CS221179B1 - Method of making the admixtures in lubricating oils of the alkylphenolate type - Google Patents

Description

The invention relates to a process for the production of an alkali-type alkylphenolate-type lubricant oil additive which allows efficient separation of contaminating solid particles from the crude product by centrifugation or filtration without solvents at elevated temperature.

In motor oils of virtually all quality grades, alkylphenol-based additives, preferably of the type of alkaline earth metal salts of alkylphenolsulfides, are widely used. Additives of this type are characterized by detergent, antioxidant, anticorrosive and neutralizing properties under demanding conditions of operation of spark-ignition engines and diesel engines, in particular, in combination with other known detergent-dispersing and multifunctional additives, providing an extended life of lubricating oil. They also contribute to a considerable extent to the good efficiency of the lubricating oil in view of the reliable and long-term function of the low wear of thermally loaded internal combustion engines, particularly in vehicles.

Additives of this type have a particularly good effect at an increased basicity of 100 to 250 mg KOH / g, which is achieved by containing colloidally dispersed carbonate and calcium hydroxide in the additive.

Methods are known for preparing additives for sulfur-based alkylphenol-based oils by reacting elemental sulfur with an alkaline earth metal alkylphenolate or a substituted phenol in the presence of alkali (USP 3,509,053, USP 3,437,595). In order to achieve a superstoichiometric alkalinity and to eliminate the corrosive effect of the additive on honey and its alloys, the reaction of sulfur with a substituted phenol and calcium hydroxide and carbonation are carried out in the presence of alkylene glycols, higher alcohols, alkanolamines, alkylene polyamines or alkylene glycol ethers. No. 900 059, French Pat No. 1,500,535, Australia Pat 401,435, UDP 3,410,798, 3,493,516 and German Pat. 1,290,645). The reaction is carried out at a temperature above 150 ° C and distilling off the higher boiling polar solvents at a temperature of up to 200 ° C. The preparation process also involves a difficult and costly solvent recovery.

Also known are methods for the preparation of basic calcium salt substituted phenol sulphides by treating the corresponding phenol sulphides in an oil oil environment, with specially prepared calcium aicoxylate (USP 3,474,035) or a dispersion of carbonated calcium oxide in methanol (USP No. 3,474,035, Australia). 400 8201

More preferred and simpler is the process for preparing a base additive for oils based on phenol derivatives according to U.S. Pat. o221179

221178 of witness 190 190, wherein the alkylphenolsulfide obtained by the preferred sulphurization of the alkylated phenol is treated in a single step with calcium hydroxide while introducing carbon dioxide in an amount of 0.4 to 0.8 mol per 1 mol of calcium hydroxide within a maximum of 2 hours to the reaction mixture. in which per 1 equivalent of substituted phenol avg, mol. weight of 200 to 800 is 1 to 5 equivalents of calcium hydroxide in a medium of a mixture of hydrocarbons, alkylarylsulfonic or petroleum sulfonic acids or salts thereof, alcohol boiling at 60 to 110 ° C and water. The carbonated reaction mixture is then heated while distilling off the lower boilers to a temperature of 150-175 ° C.

The products thus obtained exhibit satisfactory application properties as detergent and antioxidant additives for motor oils and are non-corrosive when tested for honey and its alloys according to CSN 65 60 75.

Production method according to cars. lighting. 190 767 also makes it possible to obtain products of the desired consistency, provided that the carbon dioxide is introduced into the reaction mixture in a given mol. ratio to calcium hydroxide in the shortest possible time, preferably 15 to 60 minutes, which, however, can be technically carried out in a non-pressurized device only with special measures. In addition, the crude product obtained under these conditions contains a relatively high fraction of fines of supra-colloidal size having a size of 10 ⁴ to 10 ³ mm, which separation from the crude product requires purification to be carried out in organic solvent solution and sufficiently diluted using very effective centrifuges. The purification is then followed by the need for energy-intensive distillation of a considerable amount of solvent, usually class 1 flammable, which entails the need for strict safety precautions in operation. Filtration cleaning is not possible even with the use of filtering aids, since the pores of the filter cake are almost tight.

We have found an improved process for preparing alkylphenolate-type oil additives which allows products of a suitable viscosity in the range of up to 50 mm ² / s at 100 ° C to be obtained even with a reasonable increase in carbon dioxide feed time into the reaction mixture, preferably for 2-5 hours. to achieve better conversion of carbon dioxide and reduce its losses using commercially available non-pressurized stirred reactors. Thereby, a crude product having a relatively low solids content of 10 ^-4 to 10 ^-3 mm is obtained, which can be purified with good results without the use of organic solvents by centrifugation and filtration at elevated temperature.

The present process makes it possible to prepare an oil additive with an alkylphenol sulfide type active substance having a basic value in the range of 100 to 250 mg KOH / g, depending on the amount of calcium oxide or hydroxide used and the other components of the reaction mixture.

BACKGROUND OF THE INVENTION The present invention relates to a process for the production of an alkylphenolate-type lubricating oil additive by reacting carbon dioxide on a mixed mixture of calcium or calcium hydroxide with a phenol derivative in a C 1 -C 3 aliphatic alcohol, water, liquid hydrocarbon. mol. weight 350 to 600 using 0.4 to 0.8 moles of carbon dioxide per 1 mol of basic calcium compound followed by distillation of the lower boiling components by heating to 150 to 175 ° C, at which a dispersion of 15 to 35 wt. % of calcium oxide or hydroxide in an alcohol is homogenized with a mixture of phenol derivatives of the general formula

which may contain not more than 50% by weight. % of a phenol derivative of the general formula

in which there is at least one substituent R 1, R 2, R 3, R 1 on the aromatic ring, a hydrocarbon group having from 3 to 30 carbon atoms and the other may be hydrogen and X is a "S" or "S2" group and a mixture of liquid hydrocarbons per mole of basic calcium compound, 100 to 350 g of phenol derivatives and 150 to 500 g of liquid hydrocarbons are added, and thereafter, the intensively stirred mixture is supplied with carbon dioxide in an hourly amount

0.1 to 0.2 mol per 1 mol of the basic compound. The calcium and the product depleted of the lower boiling components are purified by centrifugation and / or filtration. Liquid hydrocarbons consist of petroleum oil raffinates and a kinematic viscosity of preferably 15 to 45 cm ² / s at 50 ° C and hydrocarbons boiling at 60 to 150 ° C in an amount of 4 to 40 wt. % in the mixture.

The active ingredient of the lubricating oil additive according to the invention are the alkylphenolsulphides of the general formula, which are normally obtained by treating the alkylated phenols with a reaction with sulfur or sulfur trichloride or with elemental sulfur, for example under the conditions of automobile. certifies. 181 554 and 190 767. The technical alkylphenolsulphides used may contain, according to mol. the ratio of the components and the conditions of the synthesis also a part of the unreacted alkylphenols, which in an amount up to 50 wt. % are also a suitable component of the additive in terms of its application and physical properties. The alkylphenols and alkylphenolsulfides used in the preparation of the additive according to the invention contain hydrocarbon substituents having 3 to 10 carbon atoms. Average mol. the weight of the alkyliphonols used is preferably from 250 to 400. Oil additives prepared on the basis of alkylated phenols containing 20 to 40% of dialkyl derivatives have good properties. Suitable allyl phenols are preferably prepared by alkylating phenol with oligomers of lower olefins, such as trimers, tetramers or pentameric propene, dlisobutene, or even higher oligomers of propene and butene with an average mol. These are, for example, the distillation fractions of polypropylene oils which, in catalyzed alkylation reactions, usually give alkylphenols having a larger proportion of shorter hydrocarbon chains, for example having from 3 to 12 carbon atoms, due to the dilation and disproportionation events.

The alkylphenol used and its sulphated derivative may also contain a proportion of non-reactive, higher boiling hydrocarbons which remain as an inert diluent in the additive without affecting its quality properties. The presence of the hydrocarbon component in the phenol derivative is usually taken into account by reducing the amount of petroleum oil raffinate used in the further processing to ensure a satisfactory viscosity of the product.

Also suitable for processing into alkylphenol sulfides are the alkylphenols obtained by alkylation of the phenol with chlorinated alkenes by a Friedel-Crafts reaction containing 10 to 30 carbon atoms per molecule. Particularly good application properties have the additives prepared on the basis of the alkylphenols obtained by the reaction. phenol with propylene tetramer or distillation fraction of polypropylene oil of an average mol. weight of 300 to 400, e.g. certifies. 183 320.

Calcium oxide or hydroxide is required to be sufficiently reactive, low in contaminants, in particular carbonates and silicates. Satisfactory results are obtained using calcium hydroxide of the CSN 71 22 40 type of very pure and very fine type with a content of at least 92 active substance with a sieve residue of at most 2 wt. % and at 009 at most 8 wt. why. In view of the desired high conversion to colloidal dispersed basic calcium carbonates, it is important that the calcium oxide or hydroxide be dispersed beforehand by mixing with a lower alcohol, optionally with a water content, to form a very fine slurry. The concentration of the suspension is preferably in the range of 15 to 35 wt. % of calcium oxide or hydroxide depending on the desired base.

The alcohols are preferably methanol, and satisfactory results are also obtained using ethanol or propanols. The alcohol used remains part of the reaction medium for carbonation. Alcohols may be used in technical purity, e.g. methanol containing up to 1% water and ethanol in a concentration of 92 to 95 wt. %.

If methanol is used, only water produced by the reaction of carbon dioxide with calcium hydroxide is usually sufficient for the reaction to proceed well. At higher basicity and the processing of lime required the addition of other rafts, which can be introduced into the system together with an alcohol or during supply of carbon dioxide, or in the course of oddestilovama h <cho'u a low boiling solvent Adioma ^Jl. thereby avoiding the formation of undesirable viscous or gel-like products.

The reaction mixture preferably contains 0.5 to 10%

2.5 moles of water per mole of basic calcium compound, including water liberated during carbonation when calcium hydroxide is used.

The viscosity of the reaction medium during carbonation and treatment of the reaction mixture is also an important factor for good process performance and preparation results. In this respect, the use of a low viscosity petroleum oil raffinate having a kinematic viscosity of 15 to 4.5 mm ² at 50 ^° C in an amount of 40 to 150 wt. % for the phenol derivative used at the active compound concentration in the additive. Oil raffinate remains part of the finished additive as a modifier of its viscosity and consistency.

Depending on the desired basicity of the additive and the amount of calcium oxide or hydroxide in the reaction mixture, the hydrocarbon mixture preferably contains 4 to 40 wt. % of low boiling hydrocarbon boiling at 60-150 ° C, which, after carbonation, is distilled off from the mixture together with alcohol and water.

Aliphatic or aromatic hydrocarbons may be used, but preferred technical mixtures of gasoline fractions, e.g. a boiling point of 80 to 110 ^C C. The total amount of liquid hydrocarbons in the composition is determined according to the nature and content of the active ingredient in the additive, and the overall basicity.

On the stability of the colloidal system of sulphurated phenol derivatives and basic calcium carbonates in hydrocarbon! the presence of less than 0.4 to 4 wt. % oil-soluble alkaline earth metal salts of petroleum or alkylarylsulphonic acids. The use of all amounts of sulfonic acid salts is also possible and in many cases desirable, in particular when a mixed base oil additive is to be obtained containing sulfonates as active ingredients in addition to alkylphenol sulfide derivatives. Suitable products in terms of physical and application properties are obtained without the use of salts of petroleum or alkylarylsulphonic acids, especially in the case of mean alkaline reserve values.

The carbon dioxide introduced into the reaction mixture is generally more than 98% pure and then does not require further purification. It is reacted in an amount of 0.1 to 0.2 mol per hour of the basic calcium compound, which corresponds to a reaction time of 2 to 8 hours for a total amount of 0.4 to 0.8 mol of carbon dioxide. A carbonation time of 3 to 5 hours is advantageous in view of the good dispersion of gaseous carbon dioxide in the liquid phase and its sufficient conversion when reacting with an alkaline calcium compound in a reasonably short reaction time.

In carbonation, the initial temperature of the mixture is preferably 15 to 30 ° C and, as a result of the exothermic reaction, it can rise up to the boiling point of the mixture during the introduction of carbon dioxide. The carbon dioxide can be fed to the mixture at a uniform rate or also initially carbonation, when the content of calcium oxide or calcium hydroxide in the mixture is higher, more rapidly while slowing the feed in the final phase.

After completion of the carbonation reaction, the low-boiling components of the mixture are distilled off by gradually raising the temperature of the mixture to 150-175 ° C and can be regenerated. The presence of a sufficient quantity of alkaline calcium compounds simultaneously permits, in the sense of AO no. No. 190,767 to react at elevated temperature, preferably 160-170 ° C, with sulfur labile in the active ingredient of the product to provide an additive that has no corrosive effects on honey and its alloys. The heating to elevated temperature is conveniently carried out in a nitrogen-enriched atmosphere or even under reduced pressure in the apparatus.

The crude product obtained still contains solid particles of inorganic calcium compounds, substantially to such a size that they can be separated at a temperature above 100 ° C by centrifugation or filtration using filtration aids without solvent. For purification in technical practice, centrifugation on flow separators is best combined with automatic sludge removal with post-treatment on suitable pressure filters at a temperature of preferably 120 to 130 ° C. By using filter diatomaceous earth or perlite, a product of good purity with a solids content of less than 0.1 vol. % (determination of deposits by centrifugation, in a 1: 2 gasoline solution).

The lubricating oil additives according to the invention are well miscible with oil raffinates, in particular they have the desired physical properties and can be applied in engine oils of even the most demanding specifications, advantageous in compositions with other kinds of additives, e.g. based on zinc salts of dialkyl or diaryl esters of dithiophosphoric acids, alkaline earth metal salts of petroleum or alkylarylsulfonic acids, thiophosphonic acid derivatives or even with ash-free dispersants, of the succinimide type or of Mannich bases.

According to laboratory evaluations, the additives of the present invention in motor oils show good thermo-oxidative properties in the Wolf-Platelet Test in the temperature range of 250 to 280 ° C as well as in the Panel Coker Test, corrosion in the corrosion test for copper and Cu-Pb alloy. 65 60 75 and detergent properties in the assessment of detergent potential according to GOST 10734-64.

The good application properties of the additives according to the invention have also been confirmed for evaluations in compositions with other types of additives in base oils of several viscosity grades by tests on FETTER engines.

Example 1

In a four-necked flask equipped with a stirrer, thermometer, condenser and carbon dioxide feed tube, a dispersion of 156 g of calcium hydroxide, 97.5% pure (2.06 mol) in 610 g of methanol was prepared by mixing. 543 g of technical dodecylphenol sulphide containing 7.5% S, prepared by sulphurization of dodecylphenol containing 67.5 wt. % monoalkyl derivatives and 28.3 wt. % of dialkyl derivatives, further 15.6 g of oil concentrate containing 30% Ca-salt of petroleum sulphonic acid av. mol. wt. 430, 543 g oil raffinate kinematic] viscosity 21 mm ² / s at 50 ^° C and 30.5 g of 80/110 gasoline. In the reaction mixture there are 1 mol of Ca (OH) 2: 234 g of technical dodecylphenolsulfide, 283 g of liquid hydrocarbons containing 5.28% of hydrocarbons boiling at 80 to 110 ° C and 2.3 g of calcium sulfonate. With vigorous stirring, carbon dioxide is added to the bottom of the flask over a period of 3 hours in an amount of 0.128 l / min. The temperature is increased from 2.8 ° C to 41 ° C. By heating the carbonated mixture to 165 ° C, methanol, gasoline and water are distilled off, and the reaction mixture is kept at this temperature for a further 2 hours under reduced pressure in the apparatus to 25 to 40 kPa. The crude product is centrifuged at 120-130 ° C in a laboratory flow centrifuge at g = 10,000 and purified on a pressure heated filter using 2 wt. % with

filter diatomaceous earth type LAS-20. The average filtration rate is 4000 g / dm ² . h when cleaned to 0.1 vol. ° / o 'sediments'. The product obtained is an oil concentrate containing 55% of active ingredients, a kinematic viscosity of 24 mm% at 100 ° C, a content of 5.1% calcium, 3.5% sulfur and a total basicity of 146 mg KOH / g.

Example 2

In the apparatus of Example 1, a dispersion is prepared by successively adding 156 g of 97.5% calcium hydroxide (2.06 mol) to 610 g of methanol with stirring. 620 g of alkylphenol sulphide containing 6.4% of S, obtained from alkylphenols of average molecular weight 360 containing 60% of mono- and 23% of dialkylphenols and 15% of hydrocarbons, 360 g of oil raffinate, viscosity 21 nnn ² / s at 50 °, are added. C, 210 g elderberry 80/110 and 30 g oil concentrate, 45% Ca alkylarylsulfonate with an average molecular weight of 915.

In the reaction mixture, 2 253 g of alkylphenol sulfide, 330 g of hydrocarbons, per 1 mol of Ca (OH), account for 31% of those having a boiling point up to 150 ° C.

After homogenization, 7.66 l / h, together with 1.03 moles of carbon dioxide, i.e. hourly 0.167 moles, was fed to the mixture over 3 hours with vigorous stirring, for a total of 0.501 moles of CO2 per mole of calcium hydroxide. After carbonation, the reaction mixture is heated to 160 ° C while distilling a substantial portion of the lower boiling components and further stirred for 1 hour at 165 ° C under nitrogen inlet. The crude product obtained is pre-purified at 130 ^DEG C. in a laboratory flow centrifuge at g = 10,000 and purified on a heated pressure filter using LAS-20 filter diatomaceous earth to a pressure of 0.5 MPa. The average filtration rate is 3600 g / dm ² . . h. when cleaned to 0.1 vol. % "Sediment". The product obtained has 59% of active ingredients, a kinematic viscosity of 22.3 mm ² / s at 100 ° C, a content of 4.9% calcium, 2.8% sulfur and a total basicity of 138 mg KOH / g.

EXAMPLE 1 a d 3

In the apparatus of Example 1, a dispersion of 270 g of CaO (4.82 moles) in 860 g of ethanol (0.02%) was prepared. With vigorous stirring, 543 g of technical dodecylphenol sulfide containing 7.5% sulfur, prepared from dodecylphenol containing 67.5 wt. percent monododecylphenol and 28.3 wt. % of didodecylphenol, followed by 543 g of oil raffinate by cinemas, viscosity 21 mm ² / s at 100 ° Celsius, 110 g of oil concentrate containing 30 percent calcium petroleum sulfonic acid calcium with an average molecular weight of 430 and 50 g of 80/110 gasoline. In the reaction mixture, 113 g of technical dodecylphenolsulfide, 130 liquid hydrocarbons containing 8 wt. % of hydrocarbons boiling at 80 to 110 ° C and 13.7 g of calcium sulfonate. With vigorous stirring, carbon dioxide at a rate of 0.216 l / min, i. 0.579 mol / hr, which corresponds in total to 0.6 mol of carbon dioxide per 1 mol of calcium oxide.

The reaction mixture, after carbonation, is heated to 160 ° C and 50 ml of water are gradually added at 60 ° C. After distilling off the solvents, the mixture was maintained for 1.5 hours. at 160 ° C under reduced pressure of 25 to 40 kPa.

The crude product was at a temperature of 120 to 130 C. ^c centrifuged at room a flow centrifuge at 10,000 g =, and finally purified on a heated pressure filter using 2 wt. percent of LAS-20 kieselguhr. The average filtration rate at a pressure of 0.5 MPa is 3000 g / dm ² . h. when cleaned to 0.1 vol. % sediment. The product obtained has 55% of active ingredients, a kinematic viscosity of 28 mm ² / s at 100 ° C, containing 7.6 wt. % calcium, 3.0% sulfur, and a total basicity of 190 mg KOH / g.

Example 4

In the apparatus of Example 1, a dispersion of 102.5 g of calcium hydroxide 97.5 percent purity (1.35 mol) in 610 ml of methanol was prepared with vigorous stirring. Then 950 g of alkylphenol sulphide containing 7% sulfur, prepared by sulphating an alkylphenol containing 45.2 wt. % mono- and 20.3% dialkyl derivatives and 34.5 wt. % of hydrocarbons, further 50 g of oil raffinate of kinematic viscosity 21 mm ² / s at 50 ° C and 200 g of 80/110 gasoline. 1 mol of Ca (OH = 704 g of alkylphenol sulfide, 428 g of hydrocarbons containing 34.6% by weight of hydrocarbons boiling up to 110 ° C) is present in the mixture.

After homogenization of the mixture, carbon dioxide at 0.248 g / min, i.e. 0.338 mol / hr, was fed to the bottom of the flask over 2 hours. and a total of 0.5 moles per mole of Ca (OH) 2. After carbonation, the mixture is heated to 165 ° C, distilling the lower boiling liquid components. The mixture was stirred vigorously at this temperature for 1.5 hours. under reduced pressure of 25 to 40 kPa. The crude product is purified by filtration on a pressure heated filter at 130 ° C and 0.5 MPa using 4 wt. % Kieselguhr LAS-20 per mixture. The average filtration rate is 2300 g / dm ² . h. The product obtained has 0.1 vol. % sediment, 65% active substance, kinematic viscosity 30 mm ² / s at 100 ° C, content

3.6 wt. % calcium, 2.4% sulfur and a total basicity of 102 mg KOH / g.

Claims (2)

1. A process for the production of an additive to alkylphenolate-type lubricating oils by treating a mixed mixture of calcium or calcium hydroxide with a phenol derivative in an aliphatic alcohol having from 1 to 3 carbon atoms, water, liquid hydrocarbons and preferred alkali earth metal salts of petroleum or alkylarylsulfonic acid . weight 350 to 600 using 0.4 to 0.8 moles of carbon dioxide per 1 mol of basic calcium compound and then distilling off the lower boiling components by heating to 150 to 175 ° C, characterized in that a pre-prepared dispersion of 15 to 35 wt. % of calcium oxide or hydroxide in an alcohol is homogenized with a mixture of phenol derivatives of the general formula which may contain 50 wt. % of a phenol derivative of the general formula OH OH in which on the aromatic ring there is at least one substituent R 1, R 2, R 3, R 4, a hydrocarbon group of 3 to 30 carbon atoms and the other may be hydrogen and X is -S- or -Sz- and with a mixture of liquid hydrocarbons 100-150 g of phenol derivatives and 150-500 g of liquid hydrocarbons are added per mole of calcium compound, and thereafter carbon dioxide is added to the vigorously stirred mixture in an amount of 0.1 to 0.2 mole per mole of calcium compound and the product , free of lower boiling components, is purified by centrifugation and / or filtration. 2. A process according to claim 1, wherein the liquid hydrocarbons consist of petroleum oil raffinates having a kinematic viscosity of preferably 15 to 45 mm @ ² / s at 50 DEG ^C. and hydrocarbons having a boiling point of 60 to 150 ^DEG C. in an amount of 4 to 40 wt. . % in the mixture.