KR20150008189A - Novel low viscosity functional fluid composition - Google Patents

Abstract

A low viscosity functional fluid composition or brake fluid comprising a dry equilibrium reflex boiling point (ERBP) of at least 260 < 0 > C and / or a wet equilibrium reflux boiling point (WERBP)
(A) 15 to 90% of at least one alkoxyglycol borate ester [R ¹ -O- (CH ₂ CH ₂ -O) _n ] ₃ B _wherein R ¹ is a C ₁ - to C ₄ -alkyl radical and n Is a value of 2 to 6,
(B) from 5 to 80% of at least one alkoxy glycol component R ² -O- (CH ₂ CH ₂ -O) _m -H wherein R ² is a C ₁ - to C ₈ -alkyl radical, 6), and
(C) an additive having an anti-corrosive action of 0.1 to 10%, wherein at least one additive contained in the additive package is selected from an alkylamine ethoxylate.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel low viscous functional fluid composition,

The present invention relates to a low viscosity functional fluid composition comprising:

(A) from 15 to 90% by weight, based on the total weight of the composition, of one or more alkoxyglycol borate esters of the general formula (I)

[R ¹ -O- (CH ₂ CH ₂ -O) _n ] ₃ B (I)

Wherein R ¹ is a C ₁ - to C ₄ -alkyl radical or a radical mixture and n is a value of 2 to 6,

(B) 5 to 80% by weight, based on the total weight of the composition, of one or more alkoxyglycol components of formula (II)

R ² -O- (CH ₂ CH ₂ -O) _m -H (II)

Wherein R ² is a C ₁ - to C ₈ -alkyl radical or the radical mixture, m is a value of 2 to 6, and R ² and / or m are each different or identical to R ¹ and / or n, ,

And

(C) 0.1% to 10% by weight, based on the total weight of the composition, of one or more additives having a corrosion inhibiting action, wherein at least one additive contained in the additive package of component (C) is selected from alkylamine ethoxylates Selected.

The low viscosity functional fluid compositions are useful in a variety of applications and in particular in new electronic or automated anti-lock braking systems that require brake fluids, especially low viscosity fluids for satisfactory operation at low temperatures.

Functional fluid compositions based on borate esters are well known in the art. Useful in DOT 4 or DOT 5.1 brake fluids, for example, these borate ester based compositions maintain sufficient resistance to erosion, stability and meet other physical property requirements such as pH, reserve alkalinity and rubber swelling, In particular, it must meet stringent physical properties and performance requirements relating to minimum dry equilibrium reflux boiling point ("ERBP"), minimum wet equilibrium reflux boiling point ("WERBP") and maximum low temperature dynamic viscosity (e.g., measured at -40 ° C).

WO 00/65001 discloses a hydraulic fluid comprising an alkoxy glycol borate ester, an alkoxy glycol, and a corrosion inhibitor, further comprising a cyclic carboxylic acid derivative.

WO 02/38711 discloses a low viscosity functional fluid composition comprising an additive such as an alkoxy glycol borate ester, an alkoxy glycol component, and a corrosion inhibitor, wherein the degree of alkoxylation of alkoxy glycol borate esters and alkoxy glycols is limited to a certain narrow pattern .

There is a strong need for improved high performance hydraulic fluid compositions and brake fluids that simultaneously satisfy or exceed the minimum ERBP and especially the WERBP temperature requirements met by the hydraulic fluid compositions and brake fluids disclosed in the art and have low temperature viscosities.

In the present invention, it has been found that the above-defined functional fluid composition exhibits excellent ERBP and WERBP values and low temperature dynamic viscosity values while satisfying excellent corrosion resistance, high stability and other physical property requirements such as pH, storage alkalinity and rubber swelling . In particular, a very high WERBP value is achieved. Also, as compared to the functional fluid compositions of the state of the art, the dynamic viscosity values at cryogenic temperatures below -40 占 폚, for example -50 占 폚, are excellent.

The interaction of the alkylamine ethoxylate as part of component (C) and other components and additives of the present functional fluid composition appears to contribute to excellent performance and in particular to very high WERBP values.

The alkylamine residue in the alkylamine ethoxylate may be an ethoxylatable secondary or, preferably, a primary aliphatic monoamine. Usually, secondary or preferably primary aliphatic monoamines are used, but polyamines having one or more ethoxylatable secondary and / or primary amino groups are also usable. The alkyl moiety for the nitrogen atom usually comprises a saturated linear or branched alkyl group, but the term "alkyl " may also include unsaturated linear or branched alkyl moieties or saturated or unsaturated cycloalkyl moieties.

In a preferred embodiment, the alkylamine ethoxylates comprise at least one linear or branched C ₃ to C ₂₀ alkyl chain, preferably at least one linear or branched C ₆ to C ₁₃ alkyl chain, more preferably at least one linear Or branched C ₇ to C ₁₂ alkyl chains, more preferably one or more linear or branched C ₈ to C ₁₁ alkyl chains. Preferably, the term " alkyl chain "as used herein refers to saturated and non-cyclic hydrocarbon residues. The alkylamine ethoxylate can also be a mixture of alkyl chains, such as a mixture of alkyl- It may be included according to specific technical or natural origin.

Suitable examples of ethoxylatable single alkylamine molecules, and therefore suitable surfactants for the present invention are: n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert -Butylamine, n-pentylamine, tert-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, But are not limited to, heptylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine, n-tetradecylamine, n-pentadecylamine, (n-heptyl) amine, di- (n-octyl) amine, di- (n-hexyl) amine, (N-decyl) amine, di- (n-decyl) amine, di- (n-decyl) amine, (N-tridecyl) amine, di- (n-tridecyl) amine, di- (N-heptadecyl) amine, di- (n-nonadecyl) amine, di- (n-hexadecyl) amine, di- Eicosyl) amine, n-hexylmethylamine, n-heptyl-methylamine, n-octylmethylamine, (2-ethylhexyl) methylamine, n-nonylmethylamine, ) Methylamine, n-decylmethylamine, n-dodecylmethylamine, n-tridecylmethylamine, isotridecylmethylamine, n-tetradecylmethylamine, n-pentadecylmethylamine, n-hexadecyl Methylamine, n-heptadecylmethylamine, n-octa-decylmethylamine, n-nonadecylmethylamine and n-eicosylmethylamine.

Such alkyl residues may be entirely derivable from petrochemical manufacture, such as, for example, a technical C ₈ -C ₁₅ alkyl mixture, 2-ethylhexyl or 2-propylheptyl, or may be derived from aliphatic, such as stearylamine, oleylamine Amines, or it may be used as a basis for alkyl amine ethoxylates.

The degree of ethoxylation is typically from 1 to 35 EO units per alkylamine molecule, i.e., one or more alkylamine alkoxylates comprise from 1 to 35 EO units, preferably from 1.5 to 15 EO units, more preferably from 1.8 to 9 EO unit, and most preferably 2 to 6 EO units. The degree of ethoxylation is generally regarded as a statistical value, that is, a mixture of species (homologs) in which the alkylamine ethoxylate has a different value of the EO unit.

In a particularly preferred embodiment of the present invention, the at least one alkylamine alkoxylate comprises at least one linear C ₃ to C ₂₀ alkyl chain and from 1 to 35 EO units; More preferably, the at least one alkylamine alkoxylate comprises at least one linear C ₆ to C ₁₃ alkyl chain and from 1.5 to 15 EO units; Most preferably, the at least one alkylamine alkoxylate comprises at least one linear C ₇ to C ₁₂ alkyl chain and from 1.8 to 9 EO units, and in particular the at least one alkylamine alkoxylate comprises at least one linear C ₈ to C ₁₁ Alkyl chain and 2 to 6 EO units.

Such alkylamine ethoxylates are primary amines having one oxyethylene chain of the general formula alkyl-NH- (CH ₂ CH ₂ O) _m -H or alkylamine-N [(CH ₂ CH ₂ O) _{p -H] [(CH 2 CH 2} O) q -H] 2 oxyethylene chain having a primary amine or the formula _{(alkyl) 2 N- (CH 2 CH 2} O) 2 -H, or a primary amine of the _m , A primary amine having one oxyethylene chain and a primary amine having two oxyethylene chains, or a mixture of primary amine and secondary amine, wherein m and (p + q) , And total ethoxy. "Alkyl" in the above formulas is usually C ₃ to C ₂₀ alkyl, preferably C ₆ to C ₁₃ alkyl, more preferably C ₇ to C ₁₂ alkyl, most preferably C ₈ to C ₁₁ alkyl to be. Especially small amounts of residual alkylamine species having a low degree of total ethoxylation of less than two.

Representative suitable alkylamine ethoxylates are octylamines (caprylamines) having two commercially available EO units.

The alkylamine ethoxylates may be prepared by conventional means, such as reacting an alkylamine and ethylene oxide under a catalyst with an alkali metal hydroxide or with a double metal cyanide catalyst, as known to those skilled in the art .

The above alkylamine ethoxylates, according to the present invention, have partial corrosion inhibiting properties and partially solvent properties for functional fluid compositions or brake fluids.

The component (A) of the functional fluid composition of formula (I) contains a species of ethoxylation degree from n = 2 to n = 6, preferably n = 2 to n = 4, more preferably n = do. Component (A) may be a single species or a mixture of different species in the ethoxylation degree and / or the radical R < ¹ >. The radical R ¹ is preferably C ₁ - to C ₄ - alkyl radicals, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- butyl, n- pentyl, n- Hexyl, n-heptyl, n-octyl and 2-ethylhexyl, with ethyl and especially methyl being preferred.

The above-mentioned borate esters and their preparation methods are well known in the art. Borate esters particularly useful in the functional fluid compositions of the present invention can be prepared by reacting boric acid with a suitable alkoxy glycol component that is the same as or different from that of component (B). Typically, the alkoxyglycol component is a mixture of different species in the degree of ethoxylation and / or in the radical R < ^{1 &} gt ;.

Examples of useful borate esters are methyltriethyleneglycol borate esters, also referred to as tris- [2- [2- (2-methoxyethoxy-ethoxy) -ethyl) n-butyl triethylene glycol borate esters and mixtures thereof. Additional useful borate esters include: methyl tetraethylene glycol borate ester, methyl diethylene glycol borate ester, ethyl tetraethylene glycol borate ester, ethyl diethylene glycol borate ester, n-butyl tetraethylene glycol borate ester, n Butyl diethylene glycol borate esters and mixtures thereof.

In a preferred embodiment, component (A) comprises at least one alkoxyglycol borate ester of general formula (I) wherein the degree of ethoxylation has a value of n = 3 and R ¹ is a methyl radical.

Component (B) of the functional fluid composition of formula (II) comprises a species of degree of ethoxylation of m = 2 to m = 6, preferably m = 2 to m = Component (B) can be a single species or a mixture of different species in the ethoxylation degree and / or the radical R < ² >. R ² is preferably a C ₁ - to C ₄ -alkyl radical and is a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- , n-heptyl, n-octyl and 2-ethylhexyl, with ethyl and especially methyl being preferred.

Examples of alkoxyglycols useful as component (B) of the present invention include: methyldiglycol, methyltriglycol, methyltetraglycol, methylpentaglycol, methylhexaglycol, ethyldiglycol, ethyltriglycol, ethyltetra N-propyltetraglycol, n-propylpentaglycol, n-propylhexaglycol, n-butyldiglycol, n-butyl N-butyl pentaglycol, n-pentyldiglycol, n-pentyltriglycol, n-pentyltetraglycol, n-pentylpentaglycol, n-pentyltetraglycol, Hexyl glycerol, n-hexyl glycerol, n-hexyl glycerol, n-hexyl glycerol, n-hexyl glycerol, n-hexyl glycerol, Hexyl tetraglycol, 2-ethylhexyl pentaglycol, 2-ethylhexyl hexaglycol And mixtures thereof. To avoid doubt, "glycol" always means "ethylene glycol".

In a preferred embodiment, component (B) comprises a mixture of alkoxy glycols of the general formula (II) comprising singly or mostly of species with m = 3. Mostly, it means that at least 60% by weight, more preferably at least 75% by weight, most preferably at least 90% by weight of component (B) comprises species with m = 3. In the last case, alkoxy glycol species with m = 2 and / or m = 4 and / or m = 5 and / or m = 6 can be present in minor amounts.

A preferred mixture of such alkoxy glycols for component (B) where m = 3 is methyl tris glycol and n-butyltriglycol alone or a mixture essentially consisting of them. Typically, the weight ratio of methyltriglycol to n-butyltriglycol in the mixture is from 5: 1 to 1: 2, in particular from 2: 1 to 1: 1.

The component (C) of the present functional fluid composition may contain at least one additive having an anti-corrosive action in addition to the alkylamine ethoxylate, although the alkylamine ethoxylate itself exhibits corrosion inhibiting properties. Typical additives for corrosion inhibiting properties include fatty acids such as lauric acid, palmitic acid, stearic acid or oleic acid; Phosphate esters with phosphoric or aliphatic alcohols; Phosphites such as ethyl phosphate, dimethyl phosphate, isopropyl phosphate, n-butyl phosphate, triphenyl phosphite and diisopropyl phosphite; Nitrogen containing heterocyclic organic compounds such as benzotriazole, tolurriazole, 1,2,4-triazole, benzimidazole, purine, adenine and derivatives of such heterocyclic organic compounds; Mono- and di- (C ₄ - to C ₂₀ -alkyl) amines, i.e. n-butyl-amine, n-hexylamine, n-octylamine, 2-ethylhexylamine, isononylamine, Alkylamines such as dodecylamine, oleylamine, dn-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, cyclohexylamine and salts thereof; Mono-, di- and trimethanolamines, mono-, di- and triethanolamines, mono-, di- and tri-n-propanolamines and alkanolamines such as mono-, di- and triisopropanolamine .

The use of alkylamines and / or alkanolamines as compounds with corrosion inhibiting action in the additive package of component (C) often results in an additional viscosity reduction of the present functional fluid composition.

In addition to alkylamine ethoxylates and possibly additives with corrosion inhibiting action, further customary additives may be present in the additive package of component (C), for example stabilizers such as pH stabilizers, phenol-thiazines and phenols Antioxidants such as sex compounds, such as hydroxy anisole and bisphenol A, and defoamers and dyes.

Preferably, the additive package of component (C) comprising one or more alkylamine ethoxylates comprises a major portion of an additive having a corrosion inhibiting action and a minor portion of an antioxidant-acting additive and possibly a defoamer and a dye. Lt; / RTI > The proportion of alkylamine ethoxylates in the additive package of component (C) is usually 1 to 100% by weight, preferably 10 to 99% by weight, more preferably 25 to 98% by weight, most preferably 40 To 97% by weight, each based on the weight of the additive package of component (C).

Other than the components (A), (B) and (C), as long as attention is taken to lower the ERBP or WERBP temperature to a superior higher level of the present invention or to not raise the low temperature viscosity above an acceptable level Can be formulated into the functional fluid composition of the present invention. In one example, the functional fluid composition of the present invention may comprise, based on the total weight of the composition, one or more of polyolefins such as, for example, polyethylene oxide, polypropylene oxide, poly (C ₄ - to C ₁₀ -alkylene) - 0 to 20% by weight of a diluent such as an ester or a lubricant.

In the present invention, the three components (A), (B) and (C) are present in the functional fluid composition in the following amounts:

(A) 15 to 90% by weight, preferably 30 to 75% by weight, more preferably 45 to 65% by weight, most preferably 56 to 62% by weight;

(B) 5 to 80% by weight, preferably 20 to 65% by weight, more preferably 32 to 52% by weight, most preferably 36 to 42% by weight;

(C) 0.1 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to 4% by weight, most preferably 1.5 to 2.5% by weight.

All of the above percent values of (A), (B) and (C) relate to the total composition of the functional fluid composition of the present invention or may be a material other than components (A), (B) (B) plus (C) when the diluent and / or lubricant is present in the composition (A). The percent values for (A), (B) and (C) are 100% by weight in each case.

The functional fluid compositions of the present invention exhibit good behavior in terms of ERBP and WERBP temperatures and simultaneously low temperature viscosity performance. Preferably it is at least 260 ° C, more preferably at least 265 ° C, most preferably at least 270 ° C ERBP and preferably at least 180 ° C, more preferably at least 182 ° C, more preferably at least 184 ° C, most preferably at least 187 ° C WERBP.

The functional fluid compositions of the present invention preferably exhibit low temperature dynamic viscosities of less than 700 centistokes ("cSt") (= mm ² / s), more preferably less than 685 cSt, most preferably less than 675 cSt, It is measured at a temperature of -40 ° C.

The functional fluid compositions of the present invention preferably exhibit low temperature dynamic viscosities of less than 4000 cSt, more preferably less than 3000 cSt, most preferably less than 2600 cSt, each of which is measured at a temperature of -50 ° C, Functional fluid compositions exhibit low temperature dynamic viscosities in the range of about 4500 cSt to about 6000 cSt at -50 < 0 > C.

The low viscosity functional fluid compositions of the present invention are particularly useful in automobiles, such as brake fluids, such as new electronic or automated anti-lock braking systems that require low viscous fluids for safe operation, for example passenger cars and trucks, especially at low temperatures.

In addition to the excellent dynamics of ERBP and WERBP temperatures and low temperature viscosity performance, the functional fluid compositions of the present invention have good corrosion protection, good water usability, mild pH values, good stability at low and high temperatures, good oxidation stability, Good dynamic behavior for rubber and elastomer and good lubrication performance.

The following examples are intended to illustrate the behavior and performance of the low temperature functional fluid compositions of the present invention without limitation.

Example

The ERBP and WERBP temperature and dynamic viscosity values of the following functional fluid compositions ("FFC1" and "FFC2") according to the present invention were measured according to the test method described in the Transport Agency Standard FMVSS 116 (corresponding to SAE J 1704). For comparison, the corresponding values of Example 8 of WO 02/38711 ("FFC3"), an embodiment of the best WERPB (i.e., 186 ° C), also measured according to FMVSS 116 were compared to FFC1 and FFC2.

Composition of FFC1, FFC2 and FFC3 [wt%]:

FFC1 FFC2 FFC3

Methyl triethylene glycol borate ester 61.00 61.00 61.00

Methyltriethylene glycol 20.00 20.00 30.50

n-butyl triethylene glycol 17.345 17.145 2.00

Ethyl triethylene glycol 0 0 2.50

Hexyl diethylene glycol 0 0 2.00

Diisopropanolamine 0 1.00 2.00

Octylamine ethoxylate (2 EO unit) 1.60 0.80 0

Toluliazole 0.05 0.05 0

Phosphoric acid ester 0.005 0.005 0

ERBP, WERBP and dynamic viscosity of FFC1, FFC2 and FFC3:

ERBP [° C] WERBP [° C] Dynamic viscosity (-40 ° C) [cSt]

FCC1 277 189 659

FCC2 274 188 670

For comparison

FCC3 265 186 681

FCC2 Dynamic Viscosity (-50 ° C) [cSt]: 2523

Claims (10)

A functional fluid composition comprising:
(A) from 15 to 90% by weight, based on the total weight of the composition, of one or more alkoxyglycol borate esters of the general formula (I)
[R ¹ -O- (CH ₂ CH ₂ -O) _n ] ₃ B (I)
Wherein R ¹ is a C ₁ - to C ₄ -alkyl radical or a radical mixture and n is a value of 2 to 6,
(B) 5 to 80% by weight, based on the total weight of the composition, of one or more alkoxyglycol components of formula (II)
R ² -O- (CH ₂ CH ₂ -O) _m -H (II)
Wherein R ² is a C ₁ - to C ₈ -alkyl radical or the radical mixture, m has a value of 2 to 6, and R ² and / or m are each different or identical to R ¹ and / or n ),
And
(C) 0.1% to 10% by weight, based on the total weight of the composition, of one or more additives having a corrosion inhibiting action, wherein at least one additive contained in the additive package of component (C) is selected from alkylamine ethoxylates Selected. The functional fluid composition of claim 1, wherein the at least one alkylamine ethoxylate contained in component (C) comprises at least one C ₃ to C ₂₀ alkyl chain. 3. The functional fluid composition of claim 1 or 2, wherein the at least one alkylamine ethoxylate comprised in component (C) comprises from 1 to 35 ethylene oxide units. 4. The composition of any one of claims 1 to 3, wherein the at least one alkylamine ethoxylate contained in component (C) comprises at least one linear C ₇ to C ₁₂ alkyl chain and from 1.8 to 9 ethylene oxide units Functional fluid composition. The functional fluid composition according to any one of claims 1 to 4, wherein component (A) comprises at least one alkoxy glycol borate of formula (I) wherein n is a value of 2 to 4. The functional fluid composition according to any one of claims 1 to 5, wherein component (A) comprises at least one alkoxy glycol borate of general formula (I), wherein n is a value of 3 and R ¹ is a methyl radical. The functional fluid composition according to any one of claims 1 to 6, comprising a mixture of alkoxy glycols of the general formula (II), wherein the component (B) comprises singly or mostly of species with m = 3. The functional fluid composition according to any one of claims 1 to 7, which exhibits a dry equilibrium reflex boiling point (ERBP) of 260 DEG C or higher and / or a wet equilibrium reflow boiling point (WERBP) of 180 DEG C or higher. 9. The functional fluid composition according to any one of claims 1 to 8, which exhibits a low temperature dynamic viscosity of less than 700 centistokes as measured at a temperature of -40 占 폚. Use of a functional fluid according to any one of claims 1 to 9 as a brake fluid.