CA1265780A - Functional fluids and concentrates containing associative polyether thickeners and certain metal dialkyldithiophosphates - Google Patents

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 fluid concen-trate comprises certain basic zinc salts as cloud point raising additives; a polyether nonionic surfactant; and an associative polyether thickener.

Description

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1~1S-2 F~NCTIONAL FLUIDS AND CONCENTRATES COMTAINING
ASSOCIATIVE POLYETHER THIC~ENERS
AND CERTAIN METAL DIALKYLDITHIOPEIOSPHATES
.

Background of the Invention 1 Field of the Invention .
This invention relates to functional fluids and concentrates thickened with associative polyether thick-eners. In addition to the associative polyether thickener, the fluid~ and concantrates also contain a cloud point raising additive which is a basic zinc salt of the pre-scribed formulae, a polyether nonionic surfactant, prefer-ably an alkanolamine, and other optional ingredients.

2. Description of the Prior Art It is known to formulate functional fluids with associative polyether thickeners. See, for instance, U. S.
Patents 4,411,819 and 4,312,768. However, the fluids described in these patents have wear rates of approximately 20 milligrams per hour, and have cloud points of approx-imately 160F. Because of the high wear, these fluids are not satisfactory in pumps which operate under severe conditions such as vane pumps which may operate at high pressures (greater than 5ao psi), or in systems which may have sump te~peratures above 150F or localized temperatures ~2~71~

(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 mixing the concentrates with water. The functional Eluids can be used in hydraulic systems or as metalworking compositions to cool and lubricate surfaces 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 basic zinc salt additive having an empirical formula which i9 represented by either (i) Zn2 ~RO)~PS~] OH~ or (ii) zn4~(R)2Ps2~ 6 ' wherein R is a linear or branched alkyl, alkenyl, aryl, arylalkyl, or alkyLaryl groups having ~rom 1 to 24 carbon atoms, preferably 2 to 20.

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(b) a polyether nonionic surfactant, and (c) an associative polyether thickener.

Preferably the concentrate also contain~ a linear or branched alkanolamine having 2 to 20 carbon atoms.
Functional fluids can be prepared from the subiect 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 ~uch as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene yCGl~ tetraethylene glycol, and ~he like, or mixtures thereof. Functional fluids prepared with the subject :
concentrates have viscosities which may exceed 200 SUS àt 100F which is substantially maintained at increased temperatures. They also have cloud points as high as 205F
and, thus, are able to be utilized ~in~systemo which may have;
sump temperatures or~localized temperatures (auch as might exist where directional valves are placed) of up to 200F or 20 ~ higher. In the Vicker~ ~ane Pump Test, a widely used test~
of the antiwear properties of a hydraulic ~luid, the fluids ;~
will generally have wear rates of less than 10 mgthour and ~: ' :~

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are likely to have wear rates of less than 5 mg/hour over long term operations such as 100 hours or more.
Descrip~on of the Preferred Embodiments The cloud point raising additive is a basic zinc salt having an empirical formula as set forth previously.
These compounds are commercially available. A method of preparation i9 described by Wystrach et al, Journal_of Organic Chemistr~, "Basic Zinc Double Salts of 0,0-dialkyl Phosphorodithioic Acids," pp. 705-707, (June 1956).
In general, any polyether nonionic surfactant ~can be used in the practice o 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 most preferably 500 to 2000, which contains a hydrophobe segment and a hydrophile segment. However, they do not contain a hydrophobe segment based upon an alpha-olefin epoxide or glycidyl ether addition as do the associative thickeners described in a subsequent part of this specification.
Althou~h other polyether nonionic surfactants may work satisfactorily, three groups of surfactants have been ~2~iS~3 [11 shown 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 of 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, preferably having 3 to 4 carbon atoms. The residue of ethylene oxide in said polyether copolymer generally is at least about 70 percent by weight when the lower alkylene oxide used with ethylene oxide has 3 carbon atoms. ~'he ethylene oxide residue in the polyether obtained generally is about 80 percent by weight when a lower alkylene oxide containing 4 carbon atoms i5 utilized with ethylene oxide in the preparation of said ethoxylated surfactant. Preferably, the average molecular weight of ~aid surfactant i5 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.

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Another preferred group of polyether nonionic surfactants is ethoxylated alkyl phenol~ having 1 to about 20 carbon atoms in the alkyl group and preerably an average molecular weight of about 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 alkylene oxide, preferably having 3 to 4 carbon atoms, with an alkyl phenol. The alkyl phenol preferably has about 4 to about 20 carbon atom~ in the alkyl 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 oxide, preferably having 3 to 4 carbon atoms, provided that the ethoxylated polyether copolymer surfactant obtained thereby contains at least 60 percent to abaut 96 percent by weight of ethylene oxide residue. The ethoxylated homopolymer alkyl phenols contain the residue of about 5 to about 100 moles of ethylene oxide. Representative alkyl phenols useful in the prepara-tion of alkoxylated alkyl phenol surfactants are octyl-phenol, nonylphenol, dodecylphenol, dioctyphenol, dinonyl-phenol, dodecylphenol and mixtures thereof.
The final group o~ preferred polyether nonionic surfactant~ consist~ of ethylene oxide adduct~ o sorbitol and sorbitan mono-, di-, and triesters having average ~L2~;5~

molecular weights of 500 to 5000, preferably 500 to 2000.
These suractants are well known in the art. These surfac-tants are generally prepared by esterifying 1 to 3 moles of a fatty acid and then Eurther 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 having 3 to 4 carbon atoms provided that the ethoxylated polyether copolymer surfactant obtained thereby contains from about 20 percent to about 90 percent hy 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 INDUSTROL~ 1186.
The concentrate generally contains about 0.5 to about 10.0 parts by weight of the polyether surfactant, preferably about 1.0 to about 5.0 parts by weight per 1.0 part by weight of the cloud point raising additive.

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~ he 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. I'hese th iC ke n e r s a r e p r e p a r e d b y f i r s t 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 giycidyl ether present in the polyether thickener is ge~erally l 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 preferably having 3 to 4 carbon atoms. The ethylene oxide i~ used generally as a reactant in the proportion of at ~265~

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, alkena polyols, alkyne polyols, aromatic polyols, and oxyalkylene polyols.
Monohydric alcohol initiators which are useful include aliphatic monohydric alcohols and alkyl phenols containing ~0 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 useful initiators.
In this manner, heteric, block, and homopolymer non-associative polyether thickeners, preferably having average molecular weights of about 1000 to about 60,000, ~2GS780 preferably 5000 to 40,000, are prepared which can be used to prepare associative polyether thickeners by reacting them with long chain, aliphatic alpha-olefin epoxidss glycidyl ether.
Generally, about 0.01 part to about 50.0 parts by weight, preferably about 0.5 to about 5.0 parts by weight, of the associative polyether thickener is used per 1.0 part by weight of the cloud point raising additive~
Nitrogen-containing, phosphorous-free carboxylic solubilizers may also be used in the subject concentrates and hydraulic fluids. These are well known in the art and are disclosed .in U.S. Patents 4,368,133 and 4,481,125.
A lt ho u g h a v a r i e ty o f s u c h c o m p o u n d s a r e d i s c 1 o s e d i n t h e s e p a t e n ts , ge ne-r a 1 1 y p re fe r r e d a r e r e ac t i o n p r o d u c ts of an alkenyl succinnic anhydride and a dialkyl alkanolamine.
The concentra~e generally contains 0.1 part to 10 parts by weight, preferably 0.2 part to 5 parts by weight of the nitrogen-contalning, phosphorous-free solubilizer, said weight being based upon 1.0 part by weight of the cloud point raising additive.
As was mentioned previously, concentrates and functional fluids preferably contain linear or branched alkanolamines having from 2 to 20 carbon atoms. Specific examples of alkanolamines which may be used include:

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monoethanolamine, diethanolamine, triethanolamine, monoiso-propanolamine, diisopropanolamine, triisopropanolamine, di-sec-butanolamine, sec-butylaminoethanol, dimeth~lethanol-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 20 parts by weight, preferably 0.5 part to 5.0 parts by wei~ht per 1.0 part o the cloud point raising additive.
Other optional ingredients which may be used in the subject concentrates and functional fluids include corrosion inhibitors such as alkali metal nitrites, nitrate-s, phosphates, silicates and benzoates. Certain amines, other than the alkanolamines previously described, may also be u~eful. The inhibitors can be used individually or in combinations. Representative examples of the preferred alkali metal nitrates and benzoates which are useful are as ~ollow~: sodium nitrate, potassium nitrate, calcium nitrate, barium nitrate, lithium nitrate, strontium nitrate, ~6$78~

sodium benzoate, potassium benzoate, calcium benzoate, barium benzoate, lithium benzoate and ~trontium benzoate.
Representative amine type corrosion inhibitors are morpholine, N-methylmorpholine, N-ethylmorpholine, tri-ethylenediamine, ethylenediamine, dimethylaminopropylamine, and piperazine.
The metal deactivators may also be u~ed in the subject concentrates and functional fluids. Such materials are well Xnown in the art and individual compounds can be selected from the broad classes of materials useful for this purpose such as the various triazoles and thiazoles 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-mercaptobenzothiaæole, and N,NI-disalicyli-dene-1,2-propanediamine.
~ he corrosion inhibitors and metal deactivators are generally u~ed in amounts of Erom 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 thi~ invention in more detail. ~lowever, they are not intended in any way to limit its scope. All parts, proportions, and percentage~ are by weight, and all tempera-tures are in degrees Fahrenheit unless otherwise ~pecified~

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The follo~ling abbreviations will be used in the Examples:

AMP - 2~amino-2-methyl-1-propanol DIPAE - N,N-diisopropyl-2-aroinoethanol 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 of a mixture of C -C alcohols having an average molecular weight of 500 to 600 Surfactant B - a 9 mole ethylene oxide adduct of nonyl-: phenol : Surfactant C - a 13 mole ethylene oxide adduct of a stearic acid TEA - triethanolamine : 20 Thickener #l - 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 o~ 7S:25) with trimethylolpropane * trade mark ~265~81D

Thickener #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 (we.ight 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 - tolyltriazole (50 percent solution) .: :

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ZDP-l* - zinc dialkyldithiophosphate wherein all R
groups are 2~ethylhexyl ZDP-2* - zinc dialkyldithiophosphate wherein the R
groups are a mixture of isodecyl isomer~
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 ZDP-B - basic zinc salt wherein R is 2-ethylhexyl.

*These zinc compounds are not basic zinc salts and are represented by the formula:

\ P/ ~ Z n/ \ P /

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~2~S7~3 03 EX~MPLES
Comparative Example A
A hydraulic 1uid was formulated by mixing 92.75 parts of water with 7.25 parts of a concentrate haviny the following proportion of ingredients:

Ingredient Parts by Weight TEA 1.0 DIPAE 0.7 Surfactant A 4.0 TT 0.15 Thickener #2 1.4 The cloud point for the above fluid was 162F.
Example 1 In order to show the effect of adding an additive within the scope of the subject invention to the formulation in Comparison Example A, several other hydraulic ~luids were prepared by adding a metal dialkyldithiophosphate to the concentrate described in Comparison Example A. ~he ~pecific ~ metal dialkyldithiophosphate and the amount used is given in ~able I. In each case the amount of water used in Compar-ison Example A was reduced by the amount of the metal dialkyldithiophosphate used so that the amounts of all ingredients are based upon 100 parts of fluid.

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Example AdditiveAmount (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 Examples, 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 Weight DIPAE 1.0 TEA O.S
Surfactant B or C 4.0 ZDP-l 1.0 Thickener #2 1.3 :
When Surfactant B was used, the cloud point was 203F. When Surfactant C was used, the cloud point was 198F.

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Com~arison Example B
For comparison purposes, a fluid was for~ulated having the formulation of the fluid de~cribed in Comparison Example A except that 20 parts of Thickener #l waq used instead of ln4 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 l.S
parts by weight of ZDP-l were added, the cloud point of the fluid was 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 m ickener ~2.
Examples 8-12 will illuqtrate what wear rates are like for the hydraulic fluids within the ecope of this invention. The flulds dlsclosed 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 speclfied in ASTM D2882 and D2271.
The Vickers Vane Pump Test procedure used herein specifically requires charging the system with S gallons of the test fluid and running at temperatures ranging from 100 to 13SF at 750 to 1000 psi pump discharge pressure ' ~' ~26S~

(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 oE the test run and upon dis-assembly for weighing, visual examination of the system was made for ~igns 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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o ~ o U~ ~ o ~
o o ~ o o ~ ~ o ~o ,, ~ ~ ~ ,~ ~ o o ~n ~ o ~
O I o I o ~r o I I o I ~r ~ O ,, ~ ~ ~ ~ ~ ~ o H

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o, I I o, u~ o, ~ o , ~ a~ o U~ O O
~ o I I ~ d~

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V .~ C ~ ~ O ~, ~ ~ ,~
~ 3 ~ r ~ H ~ ~ _ _ _ Table II StlOWS that using the concentrates and fluids within the scope of this invention, it is possible to provide effective resistance again~t wear.
Ex_mple 13 This example will illustrate the use of a ba~ic zinc salt (ZDP-B) as the cloud point raising additive. The hydraulic fluid contained the following components and was prepared as in Example 1:

Component Amount (parts by weight) Surfactant A 4.00 Thickener 2 1.70 ZDP-B 0.75 TEA 1.00 DIPAE 0.70 TT 0.15 H20 To 100 partq The cloud point for the fluid was 200~ and the wear rate was 3.5 mg/hr over 89 hours.

Claims (42)

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

1. A functional fluid concentrate which com-prises:
(a) a cloud point raising basic zinc salt additive having an empirical formula which is represented by either (a) (b) wherein R is a linear or branched alkyl, alkenyl, aryl, arylakyl, or alkylaryl groups having from 1 to 24 carbon atoms;

(b) from 0.5 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, said weights based upon 1.0 part by weight of the cloud point raising additive.

2. The concentrate of claim 1 wherein from 0.1 part to 10 parts of a nitrogen-containing, phosphorous-free carboxylic solubilizer is also used, said weight based upon 1.0 part of the cloud point raising additive.

3. The concentrate of claim 2 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 0.5 part to 5.0 parts by weight; and component (d) is used in an amount of 0.2 to 3.0 parts by weight, said weights being based upon 1.0 part by weight of the cloud point raising additive.

4. The concentrate of claim 3 wherein a linear or branched alkanolamine is also used in the concentrate.

5. The concentrate of claim 4 wherein a mixture of triethanolamine and diisopropylaminoethanol is used as the alkanolamine component.

6. The concentrate of claim 5 wherein the amount of triethanolamine used is from 0.5 part to 2.5 parts by weight and the amount of diisopropylaminoethanol is from 0.5 part to 1.5 parts by weight based upon 1.0 part of the cloud point raising additive.

7. The concentrate of claim 6 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.

8. The concentrate of claim 2 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.

9. The concentrate of claim 3 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 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.

11. 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.

12. 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.

13. The concentrate of claim 2 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.

14. The concentrate of claim 3 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 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.

16. 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.

17. 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.

18. 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.

19. 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.

20. 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.

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. 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.

23. 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.

24. A functional fluid comprising water, a freezing point lowering 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.

25. 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.

26. 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.

27. 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.

28. 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.

29. 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.

30. 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.

31. 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.

32. 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.

33. 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.

34. 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.

35. 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.

36. 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.

37. 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.

38. 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.

39. 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.

40. 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.

41. 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.

42. 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.