JPH04108897A - Salicylate composition and engine oil composition containing the same composition - Google Patents

Abstract

PURPOSE:To provide the subject stabilized composition containing a specified salicylate, a specified polyalkylene oxide adduct compound of an alkylphenol condensate, etc., and other compounds and useful as a detergent for an engine oil. CONSTITUTION:An objective composition containing (A) a divalent metal salt of a salicylic acid having one or more 12-28C alkyl groups on its benzene nucleus and >=3 basicity and (B) (i) a polyalkylene oxide adduct compound of one or more formalin condensate compounds of one or more compounds among an alkyl phenol, an arylphenol and an arylalkylphenol and/or (ii) a polyalkylene oxide adduct compound of an arylphenol and/or an arylalkylphenol. The above-mentioned composition is blended in an amount of 1-60wt.% based on a mineral oil and/or a synthetic oil.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to stabilized salicylate compositions useful as detergents for engine oils and engine oil compositions containing the same.

[Conventional technology]

Engine oil usually contains various additives, such as salicylates, for the purpose of dispersing sludge and other substances to keep the inside of the engine clean, as well as neutralizing acidic substances such as sulfuric acid generated when the fuel burns. be done. These acidic substances promote oxidative deterioration of engine oil and cause wear of cylinder liners due to corrosion, so basic salicylate is preferably used as an additive to effectively neutralize this. There is.

As a basic salicylate, a highly basic product is a divalent metal salt of salicylic acid (hereinafter referred to as alkyl salicylic acid) having an alkyl group on the benzene nucleus and an excessively dispersed divalent metal carbonate. is used. Here, the basicity is expressed by the following formula using the number of moles M of divalent metal per unit duram of alkylphenol and the number S of moles of alkylsalicylic acid.

Basicity, = 2M/S-1 The higher the basicity, the smaller the amount of expensive alkyl salicylic acid is required to obtain the same basicity, which is advantageous from an economic point of view. However, alkyl salicylates with increased basicity have the disadvantage of poor storage stability. For example, problems arise in that a film is formed on the surface of the salicylate, which becomes insoluble in the base oil of the engine oil, and that the viscosity of the salicylate gradually increases during storage and eventually solidifies. As a solution to this problem, for example, Japanese Patent Application Laid-Open No. 64-85293,
Polyalkoxylated alcohols having a molecular weight of 150 to 1500 have been disclosed as salicylate stabilizers, but these have the disadvantage of worsening the oxidative stability of engine oils and are not preferred.

Therefore, it is desired to develop a salicylate composition that has high basicity, does not form a surface film, does not thicken over time, and does not reduce the oxidation stability of engine oil, and an engine oil composition containing the same. was.

[Means to solve the problem]

In view of these circumstances, the present inventors have conducted extensive research to solve the above problems, and have found that by blending a specific polyalkylene oxide adduct with a highly basic alkyl salicylate, the alkyl salicylate can be stabilized, and It was discovered that a salicylate composition having good properties as an additive for engine oil can be obtained, and the present invention was completed.

That is, the present invention provides (A) a divalent metal salicylic acid salt having at least one alkyl group having 12 to 28 carbon atoms on the benzene nucleus and having a basicity of 3 or more, and (B)
(a) Alkylphenol, arylphenol and/or
or (b) a polyalkylene oxide adduct of a formalin condensate of an arylalkylphenol, and (b) a polyalkylene oxide adduct of an arylphenol and/or an alkylphenol. Disclosed are salicylate compositions characterized by:

Furthermore, the present invention also provides an engine oil composition characterized in that the salicylate composition is blended in an amount of 1 to 60% by weight based on mineral oil and/or synthetic oil.

Salicylic acid 2 which has at least one alkyl group having 12 to 28 carbon atoms on the benzene nucleus of the component (A) used in the salicylate composition of the present invention and has a basicity of 3 or more.
The valent metal salt can be prepared by contacting an alkali metal salt of phenol having at least one alkyl group having 12 to 28 carbon atoms with carbon dioxide gas to form an alkali metal salt of salicylate having at least one alkyl group on the benzene nucleus. After that,
Decomposes with mineral acid to produce free alkyl salicylic acid,
It is produced by neutralizing it with a divalent metal oxide and/or hydroxide.

Examples of phenols having a small number of alkyl groups (both 1 and 1) having 12 to 28 carbon atoms include linear or branched alkyl-substituted phenols, such as dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, and hexadecylphenol. , heptadecylphenol, octadecylphenol, nonadecylphenol, eicosanylphenol, heneicosanylphenol, docosanylphenol, tricosanylphenol, tetracosanylphenol, and mixtures thereof.

The reaction for producing alkyl salicylic acid may be carried out according to the usual Kolbe-Schmidt reaction. In addition, as the divalent metal oxide and/or hydroxide used for neutralizing the obtained alkyl salicylic acid, an oxide and/or hydroxide of a metal belonging to Group 2 of the periodic table of elements is used. Examples include magnesium, calcium, barium, zinc, etc., particularly preferably magnesium or calcium oxides and/or hydroxides.

To produce salicylates with high basicity, divalent metal oxides and/or hydroxides are added to an amount equal to or more than the neutralization equivalent of alkyl salicylic acid, and carbon dioxide gas is blown into the divalent metal carbonates. It is preferable to generate the base component and disperse the excess base component.

Particular preference is then given to using methanol or ethylene glycol as accelerators.

Component (B) used in the present invention is alkyl salicyle)
It acts as a stabilizer against changes over time in (A), and examples of (a) polyalkylene oxide adducts of formalin condensates of alkylphenols and/or arylalkylphenols include octylphenol, nonylphenol, decylphenol, and dodecylphenol. Alkyl phenols such as phenol, tritecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, hebutadecylphenonopeoctadecylphenol, arylphenols such as phenylphenol, or arylalkylphenols such as styrenated phenol and benzylated phenol. It includes those condensed with formalin and those with ethylene oxide and/or propylene oxide added. Furthermore, mixtures of two or more of these alkylphenols, arylphenols, and arylalkylphenols are condensed with formalin and ethylene oxide and/or propylene oxide is added thereto.

(b) Polyalkylene oxide adducts of arylphenol and/or arylalkylphenol include phenylphenol, benzylated phenol, styrenated phenol, 4. Included are ethylene oxide and/or propylene oxide adducts of 4'-dihydroxydiphenyl-2,2'-propane.

Here, the number of moles of alkylene oxide added as component (B) is preferably 3 or more. Among these, one in which IILB is added from 9 to 15 is preferable. Furthermore, IILB
Those with a value of 11 to 13 are more effective.

Here, IILB is the value HL calculated using the formula below.
B=20x (Mh/Mt) Mh: Molecular weight of the hydrophilic group portion Mt; Molecular weight of the entire stabilizer (component (B))
) For the lii component, a stabilizer condensed with formalin and a stabilizer not condensed can be mixed and used. 2
The HLB when using a mixture of more than one type of stabilizer is:
The average value was calculated using the individual weight fractions assuming additivity.

The amount of component (B) added to component (A) is 0.0001
It is preferably 10% by weight, and if it is less than this, a sufficient stabilizing effect cannot be obtained. Moreover, if more than this is added, it may have the adverse effect of increasing the viscosity of salicylate (A). The stabilizer contained in the group (a) is 0.001 to 0.5% by weight, and the stabilizer contained in the group (b) is 0.
．． The amount added is preferably 0.05 to 5% by weight.

In addition, the salicylate composition of the present invention may contain other components such as sulfurized alkyl salicylates, alkyl salicylates treated with phosphoric acid, higher fatty acids, sulfonates, phenates, etc., to the extent that the effects of the present invention are not impaired. Can be blended.

If these salicylate compositions are blended in an amount of 1 to 60% by weight based on mineral oil and/or synthetic oil, an engine oil composition with excellent oxidation stability can be obtained. The mineral oil and synthetic oil used here are not particularly limited as long as they have been conventionally used as engine oil and have a normal lubricating viscosity.

The engine oil composition of the present invention also includes zinc dialkyldithiophosphate and/or zinc dialkylaryldithiophosphate, a succinimide-type or benzylamine-type ashless dispersant, a rust preventive, a viscosity index improver, a pour point depressant, etc. Agents, etc. can be added.

〔Effect of the invention〕

According to the present invention, a stable salicylate composition that has a high degree of basicity and does not form a surface film or increase its viscosity over time is provided. Further, by blending the salicylate composition, an engine oil composition with excellent oxidation stability and cleaning performance was provided.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In 21 flasks equipped with a stirrer, a thermometer and a water separator, 564 g (1.4 mol) of alkylphenol having an alkyl group having 12 to 28 carbon atoms and 150 neutral oil (kinematic viscosity at 100°C of 4.5 mol) were mixed. 242 g of 2 cSt paraffin-based lubricating oil was added, and the temperature was raised while stirring. 100
118 g of a 48% aqueous solution of caustic soda was added over 30 minutes. Further, the pressure was gradually reduced to dehydrate. The temperature was raised to 170°C and maintained at a vacuum level of 30 mmHg for 30 minutes.

Thereafter, it was cooled and brought back to atmospheric pressure, and 451 liters of carbon dioxide gas was blown into it. The blowing took 3 hours. 882 g of a brown liquid was obtained. A portion of this reaction mixture was decomposed with sulfuric acid to give free alkyl salicylic acid. Acid value (J
IS K2501) was measured and found to be 70.1. As a result, 80% of the alkylphenol initially added
% was found to be salicylated. 69 g of concentrated sulfuric acid was added to 870 g of the obtained Na salicyle and decomposed at 80° C. for 4 hours. 170 out of 939g of decomposition product
11 flask equipped with a stirrer, thermometer, and water separator. Slaked lime 62.9g, isononyl alcohol 1
80g was added and the temperature was raised to 150°C. During the process, 80 g of ethylene glycol was added at 130°C. 2 carbon dioxide 15β
It took 30 minutes to blow.

The solvent was removed under reduced pressure while increasing the temperature to 200°C.

The liquid remaining as the bottom was filtered to obtain basic salicylate. Base number of this salicylate (JISK2501
) was 370 mgKDH/g. The Koreyori basicity was calculated to be 7.2. Kinematic viscosity at 100℃ is 9
It was 5,6 cSt.

Example 2 A predetermined amount of the stabilizer shown in Table 1 was added to the salicylate obtained in Example 1, and the mixture was stirred and mixed at 60° C. for 1 hour to obtain a salicylate composition. The sample was stored in a constant temperature bath at 120°C, and the kinematic viscosity of the sample at 100°C was orally measured. On the other hand, 100m1! Five grams of the same sample was placed in a beaker, and the sample was left in an open system at room temperature, and after 7 days, the formation of a film on the salicylate surface was observed.

Margin below Example 3 Using the salicylate composition obtained in Example 2, The engine oil composition shown below was prepared and its oxidation stability was determined according to JIS. It was evaluated using the following method.

Results obtained are shown in Table 2.

Engine oil composition: Amoco9253 (benzylamine) 2.0%W Margin below Good results were obtained for both as engine oils.

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Claims (1)

[Claims] 1. (A) At least one carbon number 12 on the benzene nucleus
A divalent metal salt of salicylic acid having ~28 alkyl groups and a basicity of 3 or more, and (B) a polyalkylene oxide adduct of a formalin condensate of (a) alkylphenol, arylphenol, and/or arylalkylphenol. and (b) a salicylate composition comprising one or more compounds selected from arylphenols and/or polyalkylene oxide adducts of arylalkylphenols. 2. An engine oil composition comprising 1 to 60% by weight of the salicylate composition according to claim 1 based on mineral oil and/or synthetic oil.