DE1644928B - Functional fluids - Google Patents

Description

2 Functional fluids according to claim 1. characterized in that they are used as a component A is a mixture of polyphenyl ethers or a polyphenyl thioether or a mixture of contain at least one polyphenyl ether and at least one polyphenyl thioether.

3. Functional fluids according to Claim 1, characterized in that "they are used as polyphenyl ethers contain a phenoxy biphenyl.

4. Functional liquids according to claim I. characterized in that they are a polyphenyl ether with five aromatic hydrocarbon residues

5. Functional liquids according to claim 1, characterized in that they are the aromatic Compound in an amount of 10 to 90 percent by weight and the halogenated compound in one Amount of 90 to 10 percent by weight included.

6 functional fluids according to claim 1, characterized in that they are dihalogenated Diphenyl ether contain 3,4'-dibromodiphenyl ether and, as halobenzene, m-dibromobenzene.

7. Functional liquids according to claim 1, characterized in that they are polyphenyl ethers with five aromatic hydrocarbons and perchlorobutadiene.

8. Functional fluids according to claim 1, characterized in that they are polyphenylthioether and perchlorobutadiene.

9. Functional liquid wedges according to claim 1, characterized in that they are a polyphenyl * ether with five aromatic hydrocarbons · » contain residues and rri-dibromobenzene.

The present invention relates to new functionalities Liquids containing mixtures of certain aromatic compounds and certain halogenated compounds.

Many different materials have been used as functional fluids, and functional Liquids were used for different purposes. Such liquids have been used as electronic coolants, coolant door nuclear reactors, pirfasjonspu.mpen & fluids, synthetic lubricants, Damping fluid chains, base materials for greases, power transmission fluids (hydraulic fluids) and used as filter media for door air conditioners. Because of the multitude of uses and conditions under which functional fluids are used will necessarily vary the properties desired in a good functional fluid with the respective area of application, in which they are to be used. The respective area of application makes a functional one Liquid with a specific KJas.se of properties required.

The use of functional fluids as Hydraulic fluids, particularly as hydraulic fluids for missiles, have now arguably been used proved to be the most difficult area of application. So until a few years ago the Required nits for a hydraulic fluid for missiles can be described as follows: The hydraulic Power transmission system stars of missiles for operating various mechanisms of an aircraft place stringent requirements on the hydraulic fluid to be used. The hydraulic fluid for missiles must not only withstand heavy loads, but they should not if possible Be flammable or so little flammable in accordance with the fire resistance regulations for aircraft to be able to suffice. The liquid must have such viscosity properties that it has a wide temperature range can be used: d. h .. it must have a correspondingly high viscosity at high temperature, low viscosity at low temperature and have a small amount of viscosity change with temperature. Such a temperature range is generally from -40 to 121 C. Its pour point should be low. Their volatility should also be low and at the elevated working temperatures be balanced: i.e. there should be no selective evaporation or volatilization of any major Component occur at high working temperatures. The liquid must be a * - sufficient Lubricity and mechanical stability have to under the difficult conditions Can be used in self-lubricating pumps. Valves etc. of the hydraulic star of missiles. The liquid should also be thermally and chemically stable, especially s < Ute them to be stable to oxidation and decomposition. It should also be used in the event of strong and sudden changes in pressure and temperature strong shear forces and, in the case of famous

which metals such as aluminum, bronze, Copper and steel, retaining the desired properties. You should also not remove the seals and packings destroy the hydraulic system and not the materials that make up the respective Systems are manufactured adversely affect and in the event of a leak also not disadvantageously the various parts of the missile with which it is unfortunate in contact could come (for example the cick-

H fresh cable insulation and the color). It should not be toxic or harmful to people who come in contact with this liquid.

The evolution of commercial, super-sonic transport (UST) has now made demands on any of the hydraulic fluids used in this context, which would satisfy the earlier requirements appear to be completely unproblematic, "

A UST flight control or control system is with regard to their construction is much more complicated than the equivalent facility of a current commercial one Aircraft, since the UST system has both excellent flight control and control characteristics at below-sound as well as at over-sound velocities must have. It is estimated that a Mach 3 UST missile is roughly half its Time under ascent, entry and approach conditions does. In addition, as far as the developments the past and the present convey any clues to expect the hydraulic Functions under UST conditions more numerous are greater than those of current commercial jet engines. Everything indicates that the commercial UST with about 1000 hydraulic horsepower / u. This increased need of horsepower used to power accessories. Landing gear and control systems is needed. in itself requires considerable consideration with regard to the reliability of the hydraulic Liquid.

Besides the factor of Zah 'of constituents ¹ parts still the factor of high temperatures, where such a system is subject plays. a role. The surface temperatures of a 3 Mach missile are in the range of 232 to 316 C or higher in stagnant locations. Taking advantage of natural heat dissipation (such as in the case of fuel) in a manner used in the B-70, the hydraulic system should be operable with a fluid at an operating temperature of 204 to 260C. At the other end of the temperature range, lower temperatures such as -51.1 C. are to be expected.

The Commercial Jet Hydraulic Panel of SAE A 6. which 1% 1 for investigation and recommendation purposes to improve the current fire resistance The hydraulic systems introduced by jet engines, noted.! ate two One third of all accidents involving hydraulic systems occurred during an iVa-year period up to June 1962 external leakage of the system, mainly from parts such as pipes, fittings, Fogging, hoses and seals. This leakage problem is in terms of the control and the Control by force is of great importance. Under UST conditions, however, the meaning would be the leakage problem can be significantly increased beyond the loss of control by force, if the temperature problems that exist here are also taken into account *. Here is no longer that Given a situation in which the leakage fluid escapes into a relatively cold area, but occurs instead into an area having a temperature of, for example, 316 ° C. One in a hot room injected flammable liquid would - an intolerable condition - ■ explosion or torch-like ignite. A * <s for this reason, a fire-resistant liquid is of greater importance than ever.

The main problem, which is consequently facing the corresponding liquids manufacturing industry is the development of a UST-liquid which has a temperature compatibility in the range of -45.6 C to about ¹ 204 to 260 C together with fire resistance. In addition, a hydraulic fluid for UST use must have the above-mentioned properties including good viscosity characteristics (over a reasonably extended temperature range), low freezing point, low volatility, adequate lubricity, no toxicity, and compatibility with various metals. Seals and packings.

Taking into account the regulations of the numerous manufacturers of cells for UST purposes are the requirements expected for hydraulic fluids for UST purposes and similar supersonic missiles the following:

Hydraulic Fluid Requirements for UST Purposes

characteristic

viscosity

■ -45.6 C

204 C

Crystallization point

Thermal stability (isoteniscope)., ... ,,,

Fire-resistant wedge

Molten aluminum test,

677 ⁰ C,

Hot Manifold'Test (AMS 3150 C),

High pressure spray test (AMS 3150 C + No> 4 type)

Volatility (boiling point),
Extended ignition
Temperature,

requirement

35,000 cSt or less
0.5 cSt or more
- 45.6 C minimum
260 "C

Does not ignite without a spark

Self-extinguishing with ignition spark

Does not burn when leaving the Rölif or in the Pan,

Does not flare up to a distance of 152 cm
From the nozzle, may flare up below 152 cm, but is most extinguishing
26O ⁰ C

PREFERRED TC

6 ^y

Although at first it appears as if there are not too preferred aromatic materials

It could be difficult to meet these aforementioned requirements sln4 those that are exclusively from AUwSmW-

to fulfill for ÜST purposes, the sfoffatame bound aromatic hydrocarbons are actually

Exceedingly high demands consist of various scraps of material. The Phenoxybiphenjle, like

Founding For example, there are few if over- 5 Biphenyipbenoxyphenyläther, Biphenylyloxybonzo),

main, individual ^ compounds, which via the pis (BiphenylylojcyphenyI) ether, to {Phenaxy) biphenyl

extreme temperature range of at least 288 ° C u _r the like. serve as an example,

Remain useful (this means thermal stability. A class of preferred aromatic materials

of -45.6 ° C [crystallisation point] to 26O ⁰ C). represent the polyphenyl ethers of the formula

A few have such a useful _{? 0} η υ η ir π η ι ΓΗ

range, are fire-resistant and have '<~ 6 " ₅ υ lV ₆ n ₄ ^u h ^L 6 ⁿ s

also the desired viscosities, in which 11 is an integer from 1 to 5,

It is accordingly the object of this invention to provide examples of such polyphenyl ethers are the bis (phenfunctional Developing liquid containing an oxyphenyl) ether, (4-aromatic, in a chain through

Combination of properties, such as liquid state, ₅ 3 oxygen atoms bonded hydrocarbons

over a wide range and fire resistance carbon residues), among which bis (m-phenoxyphenyl) ether

ability to exhibit. In particular, those and the bis (phenoxyphenoxy! Benzenes are intended as examples

functional fluids are made available. Examples of the bis (Phent_v yphenoxy! Benzenes

which are suitable as hydraulic fluids m-bis (m-phenoxyphenoxy) benzo ;, m-bis (p-phen-

are, but particularly suitable for missiles, entirely _ao oxyphenoxy! benzene, o-bis (o-phenoxyphenoxy) benzene

generally, preferably for missiles with over, etc. In addition, include those possible here

Speed of sound. Polyvinyl ether which bis (Phenoxyphenoxy phenyl lather

It has now been found that functionally like bis [m-im-phenoxyphenoxy) phenyl] ether, bis-

Liquids. which for the above purposes [p- (p-phenoxyphenoxy) phenyl] ether and m- (m-phen-

the excellent properties mentioned above are ₂₅ oxyphenoxy (phenyl, m- (o-phenoxyphenoxy (pheny! -

sit, have the following composition: you ether and the bis (phenoxyphenoxyphenox \ (benzene,

stand from such as m-bis [m- (m-phenoxyphenoxy) phenoxy] benzene.

A) aromatic compounds of the groups p-bis [p- (m-phenoxyphenoxy) phenoxy] benzene and

1. one or more Po.yph-nyläther ^ Ä ^^^ SSSJSSSgc-unien

2. have one or more polypheny thioather ³ ether bonds in the meta position, since the

3. one or more dihalogenated diphe _{exclusive meta} . _bound ether especially vornyiainer unaoaer. are sometimes hard, its wide liquid range TndiSe Weeën ^{of exemplary halOgemerter Phen0X} ", and because ihrohohen thermal stability. However, ^py 35, mixtures of polyphenyl ether. either

_n ^a . ^s,, . ,. ,,,. , isomeric mixtures or mixtures of homolons

With one or more halogenated compounds, _{ethers are advantageous in some} areas of application

groups are used, especially in the areas

and from _{properties which may be determined in different colors} , such as lower

1. Halobenzenes. 40 consolidation points are desirable.

2. Perhalodienes. with not less than 4 and in particular, mixtures of polypheny 1-not have more than 8 carbon atoms and ethers. in which the non-terminal phenyl groups

3. Perhalocyclodienes with no less than 4 rings due to oxygen atoms in the meta- and para and not more than 8 carbon atom positions are bonded as particularly suitable

C) usual additives. 45 proven to create preparations with wide

Fluid areas. Among the mixes with only

Invention-> according to preparations can any meta and para bonds is a preferred poly

a combination of aromatic materials and nylon ether mixtures of this invention make up the mixture

halogenate, compounds described above, on bis (phenoxyphenoxy) benzenes. in which they are not

which lead to a viscosity of no longer 50 terminal phenylene rings due to oxygen atoms

than about 3500OcSt at -45.6C. The mei- are bound in the meta- and para-positions and

Most preparations according to the invention are made up of approximately 65 percent by weight of m-bis (m-phen-

about 10 to 90 percent by weight of aromatic veroxyphenoxy (benzene. 30 percent by weight in [m-Plu-n-

bonds of the type mentioned above or mixtures oxyphenoxyI ip phcnoxyphcnox>)] benzene and 5vie-

of these compounds and about 90 to 10 weight percentages of m-bis (p-Phcno \ yphenoxy | benzene to-

percent of one of the halogenating compounds mentioned under B). Such a mixture solidifies

bond or mixtures thereof exist. below room temperature (ei. h, unterha} b approximately

So now hydraulic fluids 21, TC), whereas the three components are separate

found that the strict requirements for aircraft at temperatures above normal room temperature

at supersonic speeds by doing this, 60 temperature solidifying.

that materials are combined with each other that Other examples of such preferred poly-

Phenyl ether mixtures which are unsuitable as individual for the stated purpose are those containing approximately 0 to

are, however, in connection with the 6 weight percent o-bis (m-phenoxyphenoxy) benzene described herein

under halogenated compounds to a high degree (1), about 40 to 85 percent by weight m-bis (m »phen-

Liquids with surprisingly superior self-65 oxyphenoxy) benzene (2), about 0 to 40 weight

properties (temperature range and fire resistance percentage ffl - [(m-phenoxyphenoxy) (p-phenoxyphenoxy)

Ability) in comparison with the separately used oxy-benzene (3), approximately 0 to 12 percent by weight

Components result. p-bis (m-PH; noxyphenoxy) benzene (4), about 0 to

10 weight percent p - [(p-phenoxyphenoxy) (nvphenoxyphenoxy)] benzene (5) and about 0 to 6 percent by weight of fn - bis (p - phenoxyphenoxy) benzene (6).

The preferred polypheriyl ether freshness are listed below. The numbers in parentheses mean those previously mentioned, with the same Numbered connections.

Typical preparations

Zubercitunecn A. B. Weight percent D. 3c component Components in 0 6th C. 4.5 63 82 5 43.5 (D 31 0 80 40 (2) 0 12th 4th 4th (3) 0 0 11th 8th (4) 6th 0 0 0 (51 0 (6)

II

III

IO

Another class of materials used in the hydraulic fluids of the invention can be used are the polyphenylthioether. The term "polyphenylthioether" as used herein includes compounds or mixtures of compounds of the general formula

30th

35

wherein m is an integer from 0 to 6, wherein A and A 'are independently oxygen and / or sulfur and at least one of A and A' Sulfur is. the general formula

40

45

wherein A and A 'are each oxygen and / or sulfur, of the general formula

50

where χ and y are integers from 0 to 3 and the sum of. \ - + y is I to 6 and A and A 'are each oxygen and / or sulfur, but at least one of A and A' is sulfur, and the i

55

general - formula -A ' Γ J £ s ) " (RJ π (R ₁ ) (R ₂ ) " ΠΙ / λ / K -A- O -A "- λ / "V

60

65

IV wherein R ₁ , R ₂ , R ₃ and R ₄ . each alky], alkoxy, halo-

Ϊ wherein said alkyl and Alkoxygfüppen VOFI 1 to 4 carbon atoms AIIF \ veiseh ₄ is hydrogen Uend / ödef halogen, A _t A 'and A "are each oxygen and / odef sulfur, provided that at least one of A, A' and A "is sulfur,)? I and / ι are integers from 0 to 3, provided that the sum of ι» + »i is at least 1, to be understood.
Examples of such polyphenylthioethers are:

i-Phenylmercapto ^ '- phenoxydiphenyl-sUlfid, 2-phenylmercapto-3'-pheno \ ydiphenyl sulfide, 2-phenoxy-3 ■ -phenylmercaptodiphenyl-sulf ^ d.

S-phenoxy ^ '- phenylmercaptodiphenyl sulfide, 2-phenoxy-4'-phenylmercaptodiphenyl-sulfide, 4-phenoxy-4'-phenylmercaptodiphenyl-sulfide, 2-phenoxy-2'-phenylmercaptodiphenyl sulfide, o-bis (phenyl mercaptolbenzene.

m-bis (phenyl mercaptolben / ol.

p-bis (phenylmercapto) ben7 (il.

Phenyl mercaptodiphenyl.

bis (Phepyimercapto) biphenyl.

Phenylmercapto (phenoxy) biphenyl.

bislo-phenyl mercaptophenyl sulfide.

bislp-PhenylmercaptophenyDsi'lfid.

bislm-phenylmercaptophenyllsulnd.

1.2.3-tris (phenylmercapto) benzene.

l-Phenylmercapto-2,3-bis (phenoxy! benzene.

1.2.4-tris (Phen> Imercapto) benzene.

1,3,5-tris (phenylmercajjio) benzene.

o-bisfo-PhenylmercaptophenylmercaptolbenzoI, p-bis (p-phenylmercaptophenyl mercaptolbenzene, p-bisfo-phenylmercaptophenylmercaptolbenzene, p-bisfm-phenylmercaptophenylmercaptolbenzene, m-bislp-phenyl mercaptophenyl mercaptoJbenzene, o-bis (p-phenylmercaptophenylmercapto) benzene, ar-bis (phenylmercapto-ar '- (phenylmercapto) -benzene.

2.2'-bis (phenylmercapto) diphenyl ether. 2.3'-bis (phenylmercapto) diphenyl ether. 2.4-bis (Phenylmercapto) diphenyl ether, 4.4-bis (m-Tolylmercapto) diphenyl ether, 3.3-bis (m-Tolylmercapto) diphenyl ether. 2,4'-bis (m-Tolylmercapto) diphenyl ether, 3.4'-bis (m-Tolyimercapto) diphenyl ether, 3,3'-bis (p-Tolylmercapto) diphenyl ether, 3.3'-bis (xylylmercapto) diphenyl ether, 4.4'-bis (xylylmercapto) diphenyl ether, 3,4'-bis (xylylmercapto) diphenyl ether, S ^ '- bisfm-IsopropylphenylmercaptoJdiphenyl-

ether,
3,3'-bis (m-isopropylphenylmercapto) diphenyI-

ether.
l ^ '- bisfm-lsopropylphenylmercaptojdiphenyl-

ether,
3 _r 4'-bis (p-tert-butylphenylmercapto) diphenyI-

ether,
4,4'-bis (p-tert-butylphenylmercapto) diphenyI-

ether,
3,3'-bis (p-tert-butylphenylmercapto) diphenyl-

ether.
3,3'-bis (m-di-tert-butylphenyl mercapto) -

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

4,4'-bis (m-chlorophenyl mercapto) diphenyl ether, 3,3'-bis (m-trifluoromethylphenyl mercapto) diphenyl ether.

4,4'-bis (m-trifluoromethylphenylniercapto} -

diphenyl ether,
3.4 '. * Jis {m-Trifluormeihylphenylmercapto) -

diphenyUether.
2,3'-bis (m-trifluoromethylphenylmercapto) -

diphenvl ether.
! M'-bislp-trifluoromethylphenyl mercapto) -

diphenvl ether.
3,3'-bis (o-rifluoromethylphenylmercaptci) -

diphenyl ether.
Bj'-bislm-methoxyphenylmercaptoldiphenyl-

ether.
S ^ '- bislm-Isopropoxyphenylmercaptoldiphenyl-

ether.
3,4'-bis (m-perfluorobutylphenyl mercapto) diphenyl ether.

2-m-Tolyloxy-2'-phenyimercaptodiphenyl-sulfide, 2-p-Tol>loxy-3'-phertylmercaptodiphenyl-sulfide, 2-o-tolyloxy-4-phenylmercaptodiphenyl-sulfide, 3-m-Tol> loxy-3 ' -phenylmercaptodiphenyl-sulfide, Sm-tolyloxy ^ -phenylmercaptodiphenyl-suIfid, 4-m-Tol \ loxy-4'-phenylmercaptodiphenyl-sulfide, 3-xylyloxy-4'-pherylmeΓcaptodiphenyl-sulnd _< SXvlyloxy-sulfaptid'-phenyl-mercaptod'-phenyl-mercaptodiphenyl 3-Phenoxy-3'-rn-tolylmercaptodiphenyl sulphate. S-phenoxy ^ '- m-tolyl mercaptodiphenyl sulfide. Z-phenoxy ^ -p-tolyl mercaptodiphenyl sulfide. S-phenoxy ^ -m-is ^ propylphenylmercapto-

diphenyl sulfide.
3-phenoxy-3'-m-isopropylphenyl mercapto-

diphenyl sulfide.
Sm-tolyloxy-Sm-isopropylphenylmercapto-

diphenyl sulfide.
4-m-Trif ^ uormethylphenoxy-4 ■ -phenylmercapto-

diphenyl sulfide.
Sm-trifluoromethylphenoxy ^ '- phenylmercapto-

diphenyl sulfide,
2-m-trifluoromethylphenoxy-4'-phenylmercapto-

diphenyl sulfide.
3-m-Trifluormethy Iphenox y-3'-phenylmercapio-

diphenyl sulfide,
Sp-chlorophenoxyO'-phenylmercaptodiphenyl-

sulfide and
Sm-bromophenoxy ^ '- phenyl mercaptodiphenyl sulfide.

Io

20th

35

40

45

Another class of aromatic materials which can be used in the preparations according to the invention are dihalogenated diphenyl ethers. either alone or as base materials in conjunction with certain mixing agents. The dihalogenated diphenyl ethers have the general formula 3-Bron>2'-chlordipheny lather,
3-bromo-2'-chlorodiphenyl sulfide, S-bromine ^ V-ehiordiphenyl-ether.
S-BromO'-chlorodiphenyl sulphate. S-Bfom ^ '- chlorodiphenyl ether. .VBromo ^ '- chlorodiphenyl sulfide, 4-bromo-3-chlorodiphenyl ether. 4-bromo-3 -chlordiphenyl sulfide, 4-bromo-4-chlorodiphenyl ether, 4-BiOiri-4-chloro Certified ^'i-enyl sulnd, 4-bromo-2 -chlordiphenyläther and 4-bromo-2'-chlordiphenyl- sulfide.

(2) with the same halogen on each ring:

2,2'-Dihromodiphenyl ether. 2,2'-dibromo

diphenyl sulfide.
2,3-dibromodiphenyl ether. 2,3'-dibromo

diphenyl sulfide.
2.4'-dibromodiphenyl ether. 2.4'-dibromo

diphenyl sulfide.
3.3'-Dibromodiphenyl ether. 3.3'-dibromo

diphenyl sulfide.
3.4 -dibromodiphenyl ether, 3.4-dibromo-

diphenyl sulfide,
4,4-dibromodiphenyl ether. 4.4'-dibromo

diphenyl sulfide.
2,2'-dichlorodiphenyl ether, 2.2'-dichloro

diphenyl sulfide.
2,3'-dichlorodiphenyl ether. 2,3 '^ dichloro

diphenyl suifid.
2,4-dichlorodiphenyl ether. 2,4'-dichloro

diphenyl sulfide.
3,3'-Di <: chlorodiphenyl ether, 3,3'-dichloro

diphenyl sulfide.
S ^ '- dichlorodiphenyl ether. 3.4'-dichlorodiphenyl sulfide.

4.4'-dichlorodiphenyl ether and 4,4'-dichlorodiphenyl sulfide.

The ethers are generally preferred over the sulphides because they are lower because of their lower Melting points are useful in a wider variety of uses. From the ethers are in turn those ethers in which the halogen substituents are in the 3,4'-connection, preferred in the functional fluids according to the invention used because their melting points are the lowest of all ethers.

In addition, another class of aromatic compounds is used in the present invention functional fluids are used, namely certain pyridine derivatives the general formula,

wherein A is oxygen or sulfur and X and Y are bromine or chlorine.

Typical examples of such ethers and sulfides are

(1) with different halogen on each ring:

l-bromo-l'-chlorodiphenyl ether,

2-bromo-2'-chlorodiphenyl sulfide, I-bromo-S'-chlorodiphenyl ether,

l-bromo-S'-chlorodiphenyl sulfide, 2-bromo-4'-chlorodiphenyl ether,

Z-bromine ^ '- chlorodiphenyl-suIfid.

where A is oxygen and / or sulfur, R5 and R _{6 are} each fluorine, chlorine and / or bromine, c is an integer from 0 to 2, d is an integer from 0 to 5 and where the sum of c 4- d 1 to 7. Mixtures of these compounds are also used. The preferred compounds of the formula VI have the above structure in which R ₅ and R _{n are} each bromine and / or chlorine and the sum

from d + c is 1 to 3, provided that when c + d is I , R ₅ or R _{6 is} Brorri,

The pyridine derivatives can be prepared (1) by reacting an alkali metal salt of a 3 ^ hydroxypyridine with halogen-containing benzene or urhge ^ returns (2) by reacting an alkali metal salt in phenol with a halogenated pyridine, in ♦ velchcin is a halogen in the 3-position. for The compounds in which A is sulfur. d. H. fc-phenyl mercaptopyridines. be the same general Procedures used except that in method (1) a 3-mercaptotoyridine in place of 3-hydroxypyridine and in process (2) a thiophenol in place of a phenol Is used. To facilitate the production of both types of connections, an inert Solvents can be used.

Examples of in the preparations according to the invention useful pyridine derivatives are

3- (2'-bromophenoxy) pyridine,

3- (3'-bromophenoxy) pyridine.

3- (4'-bromopheno) .y) pyridine,

3- (3'-fluorophenoxy) pyridine.

3- (3'-chlorophenylmercapto} -5-chloropyndine and 3- (4'-Chlorophenylmercapto) -5-chloropyridine.

The halobenzenes which can be used in the preparations according to the invention have the general formula

VII

where T is bromine. D is chlorine and 'or fluorine, e is an integer from 0 to 2 and / is an integer from 0 to 6. provided that e is at least 1. if / is less than 6. and provided that. when / is 0, e is 2 . It has now been found that p-dibromobenzene and brominated benzenes with more than 2 bromine atoms per benzene nucleus have very limited solubility in the aromatic constituents of the preparations according to the invention and for this reason cannot be used. However, mixtures of mono-bromobenzene with higher brominated benzenes, in which the average bound bromine content of the mixture has at least 2 atoms of bromine per benzene nucleus, can be used in preparations according to the invention and are referred to as halobenzene, but are not preferred.

Typical examples of halobenzenes which can be used in preparations according to the invention are

o-dibromobenzene,

I-bromo-3-chlorobenzene,

I J-dichloro-S-bromobenzene,

1 J-Difluor-S-bromobenzene,

1 -Fluoro-S-chloro-S-bromobenzoL

I ^ J ^ -Tetrachloro-S-bromobenzene,

l ^ J ^ tetrafluoro-S-bromobenzene,

1, j-dibromo-S-chlorobenzene,

1, ß-dibromo-S-fluorobenzene,

O-dibromo ^ S-dichlorobenzene,

1, S-dibromo- ^ o-difluorobenzene,

Hexafiobenzene.

Hexachlorobenzene and preferably

m-dibromobenzene.

The perhalodienes and perhalocyclodienes useful in the invention are those compounds having at least 4 and not more than 8 carbon atoms in the molecule. Typical Perhabdienc are Perchlorobutadiene, Perbfombutadicn, Perfiuorbutadien, Perchlorpenladien, Perfiuofperttadien, Perbrompentadien. Perchlorhexadiene, perbromhexadiene, perchlorheptadiene, perchloroctadiene, perbromooctadiene and perfluorooctadiene. Perchlorobutadiene will

ίο preferred. Typical perhalocyclodienes are perchlorocyclobutadiene. Perfluorocyclobutadiene, perchlorocyclopentadiene. Perbromocyclopentadiene, perfluorocyclopentadiene, Perchlorocyclohexadiene, perbromocyclohixadiene. Perchlorocycloheptadiene, perchlorocyclooctadiene and perfluorocycloocladia.

Typical properties of the aromatic materials described above are given below in Tables listed. To determine the various Properties of the fluids of the present invention were determined by the following tests or procedures accomplished:

Determination of viscosity according to
ASTMD-445-61.

Determine the automatic ignition temperature according to ASTM D-2155-63 T.

In addition, the solution or melting point of the preparations according to the invention were also determined measured. Since the preparations of the present invention are easily supercooled (also like the constituents), crystallization points are difficult to determine. However, after the solution point and crystallization point coincide with each other. the release point was generally measured.

Solution points were determined by placing the preparations to be examined in a test tube which was equipped with a stirrer. The device was immersed in a well-insulated dry ice-acetone bath. The dry ice-acetone bath was kept at a temperature in the range of -34.4 to -45.6C. This temperature range was deemed high enough to avoid the formation of a glass and low enough to accelerate the potential crystallization. After a test preparation was stirred for about 8 hours, seedlings of one of the ingredients were added. The germinated preparation was then stored in a cold container at -45.6 ° C for hours and then stirred in the dry ice-acetone bath for 8 hours. The entire process was then repeated. Those mixtures which did not crystallize after a week were warmed to room temperature to render the liquids pourable and then placed in small bottles with lids. The bottles were then stored at -51.1 ⁰ C.

The thermal stability of the ingredients and formulations of this invention were rated with a Isoteniscope according to the method of Blake and Coworkers, J. Chem. Eng. Data, 6.87 (1961). When a liquid in the isoteniscope device is heated, it exerts a vapor pressure. which can be easily measured. The steam pressure increases with the rise in temperature. according to a straight line function when the logarithm of the pressure versus

the reciprocal value of the absolute temperature is applied. The vapor pressure curve will move away from a straight line when decomposition occurs to form volatile products. The temperature at which this decomposition occurs is called the decomposition temperature (T ₀ ).

Table I.

connection

A mixture of m-bis (m-phenoxyphenoxylbenzene. 65 percent by weight: m - [(m-phenoxyphenoxy)
(p-phenoxyphynoxy)] benzene.
30 weight percent: m-bis (p-Phcn '
oxyphenoxylhcrizole. 5 percent by weight

A mixture of m-bis (phenyimercaptolbenzene. 31 percent by weight;
m-phenoxy-m-phenyl mercaptobenzene. IS weight percent;
m- (m-phenylmcrcapto) benzene.
45 percent by weight; m-chlorodiphenyl sulfide. 8 percent by weight

3,3'-dichlorodiphenyl ether

4-Bromo-3-chloro-diphenyl-ether. . .

3.3'-dibromo-diphenyl ether

3,3'-dichlorodiphenyl suIfid

3-Bromo-4-chloro-diDhenyl sulfide

m-bis (phenylmercapto) benzene

m-bis (Phenylmercaptophenyl) suIfid ..

tn-bis (m-phenoxyphenoxy) bcnzoI ....

tn-bis (phenoxyphenyl) ether

bis (phenylmercapto) biphenyl

m-bis (phenoxy) benzene

3- {2'-bromophenox> ipyridine

J- (3'-bromophenoxy | pyridine

3- (3'-fluorophenoxy ipyridine

SolutionS '

Point

"C

IZ2 22.22 28.9 13.9 40.0 1-4.44

boiling point

-c

295.56

38S

354

333.89

382

220 / oj ¹ )

260 / oj ')

_293/25 ") 241.67 / u

205 to

250 / _0J , ₅ ')

163 / _2J ')

Therm. -40 ° C * 99 C Flame * Fire stability Glass 37.8 ° C 13.1 Point Point ¹ C > 5000,000 363 2.77 "C 'C 1,972 12.41 1.27 288 349 11,680 3.77 1.46 207 260 400 4.37 1.60 319.44 2,320 6.10 1.47 324.44 4.55 1.66 363.33 35,000 3.05 (-28.9 ° C) 12.4 5.92 11.307 50.8 12.7 3.37 6.00 62.0 19.03 2.62 12.4 1.69 (-34.4 ° C) 7.47 1.60 9.220 6.13 519.1 1.15 3.29

AZT
"C

613

499

') mm Hg.
AZT = autogenous ignition temperature.

Although the compounds previously listed in Table I are a combination of physical Have properties that make them well suited for use as functional fluids, in most cases they are inadequate with regard to any property that affects their commercial properties Limited applicability. The problem with which the present invention is concerned is therefore the discharge of functional fluids that including the aforementioned combination of properties have good fire resistance, but also with regard to properties, such as low or high viscosity depending on the temperature or solution point are improved. The problem can also be in the case of those aromatic materials which does not have the desired fire resistance

; »Ways to improve their 'fire resistance without affecting the viscosity and thermal stability.

Furthermore, there is a need to obtain good liquid properties at low ones Temperatures. The solution to the problem mentioned has now been found by combining the aromatic compounds described above with certain halogenated compounds. Typical Properties of these halogenated compounds are listed in Table II below.

Table II

connection -40 ^c C Viscosity, cSt
37.8 "C 99 ^r C AZT
⁰ C Flash point
⁰ C Fire point
° C m-DibromobenzoI
Hexachlorobutadiene
Hexachlorocyclopentadiene fixed
fixed 0.866
1.479 -
2.99 0.467
0.724
1.03 621
593 no
no
no no
no

Numerous attempts have been made to measure the fire resistance of the fluids present conducted because there is no single trial that evaluates all types of fluids can be used under all expected conditions of use. The degree of fire resistance in any of the experiments is influenced by the characteristics of the liquid, the type of flame or ignition source, the total amount of liquid, the physical state the fluid and many other factors.

The original technical committee, which dealt with the development of fire-resistant hydraulic Liquids for aircraft dealt with, realized the numerous factors involved in loading mood the fire resistance must be taken into account. As a result, the SÄE and the military developed various methods of testing flammability in regulations of the suggested products.

These regulations include the same general types of fire resistance tests. In the investigations, the conditions occurring in aircraft were simulated, with A hydraulic fluid was sprayed from a damaged pipe into various ignition sources is, at annt as the "high pressure spray test" and the "hot manifold test". The experimental procedures for

Measurement of the fire resistance of the invention Preparations were as follows;

Hot Mam'fafd test AMS 3! 50 C

High pressure spray test AMS 31 -0 C

Functional fluids preferred according to the invention consist of certain polyphenyl ether and m-dibromobenzene, such preparations contain Preferably about 45 to 65 percent by weight

ίο m-dibromobenzene and about 35 to 55 percent by weight Polyphenyl ether or mixtures of polyphenyl ether. Liquid preparations that are in high Dimensions suitable for use in aircraft with supersonic conditions consist of ungeiinr 50 to 60 percent by weight m-dibromobenzene and approximately 40 to 60 percent by weight polyphenyl ether or mixtures of polyphenyl ethers.

Of particular importance are the viscosities of the preparations according to the invention of this invention, d. H. Preparations containing certain polyphenyl ethers and m-dibromobenzene have excellent Viscosity characteristics throughout occurring in aircraft with supersonic conditions Temperature range (-45.6 "C to 316'C). This finding is surprising in view of the Viscosity characteristics of the polyphenyl ethers and m-dibromobenzene, respectively, as described above.

Table II 2,000 8.21 2.14 8,500 7.6X 2.04 29,000 2.05 AZT
C. H: <t Manifold Test High pressure spray test Not flaring up preparation
Components I. 621 With interruption or burning until ~ z \ n mixture of m-bis (m-phen- Weight J,. . ... _
Percent V, skositat. cSt
Ingredients! - ^ Ci 37.8 CI 99 C gen burning ent 244 cm from the ox «phenoxy iben / ol. 65 ge 45 long edge bead. jet »Ichispro / cnt: m - [(m-phenoxy- when sprayed phcnoxyi ip-phenoxyphenoxyi] - Not flaring up Kcnzol. Ό ( weight percent. ! or burning. m-bisip Phenoxyrlicnoxvibenzol. if on pot 5 percent by weight (manifold) I ■ drips Not flaring up m-f) ihrom benzene j ι 621 With interruption or burning until a mixture of m-to (m-Phcn- 55 13.1041 genes burning 244 cm from the ■> «.;. phenoxy ibenzene. 65 Gc- 44 lan £ Rjndvvulst. jet «'Ihtvpnven !: m - [(m-phcnoxy- t uenn \ rrrspruhi phcni'xM (p-phenoxyphenoxy |] - Not flaring up hcn / ol Vi percent by weight. or burning. m-hisip-Phenoxyphenoxv ibenzol. J if on pot * Weight percent imanifoldi up drips i Not flaring up m-dibromobenzene 627 No flaring up. or burners !. '4 tJibromitiphenvlather 56 no burning up to 244 cm mn S7 the nozzle m - [) ihromhen / <i | hin Ciemisih from m-to (m-Phen- 13th oxyphenoxylbenzene. 65 Ge 37.5 weight percent; nv [(rri-Phcnoxy- pncnoxyi (p-phenoxyphcnoxy)] - benzene. Weight percent: ni-bisip-Phononyplienoxylbenzol. 5 percent by weight Mcxachlorbutadicn 62.5

The preparations according to the invention also have good Schhiiercigenschaftcii, as shown in the Investigations of these preparations with a four-ball machine obtained results can be seen.

Typical examples are listed below in Table IV. The preparation unit corresponds to the The preparation listed in the fit table has the same number.

Table JV

preparation load Scar diameter, rome 1200 rpm kg 600UpNf 0.59 1 10 0.45 1.36 50 0.77 UOl 2 10 0.74 1.25 50 1.02

IO

Test conditions
Steel on steel balls, 1 hour at 149 ^a C.

In addition, the preparations according to the invention are stable to shear and do not tend to foam, and any foam that is formed is not stable. In addition, the claimed preparations are stable even at temperatures of 316 C and under oxidizing conditions. In essence, they are non-corrosive to metals. like aluminum. Bronze, iron, silver and titanium. Another advantage of the preparations according to the invention is their extraordinary hydrolytic stability, as can be seen from the information in Table V below. The results shown in Table V were obtained by subjecting various fluids to an experiment to determine the hydrolytic stability and corrosion. In this experiment, a sample of a test liquid is placed in a stainless steel container together with weighed metal samples in the form of 12.7 x 25.4 χ T, 59 mm metal plates with a surface area of 75 cm exposed to the liquid. These samples were immersed in the liquid from the top of the container and were held apart by a glass spacer. The metals used were titanium, aluminum, silver, iron, copper and stainless steel. Water was added to the liquid in an amount of 0.5 percent by volume based on the liquid used. The "container" was connected to a device which rotated the container overhead. The device and the container were placed in an oven at 232 ^° C., in which the container rotated for 72 hours. At the end of this experiment, the metal samples were removed, rinsed to remove non-adhering material, dried and weighed to determine the weight loss or weight difference of the samples compared to the original weight before the test. The results obtained are listed below in Table V, as weight change in milligrams per square centimeter of surface area the preparation listed in Table III with the same number. The mixtures of polyphenyl ethers used in Preparation I had little or no effect on the metal samples.

^Tl i table Al V -0.14 Cu; SS preparation + 0.06 I. + 0.19 -21.74 -0.19 y + 0.04 1 + 8.34 j + 14.44 Weight change, mg ent
Ag Fe + 6.15 -0.37 m-dibromobenzene + 1.92; -L 4.75!

From the results listed in Table V it can be seen that, surprisingly, Preparation I. a preferred formulation of this invention did not reduce the weight of the iron sample, although the main ingredient of the preparation, d. H. m-dibromobenzene. himself, when he was examined individually, as proved to be extremely corrosive to iron. As mentioned earlier, they were in preparation 1 polyphenyl ether used little or no effect on any of the metallic. When examined individually.

As a result of the excellent ph) sicans Properties of the functional fluids of the invention can improve hydraulic pressure devices be made, which in communication with each other a liquid chamber and a Include operating fluid according to the invention in this chamber. In such a hydraulic device tion. in which a moving part is driven by the radio fluids described above operating characteristics are obtained that satisfy the currently available are superior.

Because of the excellent fire resistance wedge, because of the exceptionally low pour points and because of the good lubricating effectiveness of the invention functional fluids, these can be used in such hydraulic systems in which power has to be transmitted and the filing systems stressed by friction the hydraulic fluid used must be lubricated. So find the new invention functional fluids use in the transmission of power in a hydraulic System in which a pump supplies the power for the system. The parts lubricated in this way are involved it is the friction surfaces de: energy source, namely the pump, the valves, the control piston of the cylinder and the liquid motors. (Liquid motor. are usually piston pumps with constant or variable discharge that are driven by the Pressure of the hydraulic fluid of the system with the energy generated by the pump energy source is supplied to be caused to rotate

Such a hydraulic motor can be used in conjunction with a variable discharge pump to form a variable speed transmission). In some cases, t. B. in machine tools, it is the guides. Tables and slideways. The hydraulic system can either have a constant or a variable volume.

The pumps in which the radioactive fluids according to the invention are used can be of various types: t. B. the crfindurigsgemäße liquids in the piston pump, in particular in the piston pump of variable stroke, or in the piston pump of variable discharge

644 328

variable displacement, in the radial jvolbenpiimpe, in the axial piston pump, in which a rotatably mounted or reciprocating cylinder block at different angles with the piston arrangement is set, for example in the Vl'ckers axial piston pump or in a pump, in which the mechanism that drives the pistons in one The angle that can be set with the cylinder block is in a gear pump, which is a spur gear, helical gear or herringbone gear or Has variations of Tnnenyerzhnungen, or in a screw pump or in an impeller pump be used.

The liquids can also be used in valves, e.g. Stop valves, switching valves, switching or control valves, Prosseive valves, in-line valves or relief valves be used.

The functional fluids according to the invention dyes, pour point lowerers, ', stabilizers, Antioxidants, viscosity index improvers, lubricity effectiveness; (ordering funds and the like included.

Claims (4)

Claims; e, in particular hydraulic fluids, consisting of ■■ # A) aromatic compounds of the groups 1. one or more polyphenyl ethers, 2. one or more polyphenylthioethers, 3. one or more dihalogenated diphenyl ethers and / or 4. one or more halogenated phenoxypyridines; B) one or more halogenated compounds of the groups 1. Halobenzenes. 2. Perhalodienes with not less than 4 and not more than 8 carbon atoms and 3. Perhalocy clodiene with not less than 4 and not more than 8 carbon atoms and off if necessary C) usual additives.