DE2131926A1 - Hydraulic fluids with a content of quaternary phosphonium salts - Google Patents

Hydraulic fluids with a content of quaternary phosphonium salts

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Publication number
DE2131926A1
DE2131926A1 DE19712131926 DE2131926A DE2131926A1 DE 2131926 A1 DE2131926 A1 DE 2131926A1 DE 19712131926 DE19712131926 DE 19712131926 DE 2131926 A DE2131926 A DE 2131926A DE 2131926 A1 DE2131926 A1 DE 2131926A1
Authority
DE
Germany
Prior art keywords
alkyl
composition according
acid
ester
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DE19712131926
Other languages
German (de)
Inventor
Gentit William Frederick
Fred Jaffe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stauffer Chemical Co
Original Assignee
Stauffer Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Publication of DE2131926A1 publication Critical patent/DE2131926A1/en
Pending legal-status Critical Current

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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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    • C10M137/12Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
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Description

RECHTSANWALTSLAWYER

DR. JUS. DIPL-CHEM. WALTER BEIL· DR. JUS. DIPL-CHEM. WALTER BEIL

ALFiMCD MC)L=PPENER 2^1 Juni ALFiMCD MC) L = PPENER 2 ^ 1 June

DA. JUR. DiPL-CHtM. H.-J. WOLFP -.THERE. JUR. DiPL-CHtM. H.-J. WOLFP -.

DR. Jüü. HANS CHS. BEILDR. Jüü. HANS CHS. AX

FRANKFTT AM MAIN-HOCHSTFRANKFTT AM MAIN-HOCHST

Unsere' Nr. 17156Our 'No. 17156

Stauffer Chemical Company New York, N.Y., V.St.A.Stauffer Chemical Company New York, N.Y., V.St.A.

Hydraulik-Flüssigkeiten mit einem Gehalt an quaternärenHydraulic fluids containing quaternary Phosphoniumsalzen »Phosphonium salts »

Die Erfindung bezieht sich auf Hydraulik-Fluids, die zur Verbesserung ihrer Eigenschaften bestimmte quaternäre Phosphoniumsalze von Phosphorsäuren enthalten.The invention relates to hydraulic fluids that contain certain quaternary phosphonium salts of phosphoric acids to improve their properties.

Es ist eine Vielzahl von funktionellen Flüssigkeiten für die Verwendung in den hydraulischen Systemen von Flugzeugen bekannt. In diesen hydraulischen Systemen werden die hydraulischen Fluids stark beansprucht. Außerdem müssen sie schwer entflammbar sein, um den behördlichen Vorschriften zu entsprechen. Hinzu kommt, daß die hydraulischen Fluids ihren Dienst in den hydraulischen Systemen über eine sehr lange Zeitdauer versehen müssen, ohne die verschiedenen Leitungen, Ventile, Pumpen usw. zu beschädigen, welche von ihnen durchflossen werden.It is a wide variety of functional fluids for use in aircraft hydraulic systems known. In these hydraulic systems, the hydraulic fluids are heavily stressed. Besides, they have to be flame retardant to comply with government regulations. In addition, the hydraulic fluids have to provide their service in the hydraulic systems over a very long period of time, without the various lines, Damage valves, pumps etc. through which they flow.

109882/1264109882/1264

Es ist verschiedentlich von Schaden berichtet worden, die an Ventilen und anderen metallischen Teilen auftreten, welche mit Phosphatester enthaltenden Flüssig keiten in Berührung kommen. Diese Schaden äußern sich in der Abnutzung von Metallteilen. Für die Erklärung dieser Erscheinungen und die Lösung der Probleme wurden verschiedene Überlegungen angestellt. Man sprach von Hohlraum bildung, Erosion, Korrosion und anderen Erscheinungen an den Metallteilen eines hydraulischen Systems. Eine Lösung, die zur Überwindung dieses Problems angeboten wurde, be steht darin, in dem Fluid einen geringen Prozentgehalt an Wasser aufrechtzuerhalten. Aus der US-Ps ist bekannt, daß Phosphatester enthaltende Fluids, die einen geringen Prozentgehalt an Wasser aufweisen, für Flugzeughydraulik systeme geeignet sind. Unglücklicherweise mildert zwar ein kleiner Gehalt an Wasser in einigen Phosphatester enthaltenden Fluids bestimmte Arten von Schaden, hat jedoch einen unerwünschten Einfluß auf die Korrosion und die Stabilität des Fluids. Ziel dieser Erfindung ist daher ein nichtwässriges Additiv, welches alle Arten von Schaden mildert, die durch die Fluids in den Hydraulik-Systeinen hervorgerufen werden können.Damage has been reported on various occasions which occur on valves and other metallic parts, which are with liquids containing phosphate esters come into contact. This damage manifests itself in the wear and tear of metal parts. For the explanation of this Various considerations were made on phenomena and the solution to the problems. There was talk of cavity formation, Erosion, corrosion and other phenomena on the metal parts of a hydraulic system. A solution, what has been offered to overcome this problem is to have a low percentage in the fluid Maintain water. From US-Ps it is known that fluids containing phosphate esters, which have a low percentage in water, are suitable for aircraft hydraulic systems. Unfortunately, it does soften However, small levels of water in some fluids containing phosphate esters cause certain types of damage undesirable influence on the corrosion and the stability of the fluid. The aim of this invention is therefore a non-aqueous additive which mitigates all types of damage, caused by the fluids in the hydraulic systems can be.

Es wurde nun gefunden, daß die Einverleibung einer geringen Menge bestimmter quaternärer Phosphoniumverbindungen in Hydraulik-Flüssigkeiten Schäden an den Metall teilen verhindert, die mit der Flüssigkeit in Berührung kommen. Flugzeug-Hydraulikfluids, die als Basis einen Phosphatester und dazu einen geringen Gehalt an Methyltri octylphosphoniumdimethylphosphat enthalten, sind in ihrem Abnutzungs-Korrosions-Verhalten solchen Materialien überlegen, die entweder eine geringe Menge Wasser oder keineIt has now been found that the incorporation of a small amount of certain quaternary phosphonium compounds in hydraulic fluids prevents damage to the metal parts that come into contact with the fluid come. Aircraft hydraulic fluids based on a phosphate ester and a low content of methyltri octylphosphoniumdimethylphosphate contain, are superior in their wear-corrosion behavior to such materials, which either have a small amount of water or none

109882/1264109882/1264

Additive enthalten.Contains additives.

Die quaternären Phosphoniumverbindungen, die für die Einarbeitung in hydraulische Fluids gemäß der vorliegenden Erfindung geeignet sind, können durch die nach stehende Formel wiedergegeben werden:The quaternary phosphonium compounds suitable for incorporation into hydraulic fluids according to the present Invention can be represented by the following formula:

R -R -

R' ιR 'ι

P-R" ιP-R "ι

RtIlRtIl

ζ -ζ -

X η P.X η P.

Υ« ■γι ι Υ « ■ γι ι

in welcher R, R1 und R»' Alkyl-, Aryl-, Alkaryl- und Aralkyl-Gruppen mit 1 bis IO Kohlenstoffatomen und R1 ·' Alkyl- oder Aralkylgruppen mit 1 bis 10 Kohlenstoffato ■ men sind; X steht für 0 oder S, Y1 und Y·! stehen für Alkoxy-, Alkylthio-, Alkyl-, Aryl-, Alkaryl-, Aralkyl-, Aryloxy-, Arylthio- oder Alkaryloxy-Gruppen, und Z ist ein Sauerstoffatom.in which R, R 1 and R »'are alkyl, aryl, alkaryl and aralkyl groups with 1 to 10 carbon atoms and R 1 ·' are alkyl or aralkyl groups with 1 to 10 carbon atoms; X stands for 0 or S, Y 1 and Y · ! represent alkoxy, alkylthio, alkyl, aryl, alkaryl, aralkyl, aryloxy, arylthio or alkaryloxy groups, and Z is an oxygen atom.

Typische Verbindungen sind die folgenden:Typical connections are the following:

(1) Methyltrioctylphosphoniumdimethylphosphat,(1) methyltrioctylphosphonium dimethylphosphate,

(2) Äthyltrioctylphosphoniumdiäthylphosphonat,(2) ethyltrioctylphosphonium diethylphosphonate,

(3) Äthyltrioctylphosphoniumdimethylphosphat,(3) ethyl trioctyl phosphonium dimethyl phosphate,

(4) Butyltrioctylphosphoniumdibutylphosphat,(4) butyl trioctyl phosphonium dibutyl phosphate,

(5) Isobutyltrioctylphosphoniumdimethylphosphat,(5) isobutyltrioctylphosphonium dimethylphosphate,

(6) Benzyltriphenylphosphoniumdibenzylphosphat,(6) benzyl triphenyl phosphonium dibenzyl phosphate,

(7) Methylphenyldioctylphosphoniumdimethylphosphat,(7) methylphenyldioctylphosphonium dimethylphosphate,

1 09882/12641 09882/1264

-Λ --Λ -

(8) Phenyltriäthylphosphoniumäthylphenylphosphonat,(8) Phenyltriethylphosphoniumethylphenylphosphonate,

(9) Methyldiphenyloctylphosphoniumdimethylphosphat,(9) methyldiphenyloctylphosphonium dimethylphosphate,

(10) Tetraäthylphosphoniumdiäthylphosphat,(10) tetraethylphosphonium diethyl phosphate,

(11) Methyltriphenylphosphoniumdimethylphosphat,(11) methyl triphenylphosphonium dimethyl phosphate,

(12) Methyltributylphosphoniumdimethylphosphat,(12) methyltributylphosphonium dimethylphosphate,

(13) Methyltributylphosphoniumdiäthylphosphat,(13) methyltributylphosphonium diethyl phosphate,

(14) Methyltrioctylphosphoniununethylmethylphosphonat,(14) methyltrioctylphosphonium methylmethylphosphonate,

(15) Methyltrioctylphosphoniumdimethylphosphonat,(15) methyltrioctylphosphonium dimethylphosphonate,

(16) Methyltrio ctylphosphoniumdimethy!phosphat.(16) Methyltrioctylphosphonium dimethyl phosphate.

Die Herstellung von quaternären Phosphoniumverbindungen des Typs, wie er in den erfindungsgemäßen Fluids verwendet werden kann, ist bekannt und bedarf kei ■ ner Erläuterung. Solche Salze haben sich als brauchbare Polymerisationskatalysatoren, antistatische Mittel, Stabilisatoren, oberflächenaktive Mittel und Badzusätze in der Textilfärberei erwiesen.The manufacture of quaternary phosphonium compounds of the type that can be used in the fluids of the invention is known and does not require any ner explanation. Such salts have been found to be useful polymerization catalysts, antistatic agents, stabilizers, Surfactants and bath additives have been proven in textile dyeing.

Schmiermittelzusammensetzungen, denen die Phos phoniumzusammensetzungen zugesetzt werden können, werden als Grundmaterialien bezeichnet. Sie umfassen, ohne da rauf beschränkt zu sein, Ester und Amide einer Phosphor säure, Mineralöl und synthetische Kohlenwasserstofföl Grundmaterialien, Kohlenwasserstoffsilikate, Silikone, aromatische Äther- und Thioätherverbindungen, chloriertes Biphenyl, Monoester, Dicarbonsäureester, Ester mehr wertiger Verbindungen, Polyalkylenätherglycole und Alkohole, sowie deren Ester.Lubricant compositions to which the phosphonium compositions can be added are referred to as base materials. They embrace without going up to be restricted to esters and amides of a phosphoric acid, mineral oil and synthetic hydrocarbon oil base materials, Hydrocarbon silicates, silicones, aromatic ether and thioether compounds, chlorinated biphenyl, monoesters, dicarboxylic acid esters, polyvalent esters Compounds, polyalkylene ether glycols and alcohols, and their esters.

Die Konzentration an Phosphoniumzusammensetzung, die erforderlich ist, um Schaden zu verhüten, schwankt in Ab-The concentration of phosphonium composition that required to prevent harm varies

109882/1264109882/1264

_ 5 —_ 5 -

hängigkeit von dem jeweils verwendeten Grundmaterial oder Gemisch von Grundmaterialien. Vorzugsweise werden zwi sehen etwa 0,1 und etwa 10 Gew.-% der Phosphoniumzu sammensetzung verwendet. Am meisten bevorzugt sind etwa 0,5 bis etwa 2,0 Gew.-#. Die funktioneile, erfindungs gemäße Fluidzusammensetzung kann in "beliebiger, bekannter Weise behandelt werden, wenn ein Additiv in ein Grund material eingearbeitet werden soll, wobei unter Rühren eine homogene Fluidzusammensetzung erhalten wird.depending on the base material or mixture of base materials used. Preferably between will see about 0.1 and about 10 percent by weight of the phosphonium composition used. Most preferred are about 0.5 to about 2.0 weight percent. The functional, according to the invention Fluid composition can be treated in "any known manner" when adding an additive to a base material is to be incorporated, a homogeneous fluid composition being obtained with stirring.

Die funktioneilen Zusammensetzungen, die als Grundmaterialien erfindungsgemäß geeignet sind, können Ester und Amide einer Säure des Phosphors sein, die durch die folgende Formel dargestellt werden:The functional compositions which are suitable as base materials according to the invention can be esters and amides of an acid of phosphorus, which are represented by the following formula:

0
ti
0
ti

E - (I)a - P - (I1),. -E - (I) a - P - (I 1 ) ,. -

El E l

in welcher Y für Sauerstoff, Schwefel oder R,-N - steht;in which Y is oxygen, sulfur or R, -N -;

ι ·* Y1 steht für Sauerstoff, Schwefel oder R,-N-, und YP ι · * Y 1 stands for oxygen, sulfur or R, -N-, and Y P

steht für Sauerstoff, Schwefel oder Rc-N- . R, R1, R2, R-,, R, und Rc sind Alkyl-, Aryl-, substituierte Aryl- und substituierte Alkylgruppen, wobei R, R1, R2, R^, R,stands for oxygen, sulfur or Rc-N-. R, R 1 , R 2 , R- ,, R, and Rc are alkyl, aryl, substituted aryl and substituted alkyl groups, where R, R 1 , R 2 , R ^, R,

und Rc identisch oder von einem anderen Rest verschleiß and R c identical or worn from a different remainder

den sein können; a, b und c sind ganze Zahlen von 0 biswho can be; a, b and c are integers from 0 to

109882/1284109882/1284

-δι, und die Summe von a + b + c beträgt 1 bis 3.-δι, and the sum of a + b + c is 1 to 3.

Typische Beispiele für solche Alkylreste sind die folgenden :Typical examples of such alkyl radicals are the following:

Methyl, Äthyl, normal-Propyl, Isopropyl, normal-Butyl, Isobutyl, sek.-Butyl, tert.-Butyl, normal Amyl,· Isoamyl, 2-Methylbutyl, 2,2-Dimethylpropyl, 1-Methylbutyl, Diäthylmethyl, 1,2-Dimethylpropyl, tert,-Amyl, normal-Hexyl, 1-Methylamyl, 1-Äthylbutyl, 1,2,2-Trimethylpropyl, 3,3-Dimethylbutyl, 1,1,2-Trimethyl propyl, 2-Methylamyl, 1,1-Dimethylbutyl, l-Äthyl-2-me'thylpropyl, 1,3-Dimethylbutyl, Isohexyl, 3-Methylamyl, 1,2-Dimethylbutyl, 1-Methyl-l-äthylpropyl, 2-Äthylbutyl, normal-Heptyl, l,l,2,3-^etramethylpropyl, 1,2-Dimethyl-l-äthylpropyl, 1,1,2-Trimethylbutyl, 1-Isopropyl-2-methylpropyl, l-Methyl-2-äthylbutyl, 1,1-Di äthylpropyl, 2-Methylhexyl, 1,1-Dimethylamyl, 1-Isopropylbutyl, l-lthyl-3-methylbutyl, l,if-Dimethylamyl, Isoheptyl, 1-Methyl-l-äthylbutyl, l-Äthyl-2-methylbutyl, 1-Methylhexyl, 1-Propylbutyl, normal-Octyl, 1-Methylheptyl, l,l-Diäthyl-2-methylpropyl, l,l,3>3-Tetramethylbutyl, 1,1-Diäthylbutyl, 1,1-Dimethylhexyl, 1-Methyl-läthylamyl, 1-Methyl-l-propylbutyl, 2-lthylhexyl, 6-Methylheptyl (Iso-octyl)? normal-Monyl, 1-Methyloctyl, 1-Äthylheptyl, 1,1-Dimethylheptyl, 1-Ithyl-1-propylbutyl, lsl-Diäthyl-3-methylbutyl, Diisobutylmethyl, 3j5»5-Trimethylhexyl, 3,5-Diiaethylheptyl, normal-Decyl, 1-Propylhepty.l, 1,1-Diät ylhexyl, 1,1-Dipropylbutyl, 2-Isopropyl-5~methylhexyl und C11 1o Alkyl-Gruppen. Hierzu gehören auch Arallcylgruppen wie z.B. Benzyl, alpha- oder beta-Phenyläthyl, alpha-alpha-Dimethylbenzyl usw., sowie Cyclohexyl, Cycloheptyl usw..Methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, sec-butyl, tert-butyl, normal amyl, isoamyl, 2-methylbutyl, 2,2-dimethylpropyl, 1-methylbutyl, diethylmethyl, 1, 2-dimethylpropyl, tert, -amyl, normal-hexyl, 1-methylamyl, 1-ethylbutyl, 1,2,2-trimethylpropyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 2-methylamyl, 1, 1-dimethylbutyl, l-ethyl-2-methylpropyl, 1,3-dimethylbutyl, isohexyl, 3-methylamyl, 1,2-dimethylbutyl, 1-methyl-1-ethylpropyl, 2-ethylbutyl, normal-heptyl, l, 1,2,3- ^ etramethylpropyl, 1,2-dimethyl-1-ethylpropyl, 1,1,2-trimethylbutyl, 1-isopropyl-2-methylpropyl, 1-methyl-2-ethylbutyl, 1,1-diethylpropyl, 2-methylhexyl, 1,1-dimethylamyl, 1-isopropylbutyl, l-ethyl-3-methylbutyl, l, if-dimethylamyl, isoheptyl, 1-methyl-l-ethylbutyl, l-ethyl-2-methylbutyl, 1-methylhexyl, 1-propylbutyl, normal-octyl, 1-methylheptyl, l, l-diethyl-2-methylpropyl, l, l, 3> 3-tetramethylbutyl, 1,1-diethylbutyl, 1,1-dimethylhexyl, 1-methyl-ethylamyl, 1-methyl-1-propylbutyl, 2-ethylhexyl, 6 -Methylheptyl (iso-octyl) ? normal monyl, 1-methyloctyl, 1-ethylheptyl, 1,1-dimethylheptyl, 1-ityl-1-propylbutyl, 1 s 1-diethyl-3-methylbutyl, diisobutylmethyl, 3j5 »5-trimethylhexyl, 3,5-diiaethylheptyl, normal-decyl, 1-Propylhepty.l, 1,1-ylhexyl diet, 1,1-Dipropylbutyl, 2-isopropyl-5 ~ methylhexyl and C 11 1 o alkyl groups. This also includes arallcyl groups such as benzyl, alpha- or beta-phenylethyl, alpha-alpha-dimethylbenzyl, etc., as well as cyclohexyl, cycloheptyl, etc.

109882/1284109882/1284

Typische Beispiele für substituierte Alkylreste sind die Halogenalkyl-Reste, die durch die folgende Strukturformel gekennzeichnet werden können:Typical examples of substituted alkyl radicals are the haloalkyl radicals represented by the following structural formula can be marked:

R6 R 6

in welcher Hai für ein Halogenatom steht, m weniger oder gleich 2n+l ist und η irgend ein Wert von 0 bis 18 sein kann; Rg und R7 können Wasserstoff, Halogen oder Alkylreste sein. Bevorzugte Reste sind solche, in denen Hai ein Fluoratom ist, einschließlich der nachstehend aufgeführten: in which Hal stands for a halogen atom, m is less than or equal to 2n + 1 and η can be any value from 0 to 18; Rg and R 7 can be hydrogen, halogen or alkyl radicals. Preferred radicals are those in which Hai is a fluorine atom, including those listed below:

R6 R 6

CF^C-3
1
CF ^ C-3
1

R7 R7 R 7 R 7

ο tο t

CF3CH2C- CF3(CF2)2C-CF 3 CH 2 C- CF 3 (CF 2 ) 2 C-

I tI t

R7 R7 R 7 R 7

109882/1264109882/1264

CF2)5C-CF 2 ) 5 C-

!6 ! 6th

R6 R 6

CF5(C6H13)C-CF5(C7H15: CF 5 (C 6 H 13 ) C-CF 5 (C 7 H 15 :

CF5(CgH17)C-CF5CF2(C2H5)C- CF 5 (CgH 17 ) C-CF 5 CF 2 (C 2 H 5 ) C-

109882/1264109882/1264

CF3CF2(C3H7)C-CF3CF2(C4H9)C- CF 3 CF 2 (C 3 H 7 ) C-CF 3 CF 2 (C 4 H 9 ) C-

CF3CF2(C5H11)C-CF3CF2(C6H13)C- CF 3 CF 2 (C 5 H 11 ) C-CF 3 CF 2 (C 6 H 13 ) C-

CF3(C6H15)C-CF3CF2(CgH17)C- CF 3 (C 6 H 15 ) C-CF 3 CF 2 (CgH 17 ) C-

CF3 ( CF2 )2( C2Il5) C CF3(CF2)2(C3H7)C-CF 3 (CF 2 ) 2 (C 2 Il 5 ) C CF 3 (CF 2 ) 2 (C 3 H 7 ) C-

CF3(CF2)2(C^H9)C-CF 3 (CF 2 ) 2 (C ^ H 9 ) C-

)2 (C UfI 2)^5C G2H5)C-) 2 (C UfI 2 ) ^ 5 CG 2 H 5 ) C-

109882/1284109882/1284

K,-K, -

P -P -

- 10 -- 10 -

f fs-nt % (ti υ Λ η f fs-nt% (ti υ Λ η

■ -■ -

Ϊ, Ut? -; / ς s. V-Ϊ, Ut? -; / ς s. V-

10SS82/128410SS82 / 1284

- li -- li -

B6 R6 B 6 R 6

R6 R 6

wobei β,- und R7 die oben angegebene Bedeutung haben.where β, - and R 7 have the meaning given above.

Die halogenieren Alkylreste können primär, sekundär oder tertiär sein.The halogenated alkyl radicals can be primary or secondary or be tertiary.

Andere geeignete, Fluor enthaltende Reste sind fluorierte Alkoxyalkyl-Reste, insbesondere solche, die durch die folgende Formeln dargestellt werden:Other suitable, fluorine-containing radicals are fluorinated alkoxyalkyl radicals, especially those made by the following formulas are represented:

. R6. R 6

D ID I

C2H5OCH2CF2CF2C- C2H7OCH2CF2CF2C-C 2 H 5 OCH 2 CF 2 CF 2 C- C 2 H 7 OCH 2 CF 2 CF 2 C-

t »t »

R7 R7 R 7 R 7

109882/1264109882/1264

-IZ--IZ-

R6 R 6

L0CH2CF2CF2C- L 0CH 2 CF 2 CF 2 C-

H1 ^0CH1 CF3CF0C-H 1 ^ 0CH 1 CF 3 CF 0 C-

^^

CF3CF0
L C. d.
CF 3 CF 0
L C. d.

B1 B 1

E6 E 6

C1-H1 Ί OCH0CF0CF0CF0C-C 1 -H 1 Ί OCH 0 CF 0 CF 0 CF 0 C-

OCH0CF0CF0CF0C-c. c. c. c. OCH 0 CF 0 CF 0 CF 0 C- cccc

E.E.

C3H7OCH2)CF2)4C-1 C 3 H 7 OCH 2 ) CF 2 ) 4 C-1

109882/1264109882/1264

RrRr

wobei Rg und R„ die oben angegebene Bedeutung haben.where Rg and R "have the meaning given above.

Erfindungsgemäß können die Wasserstoff- und Fluor atome in den vorstehend genannten Halogenalkylresten durch andere Halogene, wie Chlor oder Brom ersetzt werden.According to the invention, the hydrogen and fluorine atoms in the haloalkyl radicals mentioned above can through other halogens such as chlorine or bromine are replaced.

Typische Beispiele für Aryl- und substituierte Aryl-Reste sind Phenyl, Cresyl, Xylyl, halogeniertes Phenyl, . alkoxyliertes Phenyl, Cresyl und Xylyl, wobei die verfügbaren Wasserstoffatome am Aryl oder substituierten Aryl teilweise oder völlig ersetzt sein können durch ein Halogen, wie z.B. beim o-, m- und p-Trifluormethyl phenyl, ο-, ρ- und p-2,2,2-Trifluoräthylphenyl, o-, m- und p-3,3,3-Trifluorpropylphenyl und o-, m- und p—^,4,Zf-Trifluorbutylphenyl. Eingeschlossen sind auch Isopropylphenyl, Butylphenyl, alpha-Alkylbenzylphenyl und alpha, alpha-Dialkylbenzylphenyl, wie z.B. alpha-Methylbenzylphenyl, alpha, alpha-Dimethylbenzylphenyl.Typical examples of aryl and substituted aryl radicals are phenyl, cresyl, xylyl, halogenated phenyl,. alkoxylated phenyl, cresyl and xylyl, the available hydrogen atoms on the aryl or substituted Aryl can be partially or completely replaced by a halogen, e.g. in the case of o-, m- and p-trifluoromethyl phenyl, ο-, ρ- and p-2,2,2-trifluoroethylphenyl, o-, m- and p-3,3,3-trifluoropropylphenyl and o-, m- and p- ^, 4, Zf-trifluorobutylphenyl. Also includes isopropylphenyl, butylphenyl, alpha-alkylbenzylphenyl and alpha, alpha-dialkylbenzylphenyl, such as alpha-methylbenzylphenyl, alpha, alpha-dimethylbenzylphenyl.

Zu den als Grundmaterialien geeigneten Orthosilikaten gehören die Tettra(octyl)orthosilikate, Tetra(2-äthylhexyl)orthosilikate und die Tetra(isooctyl)orthosilikate, sowie solche, bei denen die Isooctyl-Reste von Isooctylalkohol erhalten worden sind, der aus dem Oxo-Prozeß stammt, und die (TrialkoxysilicoJ-trialkylorthosilikate, die sonst als Hexa(alkoxy)disiloxane bezeichnet werden,Orthosilicates suitable as basic materials include the tettra (octyl) orthosilicates and tetra (2-ethylhexyl) orthosilicates and the tetra (isooctyl) orthosilicates, as well as those in which the isooctyl radicals of isooctyl alcohol obtained from the Oxo process, and the (TrialkoxysilicoJ-trialkylorthosilicates, otherwise known as hexa (alkoxy) disiloxanes,

1098827126410988271264

-ik--ik-

wie z.B. Hexa(2-äthylbutoxy)disiloxan und Hexa(2-äthylhexoxy)disiloxan. such as hexa (2-ethylbutoxy) disiloxane and hexa (2-ethylhexoxy) disiloxane.

Die bevorzugten Tetraalkylorthosilikate und Hexa (alkoixy) disiloxane sind solche, in denen die Alkyl- oder Alköxy-Reste k bis 12 Kohlenstoffatome- besitzen-und in denen die Gesamtzahl an Kohlenstoffatomen im Orthosilikat 16 bis 60 beträgt.The preferred tetraalkyl orthosilicates and hexa (alkoixy) disiloxanes are those in which the alkyl or alkoxy radicals have k to 12 carbon atoms - and in which the total number of carbon atoms in the orthosilicate is 16 to 60.

Außer den vorstehend genannten Hexa(aikoxy)disiloxanen können andere Hexa(alkoxy)disiloxane verwendet werden, in denen der aliphatische Rest der Alkoxy-Gruppen z.B. 1-Äthylpropyl, 1,3-Dirnethylbutyl, 2-Methylpentyl, 1-Methylhexyl, 1-Äthylpentyl, 2-Butylhexyl oder 1-Methyl-V-äthyloctyl ist.Except for the hexa (aikoxy) disiloxanes mentioned above other hexa (alkoxy) disiloxanes can be used, in which the aliphatic radical of the alkoxy groups e.g. 1-ethylpropyl, 1,3-dimethylbutyl, 2-methylpentyl, 1-methylhexyl, 1-ethylpentyl, 2-butylhexyl or 1-methyl-V-ethyloctyl is.

Die Orthosilikate und Alkoxypolysiloxane können durch die folgende allgemeine Strukturformel dargestellt werden:The orthosilicates and alkoxypolysiloxanes can be represented by the following general structural formula will:

Eg-O-Ego-

0 ι0 ι

Si ιSi ι

R.R.

1010

1111

0 - X ι 0 - X ι

(0)(0)

■12■ 12

(O)n, - R (O) n , - R

in welcher Rg, Rg und R10 Alkyl, substituiertes Alkyl,in which Rg, R g and R 10 are alkyl, substituted alkyl,

109882/1264109882/1264

Aryl, substituiertes Aryl und sowohl identisch, als auch voneinander verschieden sein können; 0 ist Sauerstoff, Si ist Silizium, X ist Kohlenstoff oder Silizium, m ist 0 oder 1, η ist eine ganze Zahl zwischen 1 und etwa 200, und wenn X ein Kohlenstoffatom ist, dann ist m = 0 und η = Ij Κ-ιί» rt? und %·$ können Wasserstoff, Alkyl, substituiertes Alkyl, Aryl oder substituiertes Aryl sein, und wenn X ein Siliziumatom ist, dann ist m = 1, η eine ganze Zahl von 1 bis etwa 200 oder mehr, und R1-,, R-, o und R, ., könnenAryl, substituted aryl, and both identical and different from one another; 0 is oxygen, Si is silicon, X is carbon or silicon, m is 0 or 1, η is an integer between 1 and about 200, and if X is a carbon atom, then m = 0 and η = Ij Κ-ιί » R t? and % · $ can be hydrogen, alkyl, substituted alkyl, aryl, or substituted aryl, and when X is silicon then m = 1, η is an integer from 1 to about 200 or more, and R 1 - ,, R -, o and R,., can

Ix LcL Lz> Ix LcL Lz>

Alkyl, substituiertes Alkyl, Aryl oder substituiertes Aryl sein.Be alkyl, substituted alkyl, aryl, or substituted aryl.

Typische Beispiele für substituierte Arylreste sind:Typical examples of substituted aryl radicals are:

o-, m- und p_-Chlorphenyl, o-, m- und p_-Brom -o-, m- and p_-chlorophenyl, o-, m- and p_-bromine -

phenyl, ο-, m- und jv-Fluorphenyl, alpha, alpha-Trichlorcresyl, alpha, alpha, alpha-Trifluorcresyl, Xylyl und o-, m- und g-Cresyl.phenyl, ο-, m- and jv-fluorophenyl, alpha, alpha-trichlorocresyl, alpha, alpha, alpha-trifluorocresyl, xylyl and o-, m- and g-cresyl.

Typische Beispiele für Alkyl- oder Halogenalkyl-Reste sind die oben beschriebenen.Typical examples of alkyl or haloalkyl radicals are the ones described above.

Die als Grundmaterialien geeigneten Siloxane oder Silikone können durch die folgende allgemeine Formel dargestellt werden:The siloxanes or silicones suitable as base materials can be represented by the following general formula will:

Rlif "~" R lif "~"

SiSi

- 0- 0

17 ι17 ι

Si - RSi - R

109882/126A109882 / 126A

in welcher R-τκ» R15' R16' R17' Rl8 und E19 Alkyl-, substituierte Alkyl-, Aryl- und substituierte Aryl-Reste sein können und η eine ganze Zahl von O bis etwa 2000 oder mehr ist. Typische Beispiele für Alkyl- oder Halogenalkyl-Reste sind die oben beschriebenen. Typische Beispiele für die Siloxane sind Poly(methyl)siloxan, Poly(methyl, 3>}3) 3- tr if luor propyl) siloxan.in which R-τκ » R 15 ' R 16' R 17 ' R 18 and E 19 can be alkyl, substituted alkyl, aryl and substituted aryl radicals and η is an integer from 0 to about 2000 or more. Typical examples of alkyl or haloalkyl radicals are those described above. Typical examples of the siloxanes are poly (methyl) siloxane, poly (methyl, 3>} 3) 3-trifluoropropyl) siloxane.

Typische Beispiele für substituierte Arylreste sind o-, m- und p-Chlorphenyl, o-, m- und p-Bromphenyl, o-, m- und p-Fluorphenyl, alpha, alpha, alpha-Trifluorcresyl, alpha, alpha, alpha -Trichlorphenyl, ο-, m- und p-Cresyl und Xylyl.Typical examples of substituted aryl radicals are o-, m- and p-chlorophenyl, o-, m- and p-bromophenyl, o-, m- and p-fluorophenyl, alpha, alpha, alpha-trifluorocresyl, alpha, alpha, alpha-trichlorophenyl, ο-, m- and p-cresyl and xylyl.

Dicarbonsäureester, die als Grundmaterialien geeignet sind, können durch die Strukturformel:Dicarboxylic acid esters, which are suitable as basic materials, can be given the structural formula:

0
η
0
η

- 0 - C - R21 -.C - 0 -- 0 - C - R 21 -.C - 0 -

η "η "

dargestellt werden, in welcher R2Q und R22 Alkyl, substituiertes Alkyl, Aryl oder substituiertes Aryl sein können und R21 ein zweiwertiger Rest, nämlich ein Alkylen oder substituiertes Alkylen ist, und sie werden herge stellt durch Veresterung von Dicarbonsäuren, wie Adipinsäure, Azelainsäure, Suberinsäure, Sebacinsäure, Hydroxybernsteinsäure, Fumarsäure, Maleinsäure usw. mit Alkoholen, wie z.B. Butylalkohol, Hexylalkohol, 2-Äthylhexylalkohol,in which R 2 Q and R 22 can be alkyl, substituted alkyl, aryl or substituted aryl and R 21 is a divalent radical, namely an alkylene or substituted alkylene, and they are produced by esterification of dicarboxylic acids, such as adipic acid, Azelaic acid, suberic acid, sebacic acid, hydroxysuccinic acid, fumaric acid, maleic acid, etc. with alcohols, such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol,

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Dodecylalkohol, 2,2-Dimethylheptano1, 1-Methylcyclohexylmethanol usw..Dodecyl alcohol, 2,2-dimethylheptanol, 1-methylcyclohexylmethanol etc..

Typische Beispiele für Alkyl-, Aryl-, substituierte Alkyl- und substituierte Aryl-Reste sind die oben angegebenen. Typical examples of alkyl, aryl, substituted alkyl and substituted aryl radicals are those given above.

Polyester, die als Grundmaterialien geeignet sind, können durch die folgende Strukturformel dargestellt werden: Polyesters suitable as base materials can be represented by the following structural formula:

2323

IlIl

C-OC-O

0
ti
0
ti

0 - C - R0 - C - R

CH2 CH 2

- C - CI ι- C - CI ι

CH2 t O ι C = O ι Jrto cz CH 2 t O ι C = O ι Jrto cz

■2h■ 2h

in welcher R2^ für Wasserstoff oder Alkyl steht, R2, und R25 Alkyl-, substituierte Alkyl-, Aryl- oder substituierte Aryl-Gruppen sind, a den Wert 0 oder 1 hat, Z den
Wert 1 oder 2 hat und, wenn Z=I ist, R2g ein Wasser stoffatom, eine Alkyl-, Acyloxy- oder substituierte
in which R 2 ^ is hydrogen or alkyl, R 2 and R 25 are alkyl, substituted alkyl, aryl or substituted aryl groups, a has the value 0 or 1, Z denotes
Has the value 1 or 2 and, when Z = I, R 2 g is a hydrogen atom, an alkyl, acyloxy or substituted one

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Acyloxy-Gruppe und, wenn Z = 2 ist, R-,- Sauerstoff ist; sie werden hergestellt durch Veresterung solcher Polyalkohole, wie Pentaerythrit, Dipentaerythrit, Trimethylolpropan, Trimethyloläthan oder Neopentylglycol mit solchen Säuren, wie Propionsäure, Buttersäure, Isobutter säure, n-Valeriansäure, Capronsäure, n-Heptancarbonsäure, Caprylsäure, 2-Äthylhexancarbonsäure, 2,2-Dimethylheptancarbonsäure oder Pelargonsäure. 'Typische Beispiele für Alkyl-, substituierte Alkyl-, Aryl- und substituierte Aryl-Reste sind die oben angegebenen.Acyloxy group and, when Z = 2, R is -, - is oxygen; they are produced by esterification of such polyalcohols as pentaerythritol, dipentaerythritol, trimethylolpropane, Trimethylolethane or neopentylglycol with such Acids such as propionic acid, butyric acid, isobutyric acid, n-valeric acid, caproic acid, n-heptane carboxylic acid, Caprylic acid, 2-ethylhexanecarboxylic acid, 2,2-dimethylheptanecarboxylic acid or pelargonic acid. Typical examples of alkyl, substituted alkyl, aryl and substituted aryl radicals are those given above.

Andere Ester, die als Grundmaterialien geeignet sind, sind die Monoester.Other esters that are suitable as base materials are the monoesters.

Eine weitere Klasse von Grundmaterialien, die erfindungsgemäß verwendbar ist, kann durch die folgende Formel dargestellt werden:Another class of base materials useful in the present invention can be found in the following Formula can be represented:

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in welcher A, A-, , A2 und A, Chaleogene mit einer Atom zahl von 8 bis 16, X, X-,, Xp, X^ und X, Wassers to ff atome, Alkyl-, Halogenalkyl-, Halogen-, Arylalkyl- oder substituierte Arylalkyl-Gruppen und m, η und ο ganze Zahlen mit einem Wert von 0 bis 8 sind, und a den Wert 0 oder 1 hat, mit der Maßgabe, daß dann, wenn a = 0 ist, η einen Wert von 1 bis 2 haben kann. Typische Beispiele für Alkyl- und substituierte Alkyl-Reste sind oben gegeben worden. Typi sehe Beispiele für solche Grundmaterialien sind 2- bis 7-Ring-ortho-, meta- und para-Polyphenyläther und Gemische derselben, 2- bis 7-Ring-ortho-, meta- und para-Polyphenylthioäther und Gemische derselben, gemischte PoIyphenyläther-thioäther-Verbindungen, in denen mindestens eines der durch A, A-, , Ap und A-, dargestellten Chaleogene von allen anderen Chalcogenen verschieden ist, dihalogenierte Diphenyläther, wie /f-Brom-3'-chlordiphenyläther und Bisphenoxybiphenyl-Verbindungen sowie deren Gemische.in which A, A ,, A 2 and A, chaleogens with an atomic number from 8 to 16, X, X- ,, Xp, X ^ and X, water to ff atoms, alkyl, haloalkyl, halogen, Arylalkyl or substituted arylalkyl groups and m, η and ο are integers with a value from 0 to 8, and a has the value 0 or 1, with the proviso that when a = 0, η has a value of 1 to 2 can have. Typical examples of alkyl and substituted alkyl radicals have been given above. Typical examples of such base materials are 2- to 7-ring ortho-, meta- and para-polyphenyl ethers and mixtures thereof, 2- to 7-ring ortho-, meta- and para-polyphenylthioethers and mixtures thereof, mixed polyphenyl ethers thioether compounds in which at least one of the chaleogens represented by A, A-, Ap and A- is different from all other chalcogens, dihalogenated diphenyl ethers such as / f-bromo-3'-chlorodiphenyl ether and bisphenoxybiphenyl compounds and mixtures thereof .

Kohlenwasserstofföle einschließlich Mineralöle aus Erdöl und synthetischen Kohlenwasserstoffölen sind eben falls geeignete Grundmaterialien. Die physikalischen Eigenschaften von funktionellen Fluids, die von einem Mineralöl stammen, werden unter Berücksichtigung der Erforder nisse des Fluidsystems ausgewählt, und deshalb fallen in den Rahmen dieser Erfindung Mineralöle innerhalb eines weiten Viskositäts- und Flüchtigkeitsbereiches, wie z.B. Mineralöle auf der Basis von Naphthenen, Paraffinen und Gemischen derselben.Hydrocarbon oils including petroleum mineral oils and synthetic hydrocarbon oils are also included suitable base materials. The physical properties of functional fluids by a mineral oil originate, taking into account the requirements of the fluid system is selected, and therefore within the scope of this invention, mineral oils within one fall wide viscosity and volatility range, e.g. Mineral oils based on naphthenes, paraffins and mixtures thereof.

Die synthetischen Kohlenwasserstofföle umfassen unter anderem solche öle, die bei der OligomerisierungThe synthetic hydrocarbon oils include including those oils that are used in oligomerization

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von Olefinen anfallen, wie z.B. Polybutene, und solche öle, die aus höheren alpha-Olefinen mit k bis 20 Kohlenstoffatomen durch sauer katalysierte Dimerisierung und durch Oligomerisierung unter Verwendung von Trialuminiumalkylen als Katalysatoren erhalten werden. Chlorierte Biphenyle sind ebenfalls als Grundmaterialien verwend bar. incurred from olefins, such as polybutenes, and those oils which are obtained from higher alpha-olefins with k to 20 carbon atoms by acid-catalyzed dimerization and by oligomerization using trialuminum alkyls as catalysts. Chlorinated biphenyls can also be used as basic materials.

Desgleichen fallen in den Rahmen dieser Erfindung Gemische aus zwei oder mehreren der vorstehend genannten Grundmaterialien.Mixtures of two or more of the foregoing also fall within the scope of this invention Basic materials.

Die erfindungsgemäßen Fluidzusammensetzungen können bei ihrer Verwendung auch Säureakzeptoren, Farbstoffe, Gießpunkterniedriger, Antioxidantien, Schaumverhütungsmittel, Viskositätsindexverbesserer, wie Polyalkylacrylate, Polyalky!methacrylate, polycyclische Polymere, Polyurethane, Polyalkylenoxide und Polyester, Gleitmittel, Wasser usw. enthalten. Besonders geeignete Kombinationen von Grundmaterialien mit Additiven sind z.B. in dem belgischen Patent 728 309 beschrieben.When used, the fluid compositions according to the invention can also contain acid acceptors, dyes, Pouring point depressants, antioxidants, anti-foaming agents, viscosity index improvers, such as polyalkyl acrylates, Polyalky! Methacrylates, polycyclic polymers, polyurethanes, Contain polyalkylene oxides and polyesters, lubricants, water, etc. Particularly suitable combinations of base materials with additives are described, for example, in Belgian patent 728 309.

Die vorstehend genannten Grundmaterialien können allein oder als Fluidzusammensetzungen, die zwei oder mehr Grundmaterialien in wechselnden Mengenverhältnissen enthalten, verwendet werden. Die Grundmaterialien können auch andere Fluide enthalten, wozu außer den funktioneilen Fluids solche aus Kohleprodukten, synthetischen Produkten und synthetischen ölen gehören, wie z.B. Alkylenpolymere, wie die Polymeren von Propylen, Butylen usw. und deren . Gemische, Alkylenoxidpolymere, wie die Propylenoxidpolymeren und Derivate hiervon, einschließlich der Alkylen-The above base materials can be used alone or as fluid compositions, the two or contain more basic materials in varying proportions can be used. The basic materials can also contain other fluids, including besides the functional ones Fluids those from coal products, synthetic products and synthetic oils, such as alkylene polymers, such as the polymers of propylene, butylene, etc. and their. Blends, alkylene oxide polymers such as the propylene oxide polymers and derivatives thereof, including the alkylene

109882/1264109882/1264

oxidpolymeren, die durch Polymerisation des Alkylenoxide in Gegenwart von Wasser oder Alkohol, wie Äthanol, her gestellt werden, Alkylbenzole, z.B. Monoalkylbenzole, wie Dodecylbenzol, Tetradecylbenzol usw., und Dialkylbenzole, wie z.B. n-Nonyl-2-äthylhexylbenzolj Polyphenole, wie z.B. Biphenyle und Terphenyle, halogenierte Benzole, halogenierte niedere Alkylbenzole und monohalogenierte Diphenyläther.oxide polymers obtained by polymerizing the alkylene oxides in the presence of water or alcohol, such as ethanol, are made, alkylbenzenes, e.g. monoalkylbenzenes, such as Dodecylbenzene, tetradecylbenzene, etc., and dialkylbenzenes such as n-nonyl-2-ethylhexylbenzene, polyphenols such as e.g. Biphenyls and terphenyls, halogenated benzenes, halogenated lower alkylbenzenes and monohalogenated diphenyl ethers.

Gemäß einer bevorzugten Ausführungsform der Erfindung wird die Phosphonium-Zusammensetzung kombiniert mit einem funktionellen Phosphat-Fluid als Grundmaterial. Das Grundmaterial besteht in erster Linie aus Trialkylphosphaten, die in einer Menge von 50 bis 90 Gew.-% und vorzugsweise von 65 bis 73 Gew.-% enthalten sind. Die Trialkylphosphate, die die besten Ergebnisse liefern, sind solche, in de nen jede Alkylgruppe 3 bis 12 Kohlenstoffatome, vorzugsweise 4 bis 9 Kohlenstoffatome aufweist. Die Alkylgrup en sollten geradkettige Konfiguration haben. Ein einzelnes Trialkylphosphat kann die Alkylgruppen in allen drei Positionen enthalten oder ein Gemisch aus verschiedenen Alkylgruppen besitzen. Auch Gemische von verschiedenen Trialkylphosphaten können verwendet werden. Zu den geeigneten Klassen von Tr ia],kyl phosphat en, die als Grundmaterial zusammensetzung verwendet werden können, gehören Tripropylphosphate, Tributylphosphate, Trihexylphosphate, Tri octylphosphate, Dipropyloctylphosphate, Dibutyloctylphosphate, Dipropylhexylphosphat, Dihexyloctylphosphat, Dihexylpropylphosphat und Propylbutyloctylphosphat.According to a preferred embodiment of the invention, the phosphonium composition is combined with a functional phosphate fluid as the base material. The base material consists primarily of trialkyl phosphates contained in an amount of from 50 to 90% by weight and preferably from 65 to 73 % by weight. The trialkyl phosphates which give the best results are those in which each alkyl group has 3 to 12 carbon atoms, preferably 4 to 9 carbon atoms. The alkyl groups should have a straight-chain configuration. A single trialkyl phosphate can contain the alkyl groups in all three positions or have a mixture of different alkyl groups. Mixtures of different trialkyl phosphates can also be used. Suitable classes of triacyl phosphates that can be used as the base material composition include tripropyl phosphates, tributyl phosphates, trihexyl phosphates, tri octyl phosphates, dipropyloctyl phosphates, dibutyl octyl phosphates, dipropylhexyl phosphate, dihexyloctyl propyl phosphate, dihexyloctyl propyl phosphate, dihexyloctyl phosphate.

Die Trialkylphosphate können mit mindestens einem Triarylphosphat, einschließlich Tricresylphosphat, Trixylenylphosphat, A'thylphenyldicresylphosphat oder Iso -The trialkyl phosphates can be mixed with at least one triaryl phosphate, including tricresyl phosphate, trixylenyl phosphate, Ethylphenyl dicresyl phosphate or iso -

109882/1264109882/1264

propylphenyldiphenylphosphat, Phenyl-bis-(4-alphamethylbenzylphenyDphosphat kombiniert werden. Gemäß einer bevorzugten Ausführungsform werden Tricresylphos phat und Trixylenylphosphat verwendet. Die Triarylphosphate wirken in diesem Falle als Dickungsmittel für die Trialkylphosphate. Die Menge an Tricresylphosphat und Trixylenylphosphat kann je zwischen O und 25 Gew.-# liegen. Der bevorzugte Bereich für die Triarylphosphate liegt bei 3 bis 15 % Tricresylphosphat und 5 bis 15 % Trixylenylphosphat. Das kombinierte Gemisch aus Tricresylphosphat und Trixylenylphosphat wird so miteinander vermengt, " daß es eine Viskosität von 145 bis 230 Saybolt Univer sal-Sekunden bei 38°C aufweist. Dieses Materialgemenge kann dann mit einem Trialkylphosphat in beliebiger Weise kombiniert werden.propylphenyldiphenylphosphate, phenyl-bis- (4-alphamethylbenzylphenyDphosphat. According to a preferred embodiment, tricresyl phosphate and trixylenyl phosphate are used. In this case, the triaryl phosphates act as thickeners for the trialkyl phosphates. The amount of tricresyl phosphate and trixylenyl phosphate can be between O and 25 wt. The preferred range for the triaryl phosphates is 3 to 15 % tricresyl phosphate and 5 to 15 % trixylenyl phosphate. The combined mixture of tricresyl phosphate and trixylenyl phosphate is blended together so that it has a viscosity of 145 to 230 Saybolt Universal seconds at 38 ° C. This material mixture can then be combined in any desired manner with a trialkyl phosphate.

Ein herkömmliches polymeres Material, das als ein Viskositätsindexverbesserer wirkt, wird dann mit dem Gemisch aus Trialkylphosphat und Triarylphosphat vermengt. Das erfindungsgemäß verwendbare polymere Material kann ein Gemisch aus 10 bis 35 Gew.-% Polymethacrylaten und Polyacrylaten sein. Die polymeren Materialien können in einem Lösungsmittelsystem, wie Di-2-äthylhexylsebacat, Dioctyladipat, Di-2-äthylhexyladipat oder anderen her- ^ kömmlichen Trägern vorliegen. Die polymeren Materialien können irgend eine Kombination dieser Materialien sein. . Das Material wird sorgfältig mit einer Kombination von Bestandteilen zu einer gleichförmigen Masse verarbeitet. Die Menge an eingearbeitetem Material kann zwischen 5 und 20 Gew.-% betragen.A conventional polymeric material which acts as a viscosity index improver is then blended with the mixture of trialkyl phosphate and triaryl phosphate. The polymeric material which can be used according to the invention can be a mixture of 10 to 35 % by weight of polymethacrylates and polyacrylates. The polymeric materials can be present in a solvent system such as di-2-ethylhexyl sebacate, dioctyl adipate, di-2-ethylhexyl adipate or other conventional carriers. The polymeric materials can be any combination of these materials. . The material is carefully processed into a uniform mass using a combination of ingredients. The amount of material incorporated can be between 5 and 20% by weight.

109882/1264109882/1264

Danach wird ein Rostverhüter in einem Lösungsmittel, wie z.B. ein Alkylsuccinat oder ein Derivat desselben mit dem Material vermengt. Der letztere kann in Mengen von 0,01 bis 0,5 Gew.-Sl» enthalten sein. Hierauf wird ein Korrosionsinhibitor, wie Benzotriazol, Chinizarin oder dergleichen in einer Menge von 0,001 bis 0,5 Gew.-% dem Gemisch beigemengt und sorgfältig eingearbeitet. Danach wird ein Farbstoff in einer Menge von 5 "bis 20 TpM zugesetzt und auf herkömmliche Weise eingearbeitet, üblicherweise wird schließlich ein Silikon-Schaumverhütungsmittel zugesetzt, das in einer Menge von 5 bis 50 TpM enthalten sein kann.A rust inhibitor is then mixed in with a solvent such as an alkyl succinate or a derivative thereof mixed with the material. The latter can be contained in amounts from 0.01 to 0.5 wt. Then a Corrosion inhibitor such as benzotriazole, quinizarine or the like in an amount of 0.001 to 0.5 wt% dem Mixture added and carefully incorporated. A dye is then added in an amount of 5 "to 20 ppm and incorporated in a conventional manner, usually Finally, a silicone antifoam agent is added in an amount of 5 to 50 ppm can be.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert:The invention is explained in more detail by the following examples:

Beispiel 1:Example 1:

Ein Grundmaterial, das Tricresylphosphat in einer Menge von 10,^5 Gew.-% enthält, wird sorgfältig mit 8,55 Gew.-% Trixylenylphosphat vermengt, so daß eine Viskosität von 155 Saybolt Universal-Sekunden, gemessen bei 38°C, erhalten wird. Dieses Materialgemenge wird mit 68,96 Gew.-% Tributylphosphat vermischt, bis ein homogenes Material erhalten wird. Danach werden 12 Gew.-% eines Ge misches aus etwa 40 % eines Polyalkylmethacrylats und etwa 60 % Di-2-äthylhexylsebacat (als Lösungsmittel) sorgfältig eingearbeitet. 3,Zf-Epoxycyclohexylmethyl-3,4-epoxycyclohexancarboxylat wird auf einen Additivgehalt von 1 Gew.-% einverleibt. Dann wird ein herkömmlicher Alkyl bernsteinsäure-Rostinhibitor in einer Menge von 0,02 Gew.A base material which contains tricresyl phosphate in an amount of 10.5% by weight is carefully mixed with 8.55% by weight of trixylenyl phosphate so that a viscosity of 155 Saybolt universal seconds, measured at 38 ° C., is obtained will. This material mixture is mixed with 68.96% by weight of tributyl phosphate until a homogeneous material is obtained. Thereafter, 12% by weight of a mixture of about 40 % of a polyalkyl methacrylate and about 60 % di-2-ethylhexyl sebacate (as a solvent) are carefully incorporated. 3, Zf-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is incorporated to an additive content of 1% by weight. Then a conventional alkyl succinic acid rust inhibitor in an amount of 0.02 wt.

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in einem Lösungsmittel untergemengt. Darauf werden 0,02 Gew.% Benzotriazol zusammen mit einem herkömmlichen Farbstoff und Schaumverhütungsmittel in einer Menge von 10 TpM, bezw. 15 TpM eingearbeitet. Schließlich wird Trioctylmethylphosphoniumdimethylphosphat in das Gemisch in wechselnden Mengen von 5> 3> 1 und 0,5 Gew.-% eingemischt. mixed in a solvent. Thereupon 0.02 wt. % Benzotriazole together with a conventional dye and antifoam agent in an amount of 10 ppm, respectively. 15 ppm incorporated. Finally, trioctylmethylphosphonium dimethylphosphate is mixed into the mixture in varying amounts of 5>3> 1 and 0.5% by weight.

Die in Beispiel 1 beschriebenen und andere Zusammensetzungen wurden in der nachstehend beschriebenen Appa-" ratur getestet.The compositions described in Example 1 and other compositions were made in the appa- " temperature tested.

Die Vorrichtung war eine modifizierte Boeing-Verschleißapparatur, die dazu bestimmt ist, den beengten Fluß in dem Servo-Ventil eines Flugzeug-Hydrauliksystems zu simulieren. Die Apparatur besteht aus einer luftbetrie benen Kolben-Hydraulikpumpe, Sammler, Filter, Strömungsmesser, Wärmeaustauscher, Reservoir und Abnutzungsvor richtung. Die letztere ist aus 52100 Stahl, der auf R 62 gehärtet ist, gearbeitet. Das Fluid betritt die Vor-The device was a modified Boeing wear apparatus, which is designed to cope with the restricted flow in the servo valve of an aircraft hydraulic system simulate. The apparatus consists of an air-operated piston hydraulic pump, collector, filter, flow meter, Heat exchanger, reservoir and Abnutzungsvor direction. The latter is made from 52100 steel that is on R 62 is hardened, worked. The fluid enters the front

c 2c 2

richtung durch eine 0,215 cm-I.D. Düse mit 175 kg/cm unddirection through a 0.215 cm-I.D. Nozzle with 175 kg / cm and

0,034 nrVh und prallt gegen ein flaches Blech, 0,025 mm von der Düse entfernt. Die Abnutzungsvorrichtung wird ' nach 24 Stunden Test auseinandergenommen, und der Ver schleiß an dem flachen Blech wird visuell mit und ohne Hilfe eines Mikroskops bestimmt. Die Resultate waren wie folgt:0.034 nrVh and hits a flat sheet, 0.025 mm away from the nozzle. The wear device is disassembled after a 24 hour test and the wear the flat sheet is determined visually with and without the aid of a microscope. The results were like follows:

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% Methyltrioctylphosphonium dimethylphosphat (1) % Methyltrioctylphosphonium dimethylphosphate (1)

_(Gew.-%) Relative Abnutzung Phosphatester-Fluid _ (Wt%) Relative wear phosphate ester fluid

keinsno starkstrong 0,50.5 mäßigmoderate 1,01.0 vernachlässigbarnegligible 3,03.0 ItIt 5,05.0 IlIl

Diese Ergebnisse beweißen die Möglichkeit des· Methyltrioctylphosphoniumdimethylphosphats bei der Ver besserung des Verschleißverhaltens eines Phosphatester-Hydraulikfluids zur Vermeidung von Schaden am Hydrauliksystem. These results prove the possibility of methyltrioctylphosphonium dimethylphosphate in the improvement the wear behavior of a phosphate ester hydraulic fluid to avoid damage to the hydraulic system.

Beispiele Examples Z-IG'.Z-IG '.

Typische Phosphoniumverbindungen 2 bis 16, wie vorstehend beschrieben, verringern, in das Phosphatester-Grundmaterial von Beispiel 1 eingearbeitet, ebenfalls die Verschleißwirkung des Fluids.Typical phosphonium compounds 2 to 16, as described above, decrease in the phosphate ester base material from Example 1 incorporated, likewise the wear effect of the fluid.

Äußer in Flugzeug-Hydraulikfluids können die hier beschriebenen Phosphoniumverbindungen in einer Vielzahl von Schmiermittelzusammensetzungen verwendet werden. Der hier verwendete Ausdruck "Schmiermittel11 soll FluidsOther than in aircraft hydraulic fluids, the phosphonium compounds described herein can be used in a variety of lubricant compositions. As used herein, "lubricant 11" is intended to be fluids

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umfassen, die primär wegen ihres Schmiervermögens, und
solche, die als Druckübertragungsmittel verwendet wer den. Die Phosphoniumverbxndungen sind brauchbar als Hochdruckadditive in Fluids, einschließlich Flugzeuggastur binen-Schmiermitteln, als Additive in schwer entflamm baren industriellen Schmiermitteln, einschließlich Ge triebe- und Schneidölen, und in Bremsflüssigkeiten.
include, primarily because of their lubricity, and
those that are used as a pressure transmission medium to who. The phosphonium compounds are useful as high pressure additives in fluids, including aircraft gas turbine lubricants, as additives in flame-retardant industrial lubricants, including gear and cutting oils, and in brake fluids.

109882/1264109882/1264

Claims (8)

Patentansprüche;Claims; 1. Als Hydraulik-Fluid und Schmiermittel geeignete Zusammensetzung, die aus einem Grundmaterial und mindestens einem Additiv besteht, dadurch gekennzeichnet, daß dieses Additiv eine Phosphoniumverbindung der Formel1. Suitable as hydraulic fluid and lubricant Composition consisting of a base material and at least one additive, characterized in that, that this additive is a phosphonium compound of the formula R -R - P-R" ιP-R "ι RMlRMl IlIl Z-PZ-P Y' Y"Y 'Y " ist, in welcher R, R1 und R1' Alkyl-, Aryl-, Alkaryl- oder Aralkyl-Reste mit 1 bis 10 Kohlenstoffatomen sind und R'»« ein Alkyl- oder Aralkyl-Rest mit 1 bis 10 Kohlenstoffatomen ist, X für 0 oder S steht, Y1 und Y'1 Alkoxy-, Alkylthio-, Alkyl-, Aryl-, Alkaryl-, Aralkyl-, Aryloxy-, Arylthio- oder Alkaryloxy-Gruppen sind und Z Sauerstoff darstellt.in which R, R 1 and R 1 'are alkyl, aryl, alkaryl or aralkyl radicals having 1 to 10 carbon atoms and R' »« is an alkyl or aralkyl radical having 1 to 10 carbon atoms, X represents 0 or S, Y 1 and Y ' 1 are alkoxy, alkylthio, alkyl, aryl, alkaryl, aralkyl, aryloxy, arylthio or alkaryloxy groups and Z represents oxygen. 109882/1284109882/1284 2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Grundmaterial ein Ester einer Säure des Phosphors, Amid einer Säure des Phosphors, Mineralöl, synthetisches Kohlenwasserstofföl, Kohlenwasserstoff silikat, Silikon, aromatischer Ester, eine Thioätherverbindung, ein chloriertes Biphenyl, Monoester, Dicarbonsäureester, Ester mehrwertiger Verbindungen, Polyalkylenätherglycol, Alkohol, Alkoholester oder ein Gemisch derselben ist.2. Composition according to claim 1, characterized in that the base material is an ester of a Acid of phosphorus, amide of an acid of phosphorus, mineral oil, synthetic hydrocarbon oil, hydrocarbon silicate, silicone, aromatic ester, a thioether compound, a chlorinated biphenyl, monoester, dicarboxylic acid ester, Esters of polyvalent compounds, polyalkylene ether glycol, alcohol, alcohol esters or a mixture thereof is. 3. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Grundmaterial ein Ester einer Säure des Phosphors ist.3. Composition according to claim 1, characterized in that the base material is an ester of a Is acid of phosphorus. 4. Zusammensetzung nach Anspruch 3» dadurch gekennzeichnet, daß dieser Ester ein Trialkylphosphat ist.4. Composition according to claim 3 »thereby characterized in that this ester is a trialkyl phosphate is. 5. Zusammensetzung nach Anspruch 3» dadurch gekennzeichnet, daß dieser Ester ein Gemisch aus Trialkylphosphaten und Triarylphosphaten ist.5. Composition according to claim 3 »characterized in that this ester is a mixture of trialkyl phosphates and is triaryl phosphates. 6. Zusammensetzung nach Anspruch 5> dadurch ge kennzeichnet, daß sie diese Trialkylphosphate in einer Menge von etwa 50 bis 90 Gew.-% und diese Triarylphos phate in einer Menge von bis zu etwa 50 Gew.-% enthält.6. Composition according to claim 5> characterized in that they are these trialkyl phosphates in one Amount of about 50 to 90% by weight and this triarylphosphate in an amount of up to about 50% by weight. 7. Zusammensetzung nach Anspruch 1, dadurch ge-7. Composition according to claim 1, characterized 109882/1264109882/1264 kennzeichnet, daß sie diese Phosphoniumverbindung in einer Menge von etwa 0,1 bis 10 Gew.-%, vorzugsweise von etwa ,5 bis 2,0 Gew.-% enthält..indicates that they contain this phosphonium compound in an amount of about 0.1 to 10 wt .-%, preferably of about , 5 to 2.0 wt .-% contains .. 8. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie einen Bostinhibitor und/oder einen Farbstoff und/oder ein Schaumverhütungsmittel und/oder einen Korrosionsinhibitor und/oder einen Säureakzeptor enthält,8. Composition according to claim 1, characterized in that that they have a bost inhibitor and / or a dye and / or an anti-foaming agent and / or contains a corrosion inhibitor and / or an acid acceptor, Für: Stauffer Chemical CompanyFor: Stauffer Chemical Company 109882/1264109882/1264 ORIGINAL INSPECTEDORIGINAL INSPECTED
DE19712131926 1970-06-29 1971-06-26 Hydraulic fluids with a content of quaternary phosphonium salts Pending DE2131926A1 (en)

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US5100170A 1970-06-29 1970-06-29

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US (1) US3707501A (en)
BE (1) BE769225A (en)
CA (1) CA969528A (en)
CH (1) CH563448A5 (en)
DE (1) DE2131926A1 (en)
EG (1) EG10516A (en)
FR (1) FR2096564B1 (en)
GB (1) GB1310801A (en)
IL (1) IL36930A (en)
NL (1) NL7108962A (en)
NO (1) NO131462C (en)
SE (1) SE374760B (en)
SU (1) SU404274A3 (en)
ZA (1) ZA713389B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110423A1 (en) 2010-03-08 2011-09-15 Basf Se Salts of thiophosphoric acids and their use in lubricants
US8507419B2 (en) 2010-03-08 2013-08-13 Basf Se Salts of thiophosphoric acids and use thereof in lubricants

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075115A (en) * 1972-09-18 1978-02-21 General Electric Company Silicone fluid useful as a brake fluid
US3932294A (en) * 1974-01-11 1976-01-13 Chevron Research Company Functional fluid containing a hydrolysis suppressor
US4252662A (en) * 1974-02-11 1981-02-24 Stauffer Chemical Company Functional fluids containing ammonium salts of phosphorus acids
US5205951A (en) * 1987-06-30 1993-04-27 Chevron Research And Technology Company Phosphate ester-based functional fluids containing an epoxide and a compatible streaming potential-inhibiting metal salt
US6214777B1 (en) 1999-09-24 2001-04-10 Ecolab, Inc. Antimicrobial lubricants useful for lubricating containers, such as beverage containers, and conveyors therefor
US6599866B2 (en) 2001-04-20 2003-07-29 Exxonmobil Research And Engineering Company Servo valve erosion inhibited aircraft hydraulic fluids
CA2356709A1 (en) * 2001-09-05 2003-03-05 Kenneth R. Seddon Use of phosphonium salts
US20040127370A1 (en) * 2002-11-15 2004-07-01 Poirier Marc Andre Hydraulic fluids with erosion resistance
EP1970432A1 (en) * 2006-12-19 2008-09-17 Castrol Limited Lubricating oil compositions and uses
US9957460B2 (en) * 2014-02-20 2018-05-01 Ut-Battelle, Llc Ionic liquids containing symmetric quaternary phosphonium cations and phosphorus-containing anions, and their use as lubricant additives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110423A1 (en) 2010-03-08 2011-09-15 Basf Se Salts of thiophosphoric acids and their use in lubricants
US8507419B2 (en) 2010-03-08 2013-08-13 Basf Se Salts of thiophosphoric acids and use thereof in lubricants

Also Published As

Publication number Publication date
NL7108962A (en) 1971-12-31
SE374760B (en) 1975-03-17
CA969528A (en) 1975-06-17
BE769225A (en) 1971-12-29
CH563448A5 (en) 1975-06-30
FR2096564A1 (en) 1972-02-18
IL36930A0 (en) 1971-07-28
ZA713389B (en) 1972-01-26
US3707501A (en) 1972-12-26
SU404274A3 (en) 1973-10-26
GB1310801A (en) 1973-03-21
NO131462C (en) 1975-06-04
EG10516A (en) 1976-04-30
NO131462B (en) 1975-02-24
IL36930A (en) 1974-03-14
FR2096564B1 (en) 1975-07-11

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