DE1644919C3 - Liquid mixtures - Google Patents

Description

The invention relates to liquid mixtures which are able to withstand mechanical damage These liquid mixtures are to be used to inhibit and keep under control of the parts in contact with each other which have an improved resistance to decomposition and acid formation.

Liquid mixtures that act as functional fluids are used, often have a damaging effect on the hydraulic device. For example, the mechanical components experience all in one hydraulic system, such as the pumps and valves, have a significant decrease in strength and the The geometry of the parts is changed. Such changes may decrease in the case of pumps pump performance and, in the case of valves, malfunction, excessive loss or even create dangerous conditions. This makes premature overhaul more mechanical Parts are necessary, which is costly and time consuming is. In addition, in case of damage, contaminates the metal from the metallic ones mechanical parts that are in contact with the functional fluid, the fluids, what a premature withdrawal of fluids from the system and clogging of the filters leads to a change in the physical and chemical properties of the liquids has. '

There is of course a great need for liquid mixtures that are functionally liquid can be used and the disadvantages outlined above not or at least in one have smaller dimensions than the previously known mixtures.

The invention thus relates to liquid mixtures consisting of a base material and an additive, which are characterized in that they use as base material esters and / or amides of an acid of phosphorus, di- and tri-carboxylic acid esters. Pole·, it he. Most complex. Hydrocarbon materials and or aromatic ether compounds and additives contain heavy water or a water in which the distribution of oxygen and / or hydrogen isotope deviates from the normal distribution.

According to a preferred embodiment of the invention, the liquid mixtures contain, as the base material, an aryl dialkyl phosphate in which each alkali has 1 to 20 carbon atoms. Di butyl phenyl phosphate. an N-alkyl-N-alkyl-N'-alkyl N-alkylarvlphosphordiamidai and or a Gemiscr \ on 1 sooct) ldiphenv! -phosphat and 2-ethylhexyldipheinl-phosphate.

Find the liquid mixtures according to the invention Use as a heat transfer. Power transmission or lubricants.

It is true that liquid mixtures are already known which contain the base materials which are used in the inventive Mixtures contained are similar. These mixtures contain, however, ordinary additives as an additive Water.

Such liquid mixtures are more than satisfactory in terms of their performance characteristics no longer period of time, which is probably due to it It is likely that the base materials are relatively strongly hydrolyzed by the water present will.

Surprisingly, it was found that by Use of heavy water as an additive in the liquid mixtures according to the application instead from ordinary water products can be obtained which have unexpectedly high performance characteristics have a longer period of time.

It was found that damage (including are subsequent damage to a functional fluid and mechanical, with this fluid in Understanding contact with standing parts) in an effective manner by incorporating heavy water into Functionally liquid wedges can be brought under control and inhibited. Under "heavy water" is to be understood here as water, which is any hydrogen isotope, any oxygen isotope or contains any combination of isotopes of oxygen and hydrogen. An important consideration of this invention is that the incorporation of heavy water into liquid mixtures becomes a functional fluid that has the ability. To inhibit damage without affecting the other critical properties of such liquids, like viscosity, oxidative and thermal stability, Corrosion resistance in the presence of metal parts and Sehmier qualities of the functional Adversely affecting liquids.

Examples of heavy water are HOD, D, 0, HO ¹⁸ D. D, O ' ^S. HO ⁿ D. D, O ^r and mixtures thereof. The concentration of heavy water in the functional fluid is adjusted taking into account the particular system and the functional fluid used in that system. The funktioncllen fluids contain heavy water as an additive in einor amount sufficient for inhibiting and controlling yon damage. It has thus been found that the effective amount of additive, ie the concentration of heavy water, is essential for the inhibition and control of damage

is required. in a base material see changes depending on this base material. So howl for the base materials the concentration of heavy water at .from about (UK) S percent by volume to> about I percent by volume, the respective concentration being the amount. which effectively inhibits or controls pardons. The preferred concentration of additive is about 0.10 volume percent to about 5 volume percent heavy water, although 0.005 volume percent to about 10 volume percent have also been found to be satisfactory and effective in inhibiting and controlling damage. Therefore, the present invention includes formulations comprising a functional liquid and a damage-inhibiting amount of heavy water, that is, heavy water is added in an amount sufficient to control and inhibit damage. The liquid mixtures according to the invention can be in any one of. in a manner known to those skilled in the art for incorporating an additive into a base material, such as, for example, by adding heavy water to the base material with stirring until a homogeneous liquid mixture is obtained.

The esters and amides of an acid of phosphorus. which as base materials for the invention Mixtures are suitable have the general formula

R- (Y) ₁₁ -P- (Y ₁ J ₁ -R ₂

35

where Y is an oxygen atom. Sulfur atom and or a

R ₁

ι — N-

40

-Rest

is. Y _{1 is} an oxygen atom, a sulfur atom and or

45

R ₄

-N-

-Rest

and Y, is an oxygen atom. Sulfur atom and or

-N - / - remainder

55

60

R, R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} each an alkyl, aryl, substituted aryl and / or substituted alkyl radical, where R. R ₁ . R ₂ . R ₃ . R ₄ and R _{5 can be the} same or different. X is a sulfur atom and or an oxygen atom and a. h and c are integers with a value from 0 to 1 and the sum of a + h + c is an integer from 1 to 3.

Examples of door alkylresie are:

Methyl, ethyl, n-propyl,

Isopropyl, η-butyl, isobutyl,

sec-butyl-, tert-butyl-, n-amyl-,

isoamyl, 2-methylbuiyl,

2,2-dimethylpropyl-. 1 -Methylbutyl-,

Diethyl methy I-. 1 ^ -Dimethyl-propyi-,

tert-amyl. n-hexyl-. 1-methylamyl-,

1-Ethy I-buiyl-, 1,2,2-trimethyl-propyl-.

3,3-dimethyl-butyl-. U ^ -trimethylpropyi-,

2-methyl-amyl-, l, l-dimethy! -Butvi,

1-ethyl-2-methyl-propy! -,

1,3-dimethyl-bulyl-. Isohexyl,

3-methylamyl-. Ι, '2-dimethyl-butyl-,

I -Methyl- 1-ethyl-propyl-, 2-ethyl-butyl-,

n-heptyl-, l, l, 2,3-tetramethyl-propy! -.

1,2-dimethyl-1-ethyl-propyl-,

1.1.2-trimethyl-butyl-.

1-isopropyl-2-methyl-propyl-,

l-methyl-2-ethyl-butyl-, lJ-diethylpropyl-.

2-methyl-hexyl-, 1,1-dimethyl-amyl-,

-Isopropyl-butyl-, l-ethyl-3-methyl-butyl-,

.4-dimethylamyl-. Isoheptyl,

-Methyl-1 -ethyl-butyl-.

-Ethyl-2-methvl-butyl-. 1-methyl-hexyl-,

-Propyl-butyl-, n-octyl-,

-Methyl-heptyl-,

, 1 - diethyl-2-methyl-prcpyl,

, 1,3,3-Telramethyl-butyl-,

.1-diethyl-butyl-, 1,1-dimethyl-hexyl-,

-Methyl-1 -ethyl-amyl-,

-Methyl-1-propyl-butyl-, 2-ethyl-hexyl-,
o-methyl-heptylliso-octyl) -,
n-nonyl-, 1-methyl-octyI-,

-Ethyl-heptyl-, 1.1 -Dimethyl-heptyl-,

-Ethyl-1-propyl-butyl-.

.l-diethyl-3-methyl-butyl-,
Diiso-butyl-methyl-. 3,5,5-trimethylhexyl-,
3,5-dimethyl-heptyl-. n-decyl,
l-propyl-heptyl-. 1,1-diethyl-hexyl-,
1.1-dipropyl-butvi.
2-isopropyl-5-methyl-hexyS residues and
C ₁₁ _, _M -,

It is also possible that all of the hydrogen atoms, with the exception of the hydrogen atom, are in the 1-position in the above-mentioned alkyl radicals by halogens such as fluorine. Chlorine or bromine, can be replaced or can.

The alkyl or halogenated alkyl radicals mentioned can also have oxy bonds Bonding of two carbon atoms contained in the alkyl or halogenated alkyl radicals.

Examples of aryl and substituted aryl radicals are sine Phenyl. Cresyl. Xylyl, halogenated phenyl, Kresy and xylyl. where the hydrogen atoms on the aryl or substituted aryl radical are partly or wholly through a halogen atom, an o-, m- and p-trifluoromethylphenyl-. ο ·. m- and p ^^^ - trifluoroethylphenyl-, o-, m- and p ^ JJ-Trifluorpropylphenyl- and o-, m- unc p-4.4.4-Trilluorbutylphen) lrest are replaced.

Preferred esters of an acid of phosphorus are base materials in which a, b and c are I. Y. Y ₁ and Y ₁ an oxygen atom and R, R, and R, eir alkyl-. Is aryl or substituted aryl resi. Examples of esters of an acid of phosphorus, i. H

Phosphates Miid Dibutylpheml phosphate. Triphein I-phosphate. Tricresyl phosphate. Tribuu l-pho> ph.tt, tri-2-ethylhe \\] phosphate. Trioctyl phosphate and mixtures of the abovementioned phosphates, such as mixtures son tribute \ l-phosphai and tricresyl phosphate. uiul Mixtures of isooct \ ldiphenjl-nhosphaland2-Ath \ lhexyldiphen> l-phosphate and mixtures of trialkyiphosphates and trikresj! phosphates.

Preferred amides of an acid of phosphorus> ind those in which; '. k and / have the value I and Y, Y ₁ and Y, an oxygen atom

R,

- N- and or

tind. Examples of amides of an acid of Phospho .. namely mono-, di- and tri-amides of an acid of Phosphorus (hereinafter referred to as phosphoramidates) are:

Phenyl methyl N, N -dimethyl phosphoramidate. Phenyl-methyl-N.N-di-n-butyl phosphoramidate. Mixtures of

Phenyl-m-kr-syl-N.N-dimethylphosphoramidate and

Phenyl-p-kresvl-N.N-dimethylphosphor-

amidate.
Mixtures of

m-cresyl-p-kiesyl-N.N-dimethylphosphoramidate.

Di-m-kres \ l-N, N-dimethylphosphoramidate and

Di-p-kresyi-N.N-dimethylphosphoramidate. Di-m-bromophenyl-N-methyi-N-n-but \ l-

phosphoramidate.
Di-m-chlorophenyl-N-methyl-Nn-butyl-

phosphoramidate.
Di-unu-trifluoro-m-cresyl-N-methyl-

Nn-butyl-phosphoramidate,
Di-p-bromophenyl-N-methyl-Nn-isoamyl-

phosphoramidate,
Di-p-chlorophenyl-N-methyl-Nn-isoamyl-

phosphoramidate,
p-chlorophenyl-m-bromophenyl-N-methyl-

N-n-isoamyl phosphoramidate. Phenyl-N-methyl-N-butyl-N'-methyl-

N'-butyl-phosphorodiamidate, phenyl-N.N-di-n-butyl-N'.N'-di-n-butyl-

phosphorodiamidate,
Phenyl-NN-dimethyl-N'.N'-dimethyl-

phosphorodiamidate,
m-chlorophenyl-N-methyl-Nn-butyl-N'-methyl-

N'-n-butylphosphorodiamidate, m-bromophenyl-N-methyl-N-n-butyl-N'-methyl-

N'-n-butyl-phosphorodiamidate, «, (Mi-trifluoro-m-kresyl-N-methyl-N-n-butyl-

N'-methyl-N'-n-butylphosphorodiamidate, p-chlorophenyl-N-methyl-N-isobutyl-N'-methyl-

N'-isoamyl-phosphorodiamidate, p-bromophenyl-N-methyl-N-isobutyl-

N'-methyl-N'-isoamyl-phosphorodiamidate, N-methyl-N-butyl-N'-methyl-N'-butyl-

N "-methyl-N" -butyl-phosphorus triamidate. Ν-methyl-N-butyl-N'-N '' - tetramethyl-

phosphorus triamidate,
N-di-n-Propyi-N ', N "-tetramethyl-

phosphorus triamidate and
N, N'-di-n-propyl-N "-dimethyl phosphorus triamidate.

Examples of phosphinate esters are:

PhenyJ-di-n-propyi-phosphinate, phenyl-di-n-butyl-phosphinate, Phenyl-di-sec-butyl-phosphinate, phenyl-di-n-pentyl-phosphinate,

Phenyl-di-neopentyl-phosphinate, Phenyl di-n-hexyl phosphinate, phenyl di-n-butyl thiophosphinate. p-methoxyphenyl di-n-butyl phosphinate. m-chlorophenyl-di-n-butyl-phosphinate, Phenyl (n-propyl-n-pentyl) phosphinate, phenyl (n-propyl-n-butyl) phosphinate. Phenyl- (n-propyl-n-hexyl) phosphinate, phenyl- (n-butyl-n-pentyl) phosphinate, phenyl- (n-butyl-n-hexyl) phosphinate, Pheny! - (n-pentyl-n-hexyl) phosphinate, phenyl- (neopentyl-n-propyl) phosphinate, phenyl- (neopentyl-n-butyl) phosphinate, Phenyl- (neopentyl-n-hexyl) phosphinate, thiophenyl-di-n-propyl-phosphinate, Thiophenyl-di-n-pentyl-phosphinate, cresyl-di-n-pentyl-phosphinate, tert-butylphenyl-di-n-butyl-phosphinal, n-butylphenyl-di-n-butyl-phosphinate, sec-butylphenyl-di-n-butyl-phosphinate, Ethyiphenyl-di-n-butyl-phosphinate, xylyl-di-n-butyl-phosphinate, Thiophenyl-di-n-hexyl-phosphinate, thiophenyl-di-n-butyl-phosphinate, Thiophenyl-di-n-propyl-thiophosphinate, thiophenyl-di-n-butyl-thiophosphinate, Thiophenyl-di-n-pentyl-thiophosphinate, thiophenyl-di-n-hexyl-thiophosphinate, Thiophenyl- (n-propyl-n-butyl) phosphinate, thiophenyl- (propyl-n-pentyl) phosphinate, Thiophenyl- (n-propyl-n-hexyl) phosphinate, thiophenyl- (n-butyl-n-pentyl) phosphinate, Thiophenyl- (n-butyl-n-hexyl) phosphinate, thiophenyl- (n-pentyl-n-hexyl) phosphinate, Thiophenyl- (n-propyl-n-butyl) thiophosphinate, thiophenyl- (n-propyl-n) thiophosphinate, Thiopheny! - (n-propyl-n-hexyl) thiophosphinate. Thiophenyl (n-butyl-n-pentyl) thiophosphinate. Thiophenyl (n-butyl-n-hexyl) thiophosphinate and thiophenyl-fn-pentyl-n-hexyOthiophosphinate.

Orthosilicates which can be used as base materials are tetraalkyl orthosilicates. wicTetraloctyOorthosilicates.

R _x -O-Si

R ₁₁ - (O) ₁₁₁

ο — χ

<O) ₁₁₁

- (O) ₁₁ -R ₁₃

Tclra (2-ethylhexyl) orthosilicate and the Teiraiiso octyl orthosilicates and those in which the isooeulireste of isooctyl alcohol. which originates from the Oxovcriahren, and the (Trialkoxysilico) trialkyl-orlhosilik; ite. sometimes as hexalalkoxy) disiloxanes. such as Hcxal2-äthylbutoxy) disiloxane and hexa (2-äthylhexoxy) disiloxane.

The preferred tetraalkylithosilicates and hexa- (alkoxy) disiloxanes are those in which the alkyl or alkoxy radicals have 4 to 12 carbon atoms and in which the total number of carbon atoms in the orthosilicate is 16 to 60.

In addition to the hexa {alkox \ idisiloxanes mentioned above other hexa (alko \ y) disiloxanes in which the aliphatic radical of the Alkoxy radical, for example, an I-ethylpropyl-. 1,3-dimethylbutyl, 2-methylpentyl-, 1-methylhexyl-, I-ethylpentyl, 2-butylhexyl and l-methyl-4-äthyloctylrest is.

The orthosilicates and AlKow-pohsiloxane can by the general formula

are represented in the R _s . R ₉ and R ₁ , are each an alkyl, substituted alkyl. Aryl, substituted aryl and can be identical or different, O is an oxygen atom. Si is a silicon atom. X a coal

35 material atom and or a silicon atom. into an integer, namely 0 or 1. / ι is an integer from 1 to about 200 or more and if X is a carbon atom / »ι is 0. η is I and R ₁₁ . R ₁ , and R ₁ , each a water slippery valley. an alkyl, substituted AIkU-. Arvl- and substituted Arvl radical L-,

imi

\ Silicon nt

111 I \ <i \

η is an integer from 1 to about 200 or more and R ₁₁ . R ₁ and R _{1 can} each be an alkyl, substituted alkyl, aryl and substituted aromatic radical.

Examples of substituted aryl radicals are an o-, m- and p-chlorophenyl-, o-. m- and p-bromophenyl-. O-. m- and p-fluorophynyl-. ".". "- Trichlorocresyl-,". "." - Trifluorocresyl-. XyIyI- and o-, m- and p-cresylrcsl.

Siloxanes or silicones which can be used as base materials are given by the general formula

R,

Si-O

I.
R ₁ ,,

-Si-R ₁₉

RlK

shown in the R ₁₄ . R ₁₅ . R ₁₁₁ . R ₁ -. R _1x and R _{19 can} each be an alkyl, substituted alkyl, aryl and substituted Arvl radical and / 1 'is an integer from 0 to about 2 (XK) or more. Examples of alkyl and haloalkyl radicals are those described above. Examples of siloxanes are poly / methyl isiloxane. Poly (methyl, phenyl isiloxane, poly (methyl, chlorophenyl) siloxane and poly (methyl, 3.3.3-trifluoropropyl) siloxane.

Examples of substituted aryl radicals are an o-. m- and p-chlorophenyl-, m- and p-bromophenyl-. o-, m- and p-fluorophenyl, ".". '/ - trichlorocresyl-. .!. iMi-trifluorocresyl-. O-. m- and p-cresyl and XyIyI residues.

Di- and tri-carboxylic acid esters suitable as base materials are given by the general formula

Il

CO

ρ \ Λ

shown in the ο. ο ', ρ and ρ are each integers from 0 to 1, provided. that the sum of each ο + ρ and a + ρ 'is equal to 1. A is an integer from 1 to 2. R ₂ ″ and R _{22 are} each alkyl, cycloalkyl, substituted alkyl. Alkenyl, substituted alkenyl, aralkyl, substituted aralkyl. Aryl and substituted aryl, and R ₂₁ can be hydrocarbon and substituted hydrocarbon. Examples of alkyl, aryl, substituted alkyl and substituted aryl radicals have been listed above.
Examples of di- and tri-carboxylic acid esters are:

Di (2-ethylhexyl) azelate
Di (2-ethylhexyl) sebacate,

Di-isooctyl sebacate

2-ethylhexyl-3: 5: 5-trimethylhexyl sebacate.

Di-isooctyl azelate,

Di (3: 5: 5-trimethylhexyl) sebacate.

Di (1-methyl- ^ äthyloctyljsebacat.

ν R ₂

Diisodecyl azelate.
Diisotridecyl azelate.

Did-methyl- ^ äthyloctyUglutarate.

Di (2-ethylhexyl) adipate.

Di (3-methylbutyl) azelate,

Di (3: 5: 5-trimethylhexyl) azelate.
DK2-ethylhexyl) adipate,

Di (C, _p -oxo) -adipaU

bis (diethylene glycol monobutyl ether) adipate.

Di- (isooctyl / isodecyl) adipate,

Diisotridecyl-adipai, Triethylene glycol di (2-ethylhexanoate).

Hexanediol-l, 6-di (2-ethylhexanoate) and

Dipropylene glycol dipelargonate.

Further examples are mixtures of esters derived from an aliphatic dibasic acid and a mixture of technical alcohols, such as a mixture of alcohols obtained by the oxo process.

609 619/68

Suitable polyesters as base materials are given by the general formula

10

L. I. (
j - O -R ,, I. I.
C. C -R. _4th O
Ij - C ■ - il
c — o -CH: C. H ₂ CH ₂ -IOi ₁ , - C) /. C. ----- 5 O _

in which R _{2 is} a hydrogen atom and or an alkyl radical. R ₂₄ and R ₂₅ each represent an alkyl substituted alkyl. Cycloalkyl-. Aralkyi-. Aryl and / or substituted aryl radicals, α is an integer from 0 to 1, α is an integer from 0 to 1. Z is an integer from 1 to 4. and when Z is 1 - α is 0. and R, “an acyloxy and or substituted acyloxy radical, and when Z is 2 to 4, α is I. and R _{s is} an acyl and / or substituted acyl radical.

Polyesierverbindungen can be made by reacting an acid compound with a polyhydroxy compound be prepared, the polyhydroxy compound trimethylolpropane. Trimethylol ethane, i'ntaeryt.irü ;;!, DipcinücryilniiuL Tripentaeryihritoi and tctrapenlaerythritol can be.

The acids that can be used are aliphatic monocarboxylic acids, acyclic monocarboxylic acids, aromatic monocarboxylic acids and heterocyclic monocarboxylic acids. like propionic acid. Butyric acid. Isobutyric acid. n-valeric acid, caproic acid. n-heptylic acid. Caprylic acid. 2-ethylhexanoic acid. 2,2-dimethylheptanoic acid and pelargonic acid. Examples of esters of this type are esters of trimethylolpropane (I mol) with monocarboxylic acids 13 mol), for example trimethylolpropane tri-n-octanoate. l: su-r of pentaerythritol (1 mol) with monocarboxylic acids (4MoI). Esters of di- or tripentaerylhntol (1 mole) with mono-carboxylic acids (6 or 8 moles). Examples of alkyl, substituted Alkyl, aryl and substituted aryl radicals are above been stopped.

Other esters which are also suitable as base materials are hydrocarbon monoesters with an ester group. Isooctyl stearate and 2-ethyloxyloetoate are typical examples of this.

Complex esters suitable as base materials are given by the general formula

O O

Il! I

, - O - C - R ₂₈ - c - O

shown, in which R ₂ - and R _{iu are} each a hydrogen atom, an alkyl, substituted alkyl. Alkenyl, substituted alkenyl. Aryl, substituted aryl, cycloalkyl, substituted cycloalkyl and / or a carbocyclic radical having 6 to 10 carbon atoms. R ₂₈ and R 9 are each alkylene, substituted alkylene. Alkenylene. substituted alkenylene. Phenylene and or substituted phenylene radical and .v is an integer from 1 to about 80.

Examples of complex esters can be obtained by esterifying dicarboxylic acids with a mixture of a monohydric alcohol and a glycol are obtained with the formation of complex esters.

Complex esters that can be used can by esterification of a dicarboxylic acid (1 mol) with a glycol (2 mol) and a monocarboxylic acid (2 mol) or with 1 mol each of a glycol, a dicarboxylic acid and a monohydric alcohol or with 2 moles each of a monohydroxy monocarboxylic acid and a monohydric alcohol will. Further complex esters can be obtained by esterification of a glycol (1 mol) with a mono-hydroxymonocarboxylic acid (2 moles) and one monocarboxylic acid mole).

Further complex esters, which are suitable as base materials, are polymerized by a Dihydroxy compound with a dicarboxylic acid and Implementation of the terminal hydroxyl and acid ester made with a mixture of a monocarboxylic acid and a monohydric alcohol. Examples lur polymers that can be used as additives and polymers that can be used as additives of adipic acid and 1,2-propanediol in the presence a smaller amount of short-chain mono-carbon

acidic and e.nem monohydric alcohol with formation before. Molecular weights of the olymensates produced here from about 700 to about 40,000 or higher were manufactured.

The mono-, di- and polyhydric alcohols and the

so used in the manufacture of the complex esters Carboxylic acids can also contain ether-oxygen bonds.

Examples of suitable complex esters are those of

1 }? *? ' ^{(1 mol} > - adipic acid (2MoI) and

2-Ethyhexanol (2MoI, esters manufactured by

Isth 5 ^yg ? ^{ko1 (1 mol)} <sebacic acid (2 mol) and i'iS ^y , ^eX ? u ^{O1 ll MoI)} esters produced: the esters produced by 7, a -> χ ί ³ , i ^exandio1 Π mol), sebacic acid (2MoI) and 2-ethylhexanol (2 mol, esters: the

of diethyl glycol (1 mole), adipic acid (2 moles) and n-butanol (2 moles): those of Polyglvkol 200 (1 mol), sebacic acid (2MoI) and Athy en-g! Ykol-mono (2-ethylbutyl) -ether (2 mol) produced Ester: that of sebacic acid (1 mole). Tetra

ethylene glycol (2 mol, and caproic acid (2 mol) esters produced: those of triethylenegh'kol (1 mol) ,? l ™ ^UTe C ^Mo! >. n-caproic acid Π mol) and exanol (1 mol, produced Ester: that of

aJ ^

2856

11 *

Sebacic acid (I mole). Esters produced by lactic acid (2MoI) and n-butanol (2 mol): those of tetraethylene glycol Moles), lactic acid ^ minor and butyric acid (2 moles) esters produced: those of neopentyl glycol (2MoI), dicarboxylic acids (1 mol) and monocarboxylic acids (2MoI) produced complex esters

and that of neopentvl glycol (1 mole). Dicarboxylic acids 12 mol) and monohydric neoalcohols. for example 2,2,4-trimethylpentanol (2 moles) prepared complex ester.

Other base materials that are suitable as base materials are represented by the general formula

-ti-

in which A. A ₁ , A ₂ and A _{3 are} each a chalcogen with an atomic number of 8 to 16. each t / is an integer from 1 to 5. each pure integer from 1 to 4, X, X ,, X ₂ , X, and X _{4 are} each a hydrogen atom, an alkyl, haloalkyl. Halogen, arylalkyl and or substituted arylalkyl radical. x. y and r are each integers from 0 to 8 and e is an integer from 0 to 1, provided that when e is equal to zero. y can be 1 or 2. Examples of alkyl and substituted alkyl radicals have been listed above. Examples of such base materials are the 2 to 7 rings containing ortho-, meta- and para-polyphenyl ethers and mixtures thereof, 2 to 7 rings containing ortho-, meta- and para-polyphenyl thioethers and mixtures thereof, mixed polyphenyl ether thioether compounds, in which at least one of the _{chalcogens represented by A, A 1} , A 2 and A ₃ is different from one of the other chalcogens. dihalogenated diphenyl ethers. such as 4-bromo-3'-chlorodiphenyl ether and bis-phenoxybiphenyl compounds and mixtures thereof. It is also possible for the phenyl and phenylene radicals of the aromatic ether compounds described above to be partly or wholly substituted by a heterocyclic group such as thiophene or pyridine. Such heterocyclic radicals can contain 4 to 10 atoms, which are optionally interrupted by 1 to 4 heteroatoms, such as oxygen, nitrogen and sulfur.

Examples of the polyphenyl ethers mentioned are the bis (phenoxyphenyl) ethers, for example bis (m-phenoxyphenyl) ethers, the bis (phenoxyphenoxybenzenes, for example m-bis (m-phenoxyphenoxybenzene, m-bis (p-phenoxyphenoxy) benzene. O-bis- (o-phenoxyphenoxy) benzene, the bis (Phenoxyphenoxyphenyl) ether, for example, up [m-im-I ^J-henoxyphen 3xy) phenyl] ether, bis [p- (p-phenoxyphenoxy) phenyl] -ither, m - [(m -Pheooxyphenoxy) - (o-phenoxyphenaxy)] ethers and the bis (phenoxyphenoxyphenoxy) benral, for example m-bis [m- (m-phenoxyphenoxy) - ± enoxy] benzene, p-bis [p- (m-phenoxyphenoxy) phenoxy ] benzene, m-bis [mp-phenoxyphenoxy) phenoxy] -benzene and mixtures thereof with other polyphenyl ethers.

Examples of polyphenyl thioethers and mixed Polyphenyl ethers and thio ethers are:

2-phenylmercapto-4'-phenoxy-diphenyl-sulfide,

2-phenoxy-3'-phenylmercapl: odiphenyl-suIfid, o-bis (phenylmercapto) benzene, phenylmercaptobiphenyl, bis (phenylmercapto) biphenyl, m-im-chlorophenylmercaptoJ-m-phenyl-

mercapto-benzene,

Phenylmercapto- (phenoxy) biphenyl, m-chlorodiphenyl sulfide, bis (o-phenyl mercaptophenyl) sulfide, m-bisim-pnenyl mercaptophenyl mercaptoJbenzene,

l, 2.3-tris (phenylmercapto) benzene, 1 - phenylmercapto-2,2-bis (phenoxy) benzene, o-bisio-phenylmercaptophenylmercaptojbenzene, m-bisip-phenyl mercaptophenyl mercaptoJbenzene. 2,2'-bis (phenylmercapto) diphenyl ether,

3.4'-bis (m-Tolylmercapto) diphenyl ether. 3,3'-bis (xylylmercapto) diphenyl ether, 3,4'-bis (m-isopropylphenylmercapto) diphenyl

ether, S ^ '- bisfp-tert-butylphenylmercaptoJdiphenyl-

ether, 3,3'-bis (m-chlorophenylmercapto) diphenyl-

ether,

3,3'-bis (m-trifluoromethylphenyl mercapto) diphenyl ether,

3,4'-bis (m-perfluorobutylphenylmercapto) -

diphenyl ether, 2-m-tolyloxv-2'-phenylmercaptodiphenyl-

sulfide,

o-bis (phenylmercapto) benzoL - bis (m- phenylmercaptophenylj-sulfide,

m-phenyl mercaptophenyl-p-phenyl mercaptophenyl sulfide.

£ 856

the trisphenyl mercaptobenzenes, v.ie

], 2,4-tris-phenylmercaptoben.iol.

3,3'-bis (phenylmercapto) biphenyl.

m-bisfp-phenyl mercaptophenyl mercaptolben / .ol.

m-bisfm-phenylmercaptophenylmercaptolbenzene, to [m- (m-phenylmercaptopheny] mercapto) -

phenyl] sulfide,

3.3'-bis (phenylmercapto) diphenyl ether.
3.3'-bis (phenoxy) diphenyl sulfide,
3-Phenoxy-3'-PhenyImercaptodiphenyI-sulΓld.
3-Phenylmercapto-3'-phenoxy <: iipheny] ether.
3.4'-bis (phenylmercapto) diphenyl ether.
m-bis (m-phenyl mercaptophenoxy) benzene.
3-phenylmercapto-3 '- (m-phenylmercaplo-

phenylmercapto) diphenyl ether.

Other breakable base materials are mono- and di-alkythiophenes.

Examples of thiophenes are:

2,5- (1-Hexyl-1-methylnonyydthiophene.

2,4- (1-hexyl-1-methylnonyl) thiophene.

2-tert-butyl-thiophene,

2,5-tert-butyl-thiophene,

2,5- (1,1-dimethylpropyl) thiophene.

2,5- (1-butyl-1-octyl nonyl thiophene.

2,5- (l-propylcyclobutyl) thiophene,

2-tert-butyl-4- (l-octyi-l-methyloctadecyD-

thiophene.

2,5- (l-methylcyclohexyl) thiophene,
2,5- (l-Octy! -L-methyldecyl) thiophen,
2,5- (1,1-dimethyltridecyUthiophene,
2,3- (1.1-dimethyltridecylthiophene,
2.4- (II-dimethyltridecyl) thiophene.
2.4- (l-MethylcyclopentyI) thiophene and
2.5- (In-dodecylpentyl) thiophene.

Hydrocarbon materials such as mineral oils. Heating or Fuel oil and types of kerosene are also suitable as base materials.

The following examples illustrate the invention.

in Examples 1 to 4, a nickel sample was immersed in a test liquid and vibration of 20 kilohertz in this sample. The test time was 45 minutes.

In all of the following examples the test temperature was 85 C. With relative weight loss is the total weight loss of the metal sample when tested in the liquid, which contains the additive present in each case divided by the weight loss of the metal sample if the liquid tested without the presence of an additive Is χ 100. A relative weight loss below 100 thus means that less metal has been removed from the sample when the additive is in a certain Base material was included, and therefore illustrates that liquid mixtures in which Heavy water is incorporated, inhibit damage and keep it under control.

table

example

I-liquid

Addi Vo- % tiv lum- Relat. Per- Ge zenl weight Addi loss tiv in River sig wedge

Dibutyl phenyl phosphate D ₂ O 0.50 89

68% tributyl phosphate D ₂ O 0.50 79 20% tricresylphenyl

phosphate
7.5% 2-ethylhexyl

sebacat
4.5% Acryloid VI-

Improvers

45% mixture of
5 rings having polyphenyl ether

55% m-dibromobenzene

N-methyl-N-butyl-

N'-methyl-N'-butyl-

phenyl phosphorodiamidate

D ₂ O 0.50 49

D ₂ O 0.50 65

It was found that this is to be determined

relative damage, test drivers used well with the actual test runs on the test stand of a simulated hydraulic system like the Fairey test stand.

The Fairey Test Stand is a closed hydraulic

Iical system in which the test conditions correspond to the actual Simulate fluid pressures and temperatures that would occur in a missile Such a test stand is for the purpose of testing hydraulic fluids and hydraulic loading

components have been used.

Similar results are obtained with other types of heavy water, such as HOD, HO ¹⁸ D, D ₂ O ¹⁸ . HO ¹⁷ D and D ₂ O ¹⁷ obtained.
In addition, a further test was carried out to determine the acidity of water compared to heavy water. The test consisted of placing 200 ml of a liquid sample in a stainless steel bomb in which metal test samples made of aluminum, cadmium, copper, iron and metal

contained magnesium. The bomb at 149 ° C for 72 hours let routing. The base material used in Table II was dibutylphenyl-phosphaL. The percentage reduction in the acid number was determined after the

determined by the following formula:

Reduction (%) = ^{acid number H} 2 ° ~ acid number heavy water

Acid number H ₃ O

100

2856

table H Conc
tration.
Weight
percent Sätire / ahl ⁰ O acid
number.
Down
settlement at
game Additive 0.50 14.27 5 H ₂ O 0.50 6.63 54 6th D ₂ O

'5

It has been found that the above bomb test compares well with the actual conditions to which a hydraulic fluid is exposed corresponds. This test has proven itself in the Evaluation of high temperature hydraulic fluids proven useful. Such temperatures actually occur in hydraulic systems currently in use.

The data in Table I and Table II show a significant inhibition of damage caused by the incorporation of heavy water into a base material is achieved, and the relative reduction the acid build-up when using mixtures according to the invention. Beyond that the physical properties and the operational characteristics such as lubricity, fire resistance and viscosity is not adversely affected by the additive.

As can be seen from Table I, the are functional Liquids with heavy water incorporated into them are effective for inhibition and control of damage to parts in contact with such liquids. the The effectiveness of heavy water in inhibiting and controlling damage is about of the same order of magnitude as that of water, i.e. H. of water that has no isotopes of hydrogen or oxygen contains. Thus, even at inhibiting and controlling damage, water is more mechanical Parts and functional fluids effectively. However, due to the presence of water a disadvantageous side effect occur in functional fluids, which under certain conditions promotes acid build-up. Such acid build-up can result in increased chemical reactivity of the liquid entail, leaving mechanical parts of the chemical substance

45 are attacked. As a result of the increased chemical reactivity of the liquid, seizure, wear and tear and changes in the tight tolerances of mechanical parts can occur. Premature overhaul or repair of mechanical parts and increased chemical reactivity can be a direct consequence of the acid build-up. It is therefore of particular importance that acid build-up be controlled in order to extend the life of the fluid in a functional fluid system. As can be seen from Table II, the incorporation of heavy water into a functional fluid not only has the effect of keeping it under control and inhibiting damage, but also has an approximately 54% reduction in acid build-up over the same base material in which water of the same concentration is incorporated is the consequence. Thus, heavy water improves and controls acid build-up to a far greater extent. This improvement leads to functional mixtures with extended service life, with acid build-up and damage being inhibited and brought under control.

It is also possible that the base materials described above either individually or as a mixture can be used with two or more base materials in different proportions. The base materials can also contain other liquids - in addition to those described above functional fluids - contain fluids derived from carbon products and synthetic ones contain oils, for example alkylene polymers such as polymers of propylene, butylene, etc., and Mixtures thereof, alkylene oxide polymers, such as propylene oxide polymers and derivatives thereof including alkylene oxide polymers obtained by polymerization have been prepared from alkylene oxide in the presence of water or alcohol, e.g. B. Ethyl alcohol, alkylbenzene, for example mono-alkylbenzene, such as dodecylbenzene, tetradecylbenzene, etc., and dialkylbenzenes such as n-nonyl-2-ethylhexylbenzene; Polyphenyls, such as biphenyls and terphenyls, halogenated benzene, halogenated lower alkylbenzene, mono-halogenated diphenyl ethers, trialkylphosphine oxides, Diarylalkyl phosphonates, trialkyl phosphonates, aryl dialkyl phosphonates and triaryl phosphonates.

Claims (5)

Patent claims: 1. Liquid mixtures, consisting of a base material! and an additive, thereby characterized in that they are used as the base material Esters and or amides of an acid of phosphorus. Di- and tricarboxylic acid esters. Polyester. Most complex. Hydrocarbon material and or aromatic Ether compounds and, as an additive, contain heavy water or a water in which the Distribution of oxygen and / or hydrogen isotopes deviates from the normal distribution. 2. Liquid mixture according to claim I. characterized in that it is a base material Aryl dialkyl phosphate. in which every Alk)! rest I bis Has 20 carbon atoms. Dibutyl phenyl phosphate. an N-alk> 1-N-alkyl-N'-alkyl- ~ N'-alkyl-arylphosphorodiamidate and or a mixture of isooctyl diphenyl phosphate and 2-Aih \ Ihex \ I-; ° contain diphenyl phosphate. 3. Use of the liquid mixture according to claim 1 or 2 as a heat transfer medium. 4. Use of the liquid mixture according to claim 1 or 2 as a power transmission medium. 5. Use of the liquid mixture according to claim 1 or 2 as a lubricant.