DE2339120A1 - LUBRICATING OIL ADDITIVE - Google Patents

Description

WCfITSAKWALTE OR. JUR. DlPL-CHEM. WALTER ATi ALFREO HOEPPENER F-

DR. JUR. DIFL-CHEiA H.-J. WOLFP DILJU (L HANS CHS.BtJL

«Ti f 8ANKFUST AM MAiN-HOCHST

Our no. 18 791

Chevron Research Company San Francisco, CaI., V.St

Lubricating oil additive.

Schmaa ^ ole working under severe conditions in diesel and gasoline engines are composed of numerous components, which have the task, for example, of neutralizing the acids formed by the oxidation of sulfur in the fuel and the partial oxidation of hydrocarbons, sludge and varnish-forming precursors in the oil to disperse, to inhibit oxidation and wear and to improve other lubricating properties of the oil. Ven Fesel-Lokomot ^l lubricating oils used be non-corrosive and non-reactive with silver, in addition to the usual requirements for lubricating oils for diesel and gasoline engines in the D allowed. In

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Most diesel locomotives today are made of silver used.

It is obvious that a single additive with poly- functional properties is more powerful and economical than a large number of additives. Because of the sharp Operating conditions under which a lubricating oil works in diesel and gasoline engines tend to have additives that have a certain Performing a function effectively, causing decomposition, thereby increasing the formation of deposits. In development With a special additive, it is therefore not only important that it fulfills its intended functions, but also that it is also stable under the conditions of use or that it decomposes only slowly to substances which the Do not increase the formation of deposits.

Sulphated alkaline earth metal phenoxides have been used in lubricants for a long time and phenate used. A particularly successful sulphurized metal phenate is shown in U.S. Pat 2,680,096 as normal and basic sulfated calcium phenate described. These compounds are made by adding an alkyl phenol, calcium hydroxide, and sulfur in a corresponding reaction vessel in the presence of Bringing ethylene glycol into contact with one another. The resulting The reaction product has a weight ratio of sulfur to calcium of generally between about 0.3 and o, 7 · These compounds work well as dispersants, antioxidants and agents] for neutralizing corrosive acids in lubricating oils; The more recent development of diesel and gasoline engines, the under even sharper Working conditions, however, created a new need for sulfonated metal phenates with improved properties.

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further work in the field of sulfated metal phenates led to numerous types of such compounds, which, however, also contain a proportion of sulfur to have calcium below about 1. From US-PS 2,415,833 » 2 68c o97, 2 916 454, 2 989 466, 3 178 368, 3 367 867 and further typical results of this development have become known.

The above work led to numerous new and useful sulfurized metal phenates; still exists there is still a need for a lubricating oil additive with better dispersing properties and improved antioxidant properties, which exposed parts made of silver and in particular the bearings do not adversely affect »'The sought-after new ones Additives are also said to be relatively cheap to manufacture.

The aim of the present invention is therefore to provide a sulphured metal phenate with improved antioxidant, The invention also relates to lubricants containing such additives. These should also be usable in diesel engines including diesel engines with silver bearings. The invention also relates to a process for the production of the new sulf-arylated metal phenates.

The present invention therefore provides a mixture of sulfonated alkaline earth metal phenates, which is obtained by reacting an alkaline earth metal base with a sulfated alkylphenol and which has an average atomic ratio of sulfur to metal between about 1 and 4. The erfindungsgemäiien compounds are prepared by a two SVIF sodium methods prepared in which 1, o to 5 moles of sulfur and o _t o5 to 1.5 K'ol and preferably o, 2 to 1, o Erdalkalim Koi? Tallba3e in the first stage per mole Alkylphenol

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with 8 to 35 carbon atoms in the alkyl group will. The components are in the presence of 0.1 to 4 moles and preferably from 0.2 to 1 mole of one mutual solvent used per mole of alkylphenol, the solvent being both alkylphenol and alkaline earth metal base is able to solve.

In a second process stage the sulftirated Reaction product with 0 to 1.45 moles of additional alkaline earth metal base and 0.5 to 4 moles of solvent per mole of original alkylphenol reacted under conditions which to form the sulfonated alkaline earth metal phenate product to lead.

The mechanism responsible for the multifunctional properties, and especially the good silver lubrication of the sulphonated ones Metal phenates responsible int, is not known. Although the mechanism is unknown, it is known that these compounds have excellent antioxidant properties and represent a hotie base reserve in lubricating oils.

The sulfated metal phenate mixtures according to the invention are manufactured in a two-step process. One of the advantages of the two-step process over a one-step The method is to reduce undesirable side reactions of the sulfur feedstock with the mutual solvents, and an improved base reserve.

In the first stage is an alkylated phenol with 8 to 35 carbon atoms in the alkyl radical with sulfur and one small amount of an alkaline earth metal oxide or hydroxide and a mutual solvent, preferably ethylene glycol, brought into contact. The reaction between alkyl

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phenol, metal] base and sulfur are essentially the same as follows:

OH

solvent

In the above formulas, R denotes an alkyl radical with 8 to 35 carbon atoms, χ an integer from 1 to 5, η one integer from 0 to 15, the annex Y, which can be identical or different, hydrogen or 1 / 2M, where the The ratio of hydrogen to 1 / 2M is proportional to the ratio of M su alkylphenol in the starting material, and M an alkaline earth metal.

The above equation represents a simplified version of the reaction between alkylphenol, sulfur and metal base to form the sulfonated intermediate. The intermediate is not a pure compound of uniform structure, but rather a mixture of different sulfonated compounds

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fertilize, in which η and χ can have different nevtes. The above formula indicates that a metal atom is bonded to at least one phenolic group, 1?; Öep molecule of the intermediate product. Since the reaction product is a mixture of compounds, some molecules of the sulfonated alkylphenol can also be present without metal breath, and conversely, in the case of other molecules, all phenolic groups can be neutralized by the metal base. The metal atoms can be bonded to the phenolic group via a covalent bond or ionically and can be present as cations in the intermediate product. From this it follows that the above equation, although a general representation of the reaction and the intermediate product, is the one according to the invention

reproduce
Implementation not exactly. can.

The above process stage can be continuous or discontinuous, be carried out, as described in more detail below refers to the preferred discontinuous operation. The necessary for continuous process management Modifications are obvious to a person skilled in the art, so that a detailed description is provided continuously Working method is not required.

The three reactants are introduced into a suitable reaction vessel and preferably stirred before the mutual solvent is added. After the addition of the solvent, the exothermic reaction takes place with vigorous evolution ν ^Λ η hydrogen sulfide and water vapor. Means for discharging the large volumes of exhaust gas must be provided. The reaction can be carried out at temperatures between 121 and 232 ° C. and pressures between 0.35 and 1.4-1 atmospheres absolute. Preferred sea conditions are temperatures between 135 and 2o4 C and pressures between 0.7 and 1.05 atmospheres absolute. The reaction proceeds under this

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2333120

things at a moderate rate and usually lasts about 1 to 6 hours.

A reaction diluent is preferably provided, which facilitates the handling of the reaction products. The diluent can be added to the system before, during or can be added after the reaction, and is preferably carried out the addition at the point in time at which a reduction in the viscosity of the mixture is desired.

The concentration of alkylphenol, alkaline earth metal base, sulfur and mutual solvent in the inert diluent during the reaction is not important; it can depend on the reactants and other process conditions vary.

In general, the concentrations of the various Process components in the inert reaction medium, however within the limits illustrated by the following Table I:

Table I.

Part of the broad range of the preferred range.

(Mol-50 '(Mol - / *)

Alkyl phenol 3.7-47 16-35

Alkaline earth metal base .o, 5-42 3.8-27

Sulfur 13-81 33-63

LöHunp-smi ^ tel 1,3-66 3,8-27

Thinning agent (wt .- ^)-75 0-5o

(1) with the exception of the reaction diluent.

The volume ratio of the various components is important i '^; e realization- de? critical ratio of sulfur

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to metal in the finished sulfated metal phenate. The proportions should be kept within the following limits: 1 to 5 and preferably 1.3 to 3 moles of sulfur, 0.03 to 1.5 and preferably 0.2 to 1 mole of alkaline earth metal base and 0.1 to 4 and preferably 0.2 to 1 mole of solvent per mole of alkylphenol.

Excellent results are obtained using 2 moles of sulfur, 0.3 moles of alkaline earth metal base, and 0.2 moles of each other Solvent per mole of alkylphenol in the reaction medium.

According to a preferred embodiment of the first process stage, sulfur, alkylphenol and alkaline earth metal base are used placed in a reaction vessel equipped with an exhaust line and vacuum pump. The reactor contents are below Normal pressure heated to 121 to 14o ° 0, then the mutual solvent in the course of 15 to 30 minutes admitted. During this time, hydrogen sulfide and fasser are developed 'and via the exhaust pipe from the System carried out. The reaction is continued for 1 to 2 hours at 130 to 14o ° TC, then 3 to 5 hours heated to a temperature between 177 and 185 ° G. Finally, the reactor contents are cooled and a reaction diluent is added is admitted.

The sulphurized intermediate contains at this point some elemental or polysulfite sulfur (in general 2 to 10% by weight) and is suitable for use in the second process stage. You can use the reaction mixture however, also filter to remove solid particles, or subject to other purification steps or for later Store use first.

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In the second stage of the process, the sulphurized intermediate product is brought into contact with a further amount of alkaline earth metal base and mutual solvent. Like the first stage, this stage can be carried out continuously or batchwise. The following explanation again relates to : -: ■ preferred discontinuous work. The sulfated intermediate is added to the reaction vessel along with the reaction solvent, usually a diluent oil, and the alkaline earth metal base. The three components are stirred vigorously to disperse the metal base in the mixture. Then the mutual solvent is added, which catalyzes the exothermic reaction. After the addition of the reaction medium, the evolution of hydrogen sulfide and water begins, which are immediately drawn off overhead. Delayed removal of hydrogen sulfide and water vapor favors the oxidation of some of the mutual solvents, for example from ethylene glycol to glycolic acid, oxalic acid and the like. The oxidation products in turn react with the metal base and reduce the base reserve of the product.

The reaction conditions in the second stage include temperatures between about 121 and 232 ⁰ C, preferably between 135 and 2O4 ° 0, and pressures between o, 14 and 1, o5 atmospheres absolute ^ preferably between o, 14, and o, 7 atmospheres absolute. The time required to neutralize the sulphurized intermediate with the metal base depends on the reactants and the mutual solvent, concentrations and other reaction conditions. In general, however, the reaction has ended after about 4 to 10 hours. . After completion of the reaction or during the reaction, the mutual solvent is preferably stripped off.

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The concentration of sulfurized: intermediate Erdalk ⁿ liiretallbase and mutual solvent Reaktiorsmedlum ipt not critical, apart from the requirement dai; preferably sufficient amounts of diluent should be present, which facilitate the mixing and pumping of the product. up to 0.2 moles of alkaline earth metal base and 0.5 to 4 and preferably 0.5 to 2 moles total mutual solvent per mole of original alkylphenol. The proportions of the reaction components are illustrated in the following table II:

Table Il

Component broad range, more preferred

(Mole -; =) (101-5 $)

Alk-1 phenol (from Sl ' ^1J ) 15-67 23-67

added alkaline earth metal base 0-49 6-29

Solvent 17-8o 24-63

Diluent (by weight; :) 0-75 1-5ο

(1) SI means separately tared intermediate

(2) with the exception of the reaction diluent

The end product is owned by someone. Metal] content between 0.5 ure?

15 wt. -; ' and a sulfur content between 3.5 and 1o "Jew .--; £.

The molar ratio of sulfur to metal varies between 1 uno 4 and preferably switcher 1.1 uni λ, be ^^ rz-ers before ^ u ^ t between 1.1 and 2. Dsr alkali value `` ASTM - ¹ He ^ t I) - 28Q6 ^N des sulfftr ¹ ' ^a rte ^ Iv- ^ tallphene-ts 1ϊ? Ρ · ΐ between ^ o and? Oo rrgKOF / and usually between \ <o and 15o Γ, Γί &quot;. ΊΙ / g.

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- yr -

Dip alkylated phenols which can be used according to the invention Showing formula

ÜH

wherein R is a straight-chain or branched alkyl radical Represents 8 to 35 and preferably 10 to 3o carbon atoms. The alkylre ^ t R can be located anywhere on the phenol ring, i.e. in ortho, meta or para position « The radicals R are preferably located mainly in the m? T8 or para position. That is, less than $ 40 of the remainder R in οrtho- ^ division and preferably less than $ 15 the Heste R are in this position. A particularly preferred one Alkylphenol is polypropylene phenol with 9 to 20 carbon atoms in the polypropylene chain.

Examples of suitable alkyl substituents are the Octyi-, decyl, dodecyl, ethylhexyl, Triacontylrest and the like., Petroleum hydrocarbons such as # eißöl, wax, olefin polymer (such as polypropylene "polybutylene, and the like.) Radicals derived and _# the like. Of course, mixtures of different Alkyl phenols can be used successfully in the practice of the present invention.

Various alkaline earth metal hydroxides serve as a further starting material or oxides, with calcium hydroxide, calcium hydroxide, barium hydroxide, Earium oxide and the like may be mentioned. Also mixtures of oxides and hydroxides of various alkaline earth metals can be used with Erf "Ip-. When using magnesium

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magnesium methoxide or magnesium methyl carbonate is preferred before the oxide or hydroxide. The bases calcium and barium are preferred, especially calcium, which is used as Calcium oxide and calcium hydroxide is used.

The presence of a mutual solvent is critical to the practice of the invention. The solvent can consist of any stable organic liquid that has sufficient solvent power for both the alkaline earth metal base and for the alkylphenol and the sulfated intermediate. Examples such solvents are ethylene glycol, 1,4-butanediol, Derivatives of ethylene glycol such as monomethyl ether, monoethyl ether and the like. The vicinal glycoles are preferred, in particular ethylene glycol, as it activates the neutralization reaction and thus corresponds to a catalyst, although its functionality is not exactly known. In the first reaction stage you need im. general at least 0.1 mole of mutual solvent per mole of alkylphenol, and in the second reaction stage is Minimum amount of 0.5 moles of solvent per mole of alkylphenol originally used. Above a ratio of 2: 1 the reactor volume is increased excessively and solvent reprocessing becomes difficult. In principle, however, molar ratios of up to 4i1 are possible.

The preferred reaction diluent is a mineral lubricating oil made from paraffinic, naphthenic, asphaltic or mixed crude oils with a flash point above about 177 ° C. The diluent serves to increase the viscosity of the sulfurized intermediate and the sulphonitrated metal phenate, so that these products can be easily transported by pumping. Mineral lubricating oils are preferred

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as the ultimate use of the sulfurized metal phenates is in oil additives. However, other inert, water-insoluble organic media which do not interfere with the reaction of those involved in the process can also be used. A particularly preferred reaction diluent consists of refined central continental neutral oil with a viscosity of about 100 SUS at 38 ⁰ G.

Lubricant mixtures according to the invention are obtained by simply combining the sulf-arated metal phenates obtained in the above process with a corresponding lubricating oil or lubricating oil mixture. The amount of sulfated metal phenate in the lubricating oil mixture which is necessary to achieve the superior antioxidant effect and base reserve depends on the type of sulfated metal phenate in question, the properties sought and the lubricating oil to be improved. In general, however, the amounts of sulfurized metal phenate are between 0.5 and 15 and preferably 1 to 8 wt .- ^. Thus, the lubricating oil mixtures generally obtained a sulfur content of between about o.o3 and 3 percent -. $> And a entstamme ends the phenate alkaline earth metal content between about 0.08 and o, 3 wt .- ^.

Numerous natural and synthetic lubricating oils can be used in the practice of the invention, e.g. Naphthenic or paraffinic or mixed lubricating oils Base. The oils generally have viscosities between 35 and 50,000 SUS at 38 ° C. and between 3o and 15o SUS (Saybolt universal seconds) at 99 G · Other hydrocarbon oils are e.g. oils obtained from coal products and synthetic oils, such as the alkyl polymers (e.g. propylene, Butylene polymers and mixtures thereof), alkylene oxide polymers (e.g. those made by polymerizing an alkylene oxide like propylene oxide in the presence of water or alcohols,

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e.g. ethyl alcohol), carboxylic acid esters (e.g. esters of adipic acid, azelaic acid, suberic acid, sebacic acid, alkenyl succinic acid, fumaric acid, maleic acid and the like. And alcohols such as butyl alcohol, hexyl alcohol, ^ 2-ethylhexyralcohol, pentaerythritol liquid esters of phosphoric acids and the like) , Alkylbenzenes, polyphenols (e.g. biphenyls and terphenyls), alkyl bisphenol ethers, silicon-containing polymers, e.g. tetraethyl silicate, tetraisopropyl silicate, hexyl (4-methyl-2-pentoxy) disilicate, poly (methyl) siloxane, Poly (methylphenyl) siloxane and the like. The lubricating oils can be used individually or in mixtures, the latter being possible in the case of miscible oils or when using mutual solvents.

In addition to the sulfonated metal phenates, others can also Additives are successfully used in the lubricant mixtures according to the invention without their multifunctional ones Affect properties. Examples are stabilizers, agents for high pressure loads, Adhesives, agents for lowering the pour point, lubricants, viscosity index improvers, color correctors, odor-binding agents ^ anti-wear agents, antioxidants- tien, metal deactivators, anti-corrosion agents and the like. Called.

example 1

This example illustrates the preparation of a sulf-etrated Metal phenate in a two-step process according to the present invention. One with stirrer, cooling coils, thermometer, closed reaction vessel equipped with several supply lines, an inlet tube for nitrogen and a vacuum exhaust of 15100 1 content is 816o kg of letrapropylene phenol

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and 512 kg of calcium oxide (98% none) are charged. The contents are stirred and heated to 1o4 ° 0, 188ο Schwefeipulver kg are added and the mixture is heated to I3o to 135 ⁰ O. Then follows the addition of 399 kg Äthylenglyeol, then v / ater is durph passed the cooling coils to lower the temperature of the Keaktorinhalts during the G-lycolzugabe to keep at 13o to 135 ⁰ C. The temperature can then rise by 2.8 ° G and is held at this value for about 1 hour. Then the reactor content is heated to 182 to I8o ⁰ C and kept 4 hours at this temperature. Thereafter, the reactor contents are cooled and treated with 1 189o diluent oil having a viscosity of about 1oo SUS at 38 ⁰ C. During the above reaction steps, the pressure is maintained at practically normal levels by removing hydrogen sulfide and water vapor overhead from the system immediately after they are formed.

As soon as the reactor contents are heated to 149 to 154 ° C with diluent oil is cooled, a vacuum of 25 »4 cm of mercury applied and maintained for 15 minutes. Then will

1 more diluent oil added and the sulfonated Intermediate mixed in the reactor. The molar ratio of the various components in the reactor is calculated

2 KoI sulfur, 0.3 moles calcium oxide and 0.21 moles ethylene glycol per mole of tetrapropenylphenol.

In the second stage of the process, 5,120 kg of the 68.5 percent by weight are obtained Solution of the crude sulf "tared intermediate product in the oil with cooling coils, thermometer, stirrer, Nitrogen inlet, multiple supply lines, and vacuum vent equipped closed reaction kettle from 151oo Content fed. The kettle contents are stirred, then be 0.9 kg of a foam inhibitor (liquid silicone DC-200, sold by the Dow Corning Company) and 2200 liters of diluent oil

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mixed in,

Then, 363 kg of calcium hydroxide was added and the reactor contents are maintained at a temperature from 82 to 88 ⁰ G. As soon as the addition of the calcium hydroxide is complete, a vacuum of 25.4 to 3o.5 ce mercury is applied. At the same time, 625 kg of fresh ethylene glycol are quickly added. The temperature of the system is allowed to rise slowly to 149 ° C. over the course of 2 1/2 hours. As soon as 149 ° C. are reached, a vacuum of 63.5 cm of mercury is applied and maintained for 30 minutes. The temperature is slowly increased to 199 ° C. under this vacuum, the ethylene glycol being stripped from the crude sulfonated calcium phenate. The stripping stage takes approx. 4 hours. The vacuum is then released and the reactor contents are ^{cooled to 121 °} C., then 379 l of diluent oil (100 neutral) are added.

A representative sample of the product is processed

and the sulphated metal phenate is analyzed. Man finds a typical calcium content of 4.5 wt .- ^ (ASTM D811) and a typical sulfur content of 4.9 wt .- ^ (ASTM D1552). The molar ratios of the individual components in the end product have the following values:

Molar ratios

S / Ca 1.4

S / alkylphenol ο, 9

Ca / alkylphenol o.66

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Example 2

In this example, series of tests are carried out with oils containing various sulfonated metal phenates varying proportions of sulfur to calcium, and these products are made with the product of des Example 1 compared. The test is carried out in a glass cell carried out, which from a compartment of 100 ml, a stirring mechanism and a compartment, which solid sodium or potassium hydroxide pellets used as desiccants serve, and contains an AÖsorbz for volatile acidic oxidation products. The desiccant only has Vapor phase contact with the liquid in the sample compartment. The cell is only open to a 1.5! Diving bell, which is filled with 99.85% oxygen at normal pressure. For each tea, a 25 g sample of the oil and 0.2 ml of catalyst solution are poured into the sample compartment of the cell. The oil is heated in the cell to 171 ° C. and kept at this temperature for 10 hours while stirring vigorously. The viscosity is before the influence of oxygen and after of the 10-hour test duration. The change in viscosity provides an indication of the antioxidant property of the sulphated metal phenate present in the oil with larger viscosity increases worse Designate antioxidants.

The oil used in the test consisted of a mid-continental neutral refined oil SAE 30 with 3.5 weight percent of a succinimide dispersant and 80 millimoles of calcium in one of the advanced metal phenates identified in Table III.

The oxidation catalyst, a solution of metal phenates in

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Kerosene, gives the oil to be tested 52 ppm copper, 31 ppm iron, 27 ppm tin, 26 ppm manganese and 6o3 ppm lead in öllöslictier ϊοπη.

The test results are shown in Table III:

Table e III
Attempts at oxidation

Sulphated Ms' allphenate

Compound sulfur calcium S / Ca viscosity increase

(Ge w. - ⁰ Jo) (Gew .- 'ri) (Gew «~ Vermut

tiältnis) ($)

A. (D 3? ₁ 3, -. O, 69 128 B. (1) 3, ί 4.5 C, 69 112 G (2) s * 7th 9 / ' O, 4th 11o D. (3) 4 * O 9.3 O ₁ 3 11o E. (4) 9 4 _S 5 1, 1 26th

(1) produced by reacting tetrapropylene phenol with Calcium hydroxide and the presence of ethylene glycol

(2) as (1), jedocii carbonated

(3) As (1), except that about 35% by weight of the Alkylphenols produced with a straight chain. ^ -Olefin became

(4) from tetrapropylene phenol, aluminum oxide, calcium hydroxide

and sulfur according to the / experienced τοη example 1 produced

The above table clearly illustrates the improvement in the Antioxidant effect of the si.j.f-erated metal phenate with a molar ratio of sulfur 7, u calcium of more than 1 compared to similar s ^ J-i ** fourth η phenates with molar ratios under 1, The »-'rfiticiung ^^ einäiJe Verbina-irg E er

40980? ./ 1 183

gives a viscosity increase of less than 1/4 that of with viscosity increases resulting from the other additives.

Example 3

This example illustrates the advantage of the two-stage process according to the invention over a one-stage procedure. A 3 l reaction flask equipped with a stirrer, thermometer, condenser and feed funnel is charged with 661 g of neutral oil 100, 747 g of tetra-propylene phenol, 197 g of sulfur and 144 g of calcium hydroxide. The mixture is heated to 127 ° C. under a vacuum of 10 mm mercury and stirred vigorously. Then 346 g of ethylene glycol are added in the course of 20 minutes and the temperature is allowed to rise to about 149.degree. The temperature is then held at 149 ° C. under a 25.4 cm mercury vacuum for 2 hours, then increased to 196 ° C. in the course of 2 1/2 hours, while at the same time the pressure is lowered to 11 mm mercury. The contents of the flask are kept at 196 ^° C. and 11 mm of mercury for 15 minutes, then cooled and filtered.

A sample of the crude sulfonated metal phenate is through Diatomaceous earth filtered then analysis gives 5.54 wt% Sulfur and 4.44 wt .- ^ calcium, corresponding to one Sulfur / calcium ratio of 1.56. The product owns a basicity value of 114.3 mgKOH / g, accordingly a calcium content of $ 4.07.

A sample of the sulfurized metal phenate is shown in Example 2 and compared with a sample of the sulfurized metal phenate of Example 1 described oxidation test. The results are shown in Table IV

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- 2c -

Table IV

Oxidation experiment ..
Compound manufacturing viscosity increase

Sulphurized Calciuin

phenate 1-step process 2o, 4

Sulphurized Galcium

phenate 2-step process 16.1

In the case of the product according to the invention, there is thus an increase in viscosity by $ 2ο lower.

Example 4

This example demonstrates the superiority of the invention, sulfonated metal phenates compared to other sulfonated ones Metal phenates with a sulfur / metal ratio below 1 and compared to a conventional, sulferized Ainometal Phenate. The experiment works with 6-cylinder tractor engines according to test procedure Caterpillar Tractor Company Test ET-40-I. This test is a Crankcase oil is the respective sulfated metal phenate added. The engine is operated under severe conditions, until the piston rings are tight. Then the engine is turned off, taken apart and examined. The time required until the piston rings sit tight is recorded; it serves as an indication of the dispersing time and the antioxidant effect of the respective sulphated metallic phenate.

A 6-cylinder Caterpillar D-353 TA serves as the test engine

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Motor with aftercooling with 15 »9 cm cylinder diameter,

2o cm piston stroke, 238o cm ⁵ cylinder capacity, 49o HP net power at a speed of 13oo. The tea conditions can be seen from Table V:

Table Y

Engine conditions

Speed 1300 rpm

Fuel quantity 14 8oo jieal / min

Sulfur content of the fuel 0.4 wt .- ^

Air inlet temperature ^{113 0 C}

Water inlet temperature 88 ° 0

The oil mixture in the crankcase consisted of HIM SAE 3o base oil with 2% by weight of a conventional ashless dispersant, 20 millimoles per kg of a conventional one metal-containing dispersant and 90 millimoles per kg of the sulfated metal phenate, based on the metal content, The test oil A contains a reaction of calcium hydroxide Sulphated calcium phenate made with tetrapropylene phenol and sulfur in the presence of ethylene glycol, whose weight ratio of sulfur to calcium is about 0.4. The test oil B contains a according to the method of Example 1 Sulphated calcium phenate prepared with a sulfur to calcium weight ratio of about 1.1. The results of the tests with caterpillar tractor engines are shown in Table VI:

Table VI

Test in a caterpillar tractor

Test oil for crankcase ratio sulfur / time up to

Calcium stuck d. Piston rings (std. )

Test oil A o, 4 36

Test oil B 1.1 175

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These values show the noticeable and unexpected increase the trouble-free operating time, which is achieved by the inventive Compounds with high ratio of sulfur to metal is obtained compared with conventional ones sulfonated metal phenates with a sulfur to calcium ratio below 1.

Z.09809 / 1 18 3

Claims (1)

Claims 1. Sulfurized alkaline earth metal phenate useful as a lubricating oil additive from an alkylphenol with 8 to 35 carbon atoms in the alkyl radical, 'that is an atomic ratio of sulfur to metal has between 1 and 4. 2. Sulfurized alkaline earth metal phenate according to claim 1 with an atomic ratio of sulfur to metal between 1.1 and and an alkali value between 40 and 200 mg KOH / g. 3. Sulfurized alkaline earth metal phenate according to claim 2 from tetrapropylene phenol and calcium oxide and / or hydroxide. 4. Use of the sulfurized alkaline earth metal phenates according to claim 1 to 3 in oils with lubricating viscosity in an amount of 0.5 to 15% by weight. Process for the preparation of sulphurized alkaline earth metal phenates according to claim 1 to 3, characterized in that 8.7 to 47 mol% of an alkylphenol with 8 to 35 Carbon atoms in the alkyl radical, 13 to 81 mol% sulfur, 0.5 to 42 mol% of an alkaline earth metal base and 1.3 to 66 Mol% of a mutual solvent in a liquid reaction medium at a temperature between 121 and 232 ° C and a pressure between o.35 and 1.41 atmospheres absolute for 1 to 6 hours, the Molar ratios between 0.05 and 1.5 moles of metal base, 0.1 to 4 moles of mutual solvent and 1 to 5 moles of sulfur are to be kept per mole of alkylphenol, and the reaction product thus obtained with 0 to 49 mol% of alkaline earth metal base and 17 to 80 mol% of the mutual solvent at a temperature between 121 and 232 ° and a pressure 409809/1183 between c, 14 and 1, OS Atmosvhä " ¹ "? ": absolutely smelled 4th to 1o
Hours. 6. The method according to An.ipru <"- h ^, characterized in that nan uses ethylene glycol and a2s alkaline earth metal base calcium oxide or hydroxide as a mutual solvent. 7. The method η " ⁵ Ch claim S thereby gek-nnz ^ ic ^ n ^ t that one initially grows o, 2 to 1 mol" iner Erdalknlimetallbase, o, "to 1 FoI of a gelatinous solvent un-1 1.5 bi ^c 3 KoI sulfur per FoI eip ^ s alkylphenols mi + "8 bi« ^ ¹ ^
Foal atom P in the alkyl rests at a temperature of ¹ "between 121 and 2 52 C and a pressure between o.35 and 1.41 atmospheres, absolute for 1 to 6 hours
with formation of an infused Z ^{T. i} visch ° nproducts vnd
then you-ses intermediate product with o, 2 to o, 6 KoI one
jirdalkali metal base and 0.5 to 2 Iwol of each other
per mole of alkylphenol d ^ß r first Btu ^ e a temperature of 121 to 232 ½ and a ¹ "pressure of 0.14 to 1.05 atmospheres absolute for 2 to 10 hours
converts a mixture of sulfonated metal phenates ^{under 1 ″ of a mixture.} 3. Method according to claim. 7, characterized in that iran uses ethylerglyool as the mutual solvent and calcium oxide rder calcium hydroxide as the alkaline earth metal base and the mutual solvent in egg second
otufe stripped from the sulfonated metal phenate mixture. 9. Verfa ^! ire ^M n ° cb claim S, characterized in that in the second Keakt-'onpstufe an inert Pueaktionsverdümungpnr tte] in ^ in ^ r üon? e of more than 50 G-ew.-s existi ° ri ^ Fu ^: Chevron Research Company · ¹ Francisco, "'al., V.ot.A. 409809/1183 Dr. H. X WoW BATH ORIGINAL