KR900005182B1 - Preparation method of alkyl-phenate - Google Patents

Abstract

A neutral and superbasic alkylphenate is prepd. by adding sulphur powder, alkaline earth metal and C2-4 diol to C8-20 alkylphenol to prepare alkylphenol sulphide of formula (I) [R= C8-20 hydrocarbon; x= 1-3; M= oxide or hydroxide of alkaline earth metal, e.g. Ca, Mg, Ba!, reacting (I) with excessive amt. of alkaline earth metal, high b.p. of alcohol, C2-4 diol and CO2 gas, filtering and removing unreacted soild, and distillating and removing water produced in the reaction.

Description

Method for preparing neutral and overbased alkylphenates

The present invention relates to a process for the preparation of neutral and overbased alkylphenates which are detergents added to engine oil.

More specifically, in the preparation of neutral and overbased alkylphenates, it is the continuous removal of the water produced during the preparation of alkylsulphide sulfides and during the carbonation reaction.

In the prior art, the reaction time is long without removing water when preparing the alkyl sulfide phenol, and the carbonate produced during the carbonation sinks to precipitation by water, so that a high total alkali value cannot be obtained.

Neutral and overbased alkylphenate prepared by the present invention prevents the deposition of varnish, sludge, etc. in the internal combustion engine operating at high temperature and neutralizes organic acid generated in the engine to depress corrosion of the engine or press the piston ring. It plays a very important role as a lubricant additive for internal combustion engines as a cleaning agent to keep the engine running smoothly by preventing sticking.

Since ancient times, metal salts of phenol have been used as additives for lubricating oils for internal combustion engines, and they are kneaded together with other additives to enhance the cleanliness of lubricating oils, reduce engine wear and prevent deposits of sediments inside the engine. Therefore, many attempts have been made to make oil-soluble alkylphenol metal salts, and particularly, neutral or overbased alkyl phenol metal salts have been actively prepared to impart acid neutralizing ability with cleanliness.

The metal salt of the neutral alkylphenol is a chemical equivalent amount of alkali earth metal reacted with alkylphenol, and the total alkali value is adjusted to about 150mg KOH / g by injecting carbon dioxide gas.The metal salt of the overbased alkylphenol is alkali to the alkylphenol. The earth metal is added 3 to 4 times higher than the chemical equivalent, and carbon dioxide gas is injected so that some of the added alkaline earth metal is dispersed in the oil in the form of carbonate. Especially, the overbased alkylphenate is used not only for gasoline engines but also for diesel. It is very effective in maintaining the cleanliness of the engine.

Neutral and overbased alkylphenate of the present invention is prepared by first adding an alkyl sulfide having 8 to 20 carbon atoms, sulfur powder, alkaline earth metal, and diol having 2 to 4 carbon atoms. After reacting by injecting high boiling alcohol, diol carbon dioxide gas having 2 to 4 carbon atoms, the reaction mixture is filtered to remove unreacted solids, and water, diol, and high boiling alcohol produced during the reaction are distilled and removed.

Each reaction step is described in detail as follows.

[1) Preparation of Alkyl Sulfide

In the following alkyl sulfides represented by the general formula (I), sulfur powder is injected into an alkylphenol having 8 to 20 carbon atoms and a diol having 2 to 4 carbon atoms is added together as a reaction accelerator using an oxide or hydroxide of alkaline earth metal as a reaction catalyst. Thereafter, the reaction product is reacted at 100 ° to 200 ° C. for 3 to 24 hours while continuously removing water generated during the reaction.

R is a hydrocarbon having 8 to 20 carbon atoms, x is an integer of 1 to 3, M is an oxide or hydroxide of an alkaline earth metal such as Ca, Mg, Ba.

Wherein the alkyl group of the alkylphenol is a straight chain or branched hydrocarbon, octyl, nonyldecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like. Both mixtures can be used.

Sulphides used to prepare alkyl sulfide phenols are sulfur powder, chlorine monosulfate, chlorine disulfide, and the like, and 0.5 to 3.0 molar ratios are used for alkylphenols.

Alkaline earth metals that can be used as reaction catalysts for this reaction are slaked lime, which is most commonly used as oxides or hydroxides of magnesium, barium and calcium, and the amount used is 0.01 to 1.0 mole ratio with respect to alkylphenols and most suitable is 0.05 to 0.1 mole ratio. .

Diols having 2 to 4 carbon atoms used as accelerators of the reaction include ethylene glycol, propylene glycol, butylene glycol, etc. Generally, ethylene glycol may be most used, and 0.01 to 1.0 for slaked lime, and preferably 0.05 to 0.1 mole.

Neutral and overbased alkylphenates are prepared using the alkylsulphide sulfides thus prepared.

[2) neutral and overbased reactions]

After adding high-boiling alcohol, lubricating base oil, slaked lime or raw ash, ethylene glycol, etc. to the aforementioned alkyl sulfide phenol, carbon dioxide gas is injected while continuously removing the water generated during the reaction, and then subjected to carbonation reaction to neutral and oversalt. Vaporization reaction is performed. After completion of the reaction, unreacted solids are filtered off, and ethylene glycol and high boiling alcohols are distilled off under reduced pressure to obtain neutral and overbased alkylphenates as final products.

The high-boiling alcohols used as reaction solvents in the preparation of neutral and overbased alkylphenates are higher alcohols having 8 to 16 carbon atoms, which include 2-ethylhexanol, tecanol, dodecanol, detradecanol, and hexadecane. Etc. can be used, and in the present invention, 2-ethylhexanol was used at 20 to 50% by weight based on the alkylphenol sulfide.

Generally, in the manufacture of alkylphenate, a lubricant base oil is used as a reaction medium. As such a lubricant base oil, all hydrocarbon-based lubricants such as paraffin, naphthenic, or mixed oils thereof may be used. 60 wt% and 40 to 50 wt% was used in the present invention.

Alkali earth metals used in the preparation of the neutral and overbased alkylphenate of the present invention can be calcined or quicklime, and the amount of use is 1 molar ratio of alkylphenol sulfide in the case of neutral alkylphenate, and in the case of overbased alkylphenate. 2 to 3 molar ratios are used.

On the other hand, the diol used as a reaction accelerator to prepare a metal salt of the alkyl phenol is used the same ethylene glycol as in the production of alkyl phenol sulfide, the amount used is 0.1 to 1.0 mole ratio of alkaline earth metal and 0.4 to 0.8 mole ratio in the present invention.

In the preparation of the neutral and overbased alkylphenate of the present invention, all the reactants are placed in a reactor and gradually heated to remove the water generated during the reaction, and then carbon dioxide gas is injected to carry out the carbonation reaction. At this time, if the water produced during the reaction is not removed, the carbonate particles generated in the carbonation reaction do not disperse in the lubricating base oil which is a reaction medium. It becomes difficult to get

Therefore, in the present invention, the temperature of the reactants is reduced to 50 to 100 mmHg at 120 ° to 150 ° C. to remove water generated during the reaction, and carbon dioxide gas is injected to carry out carbonization. It was kept at ° to 170 ° C. After injection of carbon dioxide gas, unreacted solids are filtered off, and diol and high boiling alcohol are removed by distillation under reduced pressure to obtain a final product.

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

Example 1

[Production of Sulfated Alkylphenol]

1-1) Put 270g of dodecylalkylphenol and 2-ethylhexane made of propylene tetramer into 135 liter of 1 liter reactor, raise the temperature to 80 ℃, add 54g of sulfur powder, and heat to 120 ℃, and add 33g of slaked lime. After the injection, 14.4 g of ethylene glycol was slowly injected over 10 minutes while maintaining the temperature. The reaction was continued for about 5 hours while removing the water and hydrogen sulfide gas produced under a reduced pressure of 10 to 50 mmHg while raising the temperature to 150 ° C. After the reaction was completed, unreacted sulfur powder and calcined lime were removed by filtration to obtain 310 g of light brown alkali sulfide phenol. As a result, the sulfur content was 10.0 wt%.

1-2) 162 g of 2-ethylhexane was injected into 324 g of a straight-chain alkylphenol made of 1-olefin having 14 to 18 carbon atoms in the same reactor as described in Example 1-1), and Prepared and finally obtained 354g. The analytical value of sulfur content was 10.0 wt%.

1-3) 270 g of mixed alkylphenol, in which 189 g of dodecyl phenol of Example 1-1) and 81 g of linear alkylphenol of Example 1-2) were mixed, were added to the same reactor as Example 1-1 described above. Alkyl sulfide was synthesized under the same reaction conditions as in 1-1), and 313 g of the final product was obtained. The sulfur content was 10.3 wt%.

Example 2

[Production of Neutral Alkylphenate]

2-1) Into the same reactor as in Example 1-1), 330g of paraffinic base oil was added to 310g of alkylphenol sulfide synthesized in Example 1-1), and heated to 120 ° C. 66.6g of hydrated lime and 27g of ethylene glycol. Was injected slowly while maintaining the temperature. Again raising the temperature to 160 ° C, water produced under a reduced pressure of 10 to 50 mmHg was completely removed, and 35 g of CO ₂ gas was injected at this temperature over 3 hours. After completion of the CO ₂ gas injection, unreacted slaked lime was filtered off, 2-ethylhexanol and ethylene glycol were distilled off under reduced pressure to obtain 710 g of dark brown neutral calcium alkylphenate.

Its analysis is as follows.

The calcium 5.6%, CO ₂ 2.6%, S 3.1% alkali was 160 mg KOH / g.

2-2) Except for adding 60 g of hydrated lime, 24 g of ethylene glycol, and 31 g of CO ₂ gas, the same procedure as in 2-1) was carried out. 699.6 g of dark brown neutral calcium alkylphenate was obtained.

Its analysis is as follows.

The calcium 5.4%, CO ₂ 2.4%, S 3.1% alkali was 145 mg KOH / g.

Example 3

[Production of Overbased Alkylphenate]

3-1) Into the same reactor as in Example 1-1), 330 g of lubricant base oil, 1133.2 g of hydrated lime, 54 g of ethylene glycol, and 70 g of CO ₂ gas were added to 310 g of the alkyl sulfide synthesized in Example 1-1). Example 2-1) was carried out in the same manner as described above. Finally, 780 g of dark brown overbased calcium alkylphenate was obtained.

The analysis results are as follows.

260 mmHg KOH / g of 9.2% calcium, 5.0% CO ₂ and 3.4% S alkali.

3-2) Into a 1 liter reactor, 354 g of alkyl sulfide synthesized in Example 1-2) was charged with 396 g of lubricating base oil, and the same amount of slaked lime, ethylene glycol, and CO ₂ gas as in Example 3-1) were injected. In the same manner as in -1), 890 G dark brown overbased calcium alkylphenate was obtained.

Its analysis is as follows.

The calcium 8.9%, CO ₂ 4.4%, S 2.9% alkali was 230 mg KOH / g.

3-3) Into a 1 liter reactor, 330 g of lubricating base oil was added to 313 g of the alkyl sulfide synthesized in Example 1-3), and the same amount of slaked lime, ethylene glycol, and CO ₂ gas as in Example 3-1) were injected. In the same manner as in Example 2-1), 783 g of a dark brown final product was obtained.

The analysis results are as follows.

Calcium 9.0%, CO ₂ 4.6%, S 3.2% alkali was 245 mg KOH / g.

[Comparative Example]

In preparing the alkyl sulfide phenol in the same reactor as in Example 1-1), the same reaction as in Example 1-1) was carried out except that the water produced under atmospheric pressure was evaporated while maintaining the reaction temperature at 150 ° C. Phenol was obtained. The analysis showed that the sulfur content was 10.2%.

330 g of lubricating base oil was added to 420 g of the synthesized alkyl sulfide phenol, and the temperature was raised to 90.5 g of ethylene glycol and 142.2 g of calcined lime at 127 ° C., followed by heating and stirring to 160 ° C. to remove evaporated water under normal pressure.

When no more water was produced, 70 g of CO ₂ gas was injected for 5 hours to obtain the product.

Its analytical value was 3.9% calcium and 150mmHg KOH / g alkalinity.

By doing in this way, reaction time becomes short and the precipitation of the produced | generated carbonate does not generate | occur | produce, and there exists an effect which can obtain neutral and overbased alkylphenate of high total alkali value.

Claims (1)

In the preparation of neutral and overbased alkylphenates, the water produced during the reaction in the alkylphenol sulfide manufacturing process is continuously removed, and the water produced during the reaction in the neutral and overbased reaction process is reduced under reduced pressure. Process for the preparation of neutral and overbased alkylphenate, characterized in that the removal.