DE2207747C2 - Sulfuration product and lubricant or power transmission fluid containing it - Google Patents

Description

R ¹ R ^J

C = C

R ² R ⁴

in which R ¹ , R ² , R ³ and R ^{4 are} hydrogen atoms or alkyl groups, the total number of carbon atoms of the olefin hydrocarbon being 12 to 24, or in which the radicals R ¹ , R ² and R 'are hydrogen atoms and the remainder R ⁴ denotes an alkyl group and the total number of carbon atoms e des

Giefinkohienwrässersiöffes is 8 to 12,

is available? _

25 2) sulfurization product according to claim 1, characterized in that it consists of 50 to 90 Volumentcilen

of the triglyceride and 50 to 10 parts by volume of the olefin hydrocarbon and one Chemically bound sulfur content of 7.5 to 11 percent by weight, based on the total weight, which is less than 2.5% by weight as active sulfur.

3) sulfurization product according to claim 1, characterized in that it consists of 70 to 88 parts by volume 30 of the triglyceride and 30 to 12 parts by volume of the olefin hydrocarbon was obtained and one Has a content of chemically bound sulfur of 16 to 25% by weight, based on the total mixture, which is present as active sulfur in a proportion of 5 to 18% by weight.

4) sulfurization product according to any one of claims 1 to 3, characterized in that the triglyceride Lard oil was used with the following data:

free fatty acids as oleic acid 12-20%

Saponification number 192-198

Pour point (ASTM) 35-50

Viscosity SUS at 37.8 ° C 200-210

40 m.p. 65-75

Density at 25 ° C 0.910-0.915

Jodzahi 60-75

5) Lubricant or power transmission fluid based on a mineral oil, characterized by the 45 Content of a sulfurization product according to one of Claims 1 to 4.

In the past few years, sulphurized spermacet oil (sperm oil) has been used as an additive, such as a Reificings-Modifi-

5o ornamental, used in numerous lubricant mixtures, such as in gear oils, worm gears and spur gears, in power transmission fluids for automatic transmissions, lubricants for guides, Permawick lubricants for bearings made of sintered bronze or sintered bearing metal, and as an additive for metalworking oils. Since spermacet oil has become scarce, efforts have been made to find materials that can be used as substitutes are suitable for sulfurized spermacet oil. Sulfurized olefins by themselves do not have the lubricant properties

55 properties that are required for many applications, such as their high stick / slip ratio (Sliding factor) is displayed. Have sulfurized, natural triglycerides, such as sulfurized lard oil insufficient solubility in paraffinic base oils.

Attempts have also been made to produce mineral oil-soluble cutting oils by using tall oil and spermacet oil or has sulfurized tall oil and esters of monohydric alcohols together (US Pat. No. 2,417,283). Later examinations

However, results have shown that in these experiments only products could be obtained which were inadequate Have solubility in mineral oils.

In the further endeavor to provide suitable lubricant additives available, according to US-PS 27 03 318 Sulfuration products are described that are produced by sulfurization of animal or vegetable oils, Fats, resins and various derivatives of these natural substances and subsequent cooking of the resulting suI

65 furation product can be formed with an olefin hydrocarbon.

Furthermore, in US-PS 34 55 896 lubricant additives are described, which by reacting sulfurized low molecular weight polybutadicnene mi! 0.5 to 1.5 times the volume of a liquid, sulfurization accessible triglyceride.

In both known processes, a single component of the mixture is therefore separately used for sulfurization and then the sulfurization product obtained with the non-sulfurized second component implemented The statements in column 1, lines 55 to 75 of US-PS 27 03 318 show that difficulties passed, on the one hand, a sufficient amount of sulfur in active form in the starting compounds to introduce, but on the other hand to avoid that the sulfurization products are unstable, hydrogen sulfide split off and lead to deposits and signs of corrosion. Because of this, it was after this prior art required the initially sulfurized starting compounds, d. H. the sulphurized Triglycerides, after sulfurization, stabilize by using unsaturated hydrocarbons have been implemented. The same applies to US Pat. No. 3,455,896, in which initially liquid polybutadienes are also defined Properties are sulfurized, after which it is necessary that this sulfurization product with liquid Triglycerides is implemented. This prior art is also based on the object of adding a lubricant that contains sulfur in sufficient quantities, but is still stable

In view of this state of the art, it was therefore not to be assumed that a stable sulfurization product can be formed if both constituents - to be sulfurized separately according to the prior art - sulfurized together, because in this case a different reaction was to be expected than in the implementation a sulfurized triglyceride with an unreacted olefin.

The lubricant additives known from the aforementioned prior art are with regard to however, their lubricant properties and their compatibility with base oils are inadequate.

The invention is therefore based on the object of providing a lubricant additive which not only shows improved lubricity, but also has better compatibility with mineral oils and therefore less prone to deposits than the known lubricants.

This object is achieved according to the invention with the aid of a sulfurization product with a content of 7.5 to 25% by weight of chemically bound sulfur, obtained from triglycerides, olefin hydrocarbons and sulfur during a reaction time of 20 minutes to 10 hours at a temperature of 165.6 to 229.4 ° C, solved, which is characterized in that it is made by joint sulfurization of a mixture

a) 50 to 90 parts by volume of one of the triglycerides lard oil, herring oil, waloi, soybean oil, cottonseed oil, Safflower oil, linseed oil, rapeseed oil, sunflower oil or peanut oil, and

b) 50 to 10 parts by volume of an olefin hydrocarbon of the structure

R- R '

C = C

R ² R ⁴

in which R ', R ² , R' and R ⁴ denote hydrogen atoms or alkyl groups, the total number of carbon atoms of the olefin hydrocarbon being 12 to 24, or in which the radicals R ¹ , R ² and R ^{3 are} hydrogen atoms and the radical R ^{4 is} one Denotes an alkyl group and the total number of carbon atoms in the olefin hydrocarbon is 8 to 12,

is available.

The product according to the invention differs from the products of the prior art explained above Technology not only because of its manufacture, but because of its extraordinarily advantageous and after Knowledge of the state of the art, beneficial effects cannot be foreseen. Like the one described later The test report shows, according to the invention, on the one hand, 100% improved wear-preventing Effects achieved, on the other hand, the product according to the invention has improved solubility in paraffinic Base oils, d. H. Properties that are used in the field of lubricants, especially in the case of high-pressure lubrication systems, are essential and highly desirable.

According to the invention, 50 to 90 parts by volume, preferably 70 to 88 parts by volume of a triglyceride and 10 to 50 parts by volume, preferably 12 to 30 parts by volume of an olefin mixed with one another, the mixture is sulfurized and then a gas is bubbled through the resulting sulfurized mixture to generate hydrogen sulfide to remove.

The triglyceride and the olefin are generally combined at a temperature of 18.3 to 171.1 ° C mixed and the sulfur added while the mixture is within this temperature range. The triglycerides used according to the invention are naturally occurring triglycerides, which because of their low price and easy accessibility are advantageous. That is preferred for the purposes of the invention The triglyceride used is lard oil. The preferred commercial lard oil is generally called "Winter quality" lard oil (see Hackh's Chemical Dictionary, McGraw-Hill Book Co., 4th ed., P. 725) designated. Oils suitable for the purposes of the invention are given in Table 1.

Table 1

35-45 35-50 200-210 200-210 65-75 65-75 0.910-0.915 0.910-0.915 60-75 60-75

Properties Preferred Suitable

Lard duties Shtnaf duties

Free fatty acids as oleic acid 2-5% 12-20%

Saponification number 192-198 192-198

Pour point (ASTM)

¹⁰ Viscosity SUS at 37.8 ° C

Melting point
Density at 25 ° C
Iodine number

The main difference between the less preferred grades, like lard oil No. 1, and the preferred quality lies in the proportion of saturated compounds present, which the solubility of the Decrease product. Preferred products listed in Table 1 include materials such as winterized Lard oil.

Thus, the inventive method is better without applying pressure to perform la ¹ * ', olefins are preferred, which preferably contain at least 12, 15 KohlenstofTatome to a O <* - finverlust be avoided by boiling off when the ^Response: onsgemisch is heated. The olefin can be straight-chain or branched

The sulfur content is in the range from 7.5 to 25% by weight, based on the mixture of triglyceride and olefin. If an inactive sulfurized product is desired, then 7.5 to 110 wt .-% sulfur, based on the mixture of triglyceride and olefin, is used. Under the conditions used, this amount of sulfur is almost completely chemically bound in an inactive form. The resulting product, which contains 7.5 to 11 weight percent sulfur based on the mixture of triglyceride and olefin, is useful as a friction modifier for a wide variety of uses, as well as a metalworking oil.

When sulfurized oils are used as metalworking oils it is often desirable that they have a relatively high content of sulfur because the sulfur itself is the most important component its antiperspirant effect. In general, these metalworking oils should 16 to 25 percent by weight of sulfur are present. The sulfur present above the limit of 11 percent by weight is in the active form. The amount of sulfur in a given oil sample can easily be determined by X-ray fluorescence determine. After the total amount of sulfur has been determined, 100 g of the Place the oil sample and 20 g copper powder in a tall 250 ml beaker that was placed on a hot plate and which is provided with a thermometer and an Auger stirrer operated at 1750 rpm. The sample is heated to 176.7 ° C within 5 minutes and kept at 176.7 ± 2.8 ° C for one hour, after which it is cooled and filtered through a paper filter to remove the copper powder. The sulfur content The sample is again determined by X-ray fluorescence, whereby the inactive sulfur is obtained. The loss of sulfur (total sulfur minus inactive sulfur) is the proportion of that in the original Sample present active sulfur.

The level of active sulfur in a sulfurized oil used as a friction modifier, should be less than 2.5 percent by weight. In general, those according to the invention contain 7.5 to

11 weight percent total sulfur friction modifier 1 to 2 weight percent active Sulfur. The inventive fc.T additives for metalworking oils containing 16 to 25 percent by weight of total sulfur generally contain 5 to 18 weight percent active sulfur. Generally will the sulfur to the triglyceride-olefin mixture for a period of 1 to 60 minutes with continuous stirring added while maintaining the mixture at a temperature of 121.1-165.6 ° C. The temperature

is not particularly ki :: isch; the value of 121.1 ⁰ C represents the softening point of the sulfur and the value of 165 ° C o represents the flash point of the triglyceride-olefin mixture when the olefin is a mixture containing 15 to 20 Koh'snstoflatome. The high sulfur oils of the invention are soluble in paraffinic oils, as illustrated by testing a 10 g sample in 100 g of oil at 2.2 ° C for 16 hours and for one week at room temperature. In contrast, commercially available, heavily sulfu-

ured triglycerides, such as sulphurised lard oil and commercially available, highly lubricated sperm acetate! from paraffinic oils after testing under the conditions specified above. In general, for use as a metalworking oil, the sulfurized oil is dissolved in the paraffinic oil to form a 5 to 20% (volume percent) solution of the sulfurized oil in the paraffinic oil. After the sulfur has been added, the mixture is heated. If the amount present is cht gewün- to

To keep active sulfur as high as possible, a lower temperature such as 165.6 ° C can be used. The sulfurized oils invention have flash points of about 229.4 ⁰ C and this value is therefore the maximum temperature that should be used in the heating step. If desired, a pressure device can be used, whereby the maximum possible temperature can be increased, but the reaction is easiest at atmospheric pressure due to economic considerations.

fts printing carried out. In addition, only minor advantages are achieved if the temperature exceeds 229.4 ° C is applied. For mixtures in which the lowest possible proportion of active sulfur is desired, should the heating ö j ;. more than 185 ° C. For mixtures in which a high proportion of active If sulfur is desired, heating should not be done above 173.9 ° C. In the eye-

In my opinion, the heating takes place for a period of 20 minutes to 10 hours.

During the heating stage, a gas is passed through the sulfurized oil! blown to remove _{H: S.} Any gas which does not noticeably react with the sulfuric oil can be used. Suitable gases include air, nitrogen, carbon dioxide and gaseous perhalogenous hydrocarbons. Air is preferred for obvious economic considerations. The simplest blow-through is done by passing the gas through the sulfurized oil. According to another embodiment, the oil can be sprayed into the gas or a curtain falling into the gas can be formed from the oil. In general, the sparging is done at a temperature from 51.7 to 121.1 ⁰ C.

The products of the invention have properties which neither sulfurized triglyceride nor sulfurized olefins or mixtures of separately sulfurized triglycerides and sulfurized olefins have. Sulfurized triglycerides have the disadvantage of poor compatibility with paraffinic lubricating oils. The sulfurized olefins do not have suitable lubricity as can be seen from their poor adhesion / slip ratios (static friction / dynamic friction when used as a lubricant additive). The combination of adhesion / slip ratio and compatibility is particularly important for power transmission fluids for automatic transmissions and differentials with limited slip. Automatic transmission power transmission fluids typically contain 75 to 98 volume percent of a paraffinic base oil and 2 to 25 volume percent additive. The additives are necessary because no oil in itself has all the properties with regard to viscosity, flash point, foaming behavior and lubricity, etc., which are usually found for a power transmission oil! For automatic transmission to be desired, in order to achieve these properties, the oil must be fortified with various additives or additives. Numerous additives are commonly used, each specific additive being designed to improve a specific property of the hydrocarbon oil. A mixture intended for use as an automatic transmission fluid will usually have a viscosity of at least 49.0 SUS at 98.9 ° C. In addition, the viscosity of the fluid must remain essentially constant during the application of the fluid. It has according to the application in an automobile, which is repeatedly accelerated so much that the temperature of the li transfer fluid to 148.9 ° C is increased, usually a viscosity of at least 46.5 SUS at 98.9 ° C. The transmission fluid should have a flash point of at least 16O ⁰ C according to D-92 comprise the determination according to ASTM. The sulfurized oils of the invention are useful as friction modifiers! in such power transmission fluids which serve to reduce static friction more than dynamic friction. In general, sulfurized oils according to the invention in an amount of 1-5 Volumpro- Mi / ent of Gesamtfiuids used. A typical power transmission fluid for an automatic transmission or an automatic transmission can have the following composition: 82.7 volume percent of a solvent refined paraffinic lubricating oil with a viscosity of 40.3 SUS at 98.9 ° C and a viscosity index of 101.3 volume percent of the sulfurized oil according to Example 10. 0.5 volume percent zinc dialkyldithiophosphonate, 0.5 volume percent 4,4'-methylenebis (2,6-di-tert-butylphenol), 0.3 volume percent. ^: S barium phosphonate,! Volume percent overbased (over-based) barium sulfonate and 15 volume percent of a hyuricficfi iiäphihenisciien lubricating oil as a sealing quenchant !.

example 1

300 g of winterized lard oil are mixed with 300 g of σ-olefins in a 5-liter kettle equipped with a vibromixer. The α-olefins are a mixture of predominantly straight-chain mono-ff-olefins which have 15 to 20 carbon atoms. The mixture is heated to 121.1 ⁰ C and operated the vibromixer at maximum velocity. These conditions are maintained and 60 g of sulfur are added within a few minutes. The temperature is increased to 190.6 ⁰ C and held for 2 hours at this value. The temperature is then reduced to 93.3 ° C and air is passed through the stirred mixture using a glass tube for one hour to remove hydrogen sulfide. The flow is carried out at a moderate rate below the speed at which splashing and mixing takes place. The resulting sulfurized oil is analyzed and found to contain 8.7% sulfur based on the total mixture. A 10 gram portion of the sulfurized oil is dissolved in 100 grams of Oil A. Oil A is a commercially available solvent-refined paraffinic base oil with a viscosity of 40.3 SUS at 98.9 ° C, a viscosity index of 101 and containing 12% aromatics as determined by ASTM D-2007. After testing at 2.2 ° C overnight and at room temperature for a week, the oil sample remains clear and no deposit is formed. When tested for 3 hours at room temperature, the copper solution does not corrode. When testing for 3 hours at 100 ° C, the oil-A solution easily attacks copper. A solution of 3.65 percent by weight of the sulfurized oil in Oil B is prepared. Oil B is a commercially available, solvent-refined paraffinic base oil with a viscosity of 47.3 SUS at 98.9 ° C, a viscosity index of 103 and an aromatic content of 13% as determined by ASTM D-2007. If this 3.65% (percent by weight) solution is tested in a standard four-ball abrasion tester under a load of 20 kilograms for 60 minutes at 1800 rpm and at a temperature of 54.4 ° C, 0.48 mm Grooves observed. When this 3.65 weight percent solution is subjected to the Falex test using one minute increments, a maximum load of 793.8 kg is obtained. The Falex tests are performed on the Falex tester from Faville Le Valley Corporation, Chicago Illinois. These tests indicate the lubricity of the mixture under high pressure conditions. In the Faiex test fixture, a. 1/4 inch (6.35 mm) diameter steel pin twisted between two horizontally loaded steel V-blocks. At intervals of 1 minute, the load is increased in increments of 113.4 kg until the shear pin or the steel pin breaks due to the failure of the lubricant film.

Example 2

Example 1 is repeated, with the modification that 120 g of sulfur are added to the mixture of lard oil and α-olefin. 10 g portions of the sulfurized mixture are mixed with 100 g of Oil A. This mixture does not attack after testing for 3 hours at room temperature, copper, but copper corroded after testing for three hours at 100 ⁰ C. A solution containing 2.96 percent by weight of the sulfurized mixture into oil contains B, is prepared and the Falcx Test and Four-Ball Abrasion Test Using one-minute steps in the Falex test, the sample failed at a load of 1587.1 kg. In the four-ball wear test 0.61 mm grooves were a load of 20 kg under obtained at a speed of 1800 rpm ίο at 130 ⁰ C after 60 minutes. .i

Example 3

2260 ml of winterized lard oil are mixed in 400 ml of tetraisobutylene according to the procedure described below described before Table 3. Mixing takes place in a 5-liter kettle with a

Vibromixer is provided. The mixture obtained is ^{heated to 121.1 0} C and the vibromixer with maximum _;

speed operated. 10 percent by weight of sulfur are added and the temperature of the mixture>

increased to 190.6 ⁰ C for 2 hours. The mixture is then ^{cooled to 110 0} C, and with the help of a glass ■:

pipe is shedding at a moderate rate below the rate at which splashing and mixing occurs, -λ

Air passed through the mixture. The sulfurized oil obtained is analyzed to find a sulfur content of ~ f

8.23% is found. A 10 gram portion of the sulfurized oil is dissolved in 100 grams of Oil A. The oil sample remains at Ϊ;

Check at 2.2 ° C overnight and at room temperature for a week to clear, and no ί forms

Deposition. '*

Example 4 |

Winterized lard oil (2550 ml) is mixed with 450 ml of triisobutylene, which is prepared according to the procedure before Table 3 |

described method was produced. Mixing takes place in a 5-liter kettle equipped with a vibromixer. The mixture is heated to 121.1 ° C. and the vibromixer is operated at maximum speed. These conditions are maintained while 266 grams of sulfur are added over a period of a few minutes. The temperature is increased during 2 hours to 190.6 ⁰ C (375 ° F). Then, the mixture is cooled to 11O ⁰ C and air takes place at a moderate rate below the rate at which spraying and mixing, fed by means of a glass tube for one hour through the mixture. The sulfurized oil obtained is analyzed and found to have a sulfur content of 8.6%, based on the total mixture. A 10 gram portion of the sulfurized oil is dissolved in 100 grams of Oil A. When tested at 2.2 ° C. overnight and at room temperature for a week, the oil sample remains clear without a deposit being formed.

Example 5

Winterized lard oil (2550 ml) is mixed in a 5-liter kettle equipped with a vibromixer with 450 ml of a commercially available mixture of C _{: 8} -branched-chain olefins, which mainly have medium-sized double bonds. DasGen.isch is heated to 121.1 ⁰ C, and the vibromixer is operated at maximum speed. These conditions are maintained while 265 grams of sulfur is added. The temperature is increased to 196.6 ° C. over 2 hours. The mixture is then ^{cooled to 110 °} C. and air is passed through the mixture for one hour with the aid of a glass tube at a moderate rate, below the speed at which splashing and mixing takes place. The resulting sulfurized oil is analyzed and found to be 8.58% sulfur. A 10 gram portion of the sulfurized oil is dissolved in 100 grams of Oil A. After testing at 2.2 ° C. overnight and at room temperature for a week, the oil sample remains clear without a deposit being formed.

Example! 6th

2646 g of a mixture of 85 percent by volume of winterized lard oil and 15 percent by volume of a mixture of predominantly straight-chain c-olefins with 15 to 20 carbon atoms are placed in a 5-liter kettle equipped with a vibromixer. The mixture is heated to 148.9 ° C and 530 grams of sulfur are added over a 30 minute period. The temperature is increased for 35 minutes to 168.3 ⁰ C. The mixture is then ^{cooled to 100 °} C. and, with the aid of a glass tube, air is passed through the mixture at a moderate rate, below the speed at which splashing and stirring takes place, for 17 hours. The resulting sulfurized oil is analyzed and found to contain 16.33 weight percent sulfur. The sulfurized oil is dissolved in Oil C to form a solution containing 28.5 percent by weight of the sulfurized oil. Oil C is a commercially available naphthenic base oil that has a viscosity of 38.2 SUS at 98.9 ° C, a viscosity index of -10, an average molecular weight of 295, and 21% aromatic carbon atoms, 37% naphthenic carbon atoms and 42% paraffinic carbon atoms according to the determination according to ASTM D 2140. Using the Falex test with one minute steps, a value of 1474.2 kg is obtained. In the four-ball weld test (ASTM-D-2783-81), when a 28.5 weight percent solution of the sulfurized oil in Oil C is used, ^{welding occurs at 80O + kg.} In the four-ball abrasion test, which is carried out for 30 minutes at 1800 U pm, 54.4 ° C. and 25 kg

0.81 mm grooves observed. 10 g of the sulfonated oil are dissolved in 100 g of Oil A to form a metal working oil solved. It is found that this oil after 16 hours standing at 2.2 ° C and after one Remains clear for a week at room temperature. In contrast, both commercial spermacet oil divorce as well as commercial lard oil, which are sulphurized to the same extent, according to the specified test from the Solution off.

Comparative example 1

This example illustrates the difference between sulfurizing the lard oil and olefin together and sulfurizing the two ingredients separately with subsequent mixing, and further shows that iü this behavior cannot be predicted due to their solubility in unsulfurized form.

50 percent by volume solutions of winterized lard oil and a mixture of 85 percent by volume winterized Lard oil and 15 volume percent of the α-olefin used in Examples 1, 2 and 6 in Oil A manufactured. These solutions showed no differences in compatibility. Both solutions are at room temperature clear. Both solutions solidify on cooling to 2.2 ° C. After heating to room temperature both solutions become clear again.

Winterized lard oil (2699 g) is placed in a 5-liter kettle equipped with a vibromixer. The lard oil is heated to 148.9 ° C and the vibromixer is operated at maximum speed. 270 grams of sulfur are added over a period of 30 minutes. The temperature is on! 90.6 ² C erhüni and for one hour at that value contents. The temperature is then reduced to 93.3 ° C. and air is passed through the sulfurized oil for 17 hours at a moderate rate below which the splashing and mixing takes place. The resulting sulfurized lard oil is analyzed to find a sulfur content of 8.54 percent by weight.

The predominantly straight-chain -olefins of the Ci5 ~ C ₂ (i-range containing mixture (2356 g) used in Examples 1, 2, 6 and Comparative Example 1 is placed in a 5-liter kettle equipped with a vibromixer. olefin is heated to 148.9 ° C and the vibromixer is operated at maximum speed. 236 g of sulfur are added over a period of 30 minutes. the temperature is raised to 168.3 ⁰ C and kept at this value for 30 minutes. Then, the temperature increased to 190.6 ⁰ C and held for one hour at this temperature. Thereafter, the temperature is reduced to 93.3 ° C and held for 17 hours in air even rate below that at the spraying and mixing, sulfurized by the The resulting sulfurized α-olefins are analyzed and found to contain 8.99 percent by weight sulfur.

The lard oil and the α-olefins, which have been sulfurized separately from one another, are then checked for their compatibility tested in oil A. When 10 g of the sulphurized bacon oil is dissolved in 100 g of Oil A, the solution becomes cloudy after testing at 2.2 ° C overnight. Dissolve 10 g of the sulphurized α-olefin in 100 g of oil A and pour over Checked overnight at 2.2 ° C, the solution remains clear and no deposit is formed. When 10 g of a mixture of the sulfurized bacon oil and the sulfurized a-Q'.efins in a ratio of 85 to 15% in 100 g of oil A. and checked overnight at 2.2 ° C, the solution becomes cloudy. Will 10 g of a mixture of the sulfurized Bacon oil and the sulphurized a-O! <: Fins in a ratio of 70 to 30% in 100 g of oil A and stored overnight at 2.2 ° C checked, the solution becomes cloudy. The turbidity indicates incompatibility between the additive and the paraffinic oil, which, when used, causes the additive to form a sludge and caher is not available to fulfill its function. In contrast, common sulfurization of lard oil and α-olefin formed a sulphurous product which at 2.2 ° C in paraffinic lubricating oils is soluble.

45 Example 7

This example illustrates the use of an inert gas to remove the H ₂ S formed during sulfurization.

2666 g of a mixture of 85 percent by volume winterized lard oil and 15 percent by volume of a mixture from predominantly straight-chain »-olefins, which contain 15 to 20 carbon atoms, are converted into one with The vibromixer is provided with a 5-liter kettle and the vibromixer is operated at maximum speed. These conditions are maintained for 534 grams of sulfur over a 30 minute period can be added. The temperature is increased to 168.3 ° C. over 35 minutes. Gaseous nitrogen becomes at a moderate rate below that at which splashing and mixing takes place for 2 hours passed through the mixture, the temperature of the mixture being maintained at 168.3 ° C. The obtained sulfurized Oil is analyzed and found to contain 16.19% sulfur.

Example 8

2644 g of a mixture of 85 percent by volume of winterized lard oil and 15 percent by volume of predominantly straight-chain ar-olefins with 15 to 20 carbon atoms are placed in a 5-liter kettle equipped with a vibromixer. The mixture is heated to 121.1 ⁰ C and 264 g of sulfur are added over a period of several minutes. The temperature is increased during 2 hours to 190.6 ⁰ C. Then the mixture is up! ! 0 ⁰ C, and air is passed through the mixture for 2 hours with the aid of a glass tube at a moderate rate below which the splashing and stirring takes place. The resulting sulfurized oil is analyzed and found to contain 8.35 percent by weight total sulfur and 0.59 percent by weight active sulfur.

8th 22 07 747 Welding point 3 vol.% In SAR 90 Talelle 2 (kg) Detention »s / - Sullured product properties 290 Hatching example 260 relationship 100% sulfu 10% by volume in oil A 270 0.77 rated oil 0.84 Copper strip Copper strips - 0.84 test test ¹ 2 1 IB - - 4th 1 IB 260 5 1 IB > 1.00 Comparative example 1 0.75 '(sulfuric lard oil) 2 2C Comparative example 1 (sulfurized α-olefin) 1 IB 1 IA

In Table 2 the copper strip test according to ASTM D-130 is carried out. A value below 2 is used for these materials ala considered suitable. The weld point listed in Table 2 is determined using the standard four ball weld test (ASTM-D-2783-81). A value of more than 250 kg is considered for a Metalworking oil considered suitable. The adhesion / slip ratio is the ratio of static Friction to Dynamic Friction. A value below 0.85 will be suitable for most door applications at.

Examples 9 to 25

Examples 9 to 25 are ^: n Tables 3 and 4 are shown. Examples 9 through 23 show numerous triglycerides which can be used for the purposes of the invention. In any event, the solubility of the sulfurized triglyceride in at least one type of paraffinic oil is achieved by sulfurizing the triglyceride together with the olefin in the amount shown in Table 3. In each of the examples listed in Table 3: the olefin used is a mixture of predominantly straight-chain mono-ar-olefins containing 15 to 20 carbon atoms. Solubility data given in Tables 3 and 4 alone are based on 10 g of the sulfurized product in 100 g of the oil given. All of the behavioral data listed in Tables 3 and 4 are for a solution of the sulfurized product in Oil C (as defined above). In every example! is the sulfurized product in such an amount in Ö! C dissolved so that a sulfur content of 0.318 percent by weight is achieved in the total mass. The Falex-Tcst carried out with oil C without any additive results

40 a value of less than 113 kg ■ force.

In Examples 9-25, the sulfurized product was prepared by adding 500 ml of the indicated olefin and triglyceride mixture to a 1000 ml glass round-bottom flask fitted with a thermometer, vibromixer, heating mantle and water-cooled reflux condenser. The temperature of the feed was increased to 121.1 ⁰ C and 50 g of sulfur were? R minutes added over a period of about eir. The temperature was increased to 190.6 ⁰ C and held for 2 hours at this value, after which the temperature was reduced to 121.1 ⁰ C. The temperature was maintained for 2 hours at 121.1 ⁰ C, and the sulfurized product was air blown for two hours, to hydrogen sulphide to be removed. The sulfur content of the product was analyzed; the amount found is given in Tables 3 and 4.

In Table 3, a mixture of 85 percent by volume of lard oil and 15 percent by volume of the in the olefins given in the table are used.

In Tables 3 and 4, RT stands for room temperature, LW for load abrasion index as determined according to ASTM D-27-83, OK means that the sulfurized product has no visible haze formation was soluble, S means that the sulfurized product separated from the oil, SIH means a slight,

apparent haze and H means visible haze. In Tables 3 and 4, Oil D is solvent-treated Bright Stock (residue micro-oil) with a viscosity of 169 SUS and a viscosity index of 95, which contains 23% aromatics.

Manufacture of tetraisobutylene

200 ml of nitromethane and 5 ml of SnCl ₄ are stirred in a 500 ml three-necked round bottom flask equipped with a gas inlet tube, a mechanical stirrer, reflux condenser, external bath and thermometer, while isobutene is introduced into the mixture, which is kept at 35 ° C will. The isobutene is fed into the flask at a rate sufficient that nothing leaks out after the air has been displaced from the flask. After 26 minutes, the flow of isobutene was stopped and the contents of the flask were transferred to a separatory funnel. The conversion of the isobutene was quantitative. After standing for 5 minutes to separate the phases, the nitromethane layer (202 ml) is drained from the lower part of the funnel. According to normal practice, the oil layer (235 ml) is washed twice with saturated aqueous sodium chloride

solution, washed once with 5% aqueous nutrium hydroxide solution and another twice with saturated aqueous sodium chloride solution. The oil layer is then dried over anhydrous calcium chloride and placed in a vacuum distillation device. It is distilled in order to remove all ^{material boiling below 80 °} C. at 0.67 mbar. The remaining oil fraction (100 ml) has the following properties (where KV stands for the kinematic viscosity, determined according to ASTM D-445): 5

KV ₉₈ ^ c = 4.25 - 10 * ⁶ nrVs KV _37-S » _C = 22.42 - 10" ⁶ m ² / s VTF-VI = 98, ASTM-VI = 104.

The distillate (100 ml) consisted of approximately 49% trimer and as analyzed by gas chromatography 49% tetramerem. All dimer would have been lost in the original (10 ml). The loss caused by the ic partial drying is about 30 mi.

Table 3

at Triglyceride Olefin viscosity / o kung product sulfur solubility 2.2 "C 2.2 »C RT oil B 2.2 ^O C RT behavior HaP- Abrasion Sweat LWl to game Pa s Pa s Wt% H I week H 1 switch management / mm eat Oil A OK OK SI.H H Fulcx Slip- (kg) O Olefin feed 0.055 OK OK RT OK SI.H test fungs-V, -J VoI.- " 0.0335 3.760 S. OK H S. OK kg -4 0.0200 1,100 8.98 RT OK S. OK H S. 0.83 0.46 200 25.4 9 Lard oil 0.044 0.610 9.56 OK OK OK OK H H 566.3 0.74 0.46 200 25.9 10 Lard oil 0 0.029 3,850 9.23 OK OK OK S. H H 453.5 11th Lard oil 15th 0.0225 1.680 9.46 OK OK OK H OK H 340.1 > 1 0.53 200 21.8 12th Soybean oil 25th 0.0195 1,000 9.41 S. OK OK H H OK 0.82 0.53 200 25.4 13th Soybean oil 0 0.013 0.725 9.48 OK OK OK H OK H 453.1 0.85 0.52 200 21.4 14th Soybean oil 15th 0.024 0.268 9.09 OK OK OK OK H OK 340.1 0.86 0.50 200 20.3 15th Soybean oil 25th 0.014 0.640 9.27 OK OK OK H Tr H 226.5 0.83 0.51 200 21.2 16 Soybean oil 30th 0.028 0.275 9.54 OK H OK OK H Tr 340.1 17th Cottonseed oil 50 0.U245 2.120 8.78 OK OK OK H OK H 453.5 18th Cottonseed oil 25th 0.023 0.550 7.45 OK OK OK OK H OK 0.84 0.57 200 25.1 19th Sunflower oil 50 0.026 1,820 9.69 OK OK H H 0.87 0.44 200 25.0 20th Sunflower oil 15th 0.020 0.950 9.37 OK solubility OK 340.1 0.83 0.47 250 24.0 21 Safflower oil 25th 0.770 7.45 OK Oil A H 340.1 0.86 0.49 200 21.3 22nd Peanut oil 25th viscosity OK 340.1 23 Herring oil 25th Loading OK RT RT 2.2 ⁰ C RT 340.1 Table 4 25th kung product sulfur 1 week Oil D 1 week Port Abrasion Sweat LWI at Pa s Pa s Wt% behavior management / mm eat game RT Faiex Ski up (kg) test fungs-V. kg

24 C-Cjo-linear α-olefin 0.0335 1.100 8.98 OK OK OK OK H

25 1-decene 0.027 0.760 9.64 OK OK OK OK OK

H 56f \, 1 0.83 0.46 200 25.4

OK 566.3 0.79 0.45 200 30.2

Comparative example 2

In this example, a mixture of lard oil and e-olefin according to the invention is sulfurized together and its properties are compared with the properties of mixtures that are described in the introduction State of the art by adding only one component and mixing the sulfured one Constituent with the other constituent of the lubricant additive were prepared (according to US-PS 55 896 and US-PS 37 03 318).

A) A cosulfurized mixture of lard oil (lard oil) and <r-olefin according to the invention was prepared in the following way: 887 g of a mixture of 85% by volume of winterized lard oil and 15% by volume of ar-olefins were poured into a 2 -1-KesseI given. The ff-olefins were a mixture of predominantly straight-chain mono-ff-olefins with 15 to 20 carbon atoms. The mixture was heated to about 121 ⁰ C and operated at the vibromixer MaximaJgeschwindi ^ ness. These conditions were maintained while 89 grams of sulfur was added over a period of several minutes. The temperature was increased to 146 ° C. and held at this value for 2 hours. The temperature was then reduced to 93.3 ° C and air was bubbled through the stirred mixture using a glass tube at a moderate rate below that where splashing and mixing occur for one hour to remove hydrogen sulfide.

B) According to US-PS 34 55 896 sulfuricrtcs polybutene was produced in the following way:

Polybutene and sulfur were mixed in a weight ratio corresponding to 10 parts of polybutene to 2 parts of sulfur. The sulfur was added over a period of a few minutes at 121 ⁰ C in a 2-1 autoclave, equipped with a system operated at maximum speed to the vibromixer polybutene. The other process steps were the same as those used above in connection with the cosulfunerten mixture of lard oil and olefin, mif except that reflux was applied while heating to 191 ⁰ C. The purified polybutene obtained as product was then stripped and fils.riert in the manner described in US Pat. No. 3,455,896. A portion of the sulphurized polybutene product was mixed with unsulphurized lard oil in a volume ratio equal to 45% sulphurized polybutene to 55% unsulphurized lard oil. Another portion of the sulfurized polybutenes was mixed with unsulfurized lard oil in a volume ratio equal to 15% sulfurized polybutene to 85% unsulfurized lard oil.

C) According to US-PS 27 03 358 sulfurized lard oil was produced in the following way:

Winterized lard oil and sulfur were part by weight of mixed sulfur in a ratio of 10 parts by weight of lard oil to 1, the sulfur was performed in a 2-l kettle equipped with a system operated at maximum speed vibromixer at a temperature of 121 ⁰ C added to the lard oil. The remaining process steps were the same as described above for the preparation of the cosulfurized mixture of lard oil and olefin. A portion <ks as a product obtained sulfürierten lard oil was mixed with unsulfuriertem dipentene in a weight ratio of 10 parts of dipentene to 90 parts sulfurized lard oil. Another part of the sulfurized lard oil obtained as the product was mixed with unsulfurized dipentene in a weight ratio of 15 parts of dipentene to 85 parts of sulfurized lard oil.

Testing and evaluation

The solubility data of the cosulfurized lard oil and olefin prepared above and the above The resulting mixtures of sulphurized lard oil and dipentene were determined in the following manner:

A 3.65% by weight solution of the product in a paraffin base oil of 200 SUS / 37.8 ° C with the in the properties shown in Table 6 was produced. The solution was left to stand for 16 days and then visually assessed to determine if it is clear or cloudy and if visible deposits have formed are or not. The results of this observation are given in Table 8 attached hereto.

In addition, the above-prepared cosulfurized mixture of lard oil and olefin and the above prepared mixtures of sulfurized polybutene and lard oil the four-ball test and the Falex test subject and determined corresponding test values.

The data for the four ball weld test and the Load Wear Index (LWI) were obtained using a solution containing 3.65% by weight of the products (A), (B) and (C) in the oil. To this end, a standard test unit was used for the four-ball wear test under a load of 20 kg applied during minutes at 1800 rpm at 54 ⁰ C.

The data from the Falex test were also obtained using 3.65% solutions with the aid of a I-alex tester from Faville LeValley Corporation, Chicago, Illinois. A rotates in this test device Steel needle with a diameter of 6.3 mm rotates between two horizontally loaded V-blocks made of steel. Pressure is then applied in increments of 113 kg at 1 minute intervals (one minute increments) to the shear needle or the steel needle breaks due to the failure of the lubricant film. The maximum load before the break is recorded as the test result. The test data thus obtained are in the attached Table 5

Comparative example 3
According to the invention

A cosulfurized mixture of soybean oil and ar-olefin was prepared in the following manner:
85 parts by weight of soybean oil and 15 parts by weight of the above ff-olefins were mixed and placed in a kettle equipped with a vibromixer. While the vibromixer was operating at maximum speed, sulfur was added over a period of several minutes. The procedure was otherwise the same as that described above for the preparation of cosulfurized lard oil and olefin.

According to US-PS 27 03 318

In another attempt, the sulfurization of soybean oil was carried out alone without the presence of the olefin carried out according to the same procedure. Part of the sulfurized soybean oil thus obtained was with unsulfurized dipentene in a weight ratio of 10 parts dipentene to 90 parts of the sulfurized one Soybean oil mixed together. Another portion of the sulfurized soybean oil was made with unsulfurized dipentene mixed in a weight ratio of 15 parts dipentene to 85 parts of the sulfurized soybean oil.

The solubility data for the cosulfurized soybean oil-olefin mixture thus prepared and those as comparative products Mixtures of sulfurized soybean oil and dipentene prepared in the following Way determined:

3.65% by weight solutions of the product in paraffin base oils with viscosities corresponding to 100 SUS / 37.8 ° C and 200 SUS / 37.8 ° C, respectively, with the properties given in Table 11, were produced. The solutions were visually inspected immediately after manufacture, 7 days later, and again 16 days later. The so The results obtained are shown in Tables 9 and 10 attached hereto.

Table 5

Comparison of the wear properties with the addition of 3.65% by weight of a sulfurization product as a lubricating oil additive to paraffinic base oil of 2OC SUS / 37.8 ° C

Wear tests method A. B. C. According to the invention According to US-PS 34 55 896 Product of common
seed sulfurization
of a mixture
85 V-% lard oil and
15 V% ^ olefin Mixture of 45 V-%
sulfurized polybutene
and 55% by volume unsulfu
rated lard oil Mixture of 15 V-%
sulfurized poly
butene and 85 V-%
unsulfurized
Lard oil Falex 1-min. Levels D 3233
Method B. 1000 500 500 Four ball test
(Four Ball Weld,
Weld Point), Kg D 2783 200 160 126 Load wear and tear
Index (LWI) June 35 24.42 14.66 Table 6 Properties of the paraffinic
Base oil 200 SUS / 37.8 ° C characteristic Test method value

Viscosity, SUS / 37.8 ° C Viscosity, SUS / 99 ° C Viscosity index aromatic content,% by weight

D 2161 208 D 2161 47.4 D 2272 103 D 2007 13.6

Table 7 Lard oil Wcrl Properties of the used l'rül'mcthoile 0.9194
4.6 characteristic D 1250
Sun Density I5.6 / I5.6 ° C (6O / 6O F)
Free fatty acid as% oleic acid

Table 8

Comparison of the solubility properties of sulfurization products with the addition of 3.65% by weight of the products to a paralTine base oil of 200 SUS / 37.8 ° C

Dissolution product Appearance after standing for 16 days at room temperature

According to the invention.

By jointly sulfurizing a mixture of 85% by volume lard oil and

15 V% ^ olefins

clear, no separation

US-PS 27 03 318:

Mixture of 10% by volume of unsulfurized dipentene and 90% by volume of sulfyrated lard oil. Turbidity, separation

US-PS 27 03 3IS:

Mixture of 15% by volume of unsulfurized dipentene and 85% by volume of sulfurized lard oil. Turbidity, separation

Table 9

Comparison of the solubility properties of 3.65% by weight of the sulfurization products in paraffinic base oil 100 SUS / 100 F

Sulfuration product

Appearance at room temperature initially after 7 days

After 16 days

(1) Cosulfurization product made from clear 85% by volume soybean oil and 15% by volume α-olefin

(2) Product according to US-PS 27 03 318, clear from 10 wt .-% dipentene and 90 wt .-% sulfurized soybean oil

(3) Product according to US-PS 27 03 318, clear from 15 V .-% dipentene and 85 V .-% sulfurized soybean oil clear,

no deposition

Turbidity,
Deposition

slight cloudiness, separation

clear,

no deposition

slight cloudiness, separation

slight cloudiness. Deposition

Table 10

Comparison of the solubility properties of 3.65% by weight of the sulfurization products in paraffinic base oil 200 SUS / 100 F

Sulfuration product

Appearance at room temperature initially after 7 days

After 16 days

1I) cosulfurization product from

85% by volume soybean oil and 15% by volume ar-olefin

(2) Product according to US-PS 27 03 318,

made from 10% by weight dipentene and 90% by weight sulfurized soybean oil

(3) Product according to US-PS 27 03 318, from 15 V .-% dipentene and 85 V .-% sulfurized soybean oil

clear slight cloudiness,

no deposition

Turbidity severe turbidity, deposition

Turbidity slight turbidity, separation

Turbidity,

no deposition

Turbidity, deposition

slight cloudiness, separation

13th

Table 11

Characteristics of the paraffinic base oils used 100 SUS / 100 F and 200 SUS / 100 F

Property Test method 100 SUS / 37.8 ° C 200 SUS / 37.8 ° C

Viscosity, SUS / 100 F D 2161 118.0 210.0 Viscosity, SUS / 210 F D2I61 40.8 46.7 Viscosity index D 2272 94 93 Aromatics, wt .-% D 2007 17.3 12.0

Claims (1)

Patent claims: 1) Sulfurization product with a content of 7.5 to 25% by weight of chemically bound sulfur was obtained from triglycerides. Olefinic hydrocarbons and sulfur for a reaction time of 20 minutes 5 to 10 hours at a temperature of 165.6 to 229.4 ° C, characterized in that it is by common sulfurization of a mixture a) 50 to 90 parts by volume of one of the triglycerides lard oil, herring oil, whale oil, soybean oil, cotton seed oil, safflower oil, linseed oil, rapeseed oil, sunflower oil or peanut oil, and
10 b) 50 to 10 parts by volume of an olefin hydrocarbon of the structure