AU623796B2 - Polysulphide compositions of unsaturated fatty substances and/or (poly)unsaturated acid esters and optionally olefins, their preparation and their use as additives for lubricants - Google Patents

Description

i i w i ii'i LII- LLr~ 623796

AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION Form

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: T~fis r..su:ci: t c~.:lis Ic~ a mcui:n s Section 10(2) b.y the Supervising L'i:r on and is crrnxt for printilng t, TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: INSTITUT FRANCAIS DU PETROLE 4 AVENUE DE BOIS-PREAU 92502 RUEIL-MALMAISON

FRANCE

c. Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

Complete Specification for the invention entitled: POLYSULPHIDE COMPOSITIONS OF UNSATURATED FATTY SUBSTANCES AND/OR (POLY)UNSATURATED ACID ESTERS AND OPTIONALLY OLEFINS, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR LUBRICANTS.

The following statement is a full description of this invention including the best method of performing it known to me:- ~c 1A I t The invention relatesto s.ulphurized.-prganic. additives imre particularly used for improving the anti-wear and extreme pressure properties of lubricants. It more particularly relates to novel unsaturated fatty substances, (poly)unsaturated acid esters and polysulphurized olefins with a high sulphur content, which have little odour, a very low chlorine content, a limited colouring and a high storage stability, their preparation and their use as additives for mineral or synthetic lubricants.

The sulphurization of unsaturated fatty substances and (poly) unsaturated acid esters, in the presence or absence of olefins, S' is generally carried out in the prior art by direct heating 4' with elementary sulphur (US Patents 3,850,825, 4,031,019, 4,149,982 I 4 t 4,188,300 and 4,321,153) and sometimes by completing i. said direct sulphurization by a supplementary sulphur chloride treatment US Patent 3,740,333).

The major disadvantages of these sulphurization processes are Si t that they lead to products which are often very highly coloured, iC S. often unstable during storage with a progressive release of

H

2 S and, in the case of sulphurization of bisulphur chlorides, 20 of generating products containing chlorine quantities incompa- Stible with the new toxilogical constraints on which future legislation will be based, with regards to lubricant additives, which will in future impose a maximum chlorine content well below 0.1% by weight in industrial products.

k j 2 The Applicant has already described in French patent application 2,636,070, published on 9.3.1990, a process for the preparation of polysulphurized olefins comprising a stage in which at least one compound chosen from among sulphur monochloride and dichloride is reacted with at least one aliphatic monoolefin with 2 to 12 carbon atoms, thus forming an adduct; a stage (2) in which the hydrogen sulphide and at least one mercaptan is reacted with an alkali metal hydroxide or ammonium hydroxide dissolved in at least one aliphatic monoalcohol with 1 to 4 carbon atoms, which is substantially anhydrous, thus giving an alcoholic solution; a stage in which the adduct obtained 0 "in stage is contacted with the alcoholic solution obtained 0 0 o° in stage a stage in which the resultant mixture is *heated and then the aliphatic monoalcohol is eliminated by distillation, whilst adding an adequate water quantity to maintain in solution the sulphurized reagents which may be in excess and the mineral products formed during said reaction; and a stage in which the aqueous phase is eliminated and the organic phase constituted mainly by the polysulphurized olefin composition is recovered.

This process uses as starting products monoolefins with 2 to 12 carbon atoms. It makes it possible to prepare polysulphurized compositions with a high sulphur content and a low chlorine content, which can be used as anti-wear, extreme pressure additives in synthetic or mineral lubricating oils used more i i u -3particularly for lubricating gears and in working metals.

It has now been found that it is possible to sulphurize the unsaturated fatty substances and/or (poly)unsaturated carboxylic acid esters, in the presence or absence of olefins, and to obtain products having high sulphur contents, a low odour level and a low chlorine content. These products are also only slightly coloured, stable during storage, soluble in mineral oils as J a function of the synthesis conditions and are usable as antiwear, extreme pressure additives. Sulphurization is carried out by a process like that described in French patent application S. 2,636,070.

a ,I In general terms, the polysulphurized compositions according to the invention can be defined as consisting of products obtained by a process with the following stages. A stage in which reaction takes place, e.g. at a temperature of 20 to 80 C, of ,at least one unsaturated fatty substance and/or at least one (poly)unsaturated carboxylic acid ester, in the presence or absence of an aliphatic monoolefin with 2 to 36 carbon atoms with, in one or more fractions, at least one compound chosen from among sulphur monochloride and dichloride, thus forming an addition product or adduct. A stage in which reaction takes place, e.g. at a temperature of 20 to 80 0 C, of hydrogen sulphide and/or a mercaptan with an alkali metal (sodium or potassium) 1 or ammonium hydroxide, dissolved in at 4 -4least one aliphatic monoalcohol with 1 to 4 carbon atoms and which is substantially anhydrous. Optionally elementary sulphur is added as a function of the proportions of sulphide, hydrov,sulphide, mercaptate, polysulphide and/or mercaptate polysulphide of alkali metals which it is desired to obtain in the mixture.

A stage in which contacting is brought about between said adduct and optionally at least one saturated or unsaturated, monohalogenated, hydrocarbon compound, as defined hereinafter, with, in one or more fractions, the alcoholic solution obtained in stage maintained at a predetermined temperature of e.g.

20 to 700C during the introduction of the reagents. A stage in which the resultant mixture is heated for a given time, *o Sat a temperature ranging e.g. between 40 and 70 C. The monoalcohol is eliminated by distillation, whilst adding an adequate volume of water to maintain in solution the mineral products formed during the reaction and optionally the sulphurized reag- 4, ents in excess. Optionally an in particular aromatic hydrocarbon solvent is added, such as e.g. toluene or xylene and which wiil a be eliminated in the following stage after settling by distillation. A stage in which, after settling, the aqueous phase is eliminated and the polysulphurized composition constituting the organic phase is recovered. There is optionally a stage in which contacting takes place between the product obtained and a weakly basic compound, such as sodium bicarbonate, followed by washing with water.

r_ i i o9 ono o o 0e00 0* o 0e 0 a a 6G o 0 0 0403 0 0 0 o a 0 00« 000 0l In stage of the preparation process of the compositions according to the invention, the fatty substances used can have an animal origin, such as e.g. lard, suet, butter, fish and sea mammal oils, etc. However, they can also have a vegetable or plant origin, such as e.g. colza, sunflower, palm, castor, copra, almond, olive, groundnut, sesame, corn, cottonseed, soya, jojoba and similar oils.

The (poly)unsaturated carboxylic acids used for the preparation of the esters can contain up to approximately 26 atoms of carbon 10 per molecule. The saturated or unsaturated alcohols used for preparing the monosaturated and/or polysaturated carboxylic acid esters are straight or branched primary or secondary alcohols having a natural or synthetic origin and containing approximately 1 to 20 and preferably 1 to 16 carbon atoms per molecule.

The olefins optionally used with the fatty substances and/or the (poly)unsaturated carboxylic acid esters can be linear or cyclic and contain 2 to 36, preferably 2 to 12 carbon atoms per molecule. The unsaturated fatty substances, the (poly) unsaturated carboxylic acid esters and/or optionally the olefins 20 are used in proportions corresponding to a number of unsaturations of 0.2 to 2.5 unsaturations per gramme molecule of sulphur monochloride and/or dichloride.

Moreover, within the unsaturated reagents used, the unsaturated fatty substances and/or the k .ly)unsaturated carboxylic acid O 00 00 0t Op 0 0 0* 0 901 ~O 0 rr -6alkyl esters represent a proportion, expressed-in-ethyTene-unsat- urations,of 1 to 100,and preferably 10 to 100%, the aliphatic monoolefins representing a proportion from 0 to 99 and preferably 0 to The sulphur chlorides are generally introduced into the olefin mixture at a temperature of 20 to 80 0 C and more specifically to 50 0

C.

The sulphur mixture prepared in stage from hydrogen sulphide j oo: and/or mercaptan can have the proportions of a sulphide, a hydro- 10 r sulphide, a polysulphide, a mercaptate or a mercaptate polysulphide of alkali metal sodium or potassium) or ammonium, or a mixture thereof. Usually sodium compounds are involved. Generally use is made of 0.01 to 1 and preferably 0.05 to 0.95 gramme molecule of hydrogen sulphide per gramme molecule of hydroxide and 0.01 to 1 and preferably 0.05 to 0.95 gramme molecule of mercaptan per gramme molecule of hydroxide. The elementary sulphur optionally used in stage together with Sa the sulphur compound, can be introduced with the hydroxide in a molar ratio from 0 to approximately 3.6/1 and more particularly 20 0 to 2.5/1.

00 0 In stage the sulphur or sulphurized compound is formed and optionally the elementary sulphur is introduced into a light aliphatic monoalcohol containing 1 to 4 carbon atoms. Examples of light aliphatic monoalcohols are methanol, ethanol, n-propanol, -7isopropanol, n-butanol, isobutanol and tert-butanol, methanol being preferred. The quantity used is advantageously 100 to 1000 and preferably 125 to 500 cm 3 per gramme molecule of hydroxide used.

The term substantially anhydrous monoalcohol is understood to mean a monoalcohol containing no more than 5% by weight water and preferably less than 1% by weight water.

In stage of the process for the preparation of the polysulphurized compositions according to the invention, the proportion o4 10 of the adduct and the monohalogenated hydrocarbon compound m *o optionally used with respect to the hydroxide used generally Scorresponds to between 1/1 to 0.5/1, preferably 0.80/1 to 0.75/1 gramme atoms of halogen per gramme molecule of hydroxide.

The monohalogenated hydrocarbon compounds usable jointly with 15 the adduct can consist of chlorides, bromides or iodides of straight or branched, C 1 to C12 (preferably C 2 to C alkyls or alkenyls, optionally substituted, C 5 to C12 (preferably C 6 cycloalkyls and/or cycloalkenyls, or optionally substituted, S, C1 to C 12 (preferably C8 and C9) aryl alkyls and/or aryl alkenyls.

These can also be monohalogenated hydrocarbon compounds containing one or more functional groups having one or several heteroatoms (such as oxygen and/or nitrogen and/or sulphur). Chlorides and bromides are mainly used.

lk 1; I -8- Particular consideration is given among these functional compounds to monohalogenated compounds containing at least one alcohol function and in particular halides of aliphatic, alicyclic or aromatic-aliphatic monoalcohols e.g. containing 2 to 18 carbon atoms, halides of polyols and halides of (poly)oxyalkylenated monoalcohols; monohalogenated compounds containing at least one phenol function, optionally substituted e.g. by alkyl groups; monohalogenated compounds containing at least one carboxylic function; monohalogenated compounds containing at least one amine function, particularly aliphatic, alicyclic or aromaticaliphatic compounds; monohalogenated compounds containing at least one amide function; monohalogenated compounds containing S at least one thiol function; compounds with hydroxyl and carb- 4t oxylic acid functions; compounds with amine and carboxylic acid functions; or compounds with hydroxyl and amine functions.

Specific examples of such functional monohalogenated compounds are given in French patent application 2,615,861 relating to "polysulphurized olefin compositions with a high sulphur content and a very low chlorine content, their preparation and their 20 use as additives for lubricants".

4 a, The proportion of the optionally used monohalogenated hydrocarbon compound is generally 1 to 70% gramme atoms of halogen based on the total number of gramme atoms of halogen of the adduct and monohalogenated hydrocarbon compound together.

A

atta 9 a *4 *4 *a a a a\ a at a' a aaa at a a a tat 44 a -9- Stage can be performed under various pressures and it can be up to 1 MPa (10 bars).

The additives according to the invention can be prepared by a continuously functioning process with parallel flows and multiple contacts. In this case, the reaction of stage is generally performed under pressure.

The polysulphurized compositions according to the invention can have a sulphur content ranging from approximately 5 to by weight, for particularly low residual chlorine contents, 10 generally below approximately 0.1 and usually 0.05% by weight, more particularly in the case where use is made of methanol and/or a low reaction pressure.

The compositions according to the invention are only slightly coloured. According to NF T 60-104, their colour corresponds to a number generally between 1.5 and 3.5. They have a low odour considering their sulphur content. They are soluble in aromatic solvents and mineral lubricating oils at adequate concentrations in order to have a notable effect on improving the extreme pressure properties of these oils. They also improve the unctousness. In addition, the natural origin of the fatty substances used as starting reagents makes it possible to obtain sulphur products with a better biodegradability than products prepared from reagents having a petroleum origin.

i I 10 The compositions according to the invention have a corrosiveness with respect to copper which, evaluated according to Standard ASTM D 130 (NF M 07-015, 3 hours at 120 0 C for a concentration corresponding to a 2% by weight sulphur content) corresponds to a rating generally from 2 c to 4 b. Those whose corrosiveness with respect to copper gives a rating of 3 or less can be used for forming gear oils or for the formulation of cutting oils for cuprous metals at doses between 0.1 and 20% by weight.

Those whose corrosiveness with respect to copper, under the S 10 conditions indicated hereinbefore, lead to a rating above 3 o can be used for the formulation of cutting oils for ferrous metals at doses between 0.1 and 20% by weight and as sulphurizing agents in an organic medium.

The following examples illustrate the invention without limiting it. In these examples, RSH or HSR stands for the mercaptan used.

Example 1 SUlphurized mixture of- castor oil/dli; butylene.

In a one litre reactor equipped with a stirrer, a refluxing device and a heating system are dissolved 34.6g of soda pellets (0.865 gramme molecule) in 600 cm 3 of anhydrous methyl alcohol and then using a funnel addition takes place in 30 minutes of 77.85g of tert-butyl mercaptan (0.865 gramme molecule). Following the reaction, addition takes place of 13.9g of flowers of sulphur (0.434 gramme atom) and the stirred mixture is heated I i 11 for 1 hour to form the alkali mercaptate polysulphide (the theoretical molar ratio HSR/S being The thus obtained mixture is transferred into an adding funnel.

Into a second, two litre reactor, equipped with a stirrer, a condenser and a heating device are introduced 150g of castor oil (approx. 0.14 gramme molecule, average molecular weight 1086 calculated on the basis of a hydroxyl number of 185), of diisobutylene (0.67 gramme molecule) and 100 cm 3 of hexane.

'4 The mixture is stirred at 20 0 C and then, using a funnel, addition 10 takes place of 58.4g of S 2 C1 2 (0.432 gramme molecule) in dropwise t, form and in 1 hour, whilst maintaining the reaction temperature below 35 C.

4 The previously obtained alkaline mercaptate polysulphide solution is then added dropwise in two hours to the sulphohalogenated 15 mixture, whilst maintaining a reaction temperature below 35 C.

SThe thus obtained mixture is heated for 24 h at 50°C, accom- 4 panied by stirring.

3 This is followed by the addition of 150 cm of toluene and 300 3 cm of water, followed by the elimination of the methanol by distillation under reduced pressure. The aqueous phase is then eliminated by decanting or settling, the organic phase is washed three times with 200 cm 3 of water, dried on anhydrous NaSO 4 the solvent being evaporated under reduced pressure at 1000C.

c 12 This gives 277g of a slightly viscous, clear, pale yellow oil, whose physicochemical characteristics are as follows: S wt 20.4 Cl 500 ppm Na 2 ppm Cinematic viscosity at 100 0 C (mm 2 7.2 Saponification number (mg KOH/g) 145 Colour NF T 60-104 2 Soluble in aromatic solvet.s .fi Very limited odour, even after storage for several months.

a S' 10 The IR analysis of the product indicates the presence of characteristic OH and C=0 bands.

f i Example 2 Sulphurized mixture of colza oil/diisobutylene.

As in Example 1, preparation takes place of an alkaline mercaptate polysulphide solution by reacting 39.6g of soda pellets (0.99 gramme molecule), 89.2g of tert butyl mercaptan (0.99 gramme molecule) and 16.7g of flowers of sulphur (0.521 gramme atom) in 600 cm 3 of anhydrous methanol (in this example the theoretical Smolar ratio HSR/S is equal to 1.9).

I S In a second reactor is prepared a halogenated mixture by reacting at between 25 and 30 0 C, 45.6g of S 2 C1 2 (0.34 gramme molecule) on a mixture constituted by 56g of diisobutylene (0.5 gramme molecule) and 106.3g of colza oil, whose iodine number is 119.3 i 1- -13unsaturation). To the mixture obtained are added approximately of the previously prepared alkaline mercaptate solution and the reaction temperature is kept at about 30 0

C.

This is followed by the introduction of a supplementary 15.15g of S 2 C1 2 (0.11 gramme molecule) and then the remainder of the alkaline mercaptate polysulphide solution. The mixture obtained is then heated, accompanied by stirring, for 24 h at 50 0

C.

I *4 Following the reaction, an addition takes place of 200 cm 3 of ,s water and then the methanol is eliminated by distillation under 0 a 10 reduced pressure. The organic phase recovered after settling 3 is washed twice with 200 cm of a mixture constituted by 150 ,3 3 cm3 of water and 50 cm of NaCl-saturated water. Following drying on Na 2

SO

4 and filtering, 203g of a pale yellow oil are recovered having the following characteristics: I I S 15 S wt 23.2 Cl 620 ppm Na 115 ppm Cinematic viscosity at 100 0 C (mm2/s) 27.7 Saponification number (mg KOH/g) 214.0 Colour NF T 60-104 Soluble in neutral solvent oil 100 and aromatic solvents.

Example 3: Sulphurized mixture of colza oil/diisobutylene.

Example 2 is repeated using the same colza oil and diisobutylene i bd, 14 quantities, but using 67.5g of S 2 C1 2 (0.5 gramme molecule) and 35.3g of flowers of sulphur (1.1 gramme atom). In the test the theoretical molar ratio HSR/S is equal to 1.

After reaction and then treatment', 246g of orange coloured oil are recovered, whose analysis leads to the following results: 0990 o a 40 S* 10 0 0 0 o ao a 0* ar S wt 30.1 Cl 440 ppm Na 120 ppm Cinematic viscosity at 100 0 C (mm2/s) 50.9 Saponification number (mg KOH/g) 303 Colour NF T 60-104 Soluble in neutral solvent oil 100 and aromatic solvents.

e *o 0000 9 a aa a. fit at a t

I

00a00 Example 4: Sulphurized colza oil.

15 Example 2 is repeated using only colza oil as the unsaturated compound (212.6g, i.e. 1 unsaturation), 67.5g S of S 2 C1 2 (0.5 gramme molecule), 99g of tert butyl mercaptan (1.1 gramme molecule), 44g of soda (1.1 gramme molecule) and 18.6g of sulphur (0.58 gramme atom). In this test the theoretical molar ratio HSR/S is 1.9. After reaction and then treatment, 230g of a yellow-orange oil are recovered having the following composition: 0 S wt 20.9 Cl 510 ppm Cinematic viscosity at 100 0 C (mm2/s) 24.7 Colour NFT 60.104 Soluble in neutral solvent oil 100 and aromatic solvents.

i: i 14a Example 5: Sulphurized colza oil Example 4 is repeated using 35.3 g of flowers of sulphur (1.1 gramme atom). In this test the theoretical molar ratio HSR/S is 1. After reaction and treatments, 230 g of a yellow-orange coloured oil are recovered having the following composition.

S wt% 24.6 Cl 480 ppm Na 95 ppm 2 Cinematic viscosity at 100 0 C (mm 26.8 r tr C 0 0 0 0 L 1 tives in synthetic or mineral lubricating oils used more 15 Saponification number (mg KOH/g) 275.0 Colour NF T 60-104 3 Soluble in neutral solvent oil 100 and aromatic solvents.

Example 6: Sulphurized colza oil.

Example 5 is repeated using 70.5g of flowers of sulphur (2.2 gramme atom). In this test the theoretical molar ratio HSR/S is 0.5. After reaction and treatment, 245g of orange coloured oil are recovered with the following composition:

S

i S wt 27.0 Cl 620 ppm 10 Na 127 ppm Cinematic viscosity at 100 0 C (mm 2 31.9 I Colour NF T 60-104 Soluble in neutral solvent oil 100 and aromatic solvents.

an Example 7: Sulphurized sunflower oil.

15 Example 2 is repeated using 195.3g of sunflower oil (iodine number 130, i.e. 1 unsaturation), 67.5g of S 2 C1 2 (0.5 gramme molecule), 99g of tert butyl mercaptan (1.1 gramme molecule), S44g of soda (1.1 gramme molecule) and 35.3g of sulphur (1.1 gramme atom). In this test the theoretical molar ratio HSR/S is equal to 1.

3 After reaction, the sulphurized oil is diluted with 150 cm of hexane and then washed four times with 150 cm 3 of Na 2

SO

4 saturated water. After settling, the organic phase is dried on anhydrous Na 2 SO filtered and then evaporated under reduced pressure to eliminate the solvent. 230g of a yellow-orange oil are recovered with the following composition: S wt 26.2 C 320 ppm Na 535 ppm Cinematic viscosity at 100 0 C (mm 15.7 Colour NF T 60-104 4 Soluble in neutral solvent oil 100 and aromatic solvents.

a i r t Example 8: Sulphurized fish oil.

S' Example 7 is repeated using 1 40.5g of fish oil (iodine number 180.7, i.e. 1 unsaturation), 33.7g of S 2 C1 2 (0.25 gramme molecule), 49.5g of tert butyl mercaptan (0.55 gramme molecule), I, ,o 22g of soda (0.55 gramme molecule) and 17.65g of sulphur (0.55 15 gramme atom). In this test the theoretical molar ratio HSR/S a°o is 1. After reaction and treatment as in Example 2, 195g of yellow-orange oil are collected with the following character- 4 oo istics: o o 0 S wt 19.4 Cl 450 ppm Na 220 ppm Cinematic viscosity at 100 0 C (mm 2 19.7 Colour NF T 60-104 3 Soluble in aromatic solvents.

17 Example 9: Sulphurized colza oil methyl ester.

In a one litre reactor equipped with a stirrer, a refluxing device and a heating system are dissolved 38.7g of soda in pellet 3 form (0.968 gramme molecule) in 600 cm of anhydrous methyl alcohol, followed by the introduction of 16.5g of gaseous H2S (0.484 gramme molecule) using a fritted tube immersed in the alkaline solution. This is followed by the addition of 5.75g of flowers of sulphur (0.18 gramme atom) and the mixture is heated, accompanied by stirring, for one hour to form the alka- :o 10 line polysulphide. After completely dissolving the alkaline O.0. solution is transferred into an adding funnel (in this test a o the theoretical molar ratio H S/S is 2.7).

o Into a second, two litre reactor, equipped with a stirrer, a condenser and a heating device are introduced 222.5g of a colza 15 oil methyl ester approx. 1 unsaturation calculated on I the basis of the iodine number of 114.1). This is followed S, by the dropwise addition of 67.5g of S 2 C1 2 (0.5 gramme molecule) in 1.5 hour, whilst maintaining the reaction temperature at between 25 and 30 0 C. The thus obtained compound contains 13% by weight chlorine and 11.6% sulphur. The alkaline polysulphide solution obtained previously is then added dropwise in two hours to the sulphohalogenated mixture, whilst maintaining a reaction temperature between 40 and 450C. The stirred mixture is allowed to react for 24 h at 500C.

i

I:

18 The organic phase is diluted with 500 cm 3 of toluene This 3 is followed by the addition of 250 cm of water in order to dissolve the NaC1 formed and the polysulphide excess, following vigorous stirring for 30 minutes settling takes place and the aqueous phase is eliminated. The organic phase is washed with 3 250 cm of a 10% by weight, aqueous C0 3 HNa solution, dried on anhydrous Na2SO4 and filtered. The solvent is then distilled at 100 0 C under reduced pressure.

o This gives 230g of a clear, yellow-orange oil with the following I r 10 physicochemical characteristics: a t a S wt 20.6 C1 350 ppm Na 230 ppm Cinematic viscosity at 100°C (mm2/s) 44.4 Saponification number (mg KOH/g) 240.0 Colour NF T 60-104 Soluble in aromatic solvents.

Very limited odour, even after several months storage.

Example 10: Sulphurized colza oil methyl ester.

Example 9 is repeated with the reaction in a two litre reactor of 58.54g of soda pellets (1.464 gramme molecule) dissolved in 910 cm 3 of methanol, 131.7g of tert butyl mercaptan (1.464 gramme molecule) and 17.4g of flowers of sulphur (0.542 gramme atom). The theoretical molar ratio HSR/S in this example is 2.7.

L ailpnatic monoaiconoi containing to -ai CIuuull c-LuOm. U- y of light aliphatic monoalcohols are methanol, ethanol, n-propanol, i; I

OWII

fi o 9 9 99 9 9 0* 9o 9 999 0 19 The experiment is continued in the second reactor with 348g of the same colza methyl ester addition product. After reaction and treatment, 400g of an orange-yellow oil is recovered with the following characteristics: S wt 23.4 Cl 675 ppm Na 710 ppm Cinematic viscosity at 100 0 C (mm2/s) 7.78 Saponification number (mg KOH/g) 149.0 Colour NF T 60-104 2 Soluble in aromatic solvents.

Very limited odour, even after several months storage.

Example 11: Sulphurized colza oil methyl ester.

Example 10 is repeated with the reaction in a two litre reactor of 58.54g of soda pellets (1.464 gramme molecule) dissolved 15 in 910 cm 3 of methanol, 87.84g of tert butyl mercaptan (0.976 gramme molecule), 16.62g of H2S (0.488 gramme molecule) and 17.4g of flowers of sulphur (0.542 gramme atom). The theoretical molar ratio of HSR H 2 S/S in this example is 2.7.

The experiment is continued in the second reactor with 348g of the same colza methyl ester addition product. After reaction and treatment, 300g of yellow-orange oil are recovered with the following characteristics: 9 t 6 *99 9999o 9 09 99 i I 20 S wt 22.4 Cl 500 ppm Na 46 ppm Cinematic viscosity at 100 0 C (mm2/s) 7.2 Saponification number (mg KOH/g) 207.0 Colour NF T 60-104 Soluble in aromatic solvents.

Very limited odour, even after several months storage.

Example 12: Sulphurized mixture of colza oil methyl ester/isobutylene.

j 10 In a one litre reactor equipped with a stirrer, a refluxing device and a heating system are dissolved 90.7g of soda pellets 3 (2.27 gramme molecule) in 600 cm of anhydrous methyl alcohol and then, via a tube terminated by a fritted glass, are added 38.7g of H2S (1.14 gramme molecule) in 30 minutes.

Following reaction, addition takes place of 13.5g of flowers of sulphur (0.42 gramme atom) and the stirred mixture is heated for 1 hour to form the alkaline polysulphide (in this test the theoretical molar ratio H 2 S/S is The thus obtained mixture is transferred into an adding funnel.

In a second two litre reactor are reacted 100g of colza methyl ester (0.45 unsaturation), lOOg of isobutylene (1.79 unsaturation) and 150g of S 2 C1 2 (1.11 gramme molecule). The product obtained (Cl 20% by weight, S 19% approx.) is diluted with adduct and monohalogenated hydrocarbon compound together.

21 18.25g of n-chlorobutane. In this mixture the chlorine proportion in the form of n-chlorobutane is approximately 8% by weight based on the total chlorine.

The alkaline polysulphide solution obtained previously is then added dropwise in two hours to the sulphohalogenated mixture, whilst maintaining a reaction temperature close to 0 C. The stirred mixture is allowed to react for 24 h at 50 0

C.

3 The organic phase is diluted with 500 cm of toluene, followed a by the addition of 250 cm 3 of water to dissolve the NaC1 formed and the polysulphide excess. After vigorous stirring for Sminutes, settling takes place and the aqueous phase is eliminated. The organic phase is washed with 250 cm 3 of an aqueous by weight, C03HNa solution for 3 h at 7500, dried on anhydrous Na 2

SO

4 and then filtered. The solvent is then distilled 15 at 1000C under reduced pressure. This gives 220g of a clear, I orange-yellow oil with the following physicochemical characteristics: i tI 4 S wt 38.5 Cl 610 ppm Na 18 ppm Cinematic viscosity at 100 0 C (mm 25.0 Saponification number (mg KOH/g) 280.0 Colour NF T 60-104 3 i toum reagents having a petroleum origin.

:1 22 ik Soluble in neutral solvent oil Very limited odour, even after 100 and aromatic solvents.

several months storage.

(4 *444 44 44 4 44f 4 4 4444 4444 4 4 4 t 4 rJI f t 4 4 4 4 4 t 4 1 t t 9.

i t Example 13: Sulphurized mixture of colza oil methyl ester/castor oil.

In a one litre reactor equipped with a stirrer, a refluxing device and a heating system are dissolved 35.93g of sulphur pellets (0.898 gramme molecule) in 400 cm 3 of anhydrous methyl alcohol. This is followed by the addition of 80.85g of tert butyl mercaptan (0.898 gramme molecule) and 10.7g of flowers 10 of sulphur (0.3334 gramme atom). The stirred mixture is heated for 1 hour to form the alkaline polysulphide and is then transferred into an adding funnel (in this test the theoretical molar ratio HSR/S is 2.7).

In a second one litre reactor reaction takes place of 125g of colza methyl ester (0.56 unsaturation), 125g of castor oil (0.35 unsaturation) and 55g of S 2 C1 2 (0.408 gramme molecule) between 20 and 25 0

C.

The previously obtained alkaline polysulphide solution is then added dropwise in two hours to the sulphohalogenated mixture, whilst maintaining a reaction temperature close to 250C. The stirred mixture is then allowed to react for 24 h at 50 C. The organic phase is diluted with 500 cm 3 of toluene, followed by the addition of 250 cm 3 of water to dissolve the NaC1 formed 23 and the excess polysulphide, after vigorous stirring for minutes settling takes place and the aqueous phase is eliminated.

3 The organic phase is washed with 250 cm of an aqueous 10% by weight, CO3HNa solution for 3 h at 750C, dried on anhydrous Na 2

SO

4 and then filtered. The solvent is then distilled at 1000C under reduced pressure. This gives 300g of a clear yelloworange oil with the following physicochemical characteristics: a. S wt 14.9 Cl 500 ppm Na 155 ppm 10 Saponification number (mg KOH/g) 148.0 SColour NF T 60-104 0a Soluble in aromatic solvents.

Very limited odour, even after several months storage.

Example 14: Measuring the corrosive activity of the additives S 15 according to the invention.

It Corrosion tests using the copper plate according to Standard ASTM D 130 (NF M 07-015) are carried out. The studied formulations were constituted by a neutral solvent mineral oil 100 S: in which were dissolved quantities of additives according to the invention such that the sulphur content of these formulations, due to these additives, was equal to 2% by weight.

The results obtained are given in Table 1. They are given by a rating consisting of a number from 1 to 4, followed by a letter defining the copper plate corrosion level.

ii 24 TABLE 1 Additive of in additive 3 hours at Example wt 1000C 1210C 4 20.9 4b 4b 5 24.6 4a 4b 4b 23.4 la 2c 3b 11 22.4 2c 4b Example 1 5 Evaluation of the extreme pressure properties of the additives according to the invention.

10 Tests were carried out to reveal the extreme pressure properties o of the additives prepared according to Examples 4,10 and 11 of the invention using the 4 ball machine of ASTM D 2783.

The lubricating formulation studied and constituted by a solventrefined mineral oil SAE 80W90, in which were dissolved quantities 15 of additives according to the invention such that the sulphur content of the oil, due to these additives, was 2% by weight.

tc The results given in Table 2 show that the additives according to the invention can be used for the formulation of metal working oils.

25 Table 2 Additive of Example Charge-wear index Welding charge 80W90 4 11 (kgf) 28.0 98.0 75.3 83.4 (kgf (N) 274.7 961.4 738.7 818.1 1569.6 6082.2 4905.0 5395.5 Ball impression diameter, 1 hout under a load of 40 kgf 60 kgf 80 kgf 392.4N 588.6N 784.8N 1.47 1.90 2.50 0.67 0.90 1.65 0.68 1.00 1.15 0.71 0.85 1.00

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Claims (12)

1. Sulphur-rich, slightly coloured, stable polysulphurized composition with a very low residual chlorine content, characterized in that it is prepared by a process comprising a stage in which reaction takes place of at least one substance chosen from the group constituted by unsaturated fatty substances, monounsaturated or polyunsaturated carb- oxylic acid esters, in the presence or absence of at least one aliphatic monoolefin having 2 to 36 carbon atoms per o, 10 molecule, with one or more fractions of at least one comp- ound chosen from among sulphur monochloride and dichloride, thus forming an adduct; a stage in which reaction takes place of at least one reagent chosen from the group consti- tuted by hydrogen sulphide and mercaptans, with at least one alkali metal or ammonium hydroxide, dissolved in at least one substantially anhydrous aliphatic monoalcohol °o containing 1 to 4 carbon atoms per molecule; a stage (3) in which contacting takes place between the adduct obtained I 44 in stage with, in one or more fractions, the alcoholic solution obtained in stage a stage in which the resultant mixture is heated, the monoalcohol eliminated by distillation, whilst adding a water volume adequate for maintaining the mineral products formed during the reaction in solution, and the possible excess sulphurized reagents; and a stage in which, after settling, the L^ 27 aqueous phase is eliminated and the polysulphurized comp- osition constituting the organic phase is recovered.

2. Polysulphurized composition according to claim 1, character- ized in that its preparation process also comprises a stage in which the polysulphurized composition obtained in stage is contacted with a slightly basic compound and it is washed with water.

3. Polysulphurized composition according to either of the o'cr, claims 1 and 2, characterized in that said ester is derived 10 from at least one monounsaturated or polyunsaturated carbo- xylic acid containing up to approximately 26 carbon atoms per molecule and at least one primary or secondary, straight or branched, natural or synthetic alcohol containing approx- imately 1 to 20 carbon atoms per molecule.

4. Polysulphurized composition according to one of the claims 1 to 3, characterized in that the proportion of said sub- stance and optionally said monoolefin is 0.2 to 2.5 unsat- urations per gramme molecule of sulphur monochloride and/or dichloride.

5. Polysulphurized composition according to one of the claims 1 to 4, characterized in that, in all the reagents used, said substance chosen from among unsaturated fatty 28 substances and (poly)unsaturated carboxylic acid alkyl esters represents a proportion, expressed in ethylene unsat- urations, from 1 to 100% and said aliphatic monoolefins represent a proportion from 0 to 99%.

6. Polysulphurized composition according to claim 5, character- ized in that the proportion of said substance is 10 to 100% and the proportion of said aliphatic monoolefin 0 Sto 90%, expressed in ethylene unsaturations.

7. Polysulphurized composition according to one of the claims S 10 1 to 6, characterized in that, in stage working takes place at a temperature of 20 to 80C in stage at 4 0 to 800C.and in stage at 20 to 700C.

8. Polysulphurized composition according to one of the claims 1 to 7, characterized in that, in stage use is made of 0.01 to 1 gramme molecule of hydrogen sulphide, 0.01 to 1 gramme molecule of mercaptan and 0 to 3.6 gramme atoms of elementary sulphur per gramme molecule of ammonium or 0 t a alkali metal hydroxide.

9. Polysulphurized composition according to one of the claims 1 to 8, characterized in that, in stage use is made of 100 to 1000 cm 3 of substantially anhydrous aliphatic monoalcohol per gramme molecule of ammonium or alkali 29 metal hydroxide. Polysulphurized composition according to one of the claims 1 to 9, characterized in that, in stage said adduct is used in a proportion corresponding to 0.5 to 1 gramme atom of halogen per gramme molecule of hydroxide used in stage o« 11. Polysulphurized composition according to one of the claims 1 to 10, characterized in that, in stage apart from said adduct, use is made of at least one monohalogenated r 10 hydrocarbon compound in a proportion of 1 to 70% gramme atoms of halogen based on the total number of gramme atoms of halogen of the adduct and monohalogenated hydrocarbon compound together.

12. Polysulphurized composition according to one of the claims 15 1 to 11, characterized in that, in stage the mixture of stage is heated to a temperature of 40 to 700C. S13. Polysulphurized composition according to one of the claims 1 to 12, characterized in that, following stage a hydrocarbon solvent is added and is then eliminated by distillation during stage L. I i 30

14. Polysulphurized composition according to one of the claims 1 to 13, characterized in that it has a sulphur content of 5 to 55% by weight and a residual chlorine content below 0.1% by weight.

15. Lubricating oil, characterized in that it comprises a major proportion of a mineral or synthetic based oil and 0.1 to 20% by weight of at least one polysulphurized compos- ition according to one of the claims 1 to 14. a t DATED THIS 26TH DAY OF JULY 1990 INSTITUT FRANCAIS DU PETROLE By its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia At -i I 4 t