DE948811C - Additive to mineral lubricating oils - Google Patents

Description

When lubricating transmission elements in self-propelled vehicles, lubricating oils are generally used related, which are reinforced by additives to give the lubricating oil the ability to under high Pressure to act lubricating. Such a product that has been in use with advantage for several years is a sulfurized and phosphorized lard oil as disclosed in U.S. Patent 2,211,306 to Whittier et al. Although the product described in this patent specification its use as a lubricating oil additive gives excellent results, it has some shortcomings since it is not soluble in all lubricating oils and a lubricating oil containing such an additive does not have a low enough trickle point to be used at very low temperatures to be able to. Here, under “Rinnpunkt” (called “Channelpoint” in English), cf. B. Coordinating Research Council Manual, January 1946, pp. 452-455) understood the temperature at which an ao Lubricant is no longer able to close a gap in 5 seconds, which by pulling through it a metal strip caused by the lubricant. Another disadvantage is that it cannot be blended into an end product that meets the proposed new SAE regulations for a combination of 75/8 degrees and 8o / o degrees lubricating oil is sufficient.

There are already phosphorous trisulfide, previously sulphurized bodies of the fat series, e.g. B.

Phosphorized, previously sulfurized propylene glycol dioleate and glycerol trioleate became known, the do not have some of the disadvantages of phosphorous, sulphurized lard oils. However, these products are apart from their inherent defects mentioned later, expensive, and it arises in the process for competitive reasons, the need to use different products in the different regions Market in order to meet the requirements there.

These and other disadvantages of the products obtained by using the additives known heretofore are remedied in the present invention by the use of a single additive, which with regard to its effect on the known types of sulphurized and phosphorous additives is equivalent and also has the property that it is common in the various types of mineral lubricating oils is soluble. The additive of the invention is also stable; i.e., it does not form a deposit during of standing, and gives the lubricating oil a low pour point, making it suitable for use is also suitable as a lubricating oil additive at low temperatures. Furthermore, lubricants, which contain the additive according to the invention, are mixed so that the mixture in each case the SAE regulations with regard to 75/80 and 80 / g degrees. Lubricating oils are sufficient.

The general practice up to now has been to sulphurize and add sulfur to one and the same body of the fat series phosphate to obtain an additive suitable for extreme pressures. This cannot be done with methyl esters of tall oil fatty acids (»Metalyn« *)) and homologous esters, since the phosphorization takes place here tends to polymerize and give unsatisfactory products. But through that Combination of a sulfurized tall oil fatty acid ester and phosphorated glycerol trioleate or this equivalent material are separated sulfur and. Phosphorus reaction products produced in combination are suitable as a mixture lubricating oil additives. U.S. Patent No. 2,541,789 already has a Mineral lubricating oil is described, which is first sulfurized and then phosphorousized with propylene and butylene glycol esters which contains oleic acid. The sulfur initially reacts with an unsaturated bond of the Ester and then the phosphorus with another part of the ester molecule. According to the present invention the so-called Metalyn is sulfurized, but not phosphorous, because it cannot be phosphorous. Compared to the known product of the USA patent, the product according to the invention has greater flexibility. For use at high speeds, however, the sulphurized is sufficient and phosphorous glycerol trioleate not. But sulfurized metalyn and phosphorous glycerol trioleate can be mixed with one another in such a way that there is a mixed product which also meets the requirements very high speeds are sufficient. Even with higher torques and with demands

*) Composition see page 3, paragraph 2 and table on page 3.

Satisfactory mixed products can be obtained with a greater film thickness, only in this case a larger proportion of phosphorus trioleate is required than at a higher speed. The sulfurized Metalyn and phosphorized glycerol trioleate mixed product has a higher thinness than the product according to US Pat. No. 2,541,789, even at a lower temperature. 20 to - 29 ⁰ C prevail. In addition, the product according to the present invention is significantly cheaper than the known product according to the USA patent specification 2 541789 ·

The invention relates to the use of an oil-soluble mixture of 3 to 5 parts by weight of a sulfurized ester of tall oil fatty acids, in particular their methyl esters, with a sulfur content of approximately 3 to 10%, preferably 6 to 26%, with one part by weight of a reaction product known as an additive to lubricants of Phosphorus trisulfide and a glycerol trioleate, ethylene, propylene or butylene glycol dioleate or a lard oil with a low percentage of acids which have more than one unsaturated bond, with a phosphorus content of approximately 0.6 to 2.5%, preferably 1.26%, optionally with the further addition of about 5 to 10 percent by weight of dibenzyl disulfide, known as a lubricant additive, as an additive to mineral lubricating oils in such amounts that the total lubricant is about 0.02 to 0.06 percent by weight phosphorus, about 0.5 to 1.5% sulfur and optionally about Contains 0.5 to 1 percent by weight dibenzyl disulfide. ^x Lard oil with a low percentage of acids with more than one unsaturated bond is a fatty oil obtained by solvent extraction of these compounds, which contain two or more unsaturated bonds in the acid radical.

By suitable selection of a mineral lubricating oil base, lubricants of a desired ⁰ SAE can easily be obtained.

It has also been found that the esters of tall oil fatty acids and alcohols with side chains, such as. B. Isopropyl and isobutyl are unsuitable as the basis for the sulphurized tall oil enoic acid esters, as these are not form stable molecules and have a tendency to polymerize.

The methyl esters of tall oil fatty acids (»Metalyn«, see below) are an easily obtainable, cheap material and therefore the tall oil fatty acid esters of other aliphatic, to prefer straight-chain monohydric alcohols. As the sulfurized methyl ester in proportion to the phosphorated glycerol trioleate, which is only added in small amounts, a proportionate are inexpensive material, the expense for the additive and total lubricant is approximate same as for the sulphurized, phosphorous lard oil. Also with regard to stability (as there is no tendency to Formation of precipitates while standing) and with regard to the EP test results with the Timken and SAE testing machines is the phos-

phorated glycine trioleate the other phosphorus-containing Components superior to the mixture used according to the invention.

Metalyn is a trademark name for methyl esters of tall oils. It is made through methyl esterification the tall oil acids obtained under increased pressure and subsequent distillation of the ester. This Product that is now manufactured by the Hercules Powder Company is said to have the following distinctive features Features:

° / "Resin acid methyl ester

% Fatty acid methyl ester

% USaponifiable modified AOCS * Ca 6b-40 not over

Saponification number (strong, Herculesmeth.)

Acid number (AOCS Ds 14-42) * not above

Iodine number (AOCS Cd 1-25) *

Acetyl value (AOCS Cd 4-40) * not above

Color (Gardner 1933) not about

Specific gravity 20 ° / 20 ° C

Flash point ° C (COC) not below

Freezing point ⁰ C not above

Viscosity at 37.78 ° C SUS ** (ASTM D 445-46 T)

Moisture (AOCS * Ca 2a-45) does not exceed

Appearance at 20730 ⁰ C ·.

45.0 typical 47.0 typical 8.0

155/170

5, o 120/130

10.0

12.0

o, 95 / o, 975 182 ⁰

IO, O °

2.17 to 3 ° Engler

0.1

clear and free from foreign matter

Of course, the sulfurized products of other esters of tall oil fatty acids, such as the of ethyl alcohol, as well as unbranched propyl, butyl and amyl alcohols in the same way as the methyl esters are sulfurized and then form part of the additive mixture. If necessary can take into account the required viscosity, pour point and other properties of the lubricating oil Mixtures of several sulfurized esters can also be used instead of a single ester.

The preferred phosphorus constituent of the mixture is because of its greater phosphorus content Glycine trioleate applied. In the production of the phosphorous glycerol trioleate preferably a glycine trioleate with the following characteristics:

Acid number not more than 10.0

Saponification number not below 187.0

% Unsaponifiables not more than 3.5

Iodine value 75/85

% Moisture content not exceeding 0.3

Acetyl value. '. not over 40.0

° / o free glycerine content .. not more than 0.25

Color water to light amber

composition
of fatty acids

Γ 80% oleic acid min.

< 12% linoleic acid Max.

I 8% saturated acid Max.

With regard to the desired uniformity of the end products, phosphating is preferred Phosphorus trisulfide applied. Other phosphorus sulfides, such as. B. phosphorus pentasulfide, cause an undesirable Polymerization. The usage of

*) "Official and Tentative Methods of American Oil Chimists Society" 2nd edition, published by the society mentioned.

**) SUS = Secondary Universal Seybold, ASTM = American Society for Testing Materials.

See ASTM Standards on Petroleum Products and Lubricants, November 1954, published by American Society for Testing Materials, ”1916, Rade Street, 3 Philadelphia, Pennsylvania.

Pure phosphorus trisulfide is required as impure material creates a dust ax. Precipitation in the end product generated.

Phosphorized propylene glycol oleate or phosphorated lard oil with a low percentage Acids which have more than one unsaturated bond are in the same way as phosphorous Glycerol trioleate can be used.

The completely sulphurized metalyn and / or homologous tall oil fatty acid ester and phosphorated glycerol trioleate or ethylene, propylene or butylene glycol dioleate or lard oil at a low percentage Acids with more than one unsaturated bond can be used separately or in a mixture in the desired Lubricating oil are introduced. In the latter case, they result in a single additive for subsequent addition.

An addition of 5 parts of sulphurized metalyn to ι part of phosphorous glycerol trioleate gives a no Admixtures with the following characteristics:

Specific gravity 0.993

Weight per liter in kg 1.00

Sulfur, weight percent 5.35

Phosphorus, weight percent 0.21 ⁿ "*

Viscosity at 98.89 ° C 1.82 ° E.

When adding the additive to the oil, which is ultimately used as a lubricant, one can approximate 10 to 30, but preferably 12 to 15 percent by weight iao of the additive in such a way that the final oil in each case approximately 0.02 to 0.06% Contains phosphorus and approximately 0.5 to 1.5% sulfur derived from the additive.

The method according to the invention is illustrated in hand illustrated by two examples showing the manufacture

of two additives to the oil that is ultimately used as a lubricant.

Additive No. ι 12 percent by weight

83.3% sulphurized metalyn 16.6% phosphorated glycerol trioleate 1.0% by weight dibenzyl disulphide 0.5% by weight
polymeric esters of methacrylic acid and higher molecular weight alcohols, according to US Pat. No. 2,681,891, 3rd column 60.0 percent by weight of lubricating oil H 26.5 percent by weight of lubricating oil L

Additive No. 2 15.0 percent by weight

83.3% sulfurized Metalyn 16.6 ° / ₀ phosphored glycerol trioleate 1.0 percent by weight of dibenzyl disulfide ao 0.5 weight percent

polymeric esters of methacrylic acid and higher molecular weight alcohols, according to the United States patent 2 681891, 3rd column 57.0 percent by weight lubricating oil H 26.5 percent by weight lubricating oil L.

Dibenzyl disulfide is added to meet the high torque performance test. the The polymeric ester is added according to U.S. Pat. No. 2,681,891 in order to lower the pour point and improve the viscosity index. Both additions are completely sufficient for the driving performance tests, by testing the oils before and after extensive use in a number of Passenger vehicle differentials are set.

Addendum No. 2 meets all requirements for the SAE 90 MIL-L-2105 "" requirement.

The lubricating oil bases H and L, in which the additional mixtures are soluble, have the following characteristics:

Lubricating oil Lubricating oil Specific gravity (15.6 ° C) .H L

(ASTM D1298-54) 0.9083 0.8772

Flash point ° C

(ASTM D-92-52),. 287.78 210.00

. Ignition point ° C

(ASTM D-92-52) 332.23 240.55

Viscosity 37.78 ° C 85.8 ° E 5.97 ° E

54.45 ° C 30.6 3.17 ⁰ E ⁰ E

98.89 ⁰ C 4,5i ° E 1.49 E ⁰

Viscosity index

(ASTM D 567-53) 91 93

Pour point ⁰ C

(ASTM 97-47) - 15-15

Gardner Color (1933) 17.0 6.5

% Char residue

(ASTM D-189-53) 1.23 0.02

% Sulfur (ASTM D 129-52). 0.78 0.38

Acid number (ASTM D 974-487) .. 0.36 0.21

*) From April 7, 1950 Military Specification Lubricant, g ₀ Gear, Universal.

This mixture not only meets the MIL-L-2105 requirements for oil, but also all regulations for an SAE-8 ° oil, excepted the Max SUS Viscosity of 100,000 at -17.78 ° C. Gogrädiges oil namely requires a viscosity of 80 or 90 to 210. This requirement can easily by the use of a stocked high viscosity index mixture in lieu of one with intermediate viscosity index during manufacture of the tested additive are complied with.

The following table gives the properties and composition of an EP lubricating oil based on highly viscous lubricating oils, which are produced by solvent extraction of petroleum / lubricating oil fractions from Mid-continent type with phenol were obtained at. These lubricating oils meet all requirements for a High pressure lubricating oil SAE 80/90, composition by weight percentage:

Sulphurized Metalyn

Viscosity at 98.89 ° C - 2.85 ° E>

% S (ASTM D 97-52) 5.30

phosphorous glycerol trioleate

% P (ASTM D 1091-54) 0.18

Dibenzyl disulfide 1.0 ° / ₀

polymeric esters of methacrylic acid and higher molecular weight Alcohols according to USA patent

Font 2 681891, 3rd column 0.5%

Mineral lubricating oil A 27.5 ° / ₀

Mineral lubricating oil B 56.0%

Mark:

Viscosity at 37.78 ° C 21.7 ° E

98.89 ° C. 2.5 ° E

Index (ASTM D-567-53) 109

Viscosity, extrapolated to ⁰ C-17.78 75,000

Pour point ° C (ASTM D 97-47) -31.67 ^{9 &}

Inlet Point (CRS-L-15-445) -43.45

Storage stability okay

Modified SAE:

Ring condition ok xoc »

Ring weight, loss 20.6 mg

Timken (CRC-L-18-545)

Payload (kg) 23.13

Pressure (kg / cm ² ) 2.253

Identification of lubricating oils A and B

Specific gravity (15.6 ° C) ^AB

(ASTM D-1298-54) 0.8708 0.8956

Flash point ° C

(ASTM-D-92-52) 215.55 304.44 "°

Ignition point ° C

(ASTM D-92-52) 246.11 332.23

Viscosity at 37.78 ° C 5.31 ° E 72.1 ° E

54.45 ° C 2.95 ° E 26.9 ° E

98.89 ° C i, 44 ° E 4.55 ° E

Viscosity index

(ASTM D 567-53) 97 97

Gardner Color (1933) 2 16

ASTM pour point ° C

(ASTM D 97-47) -15-15

Coking residue (Conradson)

(ASTM D189-52) 0.04 0.7

% Sulfur

(ASTM D-129-52) - 0.5

Acid number 1 * 5

(ASTM D-974-48 T) 0.2 4.5

In all of these cases, an additive according to the present invention can also be achieved by adding the desired Amount of dibenzyl disulfide or equivalent material as described in the U.S. patent Re 22 911, and prepared by incorporating a sufficient amount of polymeric ester to give the desired viscosity index and pour point to the desired oil. Sometimes it is also possible to add small amounts such. B.

of 0.001 weight percent of a lather reducing agent Substance recommended as described in U.S. Patents 2,416,503 and 2,416,504 is. Due to the simultaneous content of the most varied of components within a single one Additive, an inexpensive, general-purpose additive can be obtained with a any type of mineral lubricating oil can be added and the same extremely good extreme pressure properties can give. This avoids the need for manufacture and storage of several different additives.

Of course, the specific additives

which are listed here, for example, are not necessarily

• Manoeuvrable the cheapest or best additives.

By varying the amounts of sulphurized metalyn or its homologues and phosphorous Glycerol trioleate or ethylene, propylene or butylene glycol dioleate or lard oil with a low percentage of acids with more than one unsaturated Binding in the additive mixture or in the lubricating oil within the limit values according to the invention can be used a product can be produced which meets the necessary requirements for the particular at a minimum cost intended purpose is sufficient. Or you can also use a lubricating oil of maximum high pressure and lubricating properties when the cost factor does not play a decisive role. That

phosphorated glycerol trioleate, ethylene, propylene and butylene glycol dioleate or lard oil with a low acid content, which is more than a low 40 have a saturated bond, increases the lubricity and unexpectedly also promotes the weight bearing capacity of the finished additive. Therefore, if cost is not a concern, larger quantities can be used of phosphorus is incorporated in the additive and thus in the lubricating oil within the limit values according to the invention will.

Claims (1)

PATENT APPLICATION: Use of an oil-soluble mixture of 3 to 5 parts by weight of a sulfurized ester of tall oil fatty acids with straight-chain alcohols, in particular their methyl esters, with a sulfur content of approximately 3 to 10%, preferably 6 to 26%, with one part by weight of a reaction product known as an additive to lubricants a phosphorus content of about 0.6 to 2.5 ° / o, preferably 1.26 ° / ₀ from phosporus with a glycerol trioleate, ethylene, propylene or -60 Butylenglykoldioleat or lard oil with a low percentage content of acids with more than one unsaturated bond, optionally with the further addition of about 5 to 10 percent by weight of dibenzyl disulfide, known as a lubricant additive, as an additive to mineral lubricating oils in such amounts that the total lubricant is about 0.02 to 0.06 percent by weight of phosphorus, about 0.5 to 1.5 percent by weight of S. and optionally contains about 0.5 to 1 percent by weight dibenzyl disulfide. Considered publications:
U.S. Patent No. 2,541,789. © 509 696/439 2. (609 603 8.56)