AQUEOUS FUNCTIONAL FLUIDS

Abstract: The invention relates to a composition comprising at least one reaction product of (A) at least one hydrocarbyl-substituted carboxylic acylating agent having at least three carboxylic groups, with (B) at least one amine-terminated polyoxyalkylene, having a number average molecular weight from about 600 to about 10,000, or at least one salt of the reaction product. Functional fluids formulated with these reaction products or salts thereof have sufficient and stable viscosity for use in hydraulic, cutting, metal working and other lubricating fluids.

Description: AQUEOUS FUNCTIONAL FLUIDS FIELD OF THE INVENTION The invention relates to a reaction product of a hydrocarbyl-substituted carboxylic acylating agent having at least three carboxylic groups and an amine-terminated polyoxyalkylene and aqueous systems containing such materi¬ als. The aqueous systems encompass both concentrates and water-base functional fluids. INTRODUCTION TO THE INVENTION The reaction products of the present invention are formed by reacting a hydrocarbyl-substituted carboxylic acylating agent having at least three carboxyl groups, such as a trimer acid, with an amine-terminated polyoxyalkylene. These reaction products are useful as thickeners and extreme pressure/ lubricity agents for water-base function¬ al fluids. Water-base functional fluids refer to water- base lubricants, such as hydraulic, cutting and metal working fluids. Water-base functional fluids are desirable because they decrease fire hazards and environmental pollu¬ tion problems associated with oil-base functional fluids. The problem associated with water-base functional fluids is formulating a fluid with the required viscosity. Re. 30,885, which is a reissue of U.S. Patent 4,239,635 relates to diamides and lubricants containing the same. The carboxylic acid terminated acid diamides and alkali metal, ammonium or amine salts thereof have lubri- eating properties and are especially useful in aqueous metal-working fluids. Re. 31,522, which is a reissue of U.S. Patent 4,374,741, relates to polyamides and functional fluids containing the same. The polyamides are polyoxyalkylene polyamides having a terminal carboxylic acid group an d terminal amine group in the same molecule and the degree of polymerization of 210 and salts thereof are useful in SUBSTITUTESHEET 167 -2- preparing stable aqueous based metal-working and hydraulic fluids. U.S. Patent 4,107,061 relates to amino-amide lubricants derived from polymeric fatty acids and poly(oxy- ethylene) diamines. These materials are readily compatible with water in all proportions and form clear, aqueous solutions which have lubricating properties. U.S. Patents 4,661,275 and 4,664,834 relate to hydrocarbyl-substituted succinic acid and/or anhy- dride/amine-terminated poly(oxyalkylene) reaction products and aqueous systems containing the same. These reaction products are useful as sheer-stable thickeners for func¬ tional fluids. U.S. Patent 4,795,581 relates to aqueous fluids thickened with fatty acid modified polyoxyalkylene di¬ amines. These materials are useful for water/glycol-base hydraulic fluids, cosmetics and surfactants. SUMMARY OF THE INVENTION The invention relates to a composition, compris- ing at least one reaction product of (A) at least one carboxylic acylating agent having at least three carboxylic groups, with (B) at least one amine-terminated polyoxy¬ alkylene, having a number average molecular weight from about 600 to about 10,000 or at least one salt of the reaction product. Functional fluids formulated with these reaction products or salts thereof have sufficient and stable viscosity for use in hydraulic, cutting and other lubricat¬ ing operations. DETAILED DESCRIPTION OF THE INVENTION The term "hydrocarbyl" includes hydrocarbon, as well as substantially hydrocarbon, groups. Substantially hydrocarbon describes groups which contain non-hydrocarbon substituents which do not alter the predominately hydrocar¬ bon nature of the group. Examples of hydrocarbyl groups include the following: (1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic substituents and the like as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may 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 substituent; those skilled in the art will be aware of such groups (e.g., halo (especially chloro and fluoro) , hydroxy, alkoxy, mercapto, alkylmer- capto, nitro, nitroso, sulfoxy, etc.); (3) hetero substituents, that is, substituents which will, while having a predominantly hydrocarbon character within the context of this invention, contain other than carbon present in a ring or chain otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furyl, thienyl, i idazolyl, etc. In general, no more than about 2, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group. Typically, there will be no such non-hydrocarbon substituents in the hydro¬ carbyl group. Therefore, the hydrocarbyl group is purely hydrocarbon. The present invention relates to reaction prod- ucts of (A) a carboxylic acylating agent having at least TUTE SHEET -4- three carboxylic groups and (B) at least one amine-termi¬ nated polyoxyalkylene, having a number average molecular weight from about 600 to about 10,000, or to salts of the reaction products. (A) Carboxylic Acvlatinσ Aσent The hydrocarbyl-substituted carboxylic acylating agents are carboxylic acylating agents having at least three carboxyl groups, preferably three. The term acylat¬ ing agents encompasses acids, anhydrides, lower esters (C t . 7 esters) , halides, etc. Preferably, the acylating agents are acids or anhydrides. The carboxylic acylating agents of the present invention include tricarboxylic acylating agents, such as trimer acylating agents and Diels-Alder tricarboxylic acylating agents. The carboxylic acylating agents having at least three carboxyl groups have an average from about 12, generally from about 18, preferably from about 30, more preferably from about 36 to about 66, preferably to about 60 carbon atoms. Examples of tricarboxylic acylating agents include trimer and Diels-Alder tricarboxylic acylat¬ ing agents, preferably a trimer acylating agent. Trimer acylating agents are prepared by the trimerization of fatty acids. Fatty acids generally contain from about eight, preferably from about 12 to about 30, preferably to about 24 carbon atoms. Examples of fatty acids include octadeca- noic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid and tall oil acid. Particularly useful fatty acids are unsatu- rated fatty acids having 18 carbon atoms, such as oleic acid. The Diels-Alder triacids are prepared by reacting an unsaturated monocarboxylic acid with a alpha,beta-ethlen- ically unsaturated dicarboxylic acid (e.g., fumaric acid or maleic acid or anhydride) . Examples of these tricarboxylic acids include ' Empol® 1040 available commercially from Emery Industries, Hystrene® 5460 available commercially from SUBSTITUTE SHEET 7 -5- Humko Chemical, and Unidyme® 60 available commercially from Union Camp Corporation. In another embodiment, the carboxylic acylating agent is a mixture of acylating agents which contains at least 10% by weight of a carboxylic acylating agent having at least three carboxylic groups. The mixture preferably contains at least 50% by weight, preferably 80% by weight, preferably 90% by weight tricarboxylic acylating agent. The carboxylic acylating agents may be mixtures of the above-identified tricarboxylic acylating agents with mono- or dicarboxylic acylating agents or mixtures thereof. The dimer acylating agents include products resulting from the dimerization of the above-described fatty acids. Generally, the dimer acids have an average from about 18, preferably from about 28 to about 44, preferably to about 40. The dimer acids are preferably prepared from C lt fatty acids, such as oleic acids. The dimer acids are described in U.S. 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 entire disclosures of which are incorporated herein by reference. Examples of dimer acids include Empol® 1014, 1016 and 1018 Dimer Acid, each available from Emery Industries, Inc. and Hystrene® dimer acids 3675, 3680, 3687 and 3695, available from Humko Chemical. The Diels-Alder type reaction products of the above-described unsaturated fatty acids with alpha,beta- ethylenically unsaturated carboxylic acylating agent (e.g., acrylic or methacrylic acylating agents) are taught in U.S. Pat. No. 2,444,328, the disclosure of which is incorporated herein by reference. Examples of the carboxylic acid product of a Diels-Alder type reaction include Westvaco® Diacid H-240, 1525, 1550, each being commercially available from the Westvaco Corporation. SUBSTITUTESHEET -6- In another embodiment the mixture contains succinic acids or anhydrides having a hydrocarbyl group. The hydrocarbyl group generally contains from about 8, preferably from about 14 to about 40, preferably to about 30, more preferably to about 24 carbon atoms. In one embodiment, the hydrocarbyl group contains from about 16 to about 18 carbon atoms. Preferably, the hydrocarbyl group is an alkenyl group. The alkenyl group can be derived from one or more olefins having from about 8 to about 30 carbon atoms. These olefins are preferably alpha-olefins (sometimes referred to as mono-1-olefins) or isomerized alpha-olefins. Examples of the alpha-olefins include 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-penta- decene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1- nonadecene, 1-eicosene, 1-henicosene, l-docosene, l-tetra~ cosene, etc. Commercially available alpha-olefin fractions that can be used include the C l5Ai alpha-olefins, C 12 . I6 alpha- olefins, Ci 4 _ι 6 alpha-olefins, C^g alpha-olefins, C I6 ., g alpha- olefins, l& .~ 0 alpha-olefins, C^g alpha-olefins, etc. The C 16 and Cι W g alpha-olefins are particularly preferred. Isomerized alpha-olefins are alpha-olefins that have been converted to internal olefins. The isomerized alpha-olefins suitable for use herein are usually in the form of mixtures of internal olefins with some alpha- olefins present. The procedures for isomerizing alpha- olefins are well known to those in the art. Briefly these procedures involve contacting alpha-olefin with a cation exchange resin at a temperature in a range of about 80° to about 130°C until the desired degree of isomerization is achieved. These procedures are described for example in U.S. 4,108,889 which is incorporated herein by reference. The succinic.acylating agents are prepared by reacting the above-described olefins or isomerized olefins with unsatu- rated carboxylic acids such as fumaric acids or maleic acid -7- or anhydride at a temperature of about 160° to about 240°C, preferably about 185° to about 210°C. Free radical initia¬ tors (e.g., t-butyl catechol) can be used to reduce or prevent the formation of polymeric byproducts. The proce- dures for preparing the acylating agents are well known to those skilled in the art and have been described for example in U.S. Patent 3,412,111; and Ben et al, "The Ene Reaction of Maleic Anhydride With Alkenes", J.C.S. Perkin II (1977), pages 535-537. These references are incorporat- ed by reference for their disclosure of procedures for making the above acylating agents. The monocarboxylic acids may have from 2 to about 30, preferably 8 to about 30, more preferably 12 to about 24 carbon atoms. Examples of monocarboxylic acids include acetic, propionic, butyric and the above-described fatty carboxylic acids. fB) Amine-terminated Polyoxyalkylenes One or more of the above carboxylic acylating agents having at least three carboxylic groups are reacted with at least one amine-terminated polyoxyalkylene. The amine-terminated polyoxyalkylenes are preferably alpha- omega amine-terminated polyoxyalkylenes. These amines include alpha-omega diamino polyoxyethylene, alpha-omega dia ino polyoxypropylene-polyoxyethylene-polyoxypropylene or alpha-omega diamino propyleneoxide capped polyoxyethyl¬ ene. The amine-terminated polyoxyalkylenes may also be a urea condensate of such alpha-omega diamino polyoxyalkyl¬ enes described above. The amine-terminated polyoxyalkyl¬ enes may also be polyamino (e.g., tria ino, tetra ino, etc.). These compounds generally have a number average molecular weight from about 600, typically from about 2,000, preferably from about 3,000, more preferably from about 4,000 to about 10,000, preferably to about 8,000, more preferably to about 7,000. ' -8- In one embodiment, the diamines are represented by the formula H 2 NC 'HCH 2 (OC iHCH 2 ) , (OCH 2 CH 2 ) b (OCH 2 C IH) c NH 2 (I) wherein each R is independently hydrogen or an alkyl group having from 1 to about 8 carbon atoms, preferably 1 to about 3, more preferably 1; a is a number in the range of from zero to about 200; b is a number in the range of form about 10 to about 650; and c is a number in the range of from zero to about 200. These diamines preferably have number average molecular weights in the range from about 600, preferably from about 1000, more preferably from about 3000 to about 10,000, preferably to about 7000. Specific examples of the diamines include Jeffamine® ED-600 wherein a+c is approximately 2.5 and b is approximately 8.5; Jeffamine® ED-900 wherein a+c is approximately 2.5 and b is approximately 15.5; Jeffamine® ED-2001 wherein a+c is approximately 2.5 and b is approximately 40.5; Jeffamine® ED-4000 wherein a+c is approximately 2.5 and b is approxi¬ mately 86.0; and ED-6000 wherein a+c is approximately 2.5 and b is approximately 131.5. The numerical value of the Jeffamine® approximate number average molecular weight. For instance, Jeffamine® ED-6000 has an approximate number average molecular weight of 6000. In another embodiment, the amine-terminated polyoxyalkylene is a diamine preferably amine-terminated polypropylene glycols. These diamines are represented by the formula • R R I I H 2 NC(H)-CH 2 -(0CH 2 -CH) d -NH 2 (II) SUBSTITUTESHEET wherein R is defined above, d is from 1 to about 150, preferably 2 to about 100, more preferably 2 to about 75. Examples of these amines include Jeffamine® D-230 wherein q is about 2-3; Jeffamine® D-400 wherein d is about 5-6; Jeffamine® D-2000 wherein d is an average of about 33; and Jeffamine® D-4000 wherein d is an average of about 68. In another embodiment, the diamines are repre¬ sented by the formula R R O R R I I II I I H 2 NCH-CH 2 ( 0CH 2 CH ) e NH-C-NH ( CH-CH 2 0) e CH 2 CH-NH 2 (III) wherein R is defined above; e is a number sufficient to provide said compound with a number average molecular weight of at least about 600. These compounds preferably have number average molecular weights in the range of about 600 to about 2,500, more preferably about 700 to about 2,200. In one embodiment the amine-terminated polyoxy- alkylene is a monoamino polyoxyalkylene such as an amino polyoxypropylene-polyoxyethylene-polyoxypropylene, or an amino polyoxypropylene. These amines are generally pre¬ pared by the reaction of a monohydric alcohol with an epoxide, such as styrene oxide, 1,2-butene oxide, ethylene oxide, propylene oxide and the like, more preferably ethylene oxide, propylene oxide or mixtures thereof. The terminal hydroxyl group is then converted to an amino group. These amines are represented by the structure: Rj-fC -CfHJOJ f -CH-z-CH-NH*, (IV) R R wherein f is ' l to about 150., R, is an alkbxy group having 1 to about 18 carbon atoms, and each R is defined above. Preferably f is 1 to 100, more preferably about 4 to about SUBSTITUTESHEET -10- 40. Rj is preferably an alkoxy group having from 1 to 12 carbon atoms, more preferably a methoxy group. These types of amines are available from Texaco Chemical Company under the tradename Jeffamine. Specific examples of these amines include Jeffa ine® M-600; M-1000, M-2005 and M-2070 amines. In another embodiment, the amine-terminated polyoxyalkylene is a tria ine prepared by treating a triol with ethylene oxide, propylene oxide, or mixtures thereof, followed by amination of the terminal hydroxyl group. These amines are available commercially from Texaco Chemi¬ cal Company under the tradename Jeffamine® triamines. Examples of these amines include, Jeffamine® T-403, which is trimethylolpropane treated with about 5-6 moles of propylene oxide, Jeffamine® T-3000, which is glycerine treated with 50 moles of propylene oxide, and Jeffamine® T-5000, which is glycerine treated with 85 moles of propyl¬ ene oxide. The diamines and triamines that are useful in accordance with the present invention are disclosed in U.S. Patents 3,021,232; 3,108,011; 4,444,566; and Re. 31,522. The disclosures of these patents are incorporated herein by reference for their disclosure of diamines and triamines and methods of making the same. The above amine-terminated polyoxyalkylenes are reacted with the above carboxylic acylating agents at an equivalent ratio of acylating agent to amine of about (1-4:1), preferably (1-2:1), more preferably (3:2), at 125°C to 250°C, more preferably about 150°C to about 225°C. The reaction is usually accomplished within about two to about ten hours, more preferably about two to about six, more preferably about four hours, more preferably between 0.25 to about 2 hours. The reaction product of (A) a carboxylic acyl¬ ating agent and (B) an amine-terminated polyoxyalkylene or salt of the reaction product may be used in the present invention. The salt of the reaction product may be a metal salt, ammonium salt or a mixed salt, e.g., ammonium and metal salt. The ammonium salt of the reaction product may be derived from ammonia or any amine. The amine useful in making ammonium salts of amidic acids may be any of the amine-terminated polyoxyalkylenes described above. Fur¬ ther, the amine may be an alkyl monoa ine, or a hydroxy- a ine. The alkyl monoa ines are primary, secondary or tertiary monoamines. The alkyl monoamines generally contain from 1 to about 24 carbon atoms, more preferably 1 to about 12, more preferably 1 to about 6 in each alkyl group. Examples of primary monoamines useful in the present invention include methylamine, ethylamine, propyl- a ine, butylamine, octylamine, and dodecylamine. Examples of secondary monoamines are given above. Tertiary mono¬ amines include trimethylamine, tributylamine, methyldi- ethylamine, ethyldibutylamine, etc. In another embodiment the amines are hydroxy- amines. Typically, the hydroxyamines are primary, sec¬ ondary or tertiary alkanol amines or mixtures thereof. Such amines can be represented by the Formulae: H 2 N R j OH , and SUBSTITUTESHEET -12- wherein each R 2 is independently a hydrocarbyl group of one to about eight carbon atoms or hydroxyhydrocarbyl group of two to about eight carbon atoms and R 3 is a divalent hydro¬ carbyl group of about two to about 18 carbon atoms. The group -R 3 -OH in such formulae represents the hydroxyhydro- carbyl group. R 3 can be an acyclic, alicyclic or aromatic group. Typically, R 3 is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2- butylene or 1,2-octadecylene group, more preferably an ethylene or propylene group, more preferably an ethylene group. Where two l groups are present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples of such heterocyclic amines include N-(hydroxyl lower al- kyl)-morpholines, -thiomorpholines, -piperidines, -oxazoli- dines, -thiazolidines and the like. Typically, however, each R 2 is independently a methyl, ethyl, propyl, butyl, pentyl or hexyl group. Examples of these hydroxyamines include monoethanol amine, diethanol amine, triethanol amine, diethylethanol amine, ethylethanol amine, etc. The hydroxyamines can also be an ether N-(hy¬ droxyhydrocarbyl)amine. These are hydroxypoly(hydrocarbyl- oxy) analogs of the above-described hydroxyamines (these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyhydrocarbyl) amines can be conveniently prepared by reaction of epoxides with afore- described amines and can be represented by the Formulae: H 2 N (R 3 0) -H -13- and wherein x is a number from about 2 to about 15 and R 2 and R 3 are as described above. R 2 may also be a hydroxypoly- (hydrocarbyloxy) group. In a preferred embodiment, the salts of the amidic acids are formed from hydroxyamines. These hy¬ droxyamines can be represented by the formula wherein each R 3 is an alkylene group; 4 is a hydrocarbyl group; g is independently an integer from zero to 100, provided at least one g is an integer greater than zero; and h is zero or one. Preferably, ^ is a hydrocarbyl group having from 8 to about 30 carbon atoms, preferably 8 to about 24, more preferably 10 to about 18 carbon atoms. R,, is preferably an alkyl or alkenyl group, more preferably an alkenyl group. R, is preferably an octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, oleyl, tallow or soya. SUBSTITUTE SHEET -14- g is preferably one to about 100, more preferably 2 to about 50, more preferably 2 to about 20, more prefera¬ bly 3 to about 10, more preferably about 5. R 3 is as described above. Preferably, each R 3 is independently an ethylene or propylene group. The above hydroxyamines can be prepared by tech¬ niques well known in the art, and many such hydroxyamines are commercially available. They may be prepared, for example, by reaction of primary amines containing at least 6 carbon atoms with various amounts of alkylene oxides such as ethylene oxide, propylene oxide, etc. The primary amines may be single amines or mixtures of amines such as obtained by the hydrolysis of fatty oils such as tallow oils, sperm oils, coconut oils, etc. Specific examples of fatty acid amines containing from about 8 to about 30 carbon atoms include saturated as well as unsaturated aliphatic amines such as octyl amine, decyl amine, lauryl amine, stearyl amine, oleyl amine, myristyl amine, palmityl amine, dodecyl amine, and oσtadecyl amine. The useful hydroxyamines where h in the above formula (V) is zero include 2-hydroxyethylhexylamine, 2-hy- droxyethyloctylamine, 2-hydroxyethylpentadecylamine, 2-hydroxyethyloleylamine, 2-hydroxyethylsoyamine, bis- (2-hydroxyethyl)hexylamine, bis(2-hydroxyethyl)oleylamine, and mixtures thereof. Also included are the comparable members wherein in the above formula at least one a is an integer greater than 2, as for example, 2-hydroxyethoxy- ethylhexylamine. A number of hydroxyamines wherein h is zero are available from the Ar ak Chemical Division of Akzona, Inc., Chicago, Illinois, under the general trade designation "Ethomeen" and "Propomeen". Specific examples of such products include "Ethomeen C/15".which is an ethylene oxide condensate of a cocoa ine containing about 5 moles of ethylene oxide; "Ethomeen C/20" and "C/25" which also are SUBSTITUTESHEET ethylene oxide condensation products from cocoamine con¬ taining about 10 and 15 moles of ethylene oxide respective¬ ly; "Ethomeen 0/12" which is an ethylene oxide condensation product of oleylamine containing about 2 moles of ethylene oxide per mole of amine. "Ethomeen S/15" and "S/20" which are ethylene oxide condensation products 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 ethylene oxide condensation products of tallow- amine 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 oleyl amine with 2 moles propylene oxide. Preferably, the salt is formed from Ethomeen C/15 or S/15 or mixtures thereof. Commercially available examples of hydroxyamines where h is one include "Ethoduomeen T/13" and "T/20" which are ethylene oxide condensation products of N-tallow trimethylene diamine containing 3 and 10 moles of ethylene oxide per mole of diamine, respectively. The fatty polyamine diamines include mono- or dialkyl, symmetrical or asymmetrical ethylene diamines, propane diamines (1,2, or 1,3), and polyamine analogs of the above. Suitable commercial fatty polyamines are "Duomeen C" (N-coco-l,3-diaminopropane) , "Duomeen S" (N-soya-l,3-diaminopropane) , "Duomeen T" (N-tallow-1,3- diaminopropane) , or "Duomeen 0" (N-oleyl-l,3-diaminopro- pane) . "Duomeens" are commercially available diamines described in Product Data Bulletin No. 7-10R1 of Armak Chemical Co., Chicago, Illinois. In another embodiment, the secondary amines may be cyclic amines such as piper- idine, piperazine, orpholine, etc. A metal salt of reaction product of the above- described carboxylic acylating agent with the above-de¬ scribed amine-terminated polyoxyalkylene may be derived from an alkali metal, alkaline earth metal or transition SUBSTITUTE SHEET -16- metal compound, preferably an alkali metal or an alkaline earth metal compound, more preferably an alkali metal compound. Specific examples of useful metal compounds include sodium, potassium, calcium, magnesium, zinc or aluminum cation, more preferably compounds containing a sodium or potassium cation. The metal compounds are formed by treating the reaction product with a metal oxide, hydroxide, or halide. The metal salt is formed between room temperature and about 120°C, more preferably room temperature to about 80°C. The following examples relate to the reaction products of the present invention. Unless otherwise indicated in the examples and elsewhere in the specifica¬ tion and claims, temperature is in degrees Celsius, parts are parts by weight and pressure is atmospheric. Exam le 1 A reaction vessel is charged with 3503 parts (0.58 mole) of Jeffamine® ED-6000 (a diamine from Texaco Chemical Co. having an average molecular weight of 6000 and being a primary amine-terminated propylene oxide capped polyoxyethylene) and 497 parts (0.58 mole) of Unidy e® 60 (a trimer acid available commercially from Union Camp Corporation having 75% trimer acid, 25% dimer acid and derived from C lg monomeric acids) . The mixture is stirred and heated to 150°-220°C for four hours, while distillate (9.2 milliliters) is removed. The residue has a neutral¬ ization number of 7.5. Example 2 A reaction vessel is charged with 2400 parts (1.2 moles) of Jeffamine® ED-2001 and 1611 parts (1.89 moles) of Unidyme® 60. The mixture is stirred and heated to 150°- 200°C for 3.7 hours, while distillate (33 milliliters) is removed. The residue has a neutralization number of 42. -17- Example 3 A reaction vessel is charged with 3660 parts (0.61 mole) of Jeffamine® ED-6000, 260 parts (0.31 mole) of Unidyme® 60 and 202 parts (0.6 mole) of a hexadecenyl succinic anhydride available from Dixie Chemical. The mixture is heated to 160°-205 β C for four hours while 9.0 milliliters of distillate is removed. A 50% aqueous solu¬ tion of sodium hydroxide (77 parts, 0.58 mole) is added to the mixture. The mixture has a neutralization number of 12. Examples 4-6 The following Table 1 contains examples which are prepared by the procedure described in Example 1. Table 1 Amine-terminated Acylating Agent Example Polyoxyalkylene (parts) (parts) Ex. 4 900 Jeffamine® ED-900 857 Unidyme® 60 Ex. 5 5000 Jeffamine® T-5000 857 Unidyme® 60 Ex. 6 2005 Jeffamine® M-205 571 Unidyme® 60 Examples 7-10 Examples 7-10 are prepared by the general proce¬ dure of reacting a mixture of the product of the indicated example and a base as indicated in the following table. The mixture is stirred from one-half to about one hour at 100°C. Table 2 SUBSTITUTESHEET -18- (C) Surfactants The acylated amine-terminated polyoxyalkylenes, may be used alone or in combination with (C) a surfactant. The combination of an acylated amine-terminated polyoxy- alkylene and a surfactant provide improved thickening for aqueous functional fluids, specifically hydraulic fluids. The combination usually contains from about 5%, preferably from about 15%, more preferably from about 25%, more preferably from about 50% to about 95%, preferably to about 85%, more preferably to about 75% of the acylated amine- terminated polyoxyalkylene. The combination usually contains from about 5%, preferably from about 10%, more preferably from about 20% to about 90%, preferably to about 75%, more preferably to about 50% by weight of the surfac- tant. The surfactants include nonionic, cationic and anionic surfactants. The surfactants include polyoxy¬ alkylene amines, polyoxyalkylene amides, polyoxyalkylene alcohols, polyoxyalkylene esters, and fatty acid salts or mixtures of these surfactants. Any of the above-described polyoxyalkylene amines, including the above-described amine-terminated polyoxyalkylenes and hydroxyamines (Ethomeens, Ethoduomeens, etc.), may be used as surfactants in the present invention. The polyoxyalkylene glycols, useful as surfac- tants, may be polyoxyethylene glycols or polyoxypropylene glycols. Useful polyoxyethylene glycols are available from Union Carbide under the trade name Carbowax® PEG 300, 600, 1000 and 1450. The polyoxyalkylene glycols are preferrably polyoxypropylene glycols where the oxypropylene units are at least 80% of the total. The remaining 20% may be ethylene oxide or butylene oxide or other such esters, olefins and. the like which may be polarized with poly¬ propylene oxide. Useful polyoxypropylene glycols are available from Union Carbide under the trade name NIAX 425; and NIAX 1025. Useful polyoxypropylene glycols are avail- able from Dow Chemical and sold by the trade name PPG-1200, and PPG-2000. Representative of other useful polyoxyalkylene polyols are the liquid polyols available from Wyandotte Chemicals Company under the name PLURONIC Polyols and other similar polyols. These PLURONIC Polyols correspond to the formula HO-(CH 2 CH 2 0)j (CHCH 2 0) j (CH 2 CH 2 0) k -H CH 3 wherein i, j, and k are integers greater than 1 such that the -CH 2 CH 2 0-groups comprise from about 10% to about 15% by weight of the total number average molecular weight of the glycol, the number average molecular weight of said polyols being from about 2500 to about 4500. This type of polyol can be prepared by reacting propylene glycol with propylene oxide and then with ethylene oxide. A particularly useful polyoxyalkylene polyol is Pluracol® V-10 which is a poly- oxyalkylene derivative of trimethylol propane having a molecular weight of 22,000. This material is available commercially from BASF Corporation, Parsippany, New Jersey, U.S.A. In another embodiment the surfactant is an alkyl- terminated polyoxyalkylene. A variety of alkyl-terminated polyoxyalkylenes are known in the art, and many are avail¬ able commercially. The alkyl-terminated polyoxyalkylenes are produced generally by treating an aliphatic alcohol with an excess of an alkylene oxide such as ethylene oxide or propylene oxide. For example, from about 6 to about 40 moles of ethylene oxide or propylene oxide may be condensed with the aliphatic alcohol. The alkyl-terminated polyoxyalkylene polyols useful in the present invention are available commercially under such trade names as "TRITON®" from Rohm & Haas Company, "Carbowax®" and "TERGITOL®" from Union Carbide, "ALFONIC®" from Conoco Chemicals Company, and "NEODOL®" from Shell Chemical Company. The TRITON® materials are identified generally as polyethoxylated alcohols or phe- nols. The TERGITOLS® are identified as polyethylene glycol ethers of primary or secondary alcohols; the ALFONIC® materials are identified as ethoxylated linear alcohols which may be represented by the general structural formula CH 3 (CH 2 ),CH 2 (OCH 2 CH 2 ) n OH wherein 1 varies between 4 and 16 and m is a number between about 3 and 11. Specific examples of ALFONIC® ethoxylates characterized by the above formula include ALFONIC® 1012-60 wherein 1 is about 8 to 10 and m is an average of about 5 to 6; ALFONIC® 1214-70 wherein 1 is about 10-12 and m is an average of about 10 to about 11; ALFONIC® 1412-60 wherein 1 is from 10-12 and m is an average of about 7; and ALFONIC® 1218-70 wherein 1 is about 10-16 and m is an average of about 10 to about 11. The Carbowax® methoxy polyethylene glycols are linear ethoxylated polymer of methanol. Examples of these materials include Carbowax® methoxy polyethylene glycol 350, 550 and 750, wherein the numerical value approximates number average molecular weight. The NEODOL® ethoxylates are ethoxylated alcohols wherein the alcohols are a mixture of alcohols containing from 12 to about 15 carbon atoms, and the alcohols are partially branched chain primary alcohols. The ethoxylates are obtained by reacting the alcohols with an excess of ethylene oxide such as from about 3 to about 12 or more moles of ethylene oxide per mole of alcohol. For example, NEODOL® ethoxylate 23-6.5 is a partially branched chain alcoholate of 12 to 13 carbon atoms with an average of about 6 to about 7 ethoxy units. Another group of polyols are the commercially available liquid TETRONIC polyols sold by Wyandotte Chemi¬ cals Corporation. These polyols are represented by the general formula: H(OC_ H 4 ) D (OC 3 H 6 H 4 0) o H HfOC, H 4 ) n (OC 3 H 6 H 4 0) 0 H Such hydroxyamines are described in U.S. Patent No. 2,979,528 which is incorporated herein by reference. Those hydroxyamines corresponding to the above formula having a number average molecular weight of to about 10,000 wherein the ethyleneoxy groups contribute to the total number average molecular weight in the percentage ranges discussed above are preferred. A specific example would be such a hydroxyamine having a number average molecular weight of about 8000 wherein the ethyleneoxy groups account for 7.5%-12% by weight of the total number average molecular weight. Such hydroxyamines can be prepared by reacting an alkylene diamine such as ethylene diamine, propylene diamine, hexamethylene diamine etc., with propylene oxide. Then the resulting product is reacted with ethylene oxide. In another embodiment, the surfactant is a propoxylated hydrazine. propoxylated hydrazines are available commercially under the tradename Qxypruf" 1 . Exam¬ ples of propoxylated hydrazines include Qxypruf™ 6, 12 and 20 which are hydrazine treated with 6, 12 and 20 moles of propylene oxide, respectively. In another embodiment, the surfactant is a polyoxyalkylated phenol. The phenol may be substituted or unsubstituted. A preferred polyoxyalkylated phenol is a polyoxyethylate nonylphenol. Polyoxyalkylated phenols are availabe commercially from Rohn and Haas Co. under the tradename Triton® and Texaco Chemical Company under the SUBSTITUTESHEET 167 -22- tradename Surfonic®. Examples of polyoxyalkylated phenols include Triton® AG-98, N series, and X series polyoxyethyl- ated nonylphenols. In another embodiment, the surfactant is a polyoxyalkylene fatty ester. Polyoxyalkylene fatty esters may be prepared from any polyoxyalkylene polyol and a fatty acid. Preferably, the polyoxyalkylene polyol is any disclosed herein. The fatty acid is preferably the fatty monocarboxylic acid described above. Polyoxyalkylene fatty esters are available commercially from Armak Company under the tradename Ethofat™. Specific examples of polyoxyalkyl¬ ene fatty esters include Ethofat™ C/15 and C/25, which are coco fatty esters formed using 5 and 15 moles, respective¬ ly, of ethylene oxide; Ethofat™ 0/15 and 0/20, which are oleic esters formed 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 respec¬ tively. In another embodiment, the surfactant is a polyoxyalkylated fatty amide. Preferably the fatty amide is polyoxypropylated or polyoxyethylated, more preferably polyoxyethylated. Examples of fatty acids which may be polyoxyalkylated include oleylamide, stearylamide, tallow- amide, soyaa ide, cocoamide, and laurylamide. Polyoxy- alkylated fatty amides are available commercially from Armak Company under the trade name Ethomid™ and Lonza, Inc., under the tradename Unamide®. Specific examples of these polyoxyalkylated fatty amides include Ethomid™ HT/15 and HT/60, which are hydrogenated tallow acid amides treated with 5 and 50 moles of ethylene oxide respectively; Ethomid™ 0/15, which is an oleic amide treated with 5 moles of ethylene oxide; Unamide® C-2 and C-5, which are cocamides treated with 2 and 5 moles of ethylene oxide, respectively; and Unamide® L-2 and L-5, which are laur- SΌBSTΓITUTE SHEE -23- a ides treatedwith 2 and 5 moles of ethylene oxide, respectively. In a preferred emodiment, the surfactant is a tall oil, such as distilled tall oil available from Union Camp under the tradename Unitol. In another embodiment, the surfactant is a nitrogen-containing phosphorus-free reaction product of a carboxylic acylating agent having at least one hydrocarbyl group from at least 12, preferably from about 35, to about 500, preferably to about 300 carbon atoms with at least one N-(hydroxyhydrocarbyl) amine. In another embodiment, the nitrogen-containing phosphorus-free reaction product is prepared from a hydrocarbyl-substituted carboxylic acylat¬ ing agent, preferably a hydrocarbyl-substituted succinic acylating agent. The hydrocarbyl group is generally derived from a polyalkene having a number average molecular weight from about 500, preferably from about 800 to about 5000, preferably to about 2500, more preferably to about 1200. The number average molecular weight is determined by gel permeation chromatography. The polyalkene is generally derived from an olefin having from two to about eight carbon atoms, such as ethylene, propylene, butylene, preferably butylene. The amine may be a monoamine, poly¬ amine or mixtures thereof. The carboxylic acid acylating agents have been described above as well as the hydroxy- amines. Particularly useful hydroxyhydrocarbyl amines include mono, di and triethanolamine, diethyl ethanolamine, di(3-hydroxypropyl)amine, N-(3-hydroxyl-butyl) amine, N-(4- hydroxyl-butyl)amine, N,N-di(2-hydroxylpropyl) amine, N-(2- hydroxylethyl) morpholine and its thioanalogue, N-(2- hydroxyl-ethyl)cyclohexyl amine, N-3-hydroxylcyclopenthyl amine, 0,M-NP-arainophenol, N-(hydroxylethyl) piperazine, N,N'-di(hydroxyethyl)piperazine, and the like. Preferred amines are diethylethanolamine and ethanolamine or mixtures thereof. 167 -24- Often the reaction is carried out under ester forming conditions and the product thus formed is an ester/salt. Preferably, the ester/salt is an internal salt, wherein one of the hydroxyl groups of the carboxylic acylating agents becomes ionically bonded to a nitrogen atom within the same group or may be an external salt wherein the ionic salt group is formed with a nitrogen atom which is not part of the same group forming the ester. Generally, the reaction is carried out at a temperature in the range of about 50°C to about 150°C; but usually at a temperature below a 100°C. The reaction products made by reacting a carbox¬ ylic acylating agent and a hydroxyl amine which are useful surfactants are described in U.S. patents 4,329,249; 4,368,133; 4,435,297; 4,447,348; and 4,448,703. These patents are incorporated by reference for their disclosure to the reaction products of carboxylic acylating agents and hydroxyamines as well as methods for making the same. The following example relates to ester/salts which may be used in the present invention. Example A A reaction vessel is charged with 1000 parts of polybutene (number average molecular weight equals 950) substituted succinic anhydride. The anhydride is heated to about 90°C over two hours where 209 parts of N,N-diethyl- ethanolamine is added to the vessel. The reaction tempera¬ ture is maintained at 90°C for an additional hour. The mixture is cooled to room temperature to provide the desired product. WATER-BASE FUNCTIONAL FLUID The invention includes aqueous systems or compo¬ sitions characterized by an aqueous phase with the reaction products of the invention dispersed in said aqueous phase. Preferably, this aqueous phase is a continuous aqueous phase. These aqueous systems usually contain at least SUBSTI UTESHEET -25- about 40% by weight water. Such aqueous systems encompass both concentrates containing from about 40% to about 70%, preferably about 40% to about 65% water; and water-base functional fluids containing at least 40% and generally over 70% of water and a thickening or extreme pressure amount of the reaction products of the present invention, e.g., acylated amine-terminated polyoxyalkylenes. General¬ ly, the reaction products are used in an amount from about 0.1%, preferably from about 0.5%, more preferably from about 0.75% to about 10%, preferably to about 5%, more preferably to about 2% by weight in aqueous fluids. In one embodiment, the reaction products of the present invention impart extreme pressure and lubricity properties to aqueous metal working fluids. In another embodiment, the reaction products provide thickening for hydraulic fluids. The concentrates generally contain less than about 50%, prefer¬ ably less than about 25%, more preferably less than about 15%, and still more preferably less than about 6% hydrocar¬ byl oil. The water-base functional fluids contain less than about 15%, preferably less than about 5%, and more preferably less than about 2% hydrocarbyl oil. These concentrates and water-base aqueous systems can optionally include other conventional additives common¬ ly employed in water-base functional fluids. These other additives include dispersant/solubilizers, surfactants, functional additives, corrosion-inhibitors, shear stabiliz¬ ing agents, bactericides, dyes, water-softeners, odor masking agents, anti-foam agents, and the like. The concentrates are analogous to the water-base functional fluids except that they contain less water and proportionately more of the other ingredients. The concen¬ trates can be converted to water-base functional fluids by dilution with water. This dilution is usually done by standard mixing techniques. This is often a convenient procedure since the concentrate can be shipped to the point SUBSTITUTESHEET 2167 -26- of use before additional water is added. Thus, the cost of shipping a substantial amount of the water in the final water-base functional fluid is saved. only the water necessary to formulate the concentrate (which is determined primarily by ease of handling and convenience factors) , need be shipped. Generally these water-base functional fluids are made by diluting the concentrates with water, wherein the ratio of water to concentrate is usually in the range of about 80:20 to about 99:1 by weight. As can be seen when dilution is carried out within these ranges, the final water-base functional fluid contains, at most, an insignif¬ icant amount of hydrocarbyl oil. The dispersant/solubilizers that are useful in accordance with the present invention include the above- described nitrogen-containing, phosphorus-free carboxylic solubilizers. These dispersant/solubilizers are preferably used at effective levels to disperse or dissolve the various additives, particularly the functional additives discussed below, in the concentrates and/or water-base functional fluids of the present invention. In a particu¬ larly preferred embodiment of the present invention, the dispersant/solubilizer is the reaction product of a poly- isobutenyl-substituted succinic anhydride with diethylene- ethanolamine or a mixture of diethylenethanolamine and ethanolamine. The surfactants that are useful can be of the cationic, anionic, nonionic or amphoteric type. The surfactants are described above. Many such surfactants of each type are known to the art. See, for example, McCutcheon's "Emulsifiers & Detergents", 1981, North American Edition, published by McCutcheon Division, MC Publishing Co., Glen Rock, New Jersey, U.S.A., which is hereby incorporated by reference for its disclosures in this regard. -27- These surfactants, when used, are generally employed in effective amounts to aid in the dispersal of the various additives, particularly the functional addi¬ tives discussed below, in such systems. The functional additives that can be used are typically oil-soluble, water-insoluble additives which function in conventional oil-based systems as extreme pressure agents, anti-wear agents, load-carrying agents, friction modifiers, lubricity agents, etc. They can also function as anti-slip agents, film formers and friction modifiers. As is well known, such additives can function in two or more of the above-mentioned ways; for example, extreme pressure agents often function as load-carrying agents. The term "oil-soluble, water-insoluble functional additive" refers to a functional additive which is not soluble in water above a level of about 1 gram per 100 milliliters of water at 25°C, but is soluble in mineral oil to the extent of at least 1 gram per liter at 25°C. These functional additives can also include certain solid lubricants such as graphite, molybdenum disulfide and polytetrafluoroethylene and related solid polymers. These functional additives can also include frictional polymer formers. Briefly, these are potential polymer forming materials which are dispersed in a liquid carrier at low concentration and which polymerize at rubbing or contacting surfaces to form protective polymeric films on the surfaces. The polymerizations are believed to result from the heat generated by the rubbing and, possi¬ bly, from catalytic and/or chemical action of the freshly exposed surface. A specific example of such materials is dilinoleic acid and ethylene glycol combinations which can form a polyester frictional polymer film. These materials are known to the art and descriptions of them are found, SUBSTITUTESHEET for example, in the journal "Wear", Volume 26, pages 369-392, and West German Published Patent Application 2,339,065. These disclosures are hereby incorporated by reference for their discussions of frictional polymer formers. Typically these functional additives are known metal or amine salts of organo sulfur, phosphorus, boron or carboxylic acids which are the same as or of the same type as used in oil-based fluids. Typically such salts are of carboxylic acids of l to 22 carbon atoms including both aromatic and aliphatic acids; sulfur acids such as alkyl and aromatic sulfonic acids and the like; phosphorus acids such as phosphoric acid, phosphorus acid, phosphinic acid, acid phosphate esters and analogous sulfur homologs such as the thiophosphoric and dithiophosphoric acid and related acid esters; boron acids include boric acid, acid borates and the like. Useful functional additives also include metal dithiocarbamates such as molybdenum and antimony dithiocarbamates; as well as dibutyl tin sulfide, tributyl tin oxide, phosphates and phosphites; borate amine salts, chlorinated waxes; trialkyl tin oxide, molybdenum phos¬ phates, and chlorinated waxes. Mainly such functional additives are known to the art. For example, descriptions of additives useful in conventional oil-based systems and in the aqueous systems of this invention are found in "Advances in Petroleum Chemistry and Refining", Volume 8, edited by John J. McKetta, Interscience Publishers, New York, 1963, pages 31-38 inclusive; Kirk-Othmer "Encyclopedia of Chemical Technology", Volume 12, Second Edition, Interscience Publishers, New York, 1967, page 575 et seq.; "Lubricant Additives" by M.W. Ranney, Noyes Data Corporation, Park Ridge, N.J., U.S.A., 1973; and "Lubricant Additives" by C.V. Smalheer and R.K. Smith, The Lezius-Hiles Co., Cleve- land, Ohio, U.S.A. These references are hereby incorporat- SUBSTITUTESHEET ed by reference for their disclosures of functional addi¬ tives useful in the systems of this invention. In certain of the typical aqueous systems of ,the invention, the functional additive is a sulfur or chloro- sulfur extreme pressure agent, known to be useful in oil-base systems. Such materials include chlorinated aliphatic hydrocarbons, such as chlorinated wax; organic sulfides and polysulfides, such as benzyl-disulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfu- rized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfur- ized hydrocarbons, such as the reaction product of phospho¬ rus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phos¬ phites, i.e., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentyl- phenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol dithiocarbamate; and Group II metal salts of phosphorodithioic acid, such as zinc dicyclohexyl phosphorodithioate, and the zinc salts of a phosphorodithi¬ oic acid. The functional additive can also be a film former such as a synthetic or natural latex or emulsion thereof in water. Such latexes include natural rubber latexes and polystyrene butadienes synthetic latex. The functional additive can also be an anti- chatter or anti-squawk agent. Examples of the former are the amide metal dithiophosphate combinations such as disclosed in West German Patent 1,109,302; amine salt-azo- methene combinations such as disclosed in British Patent Specification 893,977; or amine dithiophosphate such as disclosed in U.S. Patent 3,002,014. Examples of anti- squawk agents are N-acyl-sarcosines and derivatives thereof such as disclosed in U.S. Patents 3,156,652 and 3,156,653; sulfurized fatty acids and esters thereof such as disclosed in U.S. Patents 2,913,415 and 2,982,734; and esters of dimerized fatty acids such as disclosed in U.S. Patent 3,039,967. The above-cited patents are incorporated herein by reference for their disclosure as pertinent to anti- chatter and anti-squawk agents useful as a functional additive in the aqueous systems of the present invention. Typically, a functionally effective amount of the functional additive is present in the aqueous systems of this invention. For example, if the functional additive is intended to serve primarily as a load-carrying agent, it is present in a load-carrying amount. The aqueous systems of this invention often contain at least one inhibitor for corrosion of metals. These inhibitors can prevent corrosion of either ferrous or non-ferrous metals (e.g., copper, bronze, brass, titanium, aluminum and the like) or both. The inhibitor can be organic or inorganic in nature. Usually it is sufficiently soluble in water to provide a satisfactory inhibiting action though it can function as a corrosion inhibitor without dissolving in water, it need not be water-soluble. Many suitable inorganic inhibitors useful in the aqueous systems of the present invention are known to those skilled in the art. Included are those described in "Protective Coatings for Metals" by Burns and Bradley, Reinhold Pub¬ lishing Corporation, Second Edition, Chapter 13, pages 596-605. This disclosure relative to inhibitors is hereby incorporated by reference. Specific examples of useful inorganic inhibitors include alkali metal nitrites, sodium di- and tripolyphosphate, potassium and dipotassiu phos¬ phate, alkali metal borate and mixtures of the same. Many suitable organic inhibitors are known to those of skill in the art. Specific examples include hydrocarbyl amine and SUBSTITUTESHEET hydroxy-substituted hydrocarbyl amine neutralized acid compound, such as neutralized phosphates and hydrocarbyl phosphate esters, neutralized fatty acids (e.g., those having about 8 to about 22 carbon atoms) , neutralized aromatic carboxylic acids (e.g., 4-tertiarybutyl benzoic acid) , neutralized naphthenic acids and neutralized hydro¬ carbyl sulfonates. Mixed salt esters of alkylated succi- nimides are also useful. Particularly useful amines include the alkanol amines such as ethanol amine, dietha- nolamine. Mixtures of two or more of any of the afore- described corrosion-inhibitors can also be used. Useful corrosion-inhibitors are described in 4,533,481 which is incorporated by reference for such disclosure. The cor¬ rosion-inhibitor is usually present in concentrations in which they are effective in inhibiting corrosion of metals with which the aqueous composition comes in contact. The following examples are corrosion inhibitors which are useful in the present invention. Example I A mixture of 405 parts of boric acid and 800 parts of water is prepared, and 1333 parts of ethanolamine are added over a period of 30 minutes. The temperature of the mixture rises to about 60°C and is maintained at 62°- 65°C for an additional 45 minutes. Dodecanedioic acid (533 parts) , 155 parts of sebacic acid and 251 parts of azelaic acid are added to the mixture in 12 minutes and the temper¬ ature of the mixture reaches 72°C. Ethanolamine (523 parts) is added over a period of 18 minutes and the mixture is maintained at 65°-72°C for one hour. The mixture is cooled and filtered. The filtrate is the desired product. Example II A mixture of 188 parts of water and 313 parts of monoethanolamine is prepared and heated to about 52°C whereupon 95 parts of boric acid is added over 30 minutes. A slightly exothermic reaction occurs and the temperature SUBSTITUTE SHEET 167 -32- is kept below about 65°C during addition and thereafter for about 45 minutes. Dodecanedoic acid (125 parts) , sebacic acid (36.4 parts) and azelaic acid (59 parts) are added in the listed order while maintaining the temperature of the mixture between about 65°-70°C. Upon completion of the addition of the azelaic acid, an additional 123 parts of monoethanolamine are added over 15 minutes followed by mixing for one hour. The mixture then is filtered, and the filtrate is the desired product containing 1.84% of boron and 10.32% nitrogen. Example III A mixture of 40.2 parts of boric acid and 60 parts of water is heated to about 48°C whereupon 119 parts of monoethanolamine are added over a period of about 15 minutes. The temperature of the reaction mixture reaches 64°C during the addition and is maintained at a temperature of from 60°-64°C for about 30 minutes. To this mixture, there is added 26.7 parts of dodecanedioic acid, 8.1 parts of sebacic acid, 12.6 parts of azelaic acid and 33.3 parts of monoethanolamine. The exothemic reaction raises the temperature to 72°C and the mixture is maintained at a temperature of from 60°-72°C for about 15 minutes. Upon cooling, the desired product is obtained. Certain of the aqueous systems of the present invention (particularly those that are used in cutting or shaping of metal) can also contain at least one polyol with inverse solubility in water. Such polyols are those that become less soluble as the temperature of the water in¬ creases. They thus can function as surface lubricity agents during cutting or working operations since, as the liquid is heated as a result of friction between a metal workpiece and worktool, the polyol of inverse solubility "plates out" on the surface of the workpiece, thus improv¬ ing its lubricity characteristics. The aqueous systems of the present invention can also include at least one bacteriocide. Such bacteriocides are well known to those of skill in the art and specific examples can be found in the aforementioned McCutcheon publication "Functional Materials" under the heading "Antimicrobials" on pages 9-20 thereof. This disclosure is hereby incorporated by reference as it relates to suitable bacteriocides for use in the aqueous compositions or systems of this invention. Generally, these bacteriocides are water-soluble, at least to the extent to allow them to function as bacteriocides. The aqueous systems of the present invention can also include such other materials as dyes, e.g., an acid green dye; water softeners, e.g., ethylene diamine tetra- acetate sodium salt or nitrilo triacetic acid; odor masking agents, e.g., citronella, oil of lemon, and the like; and anti-foamants, such as the well-known silicone anti-foamant agents. The aqueous systems of this invention may also include an anti-freeze additive where it is desired to use the composition at a low temperature. Materials such as ethylene glycol and analogous polyoxyalkylene polyols can be used as anti-freeze agents. Clearly, the amount used will depend on the degree of anti-freeze protection desired and will be known to those of ordinary skill in the art. It should also be noted that many of the ingredi¬ ents described above for use in making the aqueous systems of this invention are industrial products which exhibit or confer more than one property on such aqueous systems. Thus, a single ingredient can provide several functions thereby eliminating or reducing the need for some other additional ingredient. For example, an extreme pressure agent such as tributyl tin oxide can also function as a bactericide. SUBSTITUTESHEET 167 -34- The following examples relate to aqueous concen¬ trates or compositions of the present invention. Example A A concentrate is prepared by mixing 450 parts of tap water and 450 parts of the product of Example 1 by stirring the mixture for 45 minutes at room temperature. Example B A concentrate is prepared by mixing 2700 parts of water and 2700 parts of the product of Example 3 at room temperature for 45 minutes. Examples C-H The following examples relate to aqueous composi¬ tions of the present invention useful as hydraulic fluids. The aqueous compositions are prepared by mixing the compo- nents for 30 minutes at 50°-60°C. The amounts are parts by weight. (0 Ξ ιo </> H H ( m M —{ 20 Zinc dimethyla yl dithiophosphate 1.60 1.40 Ethomeen C/25 3.2 2.4 25 Unitol DT-40 541 0.45 0.45 0.5 Triton X-100 0.5 0.5 30 Diethylethanol- amine 700 0.5 v 10 -37- The composition of Example C was run in the Vickers Vane pump test (IP 281/80) . The test was run at constant speed of 1400 and 40 rpms with a delivery pressure of 1000 psi and a flow rate of 4.7-6.2 grams per minute. The temperature was run at 49 β C. At 500 hours, the ring wear (milligrams/hour) is 0.0148 and the brass end plates have trace deposits. These results are considered an acceptable result. The following table contains examples which are useful as aqueous metal working or cutting fluids. Table 4 Product/Component Ex. 1 Ex. 2 Ex. 3 Ex. 4 Example A 10 Example B 7 Example 2 1 Example 8 Example I 10 Example II Example III Ethomeen c/25 Triton X-100 Monoethanolamine 20 Triethanolamine Water 60 While the invention has been explained in rela¬ tion to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modi ications as fall within the scope of the appended claims.

Claims: CLAIMS 1. A composition, comprising: at least one reaction product of (A) at least one hydrocarbyl-substituted carboxylic acylating agent having at least three carboxylic groups, with (B) at least one amine-terminated polyoxyalkylene, having a number average molecular weight from about 600 to about 10,000, or at least one salt of the reaction product. 2. The composition of claim acylating agent has an average of about carbon atoms. 3. The composition of claim acylating agent has an average of about carbon atoms. 4. The composition of claim l, wherein the acylating agent (A) is a trimer acylating agent or Diels- Alder tricarboxylic acylating agent. ' 5. The composition of claim 1, wherein the amine-terminated polyoxyalkylene (B) has a number average molecular weight from about 3,000 to about 7,000. 6. The composition of claim 1, wherein the amine-terminated polyoxyalkylene (B) is represented by the formulae: H 2 N-CHCH 2 -(0CHCH 2 ),-(OCH 2 CH 2 ) b -(OCH 2 -CH) C -NH 2 (I) or R R I I H 2 NCH-CH 2 - (OCH 2 .CH) d -NH 2 ( n ) or R R 0 R R ' I I II I I H,N-CH-CH,- (0CH 2 -CH) e -NHCNH- (CH-CH,0) e -CH 2 -CH-NH 2 (III) wherein each R is independently an alkyl group having from 1 to about 8 carbon atoms, a is an average number in the range from 0 to about 200, b is an average number in the ranger from about 10 to about 650, c is an average number in the range from 0 to about 200, d is an average number in the range from about 1 to about 150, and e is a number sufficient to provide the compound with a number average molecular weight of at least about 600. 7. The composition of claim 1, wherein the carboxylic acylating agent is a mixture of a trimer acylat¬ ing agent or Diels-Alder tricarboxylic acylating agent and a mono- or dicarboxylic acylating agent. 8. The composition of claim 7, wherein the dicarboxylic acylating agent is a hydrocarbyl substituted succinic acylating agent. 9. The composition of claim 1, wherein the salt of the reaction product is derived from ammonia, at least one amine, at least one metal or mixtures thereof. 10. The composition of claim 1, wherein the salt of the reaction product is an alkali or alkaline earth metal salt. 11. The composition of claim 1, wherein the salt of the reaction product is a sodium or potassium salt. 12. A composition, comprising: at least one reaction product of (A) at least one trimer acylating agent with (B) at least one amine-termi¬ nated polyoxyalkylene, having a number average molecular weight from about 600 to about 10,000, or at least one salt of the reaction product. 13. The composition of claim 12, wherein the trimer acid has an average of about 18 to about 66 carbon atoms. 14. The composition of claim 12, wherein . the amine-terminated polyoxyalkylene (B) has a number average molecular weight from about 3000 to about 7000. SUBSTITUTESHEET 15. The composition of claim 12, wherein the trimer acylating agent is a mixture of a trimer acylating agent and a mono- or dicarboxylic acylating agent. 16. The composition of claim 12, wherein the salt of the reaction product (A) is a salt derived from ammonia, at least one amine, at least one metal or mixtures thereof. 17. The composition of claim 12, wherein the salt of the reaction product is a sodium or potassium salt. 18. A functional fluid composition, comprising: water and the composition of claim 1. 19. The composition of claim 18, wherein the composition further comprises (D) at least one surfactant. 20. The composition of claim 18, wherein the surfactant (C) is at least one polyoxyalkylene amine, polyoxyalkylene amide, polyoxyalkylene alcohol, polyoxy¬ alkylene phenol, polyoxyalkylene ether, polyoxyalkylene ester, or fatty acid salt. 21. The composition of claim 18, wherein the surfactant (C) is a polyoxyalkylene polyol. 22. A functional fluid composition, comprising: water and the composition of claim 12. 23. The composition of claim 22, wherein the composition further comprises (C) at least one surfactant. 24. The composition of claim 22, wherein the surfactant (C) is at least one polyoxyalkylene amine, polyoxyalkylene amide, polyoxyalkylene alcohol, polyoxy¬ alkylene phenol, polyoxyalkylene ether, polyoxyalkylene ester, or fatty acid salt. 25. The composition of claim 22, wherein the surfactant (C) is a polyoxyalkylene polyol. 26. The composition of claim 18, wherein the composition is a water-base hydraulic fluid. 27. The composition of claim 18, wherein the composition is a water-base metal working fluid. SUBSTITUTE SHEET AMENDED CLAIMS [received by the International Bureau on 04 January 1993 (04.01.93); original claims 1-27 replaced by amended claims 1-12 (2 pages)] __ _ . . . 1. A composition, comprising: at least one reaction product of (A) at least one hydrocarbyl-substituted carboxylic acylating agent having at least three carboxylic groups, with (B) at least one amine-terminated polyoxyalkylene, having a number average molecular weight from about 600 to about 10,000, or at least one salt of the reaction product 2. The composition of claim 1, wherein the acylating agent has an average of about 18 to about 66 carbon atoms. 3. The composition of claim 1, wherein the acylating agent (A) is a trimer acylating agent or Diels-Alder tricarboxylic acylating agent or a mixture of said acylating agents with a mono- or dicarboxylic acylating agent. 4. The composition of claim 1, wherein the amine-terminated polyoxyalkylene (B) has a number average molecular weight from about 3,000 to about 7,000. 5. The composition of claim 1, wherein the amine-terminated polyoxyalkylene (B) is represented by the formulae: or R R I I H 2 NCH-CH 2 -(OCH 2 -CH) ( rNH 2 (H) or (HI) wherein each R is independently an alkyl group having from 1 to about 8 carbon atoms, a is an average number in the range from 0 to about 200, b is an average number in the range from about 10 to about 650, c is an average number in the range from 0 to about 200, d is an average number in the range from about 1 to about 150, and e is a number sufficient to provide the compound with a number average molecular weight of at least about 600. 6. The composition of claim 4, wherein the dicarboxylic acylating agent is a hydrocarbyl substituted succinic acylating agent. 7. The composition of claim 1, wherein the salt of the reaction product is derived from ammonia, at least one amine, at least one metal or mixtures thereof. 8. The composition of claim 1, wherein the salt of the reaction product is an alkali or alkaline earth metal salt 9. A functional fluid composition, comprising: water and the composition of claim 1. 10. The composition of claim 9, wherein the composition further comprises (D) at least one surfactant. 11. The composition of claim 9, wherein the surfactant (C) is at least one polyoxyalkylene amine, polyoxyalkylene amide, polyoxyalkylene alcohol, polyoxyalkylene polyol, polyoxyalkylene phenol, polyoxyalkylene ether, polyoxyalkylene ester, or fatty acid salt 12. The composition of claim 9, wherein the composition is a water-base hydraulic fluid or a water-base metal working fluid.

Inventors: FORSBERG JOHN W, JAHNKE RICHARD W, FORSBERG, JOHN, W., JAHNKE, RICHARD, W.
Applicants: LUBRIZOL CORP, THE LUBRIZOL CORPORATION
Application year: 1992
Main classification: C10M173
IPC codes: C08G65, C08L71, C10M109, C10M133, C10M159, C10M173, C10N10, C10N20, C10N30, C10N40