PROCEDURE FOR THE PRODUCTION OF SCHWEFELHALTIGEN ETHERS AND THEIR USE.

PATENT CLAIMS 1st procedures for the production of schwefelhaltigen ethers, by the fact characterized that one connections of the formula II or their mixtures H2CI /n (ii) lo live R linear alkyl with 12 to 24 C-atoms, branched alkyl with 8 to 30 C-atoms, alkylated Phenyl or Phenylalkyl with 8 to 24 C-atoms is, X for a Sauerstoffoder sulfur atom stands and 1 n an average value within the range of 0,5 to 8 meant, in at least stöchiometrisehen quantities with Sehwefelwasserstoffoder Dialkalimetallsnlfiden (alkali metal) 2 Sx, where x = I--4 is, converts and developing Chlorwassserstoff or the alkali metal chloride from the reaction mixture entfernt.

2. Procedure in accordance with requirement 1, by the fact characterized that in the connections of the formula II, R as linear Alky116 to 24 C-atoms, as branched alkyl 8 to 24, in particular 12 9_5 to 22 C-atoms and as alkylated Phenyl or Phenylalky112 to 24 C-atoms enthält.

3. Procedure in accordance with requirement 1, where in the connections of the formula II the Phenyl and Phenylalkyl with I or 2 alkyl groups subsfituiert ist.

4. Procedure in accordance with requirement 3, woñn the alkyl groups 4 to 18 C-atoms contained and preferably branches out sind.

Procedure in accordance with requirement 1, where in the connection of the formula 1 R branched alkyl with 8 to 30 C-atoms darstellt.

6. Procedure in accordance with requirement I, where Xin Fornetti for an oxygen atom steht.

7. Use of in the procedure in accordance with requirement t manufactured schwefelhaltigen ethers as stabilizing additives to Schmiermitteln.

The available invention betñfft a procedure for the production of Mercaptanen, mono, Dioder polysulfides and mixtures of it and their use for the stabilization of Schmiermitteln.

From the US-PS 3,361,723 mercaptogruppenhaltige Polyäther is well-known, which is developed out more monooder polyfunctional alcohols and Epiehlorhydrin, by continuing to convert their conversion products for the substitution of the c1 atoms with H2 S and/or Alkalihydrogeusulfiden. These connections find as intermediate products for the production of epoxy resins use. It found that the thiolischen Polyäther described in this ameñkanischen patent is not suitable aì's lubricating oil additives, there their solubility into the betrefs5 fenden lubricants too small ist.

Generally different additives are added to lubricants for improvement their customs particularly clinging. In particular exists a need at additives, which are to sehützen the devices before friction wear, which can be lubricated. To such extreme pressure agents for lubricants the requirement posed that they are sufficient soluble, the Lasttrageveñnögen to increase and on the metal parts concerned corrosive not work. Task of available invention is it. to make available effective Zu'satzstoffe for lubricants, these requirements genügen.

The invention betñfft a procedure for the production of schwefelhaltigen ethers, which is characterized by the fact that one connections of the formula II or their mixtures R - X - K |CH2 - CH - /0- - H H2C1 (! I) n where R linear alkyl with 12 to 24 C-flavours, branched alkyl with 8 to 30 C-atoms, alkylated Phenyl or Phenylalkyl with 8 to 24 C-atoms is, X for a Sauerstoffoder sulfur atom stands and n an average value within the range of 0,5 to 8, in at least stoichiometric quantities with hydrogen sulfide or dial potash metal sulfides (alkali metal) 2 Sx, woñn x = 1 means--4 is, converts and developing Chlorwassserstoff or the alkali metal chloride from the reaction mixture entfernt.

With that in case of the conversion with hydrogen sulfide connections of the formula H2SH are formed for erí indungsgem ässen procedures, where R, X and n the indicated Bèdeutung haben.

If n in formula IL the number of 1 meant and the conversion with (alkali metal) 2Sx takes place, Dimere of the formula S x are formed, where R, X and x the meaning indicated before to have. Is &gt in the parent compounds of the formula Ii n; as 1 and the conversion takes place with (alkali metal) 2 Sx, then Verbindungsgemische.<br develop/> In the connections of the formula II X is located preferentially for an oxygen atom and n for a Durcbschnittswert from 1 to 5, whereby x in (alkali metal) 2 Sx the numbers of 1 or 2 ist.

In a preferential execution form the conversion of the connections of the formula II with Sehwefelwasserstoff or with (alkali metal) 2 Sx takes place, where x = 1 or 2 is, if n in formula 1I the number of 1 bedeutet.

R in formula 1I means linear alkyl with 12 to 24, preferably 16 to 24 C-atoms. As examples are mentioned: Dodecyl, Tñdecyl, Tetradecyl, Pentadecyl, Hexadecyl, Octadecyl, Eicosyl, Docosyl, Tetracosyl.

R in formula II means in particular branched alkyl, prefers 8 to 24, particularly 12 to 22 C-atoms enthält.

Beìspiele are: I-Octyl, 2-Propylpentyl, i-Nonyl, ì-Decyl, 2Butylhexyl, 3-Hexylpentyl, 3-Methylundecyl, i-Dodecyl, 2Methyldodecyl, 2-Äthyldecyl, 3-Propyldecyl, 2-Hexyldecyl, iHexadecyl, 2-Äthylhexadecyl, i-Octadecyl, i-Eicosyl, 2-Hexyltetradecyl, 2-Äthyleicosyl, 2-Butyloctadecyl.

Also those branched alkyl residues are suitable, itself by technical alcohols and/or Alkoholgemisehen ableiten.

These alcohols are made generally after the Zieglerverfahren of aluminum, hydrogen and Aethylen and following Hydroxytierung and represent usually mixtures of different branched alcohols. These alcohols are commercially erhãltlich, e.g. Guerbetalkohole and Alfole (manufacturer: Condea), Dobanole (manufacturer: Shell) and Oxanole (manufacturer: Ruhr chemistry) and place a preferential group dar.

R in formula I can be Phenyl or Phenylalkyl also alkylated. The group of alkyls in Phenylalkyl contains preferentially i to 3, in particular 1 C-atom. The Phenyl and Phenylalkyl are preferably substituted with 1 to 2 alkyl groups, which 4 to 18 C-atoms 628,329 contained and which are preferably branched. Examples are:

Aethylphenyl, i-Propylphenyl, t-Butylphenyl, Hexylphenyl, Octylphenyl, t-Octylphenyl, Nonylphenyl, Dodecylphenyl, Octadecylphenyl, Dimethylphenyl, Di-Nonylphenyl, methyl benzyle, Aethylbenzyl, i-Propylbenzyl, t-Butylbenzyl, Octylbenzyl, Nonylbenzyl, Dodecylbenzyl, Dimethylbenzyl, Dioctylbenzyl.

The reaction is preferably accomplished generally at temperatures up to 150°C, 60 to 120°C. It can be worked at normal print or positive pressure. With the Herx0 position of the Mercaptanderi uses one ate I-I2 S and implements the reaction favourably under positive pressure. For the achievement of a to a large extent complete reaction it is also recommendable to use a surplus of H2 S. The conversion can be accomplished without or with a solvent. Suitable solvents are alcohols, particularly methanol and Aethanol.

During the conversion with H2 S prefers a Alkalioder alkaline-earth hydroxide, particularly NaOH, admitted in at least äquimolaren quantities, related to the c1 content of the connection of the formula II.

For the isolation of the desired connection the reaction mixture is acidified and with a suitable solvent, e.g. Aethern, extracts and afterwards by means of usual methods further cleaned. 2s with the analytic determination of the Thiolgehaltes of in such a way made connection are found often lower values than that value which can be expected theoretically. One can assume that with the reaction at the same time also Thioätherverbindungen in an educated manner werden.

By means of distillative methods, e.g. the Molekulardcstillation, the thiolgruppenhaltigen connections can, if are wished, isolated in purer form. The received reaction products become however favourably direct verwendet.

If the Thioäthergehalt are decreased and/or suppressed s is, a geñnge quantity of a reducing agent can, e.g. with the production or after the reaction. Zinkstaub, admitted werden.

For the production of the connections with Tioäthergruppen one sets the connections of the formula II with (alkali metal) 2 Sx, vorzngsweise Na2 S where x = 1-4 is, in particular DIN atrium disulphide over, the polysulfides becomes e.g. in well-known way by dissolving sulfur in the Alkalimonosulfld erhalten.

Here one proceeds generally in such a way the fact that one admits the connections of the formula II to the melt of the alkali metal sulfide, preferably to Na2 S and then at higher temperature, preferably up to 100°C lets after-react. To the distance of the developed alkali chloride and a possible surplus of alkali sulfides one washes thereafter with water and diluted acids, extracted with a suitable solvent, e.g. Aethern and distills the solvent for pure representation ab.

The conversion can run in such a way that in the reaction products still another remainder content of chlorine is present. The desired characteristics do not become thereby practically beeinflusst.

The connections of the formula II will receive RXH, where R and X have the meaning indicated before, in presence of Lewissäuren according to in the USPS 3 361723 described procedures by accumulation from epichlorohydrin at alcohols or Mercaptane the formula as catalysts, like SbC13, SNC14, A1C13 or BF3:

R-XH + H2C< o “CH-CH2Cì SnC14 > R-X (? H2 - CH-O') '- Î-IH CH2Cl the conversion product is a statistic mixture, which can be used as such. The isolation of a molecular-uniform Aethers from the Umsetznngsprodukt is simple by distillative methods to manage. As favourable, the statistic mixtures themselves proved too verwenden.

In the connections of the formula II thus n can take any value between 0,5 and 8, depending on, in which relationship the reactants with the production of the connections of the Fromel II used and which reaction conditions selected werden.

According to invention manufactured the schwefelhaltigen Aether is of easy flowing, more viscously Beschaffenso waxlike to heit, depending upon which, which basic materials are used and in which relationship this. They are colorless to easily yellow colored and surprisingly well in lubricants solubly, particularly those, in which Rin formula II represents a branched remainder. They are outstanding suitable as additives for lubricants. Apart from the improvement of the high pressure characteristics is also their small corrosive effect too erwähnen.

Surprisingly also the production of Masterbatehes is möglich.

due to the good solubility According to invention the connections manufactured in the procedure work already in very small quantities as extreme pressure agents in lubricants. Thus show mineral and synthetic lubricating oils, as well as their mixture, which with 0,01 to 5 Gew. - %, related to the lubricant, and 0.05 to 3% according to invention made of a connection 6s are equipped preferably, excellent I-Iochdruck-Schmiereigenschaffen, which becomes clear by strongly reduced Abnutzungserscneinungen of the parts which can be lubricated. The which are applicable lubricants are common the specialist and z.

B. in the “lubricant paperback” (Hüthig publishing house, Heidelberg, 1974) beschrieben.

The lubricating oil can contain additionally different additives, which are added, in order to improve the characteristics, like Antioxidantien, Metallpassivat0ren, rust inhibitors, Viscositätsindex Verbesserer/Fliesspunktserniedriger, Dispergiermìttel/Detergentien and other extreme Druek/AntiabnutzungsAdditive.

According to invention the connections manufactured in the procedure can also as PVC stabilizers either alone or together with metal stabilizers or as Epoxyhärter used werden.

A) Manufacture examples of examples 1 to 6 to 0.1 mol Stearylbzw. Octadecylalkohol are admitted 0.4 ml to tin tetrachloride. Afterwards becomes under agitating 0,1; 0,3 or 0.5 mol epichlorohydrin course-drips in such a way, so that the reaction temperature 70--75°C does not exceed. For the completion of the reaction one agitates further 3 hours with 110 to 115°C.

The conversion product and 0,1; 0,3 or 0.5 mol of NaOH, solved in 150 ml methanol is satisfied with H, S, heated up in autoclaves under agitating 4 hours with 90-100°C and 20-25 atue. After the cooling the reaction solution with halfconcentrated HCI is acidified and the desired product with ether is extracted. The ether solution is dried over MgSO4 and taken off then the solvent. The composition of the received products and some analytically determined 628,329 values are indicated in table 1. The line over the indices indicates that it itself around statistic mixtures handelt.

Example connection of the formula 1 n-CI2H2 O-CI2H2 o (I-H CH2SH n-C12H25-O (CH2-CH-O) 3-H CHzSH n-CI2H2y-CI2H2y-O (CI-5--H CH2SH n-C18H3T-C18H3T-O (CH CH2SH n-CIsH3T-CIsH3T-O (C3-H CHaSH n-CIsH37-CIsH37-O (C5-H CHzSI i 4 the SH-group-content, the CI-content and S-content become jodometrisch by means of elementary analysis bestimmt.

Table remainder content total sulphur content SH-content of C! .in Molber. gef. ber.

0,2 11.6 8.9 11.9 0.5 21.1 20.4 21.7 0.3 25.2 24.5 25.8 yield on gef. Mercaptan 10.3 86.5 20.4 94 23.3 90 3 0.3,8.9,8.7,9.2 8; 4 91 3.4 19.7 14.2 18.3 11.4 64 1.6 22.2 20 3 22.9 17.4 76 examples 7 to 10 und4Stundenbei 90--95°Cweitergerührt, whereby that printingup 1 mol becomes Guerbet alcohol (manufacturer Condea) under 30 25-30 atue rises. To the cooling with diluted HC1 additive of n mol epichlorohydrin is converted. A methanolic washed, with diethylether extracts, this solution of iiber solution of the conversion product and n mol of NaOH we DIN MgSO “dried and the solvent taken off. Autoclaves under 10 atue H2 a S-Druek 1 hour during space composition of the received connections and some temperature agitated. Then the H2 S-supply characteristics are interrupted in table 2 angegeben.

3 table 2 example 7 connection of the formula I % SH-content consistency Guerbet12-O--(CH IH-O) t-h 84 CH2SH Guerbet-12-O (CHz-- H-O) z--H 98 CH2SH Guerbet-16/20-O (CHzH o) 1-H 47 CH2SH Guerbet-16/20--O (CH CH-O) ah 83 I CH2SH example 11 1 mol of Oxanol-13/15 (manufacturer Ruhr chemistry), a mixture of branched C13 /C15 - alcohols 7 with i mol epichlorohydrin became and afterwards with t-I2 S/I mol of NaOt i umgesetzt.

in accordance with example The insulating conversion product has a SH-content of 51%.

After repeated molecular distillation as a first parliamentary group a product is separated, which exhibits 100% SH-content. It is liquid and ztt more than 5% oil-solubly. The second parliamentary group, which exhibits a SH-Gehal.t of less than 15%, has a SH-content of more than 70% after the reduction with Zn/HC1.

Examples 12 and 13 liquid flüsssig liquid liquid stopped up by Na2 S2, so that a temperature of 50°C is not exceeded. One agitates still another one hour with 80°C, whereby common salt fails. Then the reaction product is extracted successively washed with water, diluted HC1, diluted NaOH and water, with diethylether, dried over MgSO4 and taken off the ethers. One receives viscose rayon, in universal oils soluble products in yields from over 90%. The products correspond to the formulas:

i-CsH17ei-CsH17--O-CHzÇHCH S--S-CH, ÇH8H! 7 I I (example 12) OH OH 1 mol of i-Octanol and/or Oxanol-13/i5 under additive of 0,7% SnCI “with 1 mol epichlorohydrin is converted and afterwards the not converted alcohol is abdestilliert. The received epichlorohydrin addition product becomes then slow a melt Oxanol-13/15-O-CHoCHCH S--S-CH CHCH OOxanol-13/15 - [- -] “OH OH (example 13) 628,329 B) example of use Mìt the shell four-ball apparatus were determined the following values: (Tentavie method IP 239/69; Extreme pressure and near lubricant test for oils and greases, from ball machine).

1.) I.S.L. = initially seizure load; that is the load, with that the oil film within a loading period of 10 seconds zusammenbricht.

2.) W.L. = weld load. (Welding load). That is the load, with that! the 4 balls within 10 seconds weld together. :

3.) “Scar dia. meter” in mm, that is the middle wear diameter after a load of 70 kg during 1 Stunde.

4.) In some cases also the korresive effect in the Kupferstreifentest (approx.-St) was examined (evaluation scale is enough of la to 3b).

As basis oil Catenex 41 (Handelsbezeiehnung of the company Shell) was used. The results are iñ table 3 angegeben'.

Connection of the example concentration (Gew. - %) 0.1 9 1.0,0.5,1.0 11 (SH-content = 100%) 1.0 12 1.0 13 1.0 table 3 cu-St ISL (kg) Weld lead (kg) Scar dia. meter in mm - 60,160 2.42 lb 100,205 0.94 la 110,220 1.02 - of 110,205 0.99 lb--2a - - - la 95,220 1.98 - - > 200,1.1 3b - > 200,1.1 M