DE1302124B - - Google Patents

Description

Neutralized reaction products from phosphorus sulfides and hydrocarbons, especially olefin polymers, are widely used as detergent-type additives for lubricating oils, especially for Lubricating oils for crankcases of internal combustion engines are used. The use of such Additives in lubricants are described in U.S. Patents 2,316,080, 2,316,082. Such Detergent type additives are under high stress and high temperature conditions very effective in operating the engine.

For power machines that are operated under moderate stress or with interruptions, where low temperatures prevail in the engine cowling and in the crankcase are against these detergent additives to avoid deposits and sludge formation at deep Temperatures occurring type, which as a result of severe contamination of the oil with at the explosive By-products formed by combustion can occur, often with only limited effectiveness.

Cleaning-type lubricating oil additives are suitable for operation under such low temperature conditions with higher alkaline earth metal to detergent phosphorus ratios. The production such additives are described in U.S. Patent 2,806,022.

The patent application P 12 97 330.7-44 relates to a process for the production of oil-soluble, alkaline earth-neutralized hydrolyzed, phosphorus-sulphurized hydrocarbons by reacting a phosphorus sulphide with hydrocarbons in a weight ratio of 10 to 25 ° / ₀ phosphorus sulphide (based on the hydrocarbons), hydrolysis of the phosphorus sulphide formed in this way Product, neutralization of the hydrolyzate obtained with a basic alkaline earth compound in the presence of water and a lower alkanol and heating of the mixture neutralized with alkaline earth to remove water and lower alkanol with introduction of carbon dioxide, which is characterized in that a hydrocarbon mixture is used as hydrocarbons, the / ₀ of a low molecular weight polymer of a monoolefin having less than 6 carbon atoms and from 10 to 60 ° ₀ of a solvent-hydrocarbon lubricating oil consists essentially of 40 to 90 ° /.

The additives thus obtained have a high ratio of alkaline earth metal, especially barium, to detergent phosphorus, and its cleaning effect is under conditions where high requirements placed on the cleaning person under both high and low temperature conditions are superior to those of known additives, but are highly viscous products.

An improved process for the preparation of such additives has now been found, which leads to products with lower viscosity, which offers advantages in practical use. The reduction in viscosity is achieved through the use of boric acid (B ₂ O ₃ ) and the incorporation of boron into the chemical structure of the additive, which also results in further advantages.

The invention relates to a process for the production of oil-soluble, alkaline-earth-neutralized, hydrolyzed, phosphorus-sulfurized hydrocarbons in a further development of the process according to patent application P 12 97 330.7-44 by reacting a phosphorus sulfide with a hydrocarbon mixture which consists essentially of 40 to 90% of a low molecular weight polymer Monoolefins with less than 6 carbon atoms and 10 to 60 ° / _{0 of} a solvent-extracted hydrocarbon lubricating oil consists, in a weight ratio of 10 to 25 ° / ₀ phosphorus sulfide (based on the hydrocarbon mixture), hydrolysis of the phosphorus-sulfurized product thus formed, neutralization of the

ίο obtained hydrolyzate with a basic alkaline earth compound in the presence of water in a lower alkanol and heating the neutralized with alkaline earth Mixture for the removal of water and lower alkanol with the introduction of carbon dioxide, the is characterized in that in the neutralization of the hydrolyzate, 0.05 to 0.5 mol Boric acid is also used per mole of phosphorus.

The exact amount of boric acid added depends of course on the viscosity that the neutralized hydrolyzate possesses without the measure according to the invention, and from the extent up to which this viscosity is to be reduced, d. H. the desired final viscosity.

If, for example, for the reaction with the phosphorus sulfide a) a monoolefin polymer and / or b) a solvent-extracted hydrocarbon lubricating oil in the upper range of the below for a) specified molecular weight or with a viscosity that is in the upper part of the viscosity range of b) are used, then the neutralized hydrolyzate has the greatest possible viscosity and requires the use of a larger amount of boric acid than that for the neutralized hydrolyzed one Product is required that is formed in the phosphorus sulfide reaction of such starting materials, their molecular weight or viscosity is in the lower part of the respective range.

In general, the use of 0.5 moles of boric acid per mole of phosphorus is sufficient for satisfactory Lowering the viscosity of the neutralized hydrolyzed product.

For example, if the neutralized, hydrolyzed reaction product of a monoolefin polymer and a solvent-extracted hydrocarbon lubricating oil with a phosphorus sulfide has a viscosity of 3000 to 5000 Saybolt Universal Seconds (SUS) at 100 ⁰ C, then by using 0.25 to 0 .5 moles of boric acid per mole of phosphorus reduced this high viscosity to a value that is more suitable for technical processing and use.

By using smaller amounts of boric acid, e.g. B. from 0.05 to 0.25 mol per mol of phosphorus, present, uncorrected viscosities of 500 to 3000 SUS at 100 ⁰ C are reduced to viscosities that are more suitable for handling and processing in practice.

Phosphorus sulfides suitable for the reaction with the hydrocarbon mixture are P ₂ S ₃ , P ₄ S ₃ , P ₄ S ₇ and preferably phosphorus pentasulfide, P ₂ S ₅ -

The monoolefin hydrocarbon polymers a) of the hydrocarbon mixture are those used in the Polymerization of ethylene, propylene, butenes, isobutylenes, hydrocarbon mixtures containing these olefins, z. B. propane-propene mixtures, butane-butylene mixtures, in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride,

Aluminum chloride or similar halide catalysts of the Friedel-Crafts type are formed.

The monoolefin polymers used or mixtures of monoolefin polymers and isomonoolefin polymers have molecular weights from 150 to 50,000 or above, preferably from about 300 to 10,000.

Such polymers may, for example, by the polymerization of a hydrocarbon mixture comprising monoolefins and isomonoolefins, such as butylene and isobutylene, in the liquid phase at a temperature of about -62 to +38 ⁰ C in the presence of a metal halide catalyst of the Friedel-Crafts type, such as Boron fluoride or aluminum chloride.

For example, isobutylene, butylenes and butanes can be used in the preparation of these polymers containing hydrocarbon mixture, which consists of petroleum gases, especially those used in the cracking of petroleum Gasoline production generated gases that has been recovered use.

As the solvent-extracted hydrocarbon lubricating oil part b) that reacted with a phosphorus sulfide The hydrocarbon mixture can be any solvent-extracted or solvent-purified Use oil, d. H. each by a common method of solvent refining of lubricating oils treated oil.

The oil may be a liquid hydrocarbon base oil having a viscosity be from 10 to 500 cSt at 38 ⁰ C, such as are used as the base oil of the SAE-10 to -50 oils.

It can be obtained as a distillate or from synthetic materials, for example from petroleum and from through The oils produced are derived from cracking, polymerization, hydrogenation and similar processes.

Solvent cleaning is well known and generally includes a physical one Separation one. Usually the chosen solvent, e.g. B. furfural, phenol, sulfur dioxide, Components such as aromatic, unsaturated substances and substances with a low viscosity index, dissolved and broken down severed this way. If necessary, a treatment with clay can follow.

If necessary, a separate deasphalting treatment carried out, for example, with propane can be used performed in conjunction with solvent cleaning.

The phosphorus sulphurized hydrocarbon is obtained by reacting the phosphorus sulphide, e.g. B. P ₂ S ₅ , with the hydrocarbon at a temperature of about 65 to 315 ⁰ C, preferably from about 148 to 260 ⁰ C, for about 1 to 10 hours. Preferably, such an amount of phosphorus sulfide is used that it reacts completely with the hydrocarbon, in order to avoid the need for further purification. However, the phosphorus sulfide can also be used in excess and the unreacted material can be filtered off.

The phosphosulfurized hydrocarbon is hydrolyzed at a temperature of about 93-260 ⁰ C, preferably 148-205 ⁰ C. For example, passing steam through the reaction mixture for 1 to 10 hours, preferably 3 to 6 hours, is suitable for hydrolysis.

Basic alkaline earth compounds such as oxides, hydroxides and carbonates can be used for neutralization and sulfides of calcium, barium, strontium or magnesium. The basic barium and Calcium compounds, especially barium oxide and calcium oxide, are preferred.

The neutralization with the use of boric acid is carried out at the reflux temperature of the lower alkanol or a constant-boiling water-alkanol mixture. Suitable temperatures range from 6O ⁰ C and above, preferably in the range of 68 to 85 ° C, when C ₁ - be used to Q-alkanols ίο.

Only a small amount of water is used for the neutralization stage, expediently 0.2 to 2 mol, preferably 1.0 mol, based on the basic compound.

On the same basis, the amount of lower alkanol is 1 to 10 moles.

Although the neutralization can be carried out with the hydrolyzed phosphorus-sulfurized hydrocarbon mixture alone, it is preferred to use the hydrolysis product with 50 to 65% by weight of a light solvent-extracted lubricating oil, a solvent-extracted SAE-5-W to -10-W oil or of another hydrocarbon, the viscosity of which is not greater, to be diluted. The oil or the other hydrocarbon only serves as a diluent in order to further facilitate handling in addition to the use of boric acid. After neutralization, the water and the lower alkanol to be removed, which may, for example, by evaporation or distillation at atmospheric pressure at temperatures in the range 93-205 ⁰ C, preferably 120 to 177 ° C.

In order to avoid that upon heating to a temperature of about 93 ⁰ C, in particular in the range 93-121 ⁰ C, forms a gel which carbon dioxide is at least within the temperature range of 93 to 122 ° C and preferably during the entire removal of Pressed water and lower alkanol into the neutralized mixture.

The detergent formed is then insoluble of insoluble salts and other undesirable insolubles Products separated. The separation can, for example, by filtration, centrifugation or Decanting done.

In the procedure described above, the proportions of the reactants are known and known conditions of temperature and the like for making alkaline earth neutralized Phosphorus sulphurized hydrocarbons, which are suitable as cleaning agents for lubricating oil, applied, but this method differs from the known in that the reaction of the Phosphorus sulfide with the low molecular weight olefin polymer in the presence of a solvent extracted Base oil is carried out, the phosphorus sulfide apparently with the latter under formation a second, clearly different type of phosphorus sulphurized hydrocarbon reacts, which is also hydrolyzed and in the presence of the boric acid used with the alkaline earth compound is neutralized, thereby introducing boron.

As a result of the process according to the invention, there is a complex-forming, organic in the neutralization stage Phosphoric acid salt, e.g. B. a zinc dialkyldithiophosphate is not required. For certain cleaning agents However, metal dialkyldithiophosphates can also be used as additives which fulfill their known function will.

In the following examples, the Percentages, unless otherwise stated

the weight " , .

example 1

A mixture of 1370 g Butylenpolymerem having a viscosity of 540 Saybolt seconds at 100 ° C and an average molecular weight of 760, 910 g of a phenolextrahierten Midcontinent-SAE-40 Basisols and 420 g of P ₂ S ₆ be 5 hours at 232 ⁰ C. implemented 0.71 ° / ₀ sulfur and 0.07% of boron containing and has a viscosity of 1040 SSU (100 ° C).

By increasing the mole ratio of boric acid to phosphorus, the viscosity of the final product obtained, as illustrated in Examples 1 to 3, be further reduced

Comparative experiment
By omitting the boric acid in the above

The reaction product is extremely viscous, not with steam for 5 hours at io procedure

149 ° C hydrolyzed to the mixed phosphoric acids. To 1070 g of these mixed acids are added in the following order:

1. 1840 g SX-5-W-Basisol,
2 40 ml water,

3. 625 ml of methyl alcohol and according to the invention

4. 4.6 grams of boric acid (0.05 moles per mole of phosphorus).

The mixture is allowed to filter back under pressure for 0.5 to 1.0 hours Product received.

Example 5

A mixture of 1373 g of polybutene having a viscosity of 1000 SSU at 100 ° C and an average molecular weight of 900, 917 g phenolextiahiertem SX-40-O1 and 420 g of P ₂ S ₅ for 5 hours at 232 ⁰ C.

implemented. Subsequently, the reaction product is hydrolyzed and accordance with the invention in the presence of flow of the alcohol (68 ⁰ C). Then 340 g of 0.1 mol of boric acid, water and methanol with BaO barium oxide are added, and the neutralization is neutralized to remove water and methanol

mixture is refluxed for a further 3 hours. The neutralized mixture is heated to 177 ° C to remove alcohol and water while injecting carbon dioxide. After filtering, one obtains a final product containing 1.36% phosphorus, 7.02% barium and 0.03% boron and a Saybolt viscosity of 436 seconds (100 ⁰ C)

having. ",.

Example 2

By increasing the amount of boric acid to be added according to the invention to 9.2 g (0.1 mol of boric acid per mol of phosphorus) in the procedure described in Example 1, an end product is obtained which contains 1.38% phosphorus, 8.03% barium, 0.85% sulfur and 0.07% of boron containing and having a Saybolt viscosity of 295 seconds (100 ⁰ C).

Example 3

heated while passing in CO ₂ and filtered. After this, as described in Example 1 carried out operation one obtains a final product containing 8.14% Barium 1.45% phosphorus, 0.91% sulfur and 0.05% of boron containing and has a viscosity of 379 SSU at 10O ⁰ C.

The cleaning agents produced according to the invention, containing barium, phosphorus and boron, which are composed of Mixtures of polymers and oils are made, the corresponding boron-free as well as the from Superior to boron-free products obtained alone.

The superiority of the cleaning agents produced according to the invention can be demonstrated by lubricating oils containing these detergents are subjected to a test carried out with a Caterpillar 1-H overloaded diesel engine is carried out. These Examination has been named "Army Ordinance Specification

By increasing the 40 mil-L-2104B "to be added in accordance with the present invention, a Caterpillar 1-H

Amount of boric acid to 23 g (0.25 mol per mol of phosphorus) obtained in the procedure described in Example 1 an end product containing 1.37% phosphorus, 7.82% barium, 0.859% sulfur and 0.15% boron and a Saybolt viscosity of 159 seconds (100 ° C) having

Comparative experiment

By omitting the boric acid in the manner described in Example 1, one obtains a final product (hereinafter referred to as product A) having a Saybolt viscosity of about 3000 seconds (100 ⁰ C).

Example 4

A mixture of 1140 g of butylene polymer with a viscosity of 540 SSU (100 ⁰ C) and an average molecular weight of 760, 684 g of polybutene with an average molecular weight of 2000, 456 g of phenol-extracted SAE-40 base oil and 420 g of P ₂ S ₅ is 5 hours at 232 ⁰ C implemented. The reaction product is hydrolyzed with steam for 5 hours at 149 ^° C. to give the mixed phosphonic acids. The neutralization with barium oxide, accordingly in the presence of 0.1 mole of boric acid per mole of phosphorus and in the presence of water and methanol, is carried out as described in Example 1. The mixture is then _{heated while passing in CO 2} to separate off water and alcohol and filtered. A final product is obtained using 8.14% barium, 1.50% phosphorus, overloaded diesel engine designed to determine the high temperature cleaning ability of crankcase oils

The test of the lubricating oil in the crankcase of the Caterpillar 1-H engine is carried out for 480 hours, after which the carbon in the ring grooves is determined The carbon in the ring grooves is printed out in percentage filling of the slot If the percentage filling in the top slot is 25% or below, the lubricating oil is considered to be satisfactory.

Furthermore, one evaluates the amount and type of Lacquer that occurs in the annular grooves 2 and 3. The following table shows the results, when using crankcase lubricants with the boron-containing barium phosphorus cleaning agents prepared according to the invention and, for comparison purposes, with a barium phosphorus cleaning agent, which was made from polymers alone and is called "100% polybutene product" was obtained became.

The comparative product is derived from a polybutene with a molecular weight of 850 which had been _{reacted with P 2} S ₅ , hydrolyzed with steam and neutralized with barium oxide, as described above.

For further comparison, the behavior of the boron-free product A is also given in the same test .

The crankcase lubricating oils were made by adding the indicated percentage of the barium phosphorus cleaner prepared into an SAE 30 base oil.

Results of the 480 hour T nnW Barium phosphorus Caterpillar 1 -Η exam paint cleaning supplies Carbon in top groove 6.6 percent by weight 100 7o polybutene 100 black Product (mole 2nd and 3rd groove weight 900) 10 (unsatisfactory) 5.6 percent by weight 48 bright of the product 2nd groove Example 3 7th (satisfactory) 60 bright 5.5 percent by weight 2nd groove Product A. 8th (satisfactory)

Claims (1)

Claim: Process for the production of oil-soluble, alkaline earth neutralized, hydrolyzed, phosphorus-sulphurized hydrocarbons in further training of the process according to patent application P12 97 330.-7-44 by reacting a phosphorus sulfide with a hydrocarbon mixture consisting essentially of 40 to 90% of a low molecular weight polymer of a monoolefin with ίο less than 6 carbon atoms and 10 to 60 ° / o of a solvent-extracted hydrocarbon lubricating oil, in a weight ratio from 10 to 25% phosphorus sulfide (based on the hydrocarbon mixture), hydrolysis of the so formed, Phosphorus sulphurized product, neutralization of the obtained Hy drolysats with a basic one Alkaline earth compound in the presence of water in a lower alkanol and heating the with Alkaline earth neutralized mixture for removal ao of water and lower alkanol with introduction of carbon dioxide, characterized in that in the neutralization of the hydrolyzate, 0.05 to 0.5 mol Boric acid is also used per mole of phosphorus. 909 583/182