CA1265779A

CA1265779A - Functional fluids and concentrates containing associative polyether thickeners and certain metal dialkyldithiophosphates

Info

Publication number: CA1265779A
Application number: CA000510703A
Authority: CA
Inventors: Mark Andrew Frentrup; James Elery Carson; Stanley Tariho Hirozawa; Daniel Edward Coker
Original assignee: BASF Corp
Current assignee: BASF Corp
Priority date: 1985-06-10
Filing date: 1986-06-03
Publication date: 1990-02-13
Anticipated expiration: 2007-02-13

Abstract

FUNCTIONAL FLUIDS AND CONCENTRATES CONTAINING
ASSOCIATIVE POLYETHER THICKENERS
AND CERTAIN METAL DIALKYLDITHIOPHOSPHATES
Abstract of the Disclosure The invention relates to functional fluid concen-trates and functional fluids which can be prepared by mixing the concentrates with water. The functional fluids can be used in hydraulic systems or as metalworking compositions to cool and lubricate surfases which are in frictional contact during operations such as the turning, cutting, peeling, or grinding of metals.

The functional fluid concentrate comprises:
(a) a cloud point raising metal dialkyldithio-phosphate additive having the following structural formula:

wherein R1, R2, R3, and R4 are individually linear or branched alkyl, alkenyl, aryl, arylalkyl and alkylaryl groups having from 1 to 24 carbon atoms: and M is selected from the group consisting of Zn, Sb, Sn, Mg, and Mn; preferably Zn or Sb;

(b) a polyether nonionic surfactant;

(c) an associative polyether thickener; and (d) a nitrogen-containing, phosphorous-free carboxylic solubilizer.

Preferably the concentrate also contains a linear or branched alkanolamine having 2 to 10 carbon atoms.

Description

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1~15-1 l-Ui`lCT:l:ONAL. ~L[IIDS i~ND CON(`ENTR~TES COMTA~MING
ASSOC:[AT:LVr, POL,YETEli4'R Tl-IICI<I~',NE.KS
AND__RTATN METAL DTALI _) THIOP~IO_rllA~rl~'S

Background oE the Invention 1. Field of the Invention This invention relates l:o functiorlal Eluids and concentrates thickened with associative polyether thick-eners. In addition to the associat:i.ve polyether thickener, the fluids and concelltrates also contain a cloud point raising additive which is a metal dialkyldithiophosphate; a polyether nonionic surfactant; a nitrogen-containing, phosphorous-Eree carboxylic solubilizer; preferably an alkanolamine; and other optional ingredients.

2. Description of the Prior Art It is known to formulate functional Eluids with associative polyether thlckeners. See, for instance, U. S.
Patents 4,4119819 and 4,312j768. However, the fluids descrlbed ln these patents have wear rates of approximately 20 milligrams per hour, and have cloud points of approx-imately 160F. Because oE the h:igh wear, these Eluids are not satisfactory in pumps which operate under severe conditions such as vane pumps which may operate at high pressures (greater than 500 psi), or in systems which may .

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have sump temperatures above 150F or localized temperature~
(such as where directional valves are placed) as high as 200F.
Summary of the Invention The invention relates to functional fluid concen-trates and functional fluids which can be prepared by mi~ing the concentrates with water. The functional fluids can be used in hydraulic systems or as metalworking compositions to cool and lubricate surface~ which are in frictional contact during operations such as the turning, cutting, peeling, or the grinding of metals.
The functional fluid concentrate comprises:
(a) a cloud point raising metal dialkyldithio-phosphate additive having the following structural formula:

R10 \ / S \ S ~ / R3 (I) / P \ M \ P \
R2o S S 4 wherein Rl, R2, R3 and R4 are individually l~near or branched alkyl, alkenyl, aryl, arylalkyl, or alkylaryl groups having rom 1 to 24 carbon atoms, preferably 2 to 20, and M
i8 selected from the group consisting of Zn, Sb, Sn, Mg, and Mn, preferably Zn or Sb, ~2~'77~

(b) a polyether nonionic surfactant, (c) an associative polyether thickener, and (d) a nitrogen-containing, phosphorous-free carboxylic solubilizer.

Preferably the concentrate also contains a linear or branched alkanolamine having 2 to 20 carbon atoms.
Functional fluids can be prepared from the subject concentrate by diluting the concentrate with water such that approximately 60 to 99.9 percent of the fluid will consist of water. Alternatively, some or all of the water of dilution may be replaced by a freezing point lowering additive such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, and the like, or mixtures thereof. Functional fluids prepared with the subject concentrates have viscosities which may exceed 200 SUS at 100F which is substantially maintained at increased temperatures. They al80 have cloud `points as high as 205F
and, thus, are able to be utilized in systems which may have sump temperatures or lc,calized temperatures (such as miyht exist where directional valves are placed) of up to 200F or

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higher. In the Vickers Vane Pump Te~t, a widely u~ed test of the antiwear properties of a hydraulic fluid, the fluid~
will generally have wear rates of les~ than 10 mg/hour and are likely to have wear rate~ of les~ than 5 mg/hour over long term operations such a~ 100 hours or more.
Description of the Preferred Embodiments The cloud point raising additive is a metal dialkyldithiophosphate having a ~tructure defined by formula I previously set forth. Particularly useful as the cloud point raising additive i~ the compound wherein M is Zn and all R groups are 2-ethylhexyl. These additives are well known in the art particularly those where M is Zn and are commercially available.
In general, any polyether nonionic surfactant can be used in the practice of this invention provided that it will mix with the associative thickener, cloud point raising additive and other ingredients in water. Such polyether nonionic surfactants are well known in the art. They are prepared by reacting an alkylene oxide with an active hydrogen-containing compound to form a molecule having an average molecular weight of approximately 300 to 10,000, preferably 500 to 5000, and mo4t preferably 500 to 2000, which contains a hydrophobe segment and a hydrophile ~egment. However, they do not contain a hydrophobe segment based upon an alpha-olefin epoxide or glycidyl ether 126577~

addition as do the associative thickeners described in a subsequent part of this specification.
Although other polyether nonionic ~urfactants may work satisfactorily, three groups of ~urfactants have been ~hown to work particularly well. The most preferred group consists of polyether nonionic surfactants prepared by reacting a preferably aliphatic alcohol, fatty acid, fatty acid amide, amine initiator ~preferably an alcohol initi-ator) having about 12 to about 18 carbon atoms, preferably about 12 to about 15 carbon atoms, with ethylene oxide to prepare a homopolymer containing the residue of about 5 to about 100 moles of ethylene oxide. Preferably, about 5 to about 20 moles o ethylene oxide are reacted with the initiator to prepare said homopolymer polyether surfac-tants. Alternatively, block or heteric copolymers can be prepared using as reactants ethylene oxide and a lower alkylene oxide, pre~erably having 3 to 4 carbon atoms. The re~idue of ethylene oxlde in said polyether copolymer generally i~ at least about 70 percent by weight when the lower alkylene oxide used with ethylene oxide has 3 carbon atoms. The ethylene oxide residue in the polyether obtained generally is about 80 percent by weight when a lower alkylene oxide containing 4 carbon atoms is utiliæed with ethylene oxide in the preparation G~ said ethoxylated surfactant. Preerably, the average molecular weight o~

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said surfactant is about 500 to about 2000. Representative aliphatic alcohol or amine initiators are octadecyl alcohol, stearyl amine, lauryl alcohol, lauryl amine, myristyl alcohol or amine, and cetyl alcohol or amine.
Another preferred group of polyether nonionic surfactants is ethoxylated alkyl phenols having 1 to about 20 carbon atoms in the alkyl growp and preferably an average molecular weight of ahout 400 to about 2000. These are derived from reaction of an alkyl phenol with ethylene oxide to produce a homopolymer. Alternatively, a block or heteric copolymer can be prepared by reacting ethylene oxide and a lower alkylena oxide, preferably having 3 to 4 carbon atoms, with an alkyl phenol. The alkyl phenol preferably has about

4 to about 20 carbon atoms in the al~yl group. Preferably, the ethoxylated alkyl phenols are derived from the reaction of said alkyl phenol with ethylene oxide or ethylene oxide and at least one lower alkylene oxLde, preferably having 3 to 4 carbon atoms, provided that the ethoxylated polyether copolymer surfactant obtained thereby contains at least 60 percent to about 96 percent by weight of ethylene oxide residue. The ethoxylated homopolymer alkyl phenols contain the residue of about S to about 100 moles of ethylene oxide. Repre~entative alkyl phenols useful in the prepara-tion o alkoxylated alkyl phenol ~urfactants are octyl-phenol, nonylphenol, dodecylphenol, dioctyphenol, dinonyl-phenol, dodecylphenol and mixture~ thereof.

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The final group of preferred polyether nonionic surfactants consists of ethylene oxide adducts of sorbitol and sorbitan mono-, di-, and triesters having average molecular weights of 500 to 5000, preferably 500 to 2000.
These surfactants are well known in the art. These surfac-tants are generally prepared by esterifying 1 to 3 moles of a fatty acid and then further reacting with ethylene oxide. The fatty acids usually contain from 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms. Alternatively, a block or heteric copolymer can be prepared by reacting ethylene oxide and a lower alkylene oxide, preferably having 3 to 4 carbon atoms with the fatty acid ester. Preferably the surfactants are prepared by the reaction of the ester with ethylene oxide or ethylene oxide and at least one lower alkylene oxide preferably havlng 3 to 4 carbon atoms provided that the ethoxylated polyether copolymer surfactant obtained thereby contains from about 20 percent to about 90 percent by weight of ethylene oxide residue. The ethoxy-lated homopolymers contain the residue of about 5 to about 100 moles of ethylene oxide. They are commercially sold under the INDUSTROL~ trademark. Particularly useful are INDUSTROL~ L20-S, INDUSTROL~ 020-S, INDUSTROL~ S20-S, INDUSTROL~ 68, and INDUSTROLo 1186.
The concentrate generally contains about 0.5 to about 10.0 parts by weight of the polyether surfactant, ~6S7~ 91 preferably abou-t 1.0 -to about S.0 parts by weight per l.0 part by weight of the cloud point raising additive.
The associative polyether thickeners which are used in the subject concentrates and functional fluids are relatively new in the art and are disclosed in U.S. Patents 4,288,639; 4,312,775; and 4,411,819. These thickeners are prepared by first reacting ethylene oxide or ethylene oxide and generally at least one lower alkylene oxide with at least one active hydrogen-containing compound and subsequently reacting therewith at least one long chain aliphatic alpha-olefin epoxide or glycidyl ether. The long chain alpha-olefin epoxide or glycidyl ether has a carbon chain length of about 12 to about 18 aliphatic carbon atoms.
The proportion of alpha-olefin epoxide or glycidyl ether present in the polyether thickener is generally 1 to about 20 percent by weight, based upon the total weight of the thickener.
The associative polyether polyol thickeners may be readily prepared by modifying a conventional non-associative polyether aqueous thickener by reacting it with an alpha-olefin epoxide or glycidyl ether having about 12 to about 18 carbon atoms or mixtures thereof. The conventional non-associative polyether polyol thickener can be an ethylene oxide-derived homopolymer or a heteric or block copolymer of ethylene oxide and at least one lower alkylene oxide "~

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~L2G57'-79 preferably having 3 to ~ carbon atoms. The ethylene oxide is used generally as a reactant in the proportion of at least 10 percent by weight based upon the total weight of the polyether thickener. Preferably, about 60 to 99 percent by weight ethylene oxide is utilized with about 40 to 1 percent by weight of a lower alkylene oxide preferably having 3 to 4 carbon atoms.
The preferred non-associative polyether thickeners used to prepare the associative thickeners are prepared by methods well known in the art. Generally this involves reacting an active hydrogen-containing compound in the presence of an acidic or basic oxyalkylation catalyst and an inert organic solvent at elevated temperatures in the range of about 50C to 150C under an inert gas pressure, gen-erally from about 20 to about 100 pounds per square inch gauge. Generally, both monohydric and polyhydric alcohol initiators are useful. Useful polyhydric alcohol initiators are selected from the alkane polyols, alkene polyols! alkyne polyols, aromatic polyols, and oxyalkylene polyols.
Monohydric alcohol initiators which are useful include aliphatic monohydric alcohols and alkyl phenols containing about 12 to about 18 carbon atoms in the aliphatic or alkyl group. In addition, aliphatic mercaptans having about 12 to about 18 carbon atoms are u~eful initiators.
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In tllis manner, heteric, block, and homopolymer non-associative polyether thickeners, preferably having average molecular weights of about 1000 to about 60,000, preferably 5000 to fiO,000, are prepared which can be used to prepare associative polyether thickeners by reacting them with long chain, aliphatic alpha-olefin epoxides glycidyl ether. Generally, about 0.01 part to about 50.0 parts by weight, preferably about 0.5 to about 5.0 parts by ~eight, of the associative polyether thickener is used per 1.0 part by weight of the cloud point raising additive.

The ni-trogen-containing, phosphorous-free-car-boxylic solubilizers are well known in -the art and are ` -disclosed in U.S. Pa-tents 4,368,133 and 4,481,125.
Although a variety of such compounds are disclosed in these patents, generally preferred are reaction products of an alkenyl succinic anhydride and a dialkyl alkanolamine.
~he concentrate generally contains 0.1 part to 10 parts by weight, preEerably 0.2 part to 5 parts by weight of the nitrogen-containing, phosphorous-free carboxylic solubili~er, said weight being based upon 1.0 part by weight of the cloud point raising additive.
As was mentioned previously, concentrates and functional Eluids preferably contain linear or branched alkanolamines having from 2 to 20 carbon atoms. Specific ;, ',. ' ':
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example~ of al~anolamines which may be used include:
monoethanolamine, diethanolamine, triethanolamine, monoiso-propanolamine, diisopropanolamine, triisopropanolamine, di-sec-butanolamine, sec-butylaminoethanol, dimethylethanol-amine, diethylethanolamine, aminoethylethanolamine, methyl-ethanolamine, butylethanolamine, phenylethanolamine, dibutylethanolamine, monoisopropylethanolamine, diisopropyl-ethanolamine, phenylethylethanolamine, methyldiethanolamine, ethyldiethanolamine, phenyldiethanolamine, dimethylisopro-panolamine, 2-amino-2-methyl-1-propanol, and 2-amino-2-ethyl-1,3-propanediol.
Particularly useful are triethanolamine, diethyl-ethanolamine, diisopropylethanolamine and mixtures ; thereof. The alkanolamines are used in amounts of 0.1 part to ~0 parts by weight, preferably 0.5 part to 5.0 parts by weight per l.C part o the cloud point raising additive.
Other optional ingredients which may be u~ed in the subject concentrates and functional fluids include corrosion inhibitors such as alkali metal nitrites, nitrates, phosphates, silicates and benzoates. Certain amines, other than the alkanolamines previously described, may also be useful. The inhibitors can be used individually or in combinations. Representative examples of the pre~
ferred alkali metal nitrates and benzoates which are useful are as follows: sodium nitrate, potassium nitrate, calcium nitrate, barium nitrate, lithium nitrate, strontiura nitrate, sodium benzoate, potassium benzoate, calcium benzoate, barium benzoate, lithium benzoate and strontium benzoate.
Representative amine type corrosion inhibitors are morpholine, N-methylmorpholine, N-ethylmorpholine, tri-ethylenediamine, ethylenediamine, dlmethylaminopropylamine, and piperazine.
The metal deactivators may also be used in the subject concentrates and functional fluids. Such materials are well known in the art and individual compounds can be selected from the broad clas~es of materials useful for this purpose such as the various triazoles and thiazole~ as well as the amine derivatives of salicylidenes. Representative specific examples of these metal deactivators are as follows: benzotriazole, tolyltriazole, 2-mercaptobenzothi-azole, sodium 2-mercaptobenzothiazole, and N,N'-disalicyli-dene-1,2-propanediamine.
The corrosion inhibitors and metal deactivators are generally used in amounts of from about 0.001 part to

5.0 parts by weight, preferably 0.001 part to 0.2 part by weight per 1.0 part of the cloud point raising additive.
The examples which follow will illustrate the practice of this invention in more detail. However, they are not intended in any way to limit its scope. All parts, proportions, and percentages are by weight, and all tempera-tures are in degrees Fahrenheit unless otherwise specified.

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The following abbreviations will be u~ed in the Examples:

AMP - 2-amino-2-methyl-1-propanol DIPAE - N,N-dii~opropyl-2-aminoethanol E-69 - a 20 mole ethylene oxide adduct of sorbitan trioleate LUBRIZOL 5603 - reaction product of polyisobutenyl succinic anhydride and an alkanolamine sold by Lubrizol Corporation P-45 - a 4 mole propylene oxide adduct of penta-erythritol `
Surfactant A - an ethylene oxide adduct oE a mixture of Cl -C15 alcohol~s having an average molecular weight o 500 to 600 Surfactant ~ - a 9 mole ethylene oxide adduct of nonyl-phenol Surfactant C - a 13 mole ethylene oxide adduct oE a stearic acid TEA - triethanolamine Thickener $1 - a non-associative polyether thickener having an average molecule weight of 23,000 prepared by reacting a mixture of ethylene oxide and propylene oxide (using an ethylene oxide/propylene oxide weight ratio of 75:25) with trimethylolpropane * Trade marlc :. :~. ~.' ':'. :

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Thic:kener ~2 - an associative polyether thickener having an average molecular weight of approx-imately 17,000 prepared by reacting a mixture of ethylene oxide and propylene oxide (weight ratio of ethylene oxide to propylene oxide of approximately 85:15) to form a heteric intermediate, and then reacting the intermediate with approx-imately 4 to 5 weight percent of a mixture alpha olefin epoxides.
TT - tolyltriaæole (50 percent solution) ZDP-l - zinc dialkyldithiophosphate wherein all R
groups are 2-ethylhexyl 2DP-2 - zinc dialkyldithiophosphate wherein the R
groups are a mixture of isodecyl isomers ZDP-3 - zinc dialkyldithiophosphate wherein the R
groups have an average of 3.8 carbon atoms ZDP-4 - antimonydialkyldithiophosphate wherein all R groups are 2-ethylhexyl - 14 ~

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EXAMPLES
Com~arative Example A
A hydraulic fluid was formulated by mixing 92.75 parts of water with 7.25 parts of a concentrate having the ollowing proportion of in~redients:

In~redient Parts b~ Weight TEA l.0 DIPAÉ. 0~7 Surfactant A 4.0 TT 0.15 Thickener #2 1.4 The cloud point for the above fluld was 162F.
Example l In order to show the efect of adding an additive within the scope of the subject invention to the formulation ~ in Comparison Example A, several other hydraulic fluids were : prepared by addin~ a metal dialkyldithiophosphate to the concentrate described in Comparison Example A. The specific metal dialkyldithiophosphate and the amount used is given in Table Io In each case the amount of water used in Compar-ison Example A was reduced by the amount of the metal dialkyldithiophosphate used ~o that the amounts of all ingredients are based upon lO0 parts of Eluid.

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TABLE I
Example Additive Amount (pbw) Cloud Point (F) 1 ZDP 3 1.0 181 2 ZDP-l 0.5 195 3 ZDP-l 1.0 206 4 ZDP-2 1.5 200 ZDP-4 1.0 206 Examples 1-5 show that the additives of this invention effectively raise the cloud point of the subject hydraulic fluid.
The next Examplesl 6-7, illustrate that this phenomenon occurs when other surfactants are used. In these ; ~ Examples, the following proportions of ingredients were used:
Ingredient Parts by_Wei~ht DIPAE 1.0 TEA 0.5 Surfactant ~ or C 4.0 ZDP~ 0 Thickener #2 1.3 When Suractant ~ was used, the cloud point was 203F. When Surfactant C was used, the cloud poln~ was 198~.

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Comparison Example B
For comparison purposes, a fluid was formulated having the formulation of the fluid described in Comparison Example A except that 20 parts of Thickener ~1 was used instead of 1.4 parts of Thickener #2. (Also, 72.65 parts by weight of water were used instead of 92.75 parts by weight.) The fluid had a cloud point of 173F. When 1.5 parts ~y weight of ZDP-l were added, the cloud point of the fluid was increased to 175C.
This comparison indicates that additives such as ZDP-l are not effective for raising the cloud point of fluids containing thickeners such as Thickener ~1 even though it does raise the cloud point of fluids having thickeners such as Thickener #2.
Examples 8-12 wcll illustrate what wear rates are like for the hydraulic fluids within the ~cope of this invention. The fluids d~sclosed in Table II were formulated by mixing the concentrate with water. The wear rates were determined by using the Vickers ~ane Pump Test. The hydraulic circuit and equipment used were as specified in ASTM D2882 and D2271.
The Vickers Vane Pump Test procedure used herein specifically requiras charging the system with 5 gallons of the test fluid and running at temperatures ranging from 100 to 135F at 750 to 1000 psi pump discharge pressure 3L~6~7~79 (load). Wear data were made by weighing the cam-ring and the vanes of the "pump cartridge" before and after the test. At the conclusion of the test run and upon dis-assembly for weighing, visual examination of the system was made for signs of deposits, varnish, corrosion, etc.
The various components and amounts used in the fluids are given in Table II along with the wear rate data.

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Table II shows that using the concentrates and fluids within the scope of this invention, it i8 possible to provide effective resistance against wear.
Examples 13 and 14 relate to hydraulic fluids having elevated cloud point which contain a nitrogen-containing, phosphorous-free carboxylic solubilixer in addition to the cloud point raising additive, polyether nonionic surfactant, and associative polyether thickener.
In these examples the following fluid was used:

Component Amount (parts by weight) DIPAE 0.7 TEA 1.0 ;

Surfactant A ~ 4 0 Thickener 2 l.S
TT See table LUBRI20L 5603 See table H2O To 100 parts .'0 The amounts of TT and LUBRIZOL S603 are given in Table III
which follows.
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An unexpected advantage of using the nitrogen-containing, phosphorous-free carboxylic ~olubilizer wa~ that the pump parts were much cleaner when they finished the pump test~ Moreover, the vanes slid more freely in the rotor and the bushings did not blacken at all. Th:is would enable the pump to run smoother for a longer period of time.

Claims

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows:

1. A functional fluid concentrate which comprises (a) a cloud point raising additive having the following structural formula:

wherein R1, R2, R3, and R4 are individ-ually linear or branched alkyl, alkenyl, aryl, arylakyl, or alkylaryl groups having from 1 to 24 carbon atoms; and M
is selected from the group consisting of Zn, Sb, Sn, Mg and Mn;

(b) from 0.5 part to 10.0 parts by weight of a polyether nonionic surfactant, and (c) from 0.01 part to 50.0 parts by weight of an associative polyether thickener; and (d) from 0.1 part to 10.0 parts by weight of a nitrogen-containing, phosphorous-free carboxylic solubilizer, said weights based upon 1.0 part of the cloud point raising additive.

2. The concentrate of claim 1 wherein the nitrogen-containing, phosphorous-free carboxylic solubilizer is the reaction product of an alkenyl succinic anhydride and a dialkyl alkanolamine.

3. The concentrate of claim 2 wherein M is Zn or Sb.

4. The concentrate of claim 3 wherein compo-nent (b) is used in an amount of 0.5 part to 5.0 parts by weight, component (c) is used in an amount of 1.0 part to 5.0 parts by weight, and compound (d) is used in an amount of 0.2 part to 3.0 parts by weight, said weights being based upon the weight of the cloud point raising additive.

5. The concentrate of claim 4 wherein a linear or branched alkanolamine is also used in the concentrate.

6. The concentrate of claim 5 wherein a mixture of triethanolamine and diisopropylaminoethanol is used as the alkanolamine component.

7. The concentrate of claim 6 wherein the amount of triethanolamine used is from 0.5 part to 2.5 parta by weight and the amount of diisopropylaminoethanol is from 0.5 part to 1.5 parts by weight per 1.0 part by weight of the cloud point raising additive.

8. The concentrate of claim 7 which contains tolyltriazole in an amount of 0.001 part to 2.0 parts by weight per 1.0 part by weight of the cloud point raising additive.

9. The concentrate of claim 4 wherein the surfactant is an ethylene oxide adduct of a mixture of C12-15 alcohols such that the average molecular weight is from 300 to 5000.

10. The concentrate of claim 5 wherein the surfactant is an ethylene oxide adduct of a mixture of C12-15 alcohols such that the average molecular weight is from 300 to 5000.

11. The concentrate of claim 6 wherein the surfactant is an ethylene oxide adduct of a mixture of C12-15 alcohols such that the average molecular weight is from 300 to 5000.

12. The concentrate of claim 7 wherein the surfactant is an ethylene oxide adduct of a mixture of C12-15 alcohols such that the average molecular weight is from 300 to 5000.

13. The concentrate of claim 8 wherein the surfactant is an ethylene oxide adduct of a mixture of C12-15 alcohols such that the average molecular weight is from 300 to 5000.

14. The concentrate of claim 4 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

15. The concentrate of claim 5 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

16. The concentrate of claim 6 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

17. The concentrate of claim 7 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

18. The concentrate of claim 8 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

19. The concentrate of claim 9 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

20. The concentrate of claim 10 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

21. The concentrate of claim 11 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

22. The concentrate of claim 12 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

23. The concentrate of claim 13 wherein the associative thickener has an average molecular weight of 5000 to 40,000 and is prepared by reacting a mixture of ethylene oxide and propylene oxide in a weight ratio of 3:1 to 10:1 with trimethylol propane and then reacting with an alpha-olefin epoxide such that the weight percent of alpha-olefin oxide in the associative thickener is from 1 to 20 percent.

24. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 1 such that about 60 to 99.9 percent by weight of the fluid is water, a freezing point lowering additive, or both.

25. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 2 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

26. A functional fluid comprising water, a freezing point lowereing additive, or both, and the concen-trate of claim 3 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

27. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 4 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

28. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 5 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

29. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 6 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

30. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 7 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

31. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 8 such that about 60 to 99 percent by weight of the fluid is water,a freezing point lowering additive, or both.

32. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 9 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

33. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 10 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

34. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 11 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

35. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 12 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

36. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 13 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

37. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 14 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

38. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 15 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

39. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 16 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

40. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 17 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

41. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 18 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

42. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 19 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

43. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 20 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

44. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 21 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

45. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 22 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.

46. A functional fluid comprising water, a freezing point lowering additive, or both, and the concen-trate of claim 23 such that about 60 to 99 percent by weight of the fluid is water, a freezing point lowering additive, or both.