through hydroxy groups results in products containing ether linkages accompanied by water separation. Mixtures of two or more of any of the above mono- or polyamines are also useful.

POLYALYKYLPOLIAMINES Alkylenepolyamines are represented by the formula: HN- (Alkylene-N), R. I I where n has a mean value of 1, or about 2 to about 10, or to about 7, or to about , 5, and the "alkylene" group has from 1, or about 2 to about 10, or to about 6, or to about 4 carbon atoms. Each R ^ is, independently, hydrogen, or an aliphatic group, or hydroxy-substituted aliphatic group, of up to about 30 carbon atoms. Rf can be defined the same as Ri. These alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc. Also included are higher homologs and related heterocyclic amines such as N-aminoalkyl-substituted piperazines and piperazines. Among the specific examples of these polyamines are ethylene diamine, diethylenetriamine (DETA), triethylenetetraamine (TETA), tris- (2-aminoethyl) amine, propylene diamine, trimethylene diamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, pentaethylenehexamine, etc. Higher homologues obtained by condensation of two or more of the aforementioned alkylene amines are also useful as are mixtures of two or more of the polyamines described above. Ethylene polyamines are useful, such as those mentioned above. These polyamines are described in detail under the heading Ethylene Amines of Kirk Othmer's "Encyclopedie of Chemical Technology", 2nd Edition, Vol. 7, pages 22-37, , 'j Interscience Publishers, New York (1965). The most convenient way to prepare these polyamines is by reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia, etc. These reactions result in the production of a complex mixture of polyalkylene polyamines including cyclic condensation products such as the piperazines described above. Mixtures of ethylene polyamines are useful. Other useful types of polyamine mixtures are those resulting from the distillation of the polyamine mixtures described above to leave as residue what is commonly known as "polyamine bottoms". In general, the backgrounds of allylenpolyamines are characterized by having less than two, usually less than 19 > (by weight) of boiling point material below 200 ° C. A typical sample of these ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Texas, designated "E-100" has a specific gravity at 15.6 ° C of 1.0168, a nitrogen percentage of 33.15 by weight and a viscosity at 40 ° C of 121 centiestokes. Analysis by gas chromatography of this sample gives a content of approximately 0.93% of "light ends" (most likely DETA), 0.72% of TETA, 21.74% of tetraethylene pentamine and 76.61% of pentaethylenehexamine and higher (by weight). These > Alkylene polyamine backgrounds include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetraamine and the like. These alkylene polyamine bottoms can be reacted only with the acylating agent or can be used with other amines, polyamines or their mixtures. Another useful polyamine is the condensation reaction between at least one hydroxy compound with at least one polyamine reagent containing at least one primary or secondary amino group. The hydroxy compounds are preferably polyhydric alcohols and amines. Polyhydroxy alcohols have been described above. Preferred hydroxyl compounds are polyhydroxy amines. The polyhydroxy amines include any of the monoamines described above that have reacted with an alkylene oxide (for example ethylene oxide, propylene oxide, butylene oxide, etc.) having two to about 20, or to about four carbon atoms. Examples of polyhydroxyl amines include tri (hydroxypropyl) amine, tris- (hydroxymethyl) amino methane, 2-amino-2-methyl-1, 3-propanediol, N, N, N ', N' -tetrakis (2- hydroxypropyl) ethylenediamine, and N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, preferably tris (hydroxymethyl) aminomethane (THAM).

The polyamines, which react with the polyhydroxylic alcohol or amine to form the condensation products or condensed amines are those described above, Among the preferred polyamine reagents are triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures thereof. of polyamines such as the "amine bottoms" described above.

IMIDAZOLINES The imidazolines useful as emulsifiers are condensation products of fatty acids and polyamines. The polyamines useful in this reaction are characterized by the presence of at least two primary amine groups or a primary amine group and a secondary amine group. The polyamines used are generally the alkylene polyamines such as ethylene diamine, diethylene triamine, triethylene tetraamine, etc. The fatty acids which can be used to form this class of imidazolines include lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, eleseaaric and ricinoleic acids. Imidazolines based on fatty acids are marketed by chemical manufacturers such as Croda Universal Ltd. r - GLYCERIN ESTERS Glycerin ester emulsifiers are formed by the reaction of fatty acids with an excess of glycerin to form a mixture of mono and diglycerides. The common fatty acids of C-12 to C-18 are suitable starting materials. Instead of fatty acid, vegetable oil can be used as raw material to react with an excess of glycerin. A typical example is glycerin monooleate (Arlacel 186-ICI).

POLIOXYALYLENE STERES The emulsifier can be a polyoxyalkylene fatty ester. The polyoxyalkylene fatty esters can be prepared from a polyoxyalkylene polyalcohol or a polyoxyalkylene alcohol and a fatty acid. The polyoxyalkylene polyalcohol and the polyoxyalkylenic alcohol, for example, alcohol or polyoxyalkylated phenol, are described above. The fatty acid is preferably the monocarboxylic fatty acid described above. Commercially available polyoxyalkylene fatty esters from Armak Company under the registered name of Ethofat. Specific examples of polyoxyalkylene fatty esters include Ethofat C / 15 and C / 25, which are coconut fatty esters obtained using 5 to 15 moles, respectively, of ethylene oxide; Ethofat 0/15 and O / 20, which are oleic esters obtained by using 5 and 10 moles of ethylene oxide; and Ethofat 60/15, 60/20 and 60/25 which are stearic esters formed with 5, 10 and 15 moles of ethylene oxide respectively.

POLIOXYALYLLEN AMINE Polyoxyalkylene polyamines, for example, polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200, or about 400 to 4000, or up to about 2000 can be used as emulsifiers. Illustrative examples of these polyoxyalkylene polyamines can be represented by the formulas: NH-alkylene (O-alkylene) mNH2, where m has a value of about 3 to 70 and preferably about 10 to 35; and R (alkylene (0-alkylene) nNH) 3-β, where n is such that the total value is from about 1 to 40 with the proviso that the sum of all n is from about 3 to about 70 and generally from about 6 to about 35 and R is a polyvalent saturated hydrocarbon radical of up to 10 carbon atoms having a valence of 3 to 6. The alkylene group can be straight or branched chain and contains from 1 to 7 carbon atoms and usually from 1 to 4 carbon atoms. The various alkylene groups present may be the same or different.

Polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamins having average molecular weights in the range of about 200 to 2000. Polyoxyalkylene polyamines are commercially available, for example, from Huntsman Chemical Company under the trade name of "Jeffaminas D-230, D-400, D-1000, D-2000, T-403, etc. There is commercially available a series of hydroxyamines in which b is zero which are from Armak Chemical Division of Akzona, Inc. , Chicago, Illinois, under the general trademark of "Ethomeen" and "Propomeen." Specific examples of these products include "Ethomeen C / 15" which is a condensate of ethylene oxide from a cocoamine containing approximately 5 moles of ethylene oxide; "Ethomeen C / 20" and "C / 25" which are also condensation products of ethylene oxide of cocoamine containing approximately 10 and 15 moles of ethylene oxide respectively; "Etomeen" 0/12 which is a condensation product of ethylene oxide of oleylamine containing about 2 moles of ethylene oxide per mole of amine. "Ethomeen S / 15" and "S / 20" which are condensation products of ethylene oxide with soyaamine containing about 5 and 10 moles of ethylene oxide per mole of amine respectively; and "Ethomeen T / 12, T / 15" and "T / 25" which are condensation products of ethylene oxide of - "'' - tallowamine containing about 2, 5 and 15 moles of ethylene oxide per mole of amine respectively." Propomeen 0/12"is the condensation product of one mole of oleylamine with two moles of propylene oxide. Preferably, the salt is formed from Ethomeen C / 15 or S / 15 or mixtures thereof Commercial examples of amines in which b is 1 include "Ethoduomeen T / 13", "T / 20" and "T / 25" which are condensation products of ethylene oxide of N-tallow trimethylene diamine containing 3, 10 and 15 moles of ethylene oxide per mole of diamine, respectively.Another group of polyoxyalkylene amines are the polyoxyalkylated amino polyalcohols TETRONIC from Wyandotte Chemicals Corporation These amines are represented by the general formula: H (OC2H4) n (OC3Hd) (C3H60) r, (C2H40) 3H H (0C2H4) n (0C3H6) or / (CsHßO), (CrH40) -H These hydroxyamines are described in U.S. Patent No. 2,979,528 which is incorporated herein by reference. The hydroxyamines corresponding to the above formula can have a molecular weight of numerical average of up to about 10,000 where the ethyleneoxy groups / * "'contribute to the molecular weight of the total numerical average of the percentage ranges discussed above.A specific example would be a hydroxyamine having a number average molecular weight of about 8000 where the ethyleneoxy groups amount to 7.5% -12%! By weight of the total number average molecular weight, these hydroxyamines can be prepared by reaction of an alkylene diamine, such as ethylene diamine, propylene diamine, hexamethylenediamine, etc., with propylene oxide, etc. The resulting product is then reacted with ethylene oxide.

ETOXYLATED ALKYLPHENOLS The ethoxylated alkyl phenol emulsifiers are obtained by the reaction of ethylene oxide with an alkyl phenol. The alkyl group may be straight or branched chain with a more common chain length of C8 to C12. In any case, 1 to 40 units of ethylene oxide may be included, however, for water-in-oil emulsions, 1 to 8 units are generally preferred. A typical example of an ethoxylated alkylphenol emulsifier is octylphenoxy polyethoxy ethanol (Triton X-15 - Union Carbide).

ETHODYLATED FATTY ALCOHOLS The ethoxylated fatty alcohol emulsifiers are obtained by reaction of alcohols with chain lengths of C8 to C18 with ethylene oxide. The number of ethylene oxide units used is generally from 2 to 20. 2 to 8 units are preferred for water-in-oil emulsions. Primary or secondary alcohols can be used in obtaining these emulsifiers. A typical example of an ethoxylated fatty alcohol emulsifier is cetyl alcohol POE (2) (Brij 52 - ICI Specialties Chem).

PREPARATION OF N-DODECIL- (2-HYDROXYETHYL SULFIDE) Example 1 A solution of 422.6 g of 2-mercaptoethanol was prepared and 6.4 g of azolisobutyronitrile (AIBN) at room temperature (Solution I). 1000 g / 1-dodecene was introduced into a reaction vessel and heated to 80 ° C by purging the vapor space r-with N 2 and 1 g of AIBN was added. It was added evenly Solution I while maintaining the reaction temperature between 80-88 ° C. After adding Solution I, 7.2 g of AIBN was added and the reaction was maintained at 80-88 ° C until the Total acid number was less than 20. The reaction product was vacuum distilled at 20 mm Hg and 149 ° C until the concentration of 1-dodecene was less than 4C. The reaction cooled to 9.3 ° C (49 ° F) and filtered.

PREPARATION OF ETHER 2, 2 '-DI- (N-DODECIL-THIO) -DYTHYLIC Example II A solution of 6500.5 g of n-dodecyl- (2-hydroxyethyl) sulfide and 775 g of mixed xylenes with a purge of nitrogen under the surface. The mixture was heated to a temperature of 90 ° C. To the mixture was added 10 g of > "" • methanesulfonic acid. The mixture was heated at 150-160 ° C and an azeotrope of water / xylene was distilled. The product was an industrial grade 2, 2 '-di- (n-dodecylthio) -dietyl ether C? 2H25 S -CH? CH2 -O-CH CH. - S - C? 2H_ £ COMPOSITIONS The compositions generally contain an emulsifying amount of an emulsifier (A), a larger amount of a mixture of brine and liquid oil, a friction modifier (B) of the following formula: R 'R " where X = 1 to 4 z = 1 to 6 Q = 0 to 2 Ri and R2 are, independently, H or an aliphatic group containing from 1 * to approximately 16 carbon atoms, provided that the sum of Ri and R2 is between 0 and about 16, R 'is an aliphatic group containing an average of about 8 to about 24 carbon atoms, and R "is selected from the group consisting of H, an aliphatic group containing between 1 and an average of about 18. carbons, and R 'srr where Q, X, z, Rj, R2, R 'and R "are as defined above, and Y is 0 to 5. In a preferred embodiment z is 1. In the most preferred embodiment, Q = 0, R, and R2 are both H, X and z are equal to 1, R 'is n-dodecyl and R "is H. The composition may optionally include a surfactant, fillers, organophilic clays and lime. The composition can contain approximately 0.288 kg (1/2 pound) to about 6.85 kg (15 pounds) of friction modifier per 158.76 liters (1 barrel) of composition. Compositions of approximately 0.457 kg (1 lb.) to about 5.48 kg (12 lb.) or about 0.914 kg (2 lb.) to about 4.57 kg. (10 pounds) of friction modifier for 158.7 liters (1 barrel) of composition. Most preferred is a ratio of about 1.8 kg (4 pounds) to about 3.65 kg (8 pounds) of friction modifier per 158.76 liters (1 barrel) of composition. The composition may optionally include bulking agents, surfactants, organophilic clays, lime, and other ingredients commonly used in well drilling muds.

SALMUERA MIXTURES - LIQUID OIL The brine is present in a mixture with liquid oil. In one embodiment, the brine is present in a mixture in an amount of about 5,. or about 10, or about 15, or about 25 to about 90, or up to about 75, or up to about 55 parts by volume. In this embodiment, the liquid oil is present in the mixture in an amount of about 10, or about 25, or about 45 to about 95, or about 90, or about 85, or about 75 parts by volume. The total volume parts of brine plus the total volume parts of liquid oil make up 100 parts by volume of the mixture. In one embodiment, the brine is a discontinuous phase and the liquid oil is a continuous phase. In another embodiment, the mixture contains a larger amount of a liquid oil, preferably about 65, or about 70, or about 75 to about 90, or about 85 parts by volume. In this embodiment, the brine is present in an amount of about 10, or about 15 to about 35, or about 20, or about 25 parts by volume of the mixture. The brine useful in the compositions and methods of the present invention may be a brine that appears naturally in the soil or a formulation of several salts. These salts include calcium chloride, magnesium chloride, sodium chloride, potassium chloride, zinc chloride and zinc bromide. The calcium chloride is generally present in an amount of 1% to about 40% by weight of the brine. Magnesium chloride is generally present in an amount of about 0.5% to about 24% by weight of brine. Sodium chloride is generally present in an amount of about 1% to about 27% by weight of brine. The potassium chloride is present in an amount of about 0.5% to about 24% by weight of brine. Zinc chloride or zinc bromide is present generally in an amount of from about 0.5% to about 80% by weight of brine. The mixture also includes a liquid oil. Examples of these oils are petroleum oils, such as lubricating viscosity oils, crude oils, diesel oils, highly refined oils, kerosenes, fuel oils, white oils and aromatic oils. Liquid oils include natural lubricating oils, such as animal oils, vegetable oils, mineral lubricating oils, mineral oils treated with solvent or acid, oils derived from coal or shales, and synthetic oils. Vegetable oils include babassu oil, castor oil, coconut oil, corn oil, cottonseed oil, hemp oil, linseed oil, ocytic oil, olive oil, palm oil, oil peanut, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil and tung oil.

• Synthetic oils include hydrocarbon oils and halogenated hydrocarbon oils such as polymerized and interpolymerized olefins, for example, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (l-octenes) , poly (1-tens); alkylbenzenes, such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- (2- ethylhexyl) benzenes; polyphenyls such as biphenyls, terphenyls, and alkylated polyphenyls; and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivatives, analogs and homologs thereof. Another class of synthetic oils are polymers and interpolymers of alkylene oxide and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. Examples thereof are the polyoxyalkylene polymers prepared by the polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers such as methyl polyisopropylene glycol ethers, polyethylene glycol diphenyl and diethyl ethers and mono- and polycarboxylic esters thereof, for example, acetic esters, mixed esters of C3-C8 fatty acid and C13 oxo-diester of tetraethylene glycol. Simple aliphatic ethers such as dioctyl ether, didecyl ether, di (2-ethylhexyl) ether can be used as synthetic oils. Another suitable class of synthetic oils is that which comprises the esters of fatty acids such as ethyl oleate, lauryl hexanoate and decyl palmitate. The esters of dicarboxylic acids such as phthalic acid, succinic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, acid Malonic, alkyl malonic acids, alkenyl malonic acids with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethyl ether, propylene glycol. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by the reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. In one embodiment, the liquid oil is a mineral or vegetable oil having a kinematic viscosity of about 3, or about 3.5, or about 4 to about 15, or up to about 11, or up to about 10, or until approximately 9 centistokes at 100 ° C. Useful mineral oils include neutral mineral oils 40, 100, 150, 200 and 300. Examples of specific liquid hydrocarbons include No.2 diesel oil, Exxon ESCAIDR 110 (a petroleum distillate comprising 20% aromatics, 56.6 % of paraffins and 23.4 of naphthenes marketed by ESSO), Total HDF 200 oil, Conoco LVT oil (a mineral oil with a viscosity of 1.8 centistokes a 40 ° C of Conoco Oil Company), and Conoco LVT 200 (a mineral oil with a viscosity of 2, 1 centistokes at 40 ° C and less than 0.5% aromatic content, from Conoco Oil Company).

SURGICAL AGENT The surfactant is generally present in the compositions in an amount of about 0.457 kg (1 lb.), or about 0.914 kg (2 lb.) to about 9.14 kg (20 lb.), or up to about 6.85. kg (15 pounds), or up to approximately 4.57 kg (10 pounds) per 158.76 liters (1 barrel) of the composition. The function of the surfactant is to promote the wetting with oil of the solid particles in the drilling fluid, especially the fillers such as barite. The surfactant compounds include polyoxyalkylene amines, polyoxyalkyl amides, alcohols polyoxyalkylene, polyoxyalkylenic phenols, polyoxyalkylenic esters, fatty acid salts, amine or alkaline earth metal or transition metal sulfonates, or reaction products of a hydroxyamine or a polyalkylene polyamine and a carboxylic acylating agent selected from the group consisting of acylating agents monocarboxylates, dicarboxylic acylating agents other than succinic acylating agents and tricarboxylic acylating agents.

The production of sulphonic acids from the by-products of the manufacture of detergents, for example, by reaction with S03 is well known to the specialists. See, for example, the article "Sulfonates" of the "Encyclopedia of Chemical Technology" by Kirk-Othmer, Second Edition, Vol. 19, pages 291 et seq., Published by John Wiley & Sons, N. Y. (1969). The sulfonic acid salt may be derived from an amine or an alkaline earth metal or transition metal compound. Any of the amines described above can be used. The alkaline earth metal salt and transition metal includes magnesium, calcium, barium, titanium, iron and zinc salts. In one embodiment, the metal salt is an alkaline earth metal salt, preferably a calcium or barium sulfonate, preferably a calcium sulfonate. The metal salts are prepared by methods known to those skilled in the art. A method for its preparation is the mixing of a sulfoic acid with an alkaline earth metal or transition metal base, such as an oxide or a hydroxide.

LOADING AGENTS The compositions of the present invention may additionally contain bulking agents. These agents increase the density of drilling muds and among them are included galena (PbS), hematite (Fe.; 03), magnetite (Fe304), ilmenite (FeTi03), barite (BaS04), siderite (FeC03), celestite (SrSO, dolomite (CaMg (C03) 2), and calcite (CaC03) • Particularly useful fillers include barium sulfate and rust It is also possible to load soluble salts, such as sodium chloride, sodium bromide, sodium carbonate, potassium chloride, potassium carbonate, , '. -, calcium bromide, zinc chloride and zinc bromide. The bulking agents may be present in an amount of about 9.14 kg (20 pounds) or about 45.7 kg (100 pounds), or about 114.25 kg (250 pounds) to about 411.3 kg (900 pounds) ) or approximately 319.9 kg (700 pounds) or approximately 274.2 (600 pounds) per 158.76 liters (1 barrel). In one embodiment, the bulking agent is present in an amount of about 137.1 /. < \ g (300 pounds) to approximately 228.5 kg (500 pounds) or to approximately 182.8 kg (400 pounds) for 158.76 1 (1 barrel).

ORGANOFILA CLAY The compositions may also contain commercial clays such as bentonite, attapulgite, sepiolite, etc. In one embodiment, the compositions may also include an organophilic clay. The organophilic clays are * "Clays, such as montmorillonite, hectorite, saponite, attapulgite and illite, which have amine salts absorbed. These clays are converted from clays that admit water (for example, present in the brine phase of the emulsion) to clays that accept oil (for example, present in the liquid oil phase) by the absorption of amine salts. The organophilic clays are preferably wettable by oil and dispersed in the oil phase to produce viscosity and gel properties. Montmorillonite, bentonite and attapulgite are preferred, with montmorillonite being most preferred. Water and methanol can be used to activate the organophilic clay. The organophilic resin is present in an amount of about 0.457 kg (1 pound), or about 0.914 kg (2 pounds) to about 4.57 kg (10 pounds) or up to about 3.65 kg (8 pounds) per 158, 76 liters (1 barrel).

The compositions of the present invention may also include lime.Lime in combination with the reaction products or their salts (A) provides an improved thickness to the compositions.Lime is generally present in an amount of about 0.457 kg (1 lb.), or about 0.914 kg (2 lb.) to about 4.57 kg ^ _. (10 pounds) or up to approximately 3.65 kg (8 pounds) for 158.76 liters (1 barrel).

WELL PUNCH COMPOSITIONS In one embodiment, the compositions of the present invention are well drilling compositions.

In one embodiment, the well drilling compositions are inverse water-in-oil emulsions. Well drilling compositions generally have a density of about 4.1 kg (9 pounds), or about 4.57 kg (10 pounds) to approximately 9.59 kg (21 pounds), or to approximately -8.22 kg (18 pounds), or to approximately 6.39 kg (14 pounds) per 3,78 liters (1 gallon). The following examples illustrate the compositions of the present invention.

EXAMPLE A-C r - Composition A is prepared by combining 165 g of Conoco LVT 200 oil, 6 g of polyamide emulsifier, 6 g of synthetic liquid mixture polyamide and 5 g of lime in an appropriately sized container. This combination is then mixed for a total of 10 minutes with a moderate shear effect in an Ha ilton Beach type mixer.

At the end of the 10 minute mixing interval, 5 g of organophilic clay is added and mixed for a further 10 minutes with high shear effect in a Hamilton Beach type mixer. To a suitable vessel is added 15 g of anhydrous calcium chloride to 49 g of tap water and mixed. To the previous mixture consisting of: Conoco LVT oil 200, polyamide emulsifier, synthetic liquid mixture Polyamide, lime and organophilic clay are added, the tempered calcium chloride solution is added slowly over 10 minutes with stirring. The complete mixture is subjected to high shear for an additional 10 minutes in a Hamilton Beach type mixer. In this case a high shear effect is reached when a deep whirlwind is observed. 339 g of barite are added to the previous mixture over a period of 10 minutes, mixing with a high shear effect on a Hamilton Beach-type mixer, continuing to mix with a high shear effect for a minimum of 10 minutes or until uniform. The composition of Example A does not contain a friction modifier and this example serves as a comparative example but is not an example of the invention In Example B, the same procedure is followed as in A, with the inclusion of 5 g of friction modifier of Example 1 added after the mixing interval of 10 minutes Mix thoroughly with a Hamilton Beach type mixer until uniform. In Example C the same procedure as in the A with the inclusion of 8 g of the friction modifiers of the Example I added at the end of the 10 minute mixing interval. Mix thoroughly in a Hamilton Beach type mixer until uniform.

Table "^ - EXAMPLE D - E Composition D is prepared by combining 165 g of Chevron Isotec alpha olefin oil, 6 g of polyamide emulsifier, 6 g of synthetic liquid mixture polyamide and 5 g of lime in a measuring vessel This combination is then mixed for a total of 10 minutes with moderate shear effect on a Hamilton Beach type mixer.After the 10 minute mixing interval, add 5 g of organophilic clay and mix for an additional 10 minutes at high Cyclone effect on a Hamilton Beach type mixer 15 g of anhydrous calcium chloride are added to a suitable vessel to 49 g of tap water with mixing to the above mixture consisting of: Chevron Isotec alpha olefin oil, emulsifier of polyamide, synthetic liquid polyamide blend, and organophilic clay, the warm calcium chloride solution is added slowly over 10 minutes while stirring. The complete mixture is subjected to high shear effect for an additional 10 minutes in a Hamilton Beach type mixer. In this case, the high shear effect is achieved when a deep whirlwind is observed. To the previous mixture 339 g of barite are added over 10 minutes mixing with high shear effect in one Hamilton Beach type mixer. Continue mixing at high shear for a minimum of 10 minutes or until uniform. The composition of Example D does not contain the friction modifier and this example serves as a comparative example but is not an example of the invention. In Example E, the same procedure as in Example D is followed by including 5 g of the friction modifier of Example II added at the end of the 10 minute mixing interval. Mix thoroughly with a Hamilton Beach type mixer until uniform.

Table TEST OF THE FRICTION COEFFICIENT The friction coefficient of the prepared drilling mud was determined using an OFITE Lubricity Tester test apparatus. This is a standardized instrument designed to determine the coefficient of friction of drilling fluids and lubricant additives. In the standardized drill fluid test, a hardened steel block and a ring are placed in contact with each other in the presence of the fluid to be tested. A load of 150 pounds (68.5 kg) inch (2.54 cm) is placed on an arm with a scale that applies a pressure of between 3,400 atm. (5,000 pounds per "-'- square inch) and 6,800 atm (10,000 pounds per square inch) on the fluid being tested lying between the block and the ring.The ring is rotated at 60 rpm.To test the oil-base drilling fluids , the test was modified to increase the load to 250 pounds inch (114 kg 2.54 cm) and a rotation speed of 160 rpm All drilling fluids tested were performed under these modified conditions and, therefore, are directly comparable The values of the coefficient of friction among themselves, although the invention has been explained in relation to its preferred embodiments, it should be understood that for the specialists in this technique various modifications thereof will be apparent upon reading the specification. therefore, it is to be understood that the invention described herein is intended to cover modifications that come within the scope of the appended claims

Claims (30)

1. ei CLAIMS 1. A drilling fluid composition comprising a water-in-oil emulsion formed from a brine, a liquid oil, an emulsifier (A), a friction modifier (B) of the following formula: where X = 1 to 4 z = 1 to 6 Q = 0 to 2 Ri and R2 are, independently, H or an aliphatic group containing 1 to about 16 carbon atoms, provided that the sum of Ri and R2 is between 0 and about 16, R 'is an aliphatic group containing an average of about 8 to about 24 carbon atoms, and "" is selected from the group consisting of H, an aliphatic group containing between 1 and a mean of about 18. carbons, and where Q, X, z, Ri, R_, R 'and R "are as defined above, and Y is 0 to 5. 2. The composition according to claim 1 wherein R" is hydrogen. 3. The composition according to claim 1 wherein X = 1. 4. The composition according to claim 1 wherein Ri is hydrogen and R.- contains 1 to 10 carbon atoms. 5. The composition according to claim 1 wherein R2 is hydrogen and Ri contains 1 to 10 carbon atoms. 6. The composition according to claim 1 wherein Ri is hydrogen and R; contains 1 to 2 carbon atoms. 7. The composition according to claim 1 wherein R2 is hydrogen and R- contains 1 to 2 carbon atoms. 8. The composition according to claim 1 wherein z is 1 to 4. The composition according to claim 1 wherein z is 1. 10. The composition according to claim 2 wherein Q is equal to zero, Ri and R2 are both hydrogen, X and z are both 1, and R 'is n-dodecyl. 11. The composition according to claim 1 wherein R "is an aliphatic group containing an average of 1 to an average of 14 carbon atoms. 12. The composition according to claim 1 wherein R "is an aliphatic group containing an average of 1 to an average of 12 carbon atoms 13. The composition according to claim 1 wherein R" is an aliphatic group containing an average of 1 to an average of 8 carbon atoms. 14. The composition according to claim 1 wherein R "is an aliphatic group containing an average of 1 to an average of 4 carbon atoms 15. The composition according to claim 1 wherein R" is represented by the structure: Where X = 1 to 4, Ri and R2 are, independently, H or an aliphatic group containing from 1 to about 16 carbon atoms, provided that the sum of Ri and R_ is between 0 and about 16, R 'is a group aliphatic containing an average of about 8 to about 24 carbon atoms, and Y is 0 to 5. '"*" 16. The composition according to claim 15 wherein Y is 1 to 4. 17. The composition according to claim 15 wherein Y is 0 to 2. 18. The composition according to claim 15 wherein Q = 0, Y = 0, Ri and R2 are both hydrogen, X and z are both 1, and R 'is n-dodecyl. 19. The composition according to claim 1 wherein the friction modifier is present at a level between about 0.228 kg (1/2 pound) and about 6.85 kg (15 pounds) of friction modifier for each 158.76 liters ( 1 barrel) of composition. The composition according to claim 1 wherein the friction modifier is present at a level between approximately 0.457 kg (1 lb.) and approximately 5.48 kg (12 lb.) of friction modifier for each 158.76 liters, - (1 barrel) of composition. The composition according to claim 1 wherein the friction modifier is present at a level between about 0.914 kg (2 pounds) and about 4.57 kg (10 pounds) of friction modifier for every 158.76 liters (1 barrel) Of composition. 22. The composition according to claim 1 wherein the friction modifier is present at a level between about 1,828 kg (4 pounds) and about 3,65 kg (8 pounds) of friction modifier per 158.76 liters (1 barrel) of composition. 23. The composition according to claim 1, which also comprises at least one surfactant. 24. The composition according to claim 1, further comprising at least one bulking agent. 25. The composition according to claim 1, further comprising at least one organophilic clay. 26. The composition according to claim 1, further comprising lime. 27. The composition according to claim 1 wherein the filler is barium sulfate, iron oxide, calcium chloride, calcium bromide, zinc bromide or zinc chloride. The composition according to claim 1 wherein the brine is present in the mixture in an amount of about 5 to about 90 parts by volume, and the liquid oil is present in the mixture in an amount of 10 to about 95 parts by volume, where the total parts by volume of brine and hydrocarbon constitute a total of 100 parts by volume. 29. The composition according to claim 1 wherein the brine constitutes a discontinuous phase and the liquid oil is a continuous phase. 30. A method comprising the steps of introducing the composition of claim 1 into the hole of a well and drilling, completing or working on the hole in the well. SUMMARY OF THE INVENTION This invention relates to a composition comprising a water-in-oil emulsion formed from a brine, a liquid oil, an emulsifier (A), a friction modifier (B) of the following formula: where X = 1 to 4 z = 1 to 6 Q = 0 to 2 Ri and R2 are, independently, H or an aliphatic group containing from 1 to about 16 carbon atoms, provided that the sum of Ri and R is between 0 and about 16, R 'is an aliphatic group containing an average of r-roxically 8 to about 24 carbon atoms, and R "is selected from the group consisting of H, an aliphatic group containing between 1 and average of approximately 18 carbons, and R '- O- CU- (CH2) Q- CH- where Q, X, z, Ri, R2, R 'and R "are as defined above, and Y is 0 to 5. In a preferred embodiment z is 1. In the most preferred embodiment, Q = 0, Ra and R2 are both H, X and z are equal to 1, R 'is n-dodecyl and R "is H. The compositions of the present invention have beneficial lubricating properties. These compositions are useful in drilling, working and completing well holes. tr. TO-'-