JPS59189195A - Metal inactivator-containing composition - Google Patents

Abstract

PURPOSE:To provide the title composition containing a metal inactivator prepared by specified synthesis and refining processes, which has a high metal inactivation effect and a low tendency toward sludge formation and is suitable for lubricating oil, etc. CONSTITUTION:The composition is prepared by adding 0.01-10.0wt.% (A) metal inactivator to (B) mineral oil and/or synthetic oil having a kinematic viscosity of 10-10,000cSt at 40 deg.C and a viscosity index of 80 or higher. (A) is obtained by adding 1-100 mol% at least one ethanolamine selected from among monoethanolamine, diethanolamine and triethanolamine to a reaction product of a compd. of the formula (where R1 and R2 are 4-18C alkyl, cycloalkyl or cycloalkyl having a side chain alkyl), formaldehyde in an equivalent mol or higher and benzotriazole or methylbenzotriazole in excess by 5mol% or higher, followed by washing. The composition has high oxidative stability and low tendency toward sludge formation and is suitable as lubricating oil for turbine oil, compressor oil, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition containing a metal deactivator, and more particularly to a composition containing an improved metal deactivator, which has a low tendency to form sludge and is preferably used as a lubricating oil. Regarding the composition.

A metal deactivator is an additive that deactivates a metal base in a bath that promotes oxidation of fuel or lubricating oil, or creates an inert film on the metal surface, and is an additive that creates an inert film on the metal surface. Although bencitazoles are excellent metal deactivators, they have low solubility in mineral oils and/or synthetic oils, and when used as additives in mineral oils and/or synthetic oils. It has the disadvantage of forming an oil-insoluble sludge, which limits its use.

Therefore, various efforts have been made to introduce oil-soluble functional groups into benzotriazole to reduce its solubility in mineral and/or synthetic oils, one of which is British Patent No. 1,061. , No. 90'1 discloses a method for attaching dialkylamines by Mannich reaction according to the following formula.

This method is an excellent method for increasing the solubility of benzotriazole in mineral oil 2 and/or synthetic oil without reducing its performance as a metal deactivator. However, due to the above Mannich reaction,
Although the dialkylamine methylbenzotriazole aminomethyl-methylbenzene is superior to benzotriazole in bath elucidation for mineral oils and/or synthetic oils, it is There is still a drawback that it generates sludge when used, and the sludge generation is extreme! ! l
There was a problem that it could not be used in situations where llt would be used.

The inventors of the present invention have made extensive research in order to solve the above-mentioned problems, and have previously filed a patent application 6-1. 5 0 8 9 2
(Japanese Patent Publication No. 58-52393), a composition containing a metal deactivator produced by a specified synthesis and purification method was invented. The refining method of the invention (d) was to wash the synthesized metal deactivator with an aqueous methanol solution, but the oil composition containing the metal deactivator has poor oxidative stability. However, it had the disadvantage of generating slightly more sludge.

Therefore, the present inventors conducted further research to improve the above method, and as a result, a composition containing dialkylaminomethylbenzotriazole or dialkylaminomethyl-methylbenzotriazole produced by the specified synthesis and purification method was found. The product has extremely superior performance compared to compositions containing the above-mentioned compounds produced by conventionally known methods.
It was discovered that the composition disclosed in No. 2 has an improved tendency to form sludge, and the present invention was completed.

The object of the present invention is to provide a composition which has a high metal deactivation effect and has a low tendency to form sludge, which is made by blending a metal deactivator produced by a specified synthesis method and purification method. shall be.

That is, the present invention relates to compounds (2) represented by the same or different alkyl groups having 4 to 18 carbon atoms, cycloalkyl groups, or cycloalkyl groups having an alkyl side chain; and (3) a reaction mixture of benzotriazole or methylbenzotriazole in an excess amount of 5 mol% or more relative to the compound of (1) selected from monoethanolamine, jetanolamine, and triethanolamine. 1 to 1 of one or more ethanolamines to the compound of (1).
Metal deactivator obtained by adding 0.00 mol% and washing, 0.001 to 10, 10 to 10,000
cSt (40°C), 111 number 80 or more, mineral oil and/or synthetic oil.

Hereinafter, the metal deactivator-containing composition according to the present invention will be explained in more detail.

The compound (1), which is the raw material for (1), which has an excellent effect as a metal deactivator according to the present invention, is generally 17
1 and R2 represent the same or different alkyl groups, cycloalkyl groups, or alkyl/chloroalkyl groups having 4 to 8 carbon atoms and having a linear or branched structure. When the number of carbon atoms is less than 4, the angle of attack of the reaction product synthesized with respect to mineral oil and synthetic oil is low and extremely sweet. (When the number of carbon atoms exceeds 18, is not suitable because the reaction product becomes less effective as a metal deactivator. Preferred specific examples of R1 and R2 d,
Butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl! ``i4i4-methylfuclohexyl group.

The compound (2) used in the present invention is formaldehyde, which is usually preferably used as an aqueous solution (formalin).

The compound (3) used in the present invention may be benzotriazole or methylbenzotriazole, or a mixture thereof. The methylbenzotriazole may be vi4-methylbenzotriazole or 5-methylbenzotriazole, or a mixture thereof.

In the present invention, the compound (,1)-(3) is converted into (1)
Formaldehyde (2) is used in an excess amount of at least 1 mol, preferably 5 mol % or more, relative to the secondary amine (2), and benzotriazole or methylbenzotriazole (3) is added in an excess of 5 mol % or more, preferably It is necessary to react by cooling to an excess amount of 10 moles or more.With this method, the WJ secondary amine of (1), which is 1F, is difficult to remove as an unreacted product after the reaction. % consumed in the reaction n,
Only formaldehyde and benzotriazole or methylbenzotriazole, which are easily removed as unreacted substances, remain in the reaction mixture.

The reaction solvent used in the above reaction is arbitrary, but alcohols such as methanol, ethanol, and isopropanol are preferred. Furthermore, methanol is particularly preferred from the viewpoint of ease of mixing the reaction product and solvent in one part. Although the reaction temperature is arbitrary, 45.-65°C is usually preferred. If the reaction temperature is less than 45°C, the reaction rate is slow, and if it exceeds 65°C, methanol cannot be used as a reaction solvent.

In the present invention, it is further important to wash the reaction mixture by adding one or more ethanolamines selected from monoethanolamine, jetanolamine and triethanolamine. The amount of ethanolamine added is as described above (1 to 100 mol, preferably 5 to 80 mol, relative to the current compound).The cleaning liquid used for cleaning may be water or an aqueous methanol solution with a concentration of 95 mol or less. preferable.

The amount of these washing liquids added to the reaction product and the number of times of washing are arbitrary, but it is usually preferable to wash 2 to 3 times.

Furthermore, during washing, it is preferable to add a non-polar organic solvent such as hexano, benzene, mineral spirit, etc. to the reaction mixture in advance to extract the reaction product, and to separate only this organic layer and wash it with a washing solution. be done.

The method of adding ethanolamine to the reaction mixture is arbitrary, but usually, ethanolamine is added to the reaction mixture, stirred and mixed well, and then this mixture is washed with a washing solution, or ethanolamine and washing solution are added to the reaction mixture at the same time. Preferred methods include washing the reaction mixture with a washing solution containing ethanolamine.

In addition, when extracting the reaction product with a non-polar organic solvent, add ethanolamine to the reaction mixture, stir and mix well, then extract the reaction product with a non-polar organic solvent and separate the organic layer. A method of cleaning only the organic layer with a full cleaning solution,
A method in which ethanolamine and a non-polar organic solvent are added to the reaction mixture at the same time, the reaction product is extracted, the organic layer is separated, and only this organic layer is washed with a washing solution. A preferred method is to simultaneously add ethanolamine and a non-polar solvent or cleaning solution.

In contrast to the present invention, when ethanolamine is not added or when a basic substance other than ethanolamine is added, a large amount of sludge is generated when it is added to mineral oil, as shown in the comparative example below. However, the thermal stability of the oil is still poor.

The metal deactivator, which is a component of the composition according to the invention, is usually obtained by filtering the reaction product thus purified and heating the filtrate under reduced pressure to remove residual solvent.

The composition according to the invention comprises 0.001 of the metal deactivator.
~1(), 0 vehicle quantity, preferably 0. Contains OJ ~ 1.0 vehicle volume coefficient, and the rest or the main part has a kinematic viscosity l C
) to 10,000 cst (40°C), preferably 20 to 1000 cst (40°C), viscosity index lA30
The composition is preferably a mineral oil and/or a synthetic oil of 90 or higher. The mineral oil preferably used here is one obtained by refining a lubricating fraction of petroleum by hydrorefining, clay refining, solvent refining, or a combination thereof1.
As the synthetic oil, polybutene, poly-α-olein, diester, polyol ester, or a mixture thereof is preferably used. The metal deactivator is 0
．． If the amount is less than 001, the effect of a metal deactivation agent may be exhibited, and if it is more than 10.0, it is economically unfavorable.

In the composition of the present invention, 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, Oiliness improvers or antifoaming agents can 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 (
Published in Sachi Shobo).

The metal deactivators and compositions thereof according to the invention are preferably used in lubricating oils, in particular:
Turbine oil, hydraulic oil, gear oil 1 Easy engine oil, teasel engine oil, marine engine oil, compressor oil, oil film bearing oil, refrigeration oil, sliding guideway lubricating oil, rolling oil, machine tool oil, automatic transmission oil absorption, various metals It is used as processing oil or grease, as well as electrical insulation oil, heat transfer oil, rust preventive oil, filler oil, etc.

In particular, the composition according to the present invention (r) is preferably used in lubricating oils, turbine oils, and compressor oils in which the formation of sludge would impede long-term safe operation of equipment.

Hereinafter, based on the synthesis-f7 example, examples, and comparative examples, Q,
The present invention will be explained in detail.

Synthesis-purification example 1 26.09 (0.22 mol) benzotriazole and 48.3 g (0.22 mol) bis-2-ethelhexylamine
20 mol) of methanol at 3001 dK was heated and stirred at 50"G in a nitrogen stream. To this was added dropwise 19.5 i (0.24 mol) of a 37% by weight formalin aqueous solution, and the mixture was refluxed at about 63°C. The reaction was allowed to proceed for 5 hours.

After the reaction was completed, the reaction mixture was allowed to cool to room temperature, and then 10.5.9 (0.10 mol) of jetanolamine was added to the reaction mixture, followed by stirring at room temperature for 1 hour. Then add hex 73.0 to this
After adding 0 ml of the mixture and stirring well, the upper hexane layer was separated. This hexane layer was washed three times with 300 rn and 1 ml of pure water, and then the hexane layer was heated under reduced pressure to remove hexane, thereby obtaining 64.5 g of a transparent pale yellow liquid.

Synthesis-purification example 2 Monoethanolamine 6 to the base of jetanolamine
,'1. An experiment was conducted under the same conditions as in Synthesis and Purification Example J except that (1 (0.1 mol)) was added, and 53 g of pale yellow liquid b was obtained.

Synthesis-purification example 3 Triethanolamine 1 instead of jetanolamine
．． The experiment was carried out under the same conditions as in Synthesis-Purification Example 1, except that 4.9 g (0.1 mol) was added, and a pale yellow liquid of 62.3.
I got a 9.

Comparative synthesis - Purification example 1 Synthesis - Purification example 1 except that jetanolamine was not added
An experiment was conducted under the same conditions as above, and 66.5 g of a pale yellow liquid was obtained.

Comparative Synthesis - Purification Example 2 Synthesis - Purification Example 1 except that ammonia gas was blown into the container for 1 hour to which jetanolamine was added.
An experiment was conducted under the same conditions as above, and a light yellow liquid of 56.0. ! I got a 7.

Comparative synthesis-purification example: 3 Synthesis-purification example except that instead of adding jetanolamine, 25% ammonia water], Oml was added (
An experiment was conducted under the same conditions as above, and 602 g of a pale yellow liquid was obtained.

Comparative Synthesis - Purification Example 4 A metal deactivator was produced according to the method of Machi 4A No. 56-150892. That is, bencitriazol, bis-2-ethylhexylamine, and formaldehyde were reacted under the same conditions as in Synthesis-Purification Example 1. After the reaction was completed, 100 mi of water was added to the reaction mixture and after stirring,
Let it stand for a while. Take out the reaction product and proboscis that were placed at the bottom and add this to an 82 molar aqueous methanol solution], O'Om
The unreacted substances and regular products were extracted and removed.

Again, 69 mol% methanol aqueous solution 'J, 0
It was washed with 0ml and subjected to extraction and purification. After filtration of the obtained reaction product through a filter, the filtrate was heated under reduced pressure to remove residual solvent, yielding a transparent pale yellow liquid 59.7.9.

Examples 1 to 3 and Comparative Examples 1 to 5 The metal deactivators obtained in Synthesis-Purification Examples 1 to 3 and Comparative Synthesis-Purification Examples 1 to 4 were purified by Nippon Oil Co., Ltd.
B K turbine 32 (kinematic viscosity 32°3) as (40
A composition containing a metal deactivator was prepared by adding a metal deactivator to "C)" and a viscosity index of 102), and the following tests were conducted.

Show the results on the clothes.

Oxidation test, test> Turbine oil oxidation stability test according to JISK2514 (test temperature 95°C, copper-iron catalyst) was conducted and the total acid value was 1 and the total acid value was 2.0.
(d
It turned flat.

<Sludge test> The amount of sludge after 1,000 hours was measured using a JIS K2514 tester specified in MIL-L-]7331F for evaluation.

<Thermal stability test> Method according to JIS' 25/IQ (test temperature 170'
C, 320 degrees).

From the table, it can be seen that the composition according to the present invention exhibits very good oxidative stability, and in the extreme sludge test and thermal stability test, the composition containing the Kinki deactivator obtained by the conventional synthesis-refining method It can be seen that the tendency of sludge formation is incomparably lower than that of the conventional method.

Therefore, these results indicate that the composition according to the present invention
This shows that it is very suitable as a lubricating oil for turbine oils, compressor oils, etc., which require high oxidation stability and a low tendency to form sludge.

Patent applicant: Nippon Oil Co., Ltd.

Claims (1)

[Scope of Claims] A compound (2) represented by /represents the same or different alkyl group, cycloalkyl group, or cycloalkyl group having an alkyl side chain having 1 to 18 carbon atoms; ) Monoethanolamine, jetanolamine and A metal deactivator obtained by adding 1 to 1.00 molar amount of one or more ethanolamines selected from triethanolamine to the compound (1) (/c) and washing, 0.001 to 10 ,0 weight class and 01] kinematic viscosity 10~]-o, o 00 cS also (4
0''C), mineral oil and/or synthetic oil having a viscosity index of 80 or more.