DE1149016B - Process for the preparation of carbalkoxyalkyldiphenyl ethers useful as lubricants - Google Patents

Description

GERMAN

PATENT OFFICE

C 19079 IVb / 12q

REGISTRATION DATE: MAY 29, 1959

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL: MAY 22, 1963

The invention relates to a method for producing radiation against the action of atomic nuclear radiation stable carbalkoxyalkyldiphenyl ethers which can be used as lubricants. The procedure is through characterized in that diphenyl ether with ethyl undecylenate in a molar ratio of 1: 1 in the presence of aluminum chloride in a known manner and the resulting ester mixture of 1- (Γ-methyl-9'-carbäthoxynonyl) -4-phenoxybenzene and 4,4'-di - (1 "-methyl - 9" - carbäthoxynonyl) - diphenyl ether optionally separates by distillation.

The new compounds are liquid at normal temperatures and work well as lubricants, as base oils for lubricant compositions for lubricating internal combustion engines, as Base oils for grease compositions and lubricants in general. These new oils are against Atomic nuclear radiation particularly resistant.

The new oils are used to manufacture lubricants that are exposed to nuclear radiation are. By irradiating organic liquids with neutrons, X-rays or gamma rays their viscosity increases. It is believed that the increase in viscosity is due to polymerization and Networking is due. When using nuclear energy to generate electrical power there are many friction surfaces on gears, bearings, journals, etc., all of which have to be lubricated. the Irradiation of the usual lubricants leads to the formation of heavier viscous or solid substances, which than Lubricants are ineffective. In addition, the

C ₆ H ₅ -O —CÄ —CH method of manufacture

of carbalkoxyalkyldiphenyl ethers which can be used as lubricants

Applicant:

California Research Corporation, San Francisco, Calif. (V. St. A.)

Representative: Dr. W. Beil

and A. Hoeppener, lawyers,

Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority: V. St. v. America 29 May 1958 (No. 738 649)

Donovan Ray Wilgus, Richmond, Calif. (V. St. Α.), Has been named as the inventor

Irradiation generally greatly intensifies the oxidation of lubricants. The new lubricants do not show these disadvantages.

The new compounds can be represented by the following formulas:

- COOC ₂ H ₅

C ₂ H ₅ OOC - (CH ₂ ) ₈ - CH - C ₆ H ₄ - O - C ₆ H ₄ - CH - (CHJ ₈ - COOC ₂ H ₅

CH _a

example

A mixture of 170 g (1.0 mol) of diphenyl ether and 133 g (1.0 mol) of anhydrous aluminum chloride is placed in a reaction vessel equipped with a stirrer. 212 g (1.0 mol) of ethyl undecylenate are slowly (dropwise) added to this mixture. The reaction temperature was maintained at 45 to 50 ° C using ice water as an external coolant until the undecylenic acid ester was completely added. The mixture was then heated to 60-70 ° C for 5 hours, then with the CH ₃

diluted equal volume of benzene and then poured onto hydrochloric acid diluted with ice. When the mixture was heated, the benzene layer separated from the aqueous phase. The benzene layer was washed with water until neutral, then dried over anhydrous sodium sulfate and filtered. The benzene was removed by distillation, followed by the monocarboxylic acid ester in one yield of 31.4% and the dicarboxylic acid ester with a yield of 16.5%, in each case based on the used Reaction components, were obtained by distillation under reduced pressure.

309 597/329

3 4

Table I shows the physical properties of the products of the example.

Table I.

Monocarbon
acid ester Dicarbon
acid ester Boiling range of the middle fraction at 0.5 mm Hg, ⁰ C.
Viscosity in centistokes
at 38 ° C 190 to 210
25.7
4.53 290 to 317
87.4
10.6 at 99 ° C 236 321 Temperature in ⁰ C with a viscosity of
1 cSt -25
-37 - 9
-22 2500 cSt 98
-52
170,000
1.5187 111
-48
1,000,000
1.5038 13000 cSt Viscosity index Pour point, ⁰ C Viscosity at pour point in centistokes
Refractive index, n ² g

In Table II are the results of the investigations on the radiation resistance of the new Connections recorded.

The resistance of the new Carbalkoxyalkyldipb.enylatb.er versus irradiation was determined by exposing the compounds to gamma rays. A 10 cc sample of the substance to be tested was placed in a Enclosed stainless steel capsule. The liquids were at about 15 ° C with two different Dosages irradiated, whereupon the changes in their viscosity were noted. the gamma radiation used here was taken from spent nuclear reactor fuel.

Table II

Monocarboxylic acid ester

Dicarboxylic acid ester

Change in viscosity at 38 ° C after irradiation

with 1.13 x 10 ¹⁰ ergs / g carbon

with 5.31 x 10 ¹⁰ ergs / g carbon

Change in viscosity at 99 ° C after irradiation

with 1.13 x 10 ¹⁰ ergs / g carbon

with 5.31 x 10 ¹⁰ ergs / g carbon

+ 37.7
+ 187.0

+ 24.4
+ 93.0

+ 2.53
+ 19.2

- 0.88
+ 11.2

+ 5.25 + 106.0

+ 3.49 + 29.2

*) Colorless Californian petroleum oil with a viscosity index of 70 cSt at 38 ⁰ C.

Claims (1)

PATENT CLAIMS: Process for the preparation of carbalkoxyalkyldiphenyl ethers which can be used as lubricants, characterized in that diphenyl ether is reacted with undecylenic acid ethyl ester in a molar ratio of 1: 1 in the presence of aluminum chloride in a manner known per se, and the resulting ester mixture consists of l- (l'-methyl-9'-carbäthoxynonyl ) -4-phenoxybenzene and 4,4'-di (I "methyl-9" -carbethoxynonyl) - diphenyl ether optionally separated by distillation. Considered publications: German patent specifications No. 615 530, 536 550. © 309 597/329 5.63