RU2469075C2 - Method of producing sulphur-containing additive - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: additive is obtained by reacting C₁₀-C₁₂ α-olefins with sulphur at temperature of 130-140°C in the presence of 0.5-2.0 wt % catalyst - calcium thio-bis(alkylphenolate).

EFFECT: high output of the sulphur-containing additive and simple process.

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Description

The present invention relates to the field of synthesis of sulfur-containing additives having enhanced extreme pressure, antiwear properties, high thermal and oxidative stability.

These additives are used for the manufacture of technological lubricants, including those applicable for operations of cold forging and metal upsetting.

A known method of producing a sulfur-containing additive by the interaction of α-olefins of the C ₁₆ -C ₁₈ fraction with elemental sulfur and hydrogen sulfide at a ratio of the starting components of 1: 1, 5: 0.5 and a temperature of 171 ° C. Sulfidated α-olefins contain 20.6% sulfur [International application PCT (WO) No. 88/02771, cl. C10M 135/02, 141/08, 1987].

The disadvantages of this method are:

1. The use as a reagent and catalyst of highly toxic hydrogen sulfide, which requires special conditions for safe process.

2. The formation in the presence of hydrogen sulfide of mercaptans, giving the resulting sulfur-containing additive difficult to tolerate smell.

3. The need to remove hydrogen sulfide and the resulting mercaptans from the obtained sulfur-containing additives in order to give the latter the required organoleptic properties.

4. The presence of a significant amount of gas emissions containing hydrogen sulfide and mercaptans.

A known method of producing a sulfur-containing additive by the interaction of α-olefins of the C ₂₈ -C ₄₀ fraction at a temperature of 170 ° C for 2 hours in the presence of a diphenylamine catalyst [K.I.Sadykhov, R.Sh. Mamedova, M.A. Kabakov. Antiwear and extreme pressure additives for lubricating oils. // Chemistry and technology of fuels and oils. 1986. No. 11. P.10].

The disadvantages of the method are:

1. Low sulfur content in sulfidated α-olefins - 8.6%.

2. In order to remove unreacted sulfur, the reaction mass is dissolved in hexane, filtered, and the solvent is removed by distillation, which complicates the whole process of obtaining sulfur-containing additives.

The closest in technical essence and the obtained results is a method of obtaining extreme pressure additives OTP [A. M. Ravikovich, E. I. Petyakina, I. D. Maslova, P. P. Bagryantseva. Anti-seize additive OTP for gear oils. // Chemistry and technology of fuels and oils. 1968. No. 1. S.50].

The additive OTP is obtained by sulfidation of a fraction of propylene polymers containing mainly tetramers and pentamers of propylene at a temperature of 150-160 ° C and a duration of 10-15 hours. The resulting additive is treated with a 25-30% aqueous solution of sodium sulfide at a temperature of 85-95 ° C in order to remove hydrogen sulfide and low molecular weight mercaptans.

The purified additive after settling at 70-80 ° C is distilled under vacuum at a residual pressure of 5-10 mm Hg. and a temperature of 120-140 ° C to remove unreacted raw materials. The remainder of the vacuum distillation is mixed with 5% of bleaching earth and 1% zinc oxide at 110-120 ° C for 0.5 h and then filtered. The yield of additives is 50-60 wt.% For raw materials.

The disadvantages of this method are:

1. Low yield of sulfur-containing additives of 50-60%.

2. The insufficiently high sulfur content in the sulfidized additive is 20-25 wt.%.

3. The multi-stage method.

The objective of the invention is to increase the yield of sulfur-containing additives and the simplification of process technology.

This problem is solved by obtaining a sulfur-containing additive by the interaction of α-olefins of fraction C ₁₀ -C ₁₂ with S ₈ . According to the invention, the process is carried out in the presence of catalytic amounts of 0.5-2.0 wt.% Calcium thio-bis (alkyl phenolate) (additive C-150) at a lower temperature of 130-140 ° C for 6 hours. The output of sulfur-containing additives is 92-95 wt.%; the sulfur content in the additive reaches 42 wt.%.

The synthesized sulfur-containing additive without any subsequent processing and separation of the catalyst can be used to obtain various technological lubricants, including for cold die stamping and metal upsetting.

The method is as follows.

Α-olefins of the fraction C ₁₀ -C ₁₂ , 0.5-2.0 wt.% With respect to α-olefins of the catalyst of thio-bis (alkyl phenolate) calcium are loaded into a thermostated reactor equipped with an effective stirrer, a refrigerator and a thermometer, and the temperature is increased up to 130 ° C. Upon reaching a temperature of 130 ° C., powdered or liquid sulfur is supplied to the reactor. Then the temperature is increased to 140 ° C and within 6 hours carry out the synthesis of sulfur-containing additives.

The reaction mass is cooled to 40 ° C and the unconverted sulfur is separated by filtration.

The method is illustrated by the following examples.

Example 1. In a thermostatic glass reactor equipped with an effective stirrer, thermometer, reflux condenser, load 600 g of α-olefins fraction C ₁₀ -C ₁₂ , 0.5 wt.% Thio-bis (alkyl phenolate) calcium and the temperature is increased to 130 ° C . 450 g of powdered sulfur are fed into the reactor within 1 hour, after which the temperature is increased to 140 ° C and the reaction of sulfur with α-olefins is carried out for 6 hours. The reaction mass is cooled to 40 ° C and separated from unconverted sulfur by filtration. Received 965.2 g of an additive with a sulfur content of 39.8 wt.%.

Example 2. 600 g of α-olefins of fraction C ₁₀ -C ₁₂ , 1.0 wt.% Calcium thio-bis (alkyl phenolate) are loaded into the reactor, and the temperature is increased to 130 ° C. 450 g of sulfur are fed into the reactor within 1 hour, then the temperature is increased to 140 ° C and the reaction of sulfur with α-olefins is carried out for 6 hours. After cooling the reaction mass to 40 ° C and filtering, 986.9 g of an additive with a sulfur content of 41.9 wt.% Were obtained.

Example 3 is carried out analogously to example 1, but the catalyst use 2.0 wt.% On α-olefins. Received 996.6 g of additives with a sulfur content of 42.1 wt.%.

Example 4 is carried out analogously to example 1, but the catalyst use 3.0 wt.% On the taken α-olefins. Received 997.1 g of additives with a sulfur content of 42.2 wt.%.

Thus, the proposed method for producing sulfur-containing additives in comparison with the prototype has the following advantages:

1. The reaction of elemental sulfur with α-olefins of fraction C ₁₀ -C _{12 is} carried out in the presence of catalytic amounts of 0.5-2.0 wt.% On calcium thio bis (alkyl phenolate) feed and a lower temperature of 130-140 ° C.

2. The sulfur content in the additive by 15-20 wt.% Exceeds the prototype.

3. The output of sulfur-containing additives is 92-95 wt.%; in the prototype - 50-60 wt.%.

4. The method is characterized by one-stage and simplicity of technology.

5. The process does not generate wastewater and industrial waste.

6. The resulting additive does not require additional purification from the used catalyst.

Claims (1)

A method of producing a sulfur-containing additive by reacting α-olefins with elemental sulfur at an elevated temperature in the presence of a catalyst, characterized in that calcium thio-bis (alkyl phenolate) is used as a catalyst in an amount of 0.5-2.0 wt.% With respect to α -olefin fraction C ₁₀ -C ₁₂ .