JPS6124437B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to metal deactivators and compositions thereof. Specifically, the present invention relates to a metal deactivator having a novel structure and a composition thereof, which is preferably used as a lubricating oil additive. Metal deactivators are additives that inactivate dissolved metal salts that promote the oxidation of fuels and lubricating oils, or create inert films on metal surfaces, and commonly include benzotriazole, its derivatives, and thiadiazole. Although known, the performance when using these compounds was not necessarily sufficient. As a result of searching for the synthesis of a large number of compounds, the inventors of the present application discovered that an oxyquinoline derivative having a specified structure has superior performance compared to the conventionally known above-mentioned compounds. It was done. That is, the present invention is based on the formula (); and expression (); The present invention relates to a metal deactivator comprising at least one oxyquinoline derivative selected from the group consisting of: Here, in formula () and formula (),
R ₁ , R ₂ and R ₃ may be the same or different, and C ₁ to
_C20 alkyl group, _C2 - _C20 alkenyl group, _C5 - _C12
Cycloalkyl group, _C5 - _C10 aryl group, _C7 - _C9
Aralkyl group, or R ₄ O (R ₅ O) _o R ₆ [R ₄ is a hydrogen atom or a C ₁ - _{C 20} alkyl group, R ₅ and R ₆ are C ₂ -
C ₃ alkylene group, n is 0 to 4]. Hereinafter, the metal deactivator according to the present invention will be described in more detail. In formulas () and (), R ₁ R ₂ and
R ₃ may be the same or different. i.e. expression ()
When using a compound of formula (), R ₁ and R ₂ may be the same or different; when using a mixture of a compound of formula () and a compound of formula (), R ₁ , R ₂ and R ₃
may be of the same or different species. When any or more of _R1 to _R3 is an alkyl group, a _C1 to _C20 , more preferably a _C3 to _C18 alkyl group is used, and preferred specific examples include butyl,
Hexyl, octyl, 2-ethyl-hexyl, decyl, dodecyl, hexadecyl or octadecyl groups. When one or more of R ₁ to _{R 2} is an alkenyl group, C ₂ to C ₂₀ , more preferably C ₃ to
C ₁₈ alkenyl groups are used, preferred examples being butenyl, octenyl, decenyl, dodecenyl, tetradecenyl and octadecenyl (oleyl) groups. When any or more of _R1 to _R3 is a cycloalkyl group, a _C5 to _C12 cycloalkyl group is used, and a preferred specific example is a cyclohexyl group. When any or more of R ₁ to _{R 3} is an aryl group, a C ₅ to _{C 10} aryl group is used, and preferred specific examples are phenyl and naphthyl groups. When any or more of R ₁ to _{R 3} is an aralkyl group, a C ₇ to _{C 9} aralkyl group is used, and a preferred specific example is a benzyl group. Any or more of R ₁ to R ₃ is R ₄ O (R ₅ O) _o
In the case of the group represented by R ₆ , R ₄ is a hydrogen atom or
A _C1 - _C20 alkyl group, more preferably a hydrogen atom or a _C1 - _C3 alkyl group, even more preferably a hydrogen atom, _R5 and _R6 are a _C2 - _C3 alkylene group, n is 0-4, More preferably it is 0. Preferred specific examples are hydroxyethyl, methoxyethyl, n-
butoxyethyl, methoxyethoxyethyl, n-
butoxyethoxyethyl and n-octyloxypropyloxy groups. The method for producing oxyquinoline derivatives in the present invention is not particularly limited, but for example, in order to obtain the compound of formula (), 8-hydroxyquinoline, a secondary amine satisfying the conditions R ₁ and R ₂ above, and an aldehyde are used. Mannitz reaction is preferred, and in order to obtain the compound of formula (), Mannitz reaction of 8-hydroxyquinoline, a primary amine satisfying the above-mentioned _R3 condition, and formaldehyde is preferred. Among the metal deactivators according to the present invention, more preferred are compounds represented by the formula (), in particular, R ₁ and R ₂ are the same or different, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl group. belongs to. The metal deactivator according to the invention is preferably used in lubricating oils, and preferred lubricating oil compositions contain 0.001 to 10.0% by weight, preferably 0.01 to 1.0% by weight of the metal deactivator, All or the main part of the remainder has a kinematic viscosity of 10 to 10,000 cSt (40℃),
The composition is preferably a mineral oil and/or synthetic oil of 20 to 1000 cSt (40° C.) and a viscosity index of 80 or more, preferably 90 or more. The mineral oil preferably used here is one obtained by refining a lubricating oil fraction of petroleum by hydrorefining, clay refining, solvent refining, or a combination thereof. As the synthetic oil, polybutene, poly-α-offrein, diester, polyol ester, or a mixture thereof is preferably used. If the amount of the metal deactivator is less than 0.001% by weight, the intended effect as a metal deactivator cannot be exhibited, and if it is more than 10.0% by weight, it is economically unfavorable. In the above lubricating oil composition, in addition to the metal deactivator, if necessary, an antioxidant, a detergent dispersant, a viscosity index improver, a pour point depressant, a rust inhibitor, an extreme pressure agent, etc. , an oiliness improver or an antifoaming agent may also be added. For details on these various additives, see, for example, the Journal of the Japan Society of Lubrication, Vol. 15, No. 6, or "Petroleum Product Additives" edited by Toshio Sakurai.
(Saiwai Shobo). The metal deactivator according to the present invention is preferably used in lubricating oils, specifically turbine oils, hydraulic oils, gear oils, gasoline engine oils, diesel engine oils, marine engine oils, compressor oils, Used in oil film bearing oil, refrigeration machine oil, sliding guideway lubricating oil, rolling oil, machine tool oil, automatic transmission oil, various metal working oils and greases, as well as electrical insulation oil, heat transfer oil, rust prevention oil, etc. used. Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples, Examples, and Comparative Examples. Synthesis example 16.0g of 8-hydroxyquinoline and bis(2
-Ethylhexyl)amine (24.2 g) was taken, 150 ml of methanol was added thereto, and the mixture was stirred at 20°C. 35% here
10.4 ml of formalin aqueous solution was added dropwise, and the mixture was reacted at 20°C for 1 hour, and then refluxed at the boiling point of methanol for 3 hours. After adding water and methanol to the reaction mixture, it was extracted with n-hexane, the solvent was removed, and dried to obtain 7-bis(2-ethylhexyl).
22.5 g of aminomethylene-8-hydroxyquinoline (a compound in which R and R ₂ are both 2-ethylhexyl groups in formula ()) was obtained. Similarly below,
Oxyquinoline derivatives 1 to 13 represented by formula () and oxyquinoline derivatives 14 to 17 represented by formula () were synthesized by Mannitz reaction.

【table】

[Table] Examples and Comparative Examples The oxyquinoline derivatives 1 to 17 according to the synthesis examples were added to mineral oil, and their performance as metal deactivators was evaluated by the copper plate corrosion test and oxidation test shown below. The results are shown in Table 3. <Copper plate corrosion test> Sulfurized offrain (sulfur concentration 40.8%) was added to commercially available turbine oil with a kinematic viscosity of 32.5 cSt (40°C) and a viscosity index of 102.
The sample oil was prepared by adding 1.0% by weight, and 0.01% by weight (in) of oxyquinoline derivative was added to it.
Copper plate corrosion test according to JIS K2513 (test temperature 100
°C for 3 hours). <Oxidation test> 0.1% by weight (in) of oxyquinoline derivative was added to the above commercially available turbine oil 32, and ASTM D2272
Rotary bomb oxidation test (test temperature 150℃,
(oxygen pressure 13 Kg/cm ² , copper wire catalyst), and the results were evaluated based on the time it took to absorb 1.8 Kg/cm ² of oxygen.

[Table] The oxyquinoline derivative according to the present invention showed excellent performance in copper plate corrosion tests and oxidation tests, and also showed favorable performance when used as lubricating oils such as turbine oil and hydraulic oil.

Claims (1)

[Claims] 1 Formula (); and expression (); A metal deactivator comprising at least one oxyquinoline derivative selected from the group consisting of: [However, in formula () and formula (),
R ₁ , R ₂ and R ₃ may be the same or different, and C ₁ to
_C20 alkyl group, _C2 - _C20 alkenyl group, _C5 - _C12
Cycloalkyl group, _C6 - _C10 aryl group, _C7 - _C9
Aralkyl group, or R ₄ O (R ₅ O) _o R ₆ [R ₄ is a hydrogen atom or a C ₁ to _{C 20} alkyl group, R ₅ and R ₆ are C ₂ to
C ₃ alkylene group, n is a group represented by 0 to 4]. ]