JP2509263B2 - Method for producing mixed overbased sulfonate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a mixed overbasic sulfonate, and more specifically, it uses an alkylbenzene and a mineral oil having specific properties as a raw material and dissolves it in various lubricating base oils. The present invention relates to a method for efficiently producing a mixed overbased sulfonate having excellent properties.

[Problems to be Solved by Prior Art and Invention]

Conventionally, various methods are known as methods for producing alkylbenzene sulfonates and overbased sulfonates. For example, a method in which a synthetic alkylbenzene is directly sulfonated (US Pat. Nos. 2,676,925 and 2,924,618).
No. 3470097), a method of using a highly refined mineral oil containing almost no synthetic alkylbenzene and an aromatic component as a raw material and sulfonation thereof (US Pat. No. 3470097).
dustrial & Engineering Chemistry Vol.50, No.7, p99
7), further sulfonation of synthetic alkylbenzene,
A method for producing an overbased alkylbenzene sulfonate by further overbasing the sulfonate (JP-A-54-14)
No. 919 bulletin).

However, the alkylbenzene sulfonates and the overbased alkylbenzene sulfonates obtained by the method as described above have various problems as additives for lubricating oils because they have insufficient solubility in lubricating base oils. there were.

Therefore, the present inventor has conducted intensive studies to solve the above-mentioned drawbacks of the prior art and develop an overbased sulfonate having excellent properties.

[Means for solving problems]

As a result, a mixture of synthetic alkylbenzene and mineral oil having a high aromatic content as a raw material, or a sulfonate or an overbased sulfonate obtained by using a sulfonic acid of this mixture can achieve the above object. Found. The present invention has been completed based on such findings.

That is, the present invention relates to an overbased sulfonic acid of a mixture of argylbenzene sulfonic acid (A) and sulfonic acid (B) of mineral oil having a kinematic viscosity at 40 ° C. of 100 to 500 cSt or more and an aromatic content of 3% or more. A mixed overbased sulfonate having a salt as a main component is provided. The present invention also provides a method for producing this mixed overbased sulfonate, which has a kinematic viscosity of 100 to 500 cSt at alkylbenzene and 40 ° C.
Above, a mixture of mineral oils having an aromatic content of 3% or more is sulfonated and then neutralized with an alkali compound to give a sulfonate, after which at least a part of the sulfonate is carbonated with an excess of an alky compound. It also provides a method for producing a mixed overbased sulfonate by contacting with gas to form an overbased sulfonate.

The mixed overbased sulfonate prepared by the method of the present invention is mainly composed of the overbased sulfonate of both sulfonic acids (A) and (B) as described above. Here, as the mineral oil which is a raw material of the sulfonic acid of the mineral oil which is the component (B), the kinematic viscosity at 40 ° C. is 100 to 500 cSt,
(% By n-d-M method C _A) aromatic content content of 3% or more,
It is preferably 5 to 60%. When the kinematic viscosity at 40 ° C. is less than 100 cSt or the aromatic content is less than 3%, the solubility of the obtained mixed overbasic sulfonate in the lubricating base oil is insufficient. Such mineral oil is not particularly limited as long as it has the above properties,
For example, a refined oil obtained by treating a distillate obtained by distilling a paraffin-based, intermediate-based or naphthene-based crude oil under atmospheric pressure or under reduced pressure by various refining methods is used.

In addition, the kind of the mixed overbased sulfonate of the present invention is not particularly limited, but usually includes calcium salt, magnesium salt, barium salt, copper salt, sodium salt, potassium salt, lithium salt, etc. Calcium salts are preferred.

The mixed overbased sulfonate of the present invention has the above (A),
The overbased sulfonate of the mixture of both sulfonic acids of (B) is the main component, and the ratio may be appropriately determined, but usually (A) component / (B) component = 1/4 to 4/1 ( The weight ratio may be selected within the range.

The mixed overbased sulfonate of the present invention is (A)
A mixture of an alkylbenzene sulfonic acid as a component and a sulfonic acid of mineral oil as a component (B) must be an overbased sulfonic acid salt, and both sulfonic acids of (A) and (B) are separated from each other. With overbased sulfonate,
A product prepared by mixing them cannot exhibit the desired performance of the present invention.

The mixed overbased sulfonate of the present invention can be produced by various methods. According to the above-mentioned method,
A mixed sulfonate having extremely high efficiency and excellent performance can be obtained.

In the method of the present invention, alkylbenzene as a raw material and the above-mentioned mineral oil having a kinematic viscosity at 40 ° C. of 100 to 500 cSt or more and an aromatic content of 3% or more are blended at an appropriate ratio, preferably the former / latter = 1/4. ~ 4/1 (weight ratio), the mixture is mixed first with a sulfonating agent such as fuming sulfuric acid to give sulfonic acid.
After diluting with 50 neutral oil or the like (however, it is preferable to add it in an amount equal to or less than the weight of sulfonic acid), and then use an alkaline compound such as water such as calcium hydroxide, magnesium hydroxide, barium hydroxide or copper hydroxide. Neutralize using oxides or oxides of these metals,
With sulfonates, mixed sulfonates are obtained.
Also, after neutralizing sulfonic acid with sodium hydroxide or the like to form an alkali metal salt such as sodium sulfonate, an alkaline earth metal halide (eg, calcium chloride)
Even when the metathesis is carried out with, a similarly suitable mixed sulfonate can be obtained.

The conditions for the sulfonation treatment and the neutralization treatment when carrying out this method are not particularly limited and may be conventional methods.

Next, at least a part of the mixed sulfonate obtained above, that is, a part or all of the mixed sulfonate is brought into contact with carbon dioxide gas together with an excess of an alkali compound to give an overbased sulfonate (that is, a part of the mixed sulfonate is Overbasing gives a mixture of sulfonates and overbased sulfonates, and overbasing all of the mixed sulfonates yields all overbased sulfonates.) It is a thing. Here, in converting the sulfonate into an overbased compound, usually, the mixed sulfonate is added to a mixed solvent of water and an organic solvent (alcohol such as methanol) together with an alkali compound while stirring. It is carried out by introducing carbon dioxide gas, carrying out a contact treatment, and further reacting an alkali compound as necessary. The processing condition at this time is not particularly limited, and may be appropriately set according to the situation.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 325 g of alkylbenzene bottom and 325 g of mineral oil III shown in Table 1 were weighed in a reaction flask and stirred. After the obtained mixture was cooled to 20 ° C. or lower, 216 ml of 25% fuming sulfuric acid was added dropwise over about 30 minutes. At this time, the temperature of the mixture is 38 ° C.
The dropping rate was adjusted so that After the dropping is completed,
The temperature of the mixture was kept at 36-38 ° C for 3 hours. After the completion of the sulfonation reaction, the sulfonic acid solution and the sulfuric acid sludge were separated.

250 g of this sulfonic acid and 50 g of 100 neutral mineral oil were weighed into a reaction vessel, and 200 g of toluene and calcium hydroxide were added.
20 g was added and stirred for 1 hour. Thereafter, the solid matter was separated, and 120 g of methanol, 15 g of water and 90 g of calcium hydroxide were added to a clear solution (a toluene solution of calcium sulfonate), and 44 g of carbon dioxide gas was introduced over 4 hours while stirring.
Then, after adding 15 g of calcium hydroxide and stirring for 30 minutes,
The solvent was distilled off, and the mixture was kept at 150 ° C for 30 minutes and then cooled. When the temperature of the mixture had dropped to near room temperature, 300 g of toluene was added and stirred for 30 minutes, and this was centrifuged to collect the supernatant. Further, the supernatant was distilled to obtain a composition containing calcium overbased sulfonate. The base number (TBN) of this product is 3
It was 15 mg KOH / g. The properties of this composition are shown in Table 2.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that Mineral Oil I was used instead of Mineral Oil III shown in Table 1.
The TBN of this product was 300 mg KOH / g. The properties of this composition are shown in Table 2.

Comparative Example 2 A composition was obtained by performing the same operation as in Example 1 except that the mineral oil II was used instead of the mineral oil III shown in Table 1.
The TBN of this product was 320 mgKHO / g. The properties of this composition are shown in Table 2.

Example 2 A composition was obtained by performing the same operation as in Example 1 except that mineral oil IV was used instead of mineral oil III shown in Table 1 and that water was changed from 15 g to 10 g. This product has a TBN of 315 mg
It was KOH / g. The properties of this composition are shown in Table 2.

Example 3 A composition was obtained in the same manner as in Example 1 except that mineral oil V was used instead of mineral oil III shown in Table 1 and that water was changed from 15 g to 10 g. This product has a TBN of 300 mg
It was KOH / g. The properties of this composition are shown in Table 2.

Example 4 A composition was obtained in the same manner as in Example 1 except that mineral oil VI was used instead of mineral oil III shown in Table 1 and that water was changed from 15 g to 10 g. This product has a TBN of 300 mg
It was KOH / g. The properties of this composition are shown in Table 2.

Example 5 Using 150 g of sulfonic acid obtained in the process of Example 3, 150 g of 100 neutral mineral oil and 10 g of water, overbasing was carried out in the same manner as in Example 1 below. TBN of the obtained composition is 300 mg
It was KOH / g. The properties of this composition are shown in Table 2.

Comparative Example 3 A composition was obtained by performing the same operation as in Example 1 except that the mineral oil VII shown in Table 1 was used in place of the mineral oil VII.
The TBN of this product was 270 mg KOH / g. The properties of this composition are shown in Table 2.

Comparative Example 4 325 g of alkylbenzene bottom was sulfonated according to Example 1 and mineral oil 1 was then added to 325 g for dilution.
Thereafter, overbasing was carried out in the same manner as in Example 1. The TBN of the obtained composition was 270 mgKOH / g. The properties of this composition are shown in Table 2.

Comparative Example 5 A mixture of 150 g of calcium alginylbenzene sulfonate obtained without using Mineral Oil III and 150 g of commercially available natural sulfonate was overbasified under the same conditions as in Example 1. The resulting composition had a TBN of 280 mg KOH / g. The properties of this composition are shown in Table 2.

[Effect of the Invention] The mixed overbased sulfonate produced by the method of the present invention is superior in solubility and detergency to a lubricating base oil as compared with a conventional alkylbenzene sulfonate, and also has an appearance. Light color and good. Therefore,
The mixed overbased sulfonate produced by the method of the present invention is effectively utilized as an additive for various lubricating oils such as detergent dispersant and rust preventive. Further, according to the method of the present invention,
The mixed overbased sulfonic acid salt can be obtained with extremely high efficiency and high performance, and is of high practical value.

Claims (1)

(57) [Claims] 1. A mixture of an alkylbenzene and a mineral oil having a kinematic viscosity at 40 ° C. of 100 to 500 cSt and an aromatic content of 3% or more is sulfonated, and then neutralized with an alkali compound to give a sulfonate. A method for producing a mixed supercharged valence sulfonate, which comprises contacting at least a part of the sulfonate with carbon dioxide together with an excess of an alkali compound to form an overbased sulfonate.