DE1948944A1 - Process for the preparation of improved olephilic metal sulfides - Google Patents

Description

PATENT LAWYERS

DR.-ING. BY KREISLER DR.-ING. SCHDNWALD DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLOPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, 22 »9.1969 lu / ax

The British Petroleum Company Limited, Britannic House, Moor Lane, London, E.C. 2 (England).

Process for making improved oleophilic metal sulfides

The invention relates to metal sulfides, particularly oleophilic Metal sulfides.

Oleophilic metal sulfides have a ratio of the heat of adsorption of η-dotriacontane from n-heptane to adsorption "5 heat of n-butanol from n-heptane of at least 1: 2, preferably at least 1: 1, and a surface area of

ο
at least 10 m / g. The heat of adsorption can be measured with a flow _{microcalorimeter, which is described in "Chemistry and Industry" of 20 e} 3 «1965, pages 482-485«

Oleophilic metal sulfides can preferably be prepared by grinding metal sulfides in an organic grinding liquid be made with the practical exclusion of air, doh. the metal sulfide is during the grinding process preferably below the surface of the organic liquid. This process for the production of oleophilic Metal sulfides is in the British patent

1 162 223 and in German patents _o ...

(Patent application P 16 44 855.8) and (patent application

0098 U / 1705

message P 16 6? 833.4) by the applicant.

Good products can be obtained by milling in most organic liquids, but it is convenient to use an organic liquid which for the most part can easily be removed from the oleophilic metal sulfide. Therefore, liquids boiling below 50O ⁰ G and have a viscosity of little than 600 cS "at 38 ⁰ C are preferred. Liquids having a surface tension below 72 Ityn / em 'preferably τοπ 10 to 40 dynes / cm at 25 ⁰ C have , are preferred Liquids

with a viscosity of less than 1 cS are suitable P nice.

"Suitable organic liquids are hydrocarbons, including straight-chain or branched, saturated or unsaturated aliphatic, saturated or unsaturated, substituted or unsubstituted cycloaliphatic and substituted or unsubstituted aromatic compounds, which preferably contain up to 10 carbon atoms. Examples of such compounds." are n-heptane »octene-2 _f 2» 2 _? 4-trimethylpentane,

Cyclohexane, benzene and toluene. Especially preferred are branched aliphatic compounds ^ "Other suitable organic liquids compounds containing fluorine, chlorine or phosphorus and chlorine ™ contain ₉ z _e B. tetrachloro-

carbon. Other suitable organic liquids are the polar oxygen compounds, e.g. isopropyl alcohol * Liquid silicones can also be used will.

For best results, the amount of j Metal silfids in a mixture of metal sulfide and organic Grinding liquid do not exceed 50% by weight. Preferably it should be 2 to 20% by weight.

The grinding can take place in any suitable mill or device and is expediently carried out for as long as

009814/1705

19489U

"until an oleophilic metal sulfide has been formed which has a surface area (determined by nitrogen adsorption) of from 10 to 400, preferably from 30 to 200 m / g. This can usually be achieved by milling at normal temperatures for the required duration, but the The temperature of the mixture can optionally be artificially ^{increased, for example to 400 °} C. In this case, liquids with a viscosity of up to 600 cS at 38 ^° C., for example mineral lubricating oils from spindle oil to "bright stocks", can be used that a vibrating ball mill is used for grinding.

During the grinding process, the air should be excluded as far as possible * This is easiest to do by putting in the mill first the organic liquid, then the balls and the metal sulfide fills. After a suitable working method, first the liquid, then half of the liquid, is put into the mill Balls, then the metal sulfide and finally the rest of the balls.

When using a ball mill, it is of course advisable to Kj ^ eIn to be used from a material that is compatible with the metal sulfide does not react and changes during grinding does not wear out excessively. Vibratory ball mills usually contain steel balls, which can also be used for the purpose of Invention. A hard type of steel is particularly preferred for the balls. Vibratory ball mills are preferred used with a vibration amplitude of at least 2 mm and a vibration frequency of 1500 / minute.

A magnetic filter can be used to remove small steel particles from the slurry. A circulation system can also be used at de:., the slurry through pumped an internally arranged magnetic filter and then to Mu: Ie is returned.

00981 4/1705

A vibrating ball mill is suitable, which is available under the name "Megapact" (manufacturer Pilamec Limited) " The grinding action is brought about by the impact of the balls on the metal sulfide and on each other as well as on the case.

The slurry of the oleophilic metal sulfide can be separated from the spheres by sieving or by displacement with another liquid and sieving _β

β It has been found that all forms of metal sulfides in ^f

.10 are acidic to different degrees, the acidity being on polar spots is restricted. It is assumed that the acidity results from oxidation reactions.

Since oleophilic metal sulfides are used as solid lubricants and If lubricant additives are used, their corrosive properties must be reduced as much as possible will. It has been found that by treating the metal sulfide with a base during milling or after grinding, the corrosive nature of the oleophilic metal sulfide is reduced.

The invention relates to a method for production

oleophilic
of improved / metal sulfides, which is characterized in that a metal disulfide is ground in an organic liquid to a surface area of at least 10 m / g and the metal sulfide is brought into contact with a base during or after grinding.

In the method according to the invention, the grinding conditions can be used, which are used above for the preparation of oleophilic metal sulfides.

As metal sulfides, molybdenum disulfide, tungsten disulfide, Lead sulfides and tin sulfides can be used. Molybdenum disulfide is preferred as the metal sulfide.

0098 U / 1705

• 19489U

Any bases can be used provided they are sufficiently "basic" to substantially neutralize the acidic sites present and the base as such is non-corrosive or capable of adversely affecting the nature of the oleophilic metal sulfide. The bases can be composed entirely of organic groups or of metal atoms in one or more organic uppen G _r are bonded, consist "

Organic bases are the organic amines, especially primary amines such as propylamine, the butylamines, Hexylamines and alkyl substituted hexylamines. Bases that Contain metal groups bound to one or more organic groups, e.g. zinc and alkali metal carboxylates and phenolates, often themselves have desirable lubricating properties, so that these bases are particularly advantageous are"

If the base with the metal sulfide during milling in Is brought into contact, the grinding media and base should be chosen so that the base is in the grinding liquid is soluble or miscible therewith.

If the base is contacted with the oleophilic metal sulfide and the base is not liquid, it will preferably dissolved in an organic solvent. Aliphatic hydrocarbons are suitable as solvents and alcohols After treatment with the base, the excess base can be removed by conventional methods, e.g. Distillation or solvent extraction.

When the base is dissolved in the milling liquid, amounts are from 1 to 50 wt ~ $ »preferably 5 to 20 wt -.. Suitable ^C J>.

Oleophilic metal sulfides have the ability to thicken oils into fats. They also have better lubricating properties in dispersions as non-oleophilic metal sulfides.

00981 4/1705

19489 «

These uses of oleophilic metal sulfides are discussed in British Patent 1,162,222.

Oleophilic molybdenum diaulfide can be pressed into solid materials, as in the German patent .... _Λ . (Patent application P 17 96 086 * 0) described by the applicant «

example

Two commercially available molybdenum disulfide powders of different types Purity were measured in a "Megapaef vibrating ball mill." (Manufacturer Pilamec Limited), ground. The grinding chamber was filled with n-heptane, whereupon the balls . and the molybdenum disulfide was filled. The Mahlkainmer was then closed. »The oscillation amplitude was 4 mm and the visual oscillation frequency 3000 / minute .. Die Mahl_ duration was 8 hours «

The resulting powders were contacted with excess n-butylamine and the excess n-butylamine was removed. Then it was ground again, with the
n-heptane contained 12 wt .-> n-butylamine. The powders obtained were pressed under a pressure of 4570 kg / cm and the solid materials with an oil tester
Pin and washer checked · The K-value is a measure of the
Corrosion resistance and wear resistance of the
massive material. Like the values in the following

Table shows is obtained by treating the oleophilic molybdenum disulfide with n-butylamih an increase in corrosion resistance of the massive material made of molybdenum disulfide.

0 9 8 14/1705

Density, hardness wear

fc—
Type treatment g / cm ⁵ R. strength,
K value,
cm ² / cm e
χ 10 ~ ¹ * A. unground 4.17 ge
bursts 31.2 A. ground in n-heptane 3.75 70 40.0 A. ground inn-heptane
and then with over
shed n-butyl
amine treated 3.61 78 • 8.7 A. in n-heptane + $ 12
Ground n-butylamine 3.87 85 7.5 B. unground 4.56 63 7.9 B. in nC ₇ + 12 $ n-butyl-
ground amine 3.70 89 6.2

Π0 9 8 U / 1705

Claims (2)

19489U - fa - claims 1. A process for the production of oleophilic metal sulfides by grinding the metal sulfide immersed in an organic grinding liquid up to ~ u a surface of the metal sulfide of at least Io m ~ / g, characterized in that it is carried out with organic grinding liquids which are 2 to 2o wt. ^ an organic amine contained dissolved. 2. The method according to claim 1, characterized in that one works with grinding liquids containing n-ßutylamine. 3. Process according to claims 1 and 2, characterized in that molybdenum oxide is subjected to the process. BAD ORSGfNAL Π98 1 i / 1705