FR2531098A1 - MULTIFUNCTIONAL ADDITIVE FOR LUBRICATING OILS CONTAINING THIOCYANO GROUPS, PROCESS FOR PREPARING THE SAME AND LUBRICATING COMPOSITIONS CONTAINING SAID ADDITIVE - Google Patents

Abstract

MULTIFUNCTIONAL ADDITIVE FOR LUBRICATING OILS CONTAINING THIOCYANO GROUPS, ITS PREPARATION PROCESS AND LUBRICATING COMPOSITIONS CONTAINING THIS ADDITIVE. THE LUBRICANT COMPOSITIONS INCLUDE A LUBRICATING OIL AND A MULTIFUNCTIONAL ADDITIVE CONSTITUTED BY AN ORGANIC COMPOUND HAVING AT LEAST ONE GROUP OF FORMULA: (CF DRAWING IN BOPI) IN WHICH X IS 1 OR 2. THE ADDITIVE IS PREPARED BY REACTING A SULFUR MONO OR DICHLORIDE WITH A HYDROCARBON COMPOUND HAVING AT LEAST A DOUBLE OLEFINIC BOND IN ITS MOLECULE, OR WITH AN ALKYL ESTER COMPOUND HAVING AT LEAST A DOUBLE OLEFINIC BOND, TO OBTAIN AN INTERMEDIATE SULFOCHITORIC PRODUCT WITH A REALIZED SULFOCHLORE THIOCYANATE OF AN ALKALINE OR AMMONIUM METAL. IN THESE LUBRICATING OIL COMPOSITIONS, THE MULTIFUNCTIONAL ADDITIVE HAS AN ANTIOXIDANT EFFECT, PREVENTS CORROSION DUE TO SULFUR AND ITS DERIVATIVES, PREVENTS THE FORMATION OF LEAD PASTE AND ALSO HAS ANTI-WEAR PROPERTIES. USE OF THIS ADDITIVE IN LUBRICANTS FOR INTERNAL COMBUSTION ENGINES, FOR EXAMPLE.

Description

Multifunctional additive for lubricating oils

  method of preparation and lubricant-containing compositions -

this additive.

  The present invention relates to a multifunctional ashless additive for lubricating oils; The present invention also relates to the process for the preparation of this additive and lubricating oil compositions which contain this additive. The problem of oil deterioration

  lubricants requires careful study of their formulation.

  This is because their deterioration leads to the formation of products that are corrosive to metal surfaces with which the lubricating oils

come into contact.

  In recent years, it has become common practice to incorporate additives into lubricating oils that are capable of preventing deterioration of the oil and the formation of harmful deposits. These additives are generally classified into groups according to their effect on

  the improvement of the lubricating oil.

  Thus, the additives of a group prevent the cor-

  erosion and stabilize the lubricating oil with respect to oxidative degradation Another group includes corrosion inhibitors that oppose the properties of

  corrosive products of degradation of the lubricating oil

  The other group comprises antiwear agents which prevent metal-to-metal contact between the moving metal surfaces. Several additives are often needed to

  to give the lubricating oil a certain number of properties

  This is a disadvantage both for questions of price and for questions of mutual compatibility between additives. Therefore, the classical research is oriented towards the development of so-called multifunctional additives able to give lubricating oils several desirable properties. For example, U.S. Patent No. 2,615,464 discloses lubricating oil compositions comprising an alkylmonothiocyanate to provide oxidation resistance and to prevent corrosion. US Pat. No. 2,719,126 discloses polysulfurethiodiazoles as antioxidants and as anti-wear additives for

lubricating oils.

  O 10 However, it has been discovered that the characteristics

  The antioxidant and anti-wear properties of the known additives are not always entirely satisfactory. There is also some interest in these additives in addition to said characteristics also preventing corrosion and

the formation of lead pellets.

  Therefore, an object of the present invention is an ashless multifunctional additive for lubricating oils which gives a maximum antioxidant and antiwear effect and prevents sulfur induced corrosion and

  its derivatives and the formation of lead pellets.

  Another object of the present invention is a

  process for preparing said additive.

  Another object of the present invention is the provision of lubricating oil compositions containing this

additive.

  Other objects of the invention will appear as

  and as the description and experimental examples

given later.

  More particularly, the multifunctional ashless additive according to the present invention is an organic compound having a molecular weight of between about 300 and about 1200, and containing in its molecule at least one group of this kind having the formula: ## STR1 ##

I I

_C C

S

I I

_, C C

I I

  NCS wherein x is 1 or 2, and the bonds of carbons other than those bound to isocyanic groups, are connected to alkyl radicals or alkyl ester radicals

  carboxylic acid or carbonic acid.

  Preferably, the additive of the present invention is liquid at room temperature (20-25 C) and has a

  molecular weight between 400 and 1000.

  The process for preparing the additive of the present invention comprises reacting mono or sulfur dichloride with a hydrocarbon compound having at least one olefinic double bond in its molecule, or with an alkyl carboxylic acid ester or carbonic acid having at least one olefinic double bond to obtain a sulfochlorinated intermediate and then reacting said intermediate with an alkali metal or ammonium thiocyanate

  Unsaturated hydrocarbons that can be used

  These include linear or branched olefins in general and in particular oligomers of propylene, butane and isobutene and C 4 -C 2 alpha olefins. In the reaction with sulfur mono- or dichloride, terpene hydrocarbons can also be used as well as the alkyl esters of carboxylic acids or carbonic acid which have at least one unsaturated olefinic bond such as oleic acid derivatives, jujube oil, lard oil and carbonic esters unsaturated such as allylalkylcarbonates and oleylalkylcarbonateso The sulfochlorination consists in treating the abovementioned unsaturated compounds with sulfur chlorides and, in particular with sulfur mono- or dichloride. The reaction comprises the addition of the sulphochlorination agent to the unsaturated compound, the actual reaction itself and the final purification According to the reactivity of the unsaturated compound, the reaction Deut be conducted either in the mass or in an inert solvent at a temperature between 0 and 100 C, preferably between 20 and 80 QC for a period of time

between 1 and 10 hours.

  The sulphochlorinated intermediate product obtained in this way can be represented schematically by the following formula:

I I

-C

I I

S

He

_CC -

  C 1 Cl in which x is 1 or 2 The amount of sulfur chloride used in the reaction is at least equal to

  stoichiometric amount to form the intermediate product

diary.

  The reaction between the sulpho

  chlorinated and the sulphocyanide of the alkali metal or ammonium can be carried out either in the mass under homogeneous or heterogeneous conditions, or in a suitable non-reactive solvent at a temperature between 0 and 200 C, for a period ranging from 1 to 10 As regards the proportion of reactants, at least one mole of sulfocyanide is used per gram atom of chlorine in the sulfochlorinated intermediate product. Because of its numerous effects and the absence of ash, the additive of the present invention obtained in this way it can be applied in the most varied fields in which the effect of the lubricant is necessary Thus, it can be used in motor oils, in transmission fluids and hydraulic fluids, in machining oils. metals, etc. at a concentration of between 0.1 and 10% by weight, and

  preferably between 0.3 and 3% by weight.

  In particular, the additive of the present invention can be added to a broad range of lubricants including hydrocarbons of mineral or synthetic origin, carboxylic acid esters, polyglycols, polyolefins, alkyl esters of carboxylic acids and the like. /

  or phosphoric and mixtures thereof in all proportions.

  The additive can be dissolved in the oil in the presence of other agents such as dispersants, detergents, reducing agents, pour point depressants, products

  improving the viscosity index, anti-wear agents, additives

  extreme pressure, anti-foam emulsifiers, etc.

  The use of the additive is particularly suitable

  In the formulation of motor oils in which more than in others its multiple effect is completely used. Non-limiting examples of these formulations are given in the table below:

W / 50 15 W / 40 15 W / 50 SAE 30

  Mineral oil (% by weight) 76 79.1 60.5 91.9

Ester base (% by weight) 15 -

  Detergent-dispersant-inhibitor (% by weight) package 11.9 9.5 8.1 Viscosity index improving polymer

(% by weight) 14 9 15 -

  Constituents may be different for different

formulations.

  The additive of the present invention provides an antioxidant effect, prevents corrosion due to sulfur and its derivatives, prevents the formation of lead paste / and manifest

anti-wear properties.

  The present invention is illustrated by the

  descriptive and nonlimiting examples below.

EXAMPLE 1

  67.5 g (0.5 mole) of sulfur monochloride are added slowly with stirring to 224 g (1 mole) of 1-hexadecene. The reaction is carried out under a nitrogen atmosphere at room temperature for a period of 3 hours. 5 hours until the acid value of the mixture falls to about 3 mg KOH / g. A stream of nitrogen is then passed through the reaction mixture until the acidity

  falls to a value of the order of 0.3 mg KOH / g.

  60.6 g (0.75 mole) of sodium thiocyanate are added to 200 g of the intermediate product thus obtained; containing 24 g of chlorine (0.68 gram atom) The reaction mixture is heated to 160-170 ° C with stirring and in an inert atmosphere and these conditions are maintained for 7 hours. After cooling, the sodium chloride by-product of reaction is filtered using a filter aid The additive of the present invention is then obtained in the form of a liquid

  viscous brown soluble in oil at ordinary temperature.

  The additive obtained in Example 1 increases the

  stability of the oil of degreasing vis-à-vis the oxidation.

  In order to evaluate this characteristic, an oxidation test is used in which

  air according to the modified IP 48 process.

  The parameters of the test are as follows: temperature 175 C, air flow 50 ml / minute, duration 48 hours,

  presence of copper ribbon and iron ribbon.

  The following table shows the viscosity indices

  at 40 C samples before and after the oxidation test.

  and the percentage changes in the viscosity of the samples thus treated. For comparison, the test is also carried out with a thiodiazolpolysulphide additive.

  The results are shown in the table below.

  below: Oil SN 450 as such Additive of Example 1 (0.3%) Additive of Example 1 (1%) Commercial additive (0.3%) Trade additive (1%) Initial V 400 c ( cst) Final V 40 o C (cst) 94.3 94.2 99.6 103.0

  The additive of Example 1 regulates and prevents corrosion

  copper by sulfur and its derivatives.

  In addition, having a high classification point in the ASTM D 130 test, this additive improves that of a sulfochlorinated compound containing active sulfur such as the compound obtained as intermediate in the example.

1 above.

  Additive of Product in Additive + 2 Additive Additive + 1, The results of the tests are as follows: Classification Example 1 (1% by weight) lb intermediate of Example 1 (5% by weight) 4 c Intermediate product (5 + 0.3% by weight) 2 intermediate product (5 + 1% by weight) The additive of Example 1 prevents the formation of

lead pasta.

  This property is evaluated using a lead-point filter on an Alfetta Z motor. A unrefined SAE formulation containing 8.1% by weight of a detergent-dispersant-inhibitor (zinc-sulphonate-polyisobutenyl succinimidedithiophosphate) assembly, which increases the formation of lead pastes, is used as a reference The test results on engine 1 that were obtained after 30 hours, are as follows Merit Forpulation SAE 30 84 Formulation SAE 30 + 0.3% additive of Example 1 98 av (%), 9, 8 17,2 úD The additive of Example 1 has good properties

  anti-wear in the tribological examination.

  In this respect, the results of the pro-

  properties obtained on the LFW-1 machine using the ASTM D 271468 method and on the 4-ball abrasion machine using steel balls, and operating under the following conditions: Angular velocity 126 rad / s Load 40 da N Oil temperature 750 C Test time 1 hour The following results relate to the wear in mm using oil SN 450 such that and oil SN 450 containing 1% by weight of additive of the example By way of comparison, the results are given for an SN 450 oil composition containing 1% by weight of thiodiazolepolysulfide commercial additive. LEV-1 wear abrasion machine (mm) 4 balls us ^ worn diameter (mm)

SN 450 2.96 1.26

SN 450

  SN 450 + 1% of additive of Example 11.03 0.50 SN 450 + 1% of commercial additive 1.40 0.65

EXAMPLE 2

  37.9 g (0.46 mol) of sodium thiocyanide are added to 200 g of sulphochlorinated jujube oil, by the same method as that used in the preparation of the intermediate product of Example 1, and containing 15 g chlorine

(0.42 gram atom).

  The reaction is carried out as in Example 1, until the additive is obtained in the form of a

  very viscous liquid soluble in oil.

EXAMPLE 3

  In a similar manner to the preceding examples, 38.8 g (0.47 mole) of sodium thiocyanate are added to 300 g of sulfochlorinated allyloleylcarbonate containing 15.3 g of chlorine (0.43 gram atom). in Example 1, the additive is obtained in the form of a viscous liquid

Dark brown oil soluble.

  The property of the additive obtained in Examples 2 and 3 is similar to that of the additive obtained in Example 1.

Claims (1)

1 lubricating composition characterized in that it comprises a larger amount of lubricating oil and a smaller amount of an additive consisting of an organic compound having a molecular weight between about 300 and about 1200, which contains in its molecule at least one group of formula -NCS -cc I Io l XI -C wherein x is 1 or 2 let the bonds of the carbons other than those connected to the thiocyanic group are connected to the alkyl radicals or carboxylic acid alkyl ester radicals or carbonic acid. 2 Composition according to Claim 1, characterized in that the additive has a molecular weight of between 40 and 1000. 3 Composition according to Claim 1, characterized in that it contains a quantity of additive of from 0.1 to 10% by weight. 4. Composition according to claim 3, characterized in that the amount of said additive is between 0.3 to 3% by weight. Process for the preparation of the additive for lubricating compositions according to Claim 1, characterized in that it consists in reacting sulfur mono- or dichloride with a hydrocarbon compound containing in its molecule at least one olefinic double bond or with an alkyl ester of a carboxylic acid or carbonic acid which comprises at least one olefinic double bond, to obtain a sulfochlorinated intermediate which is then reacted with an alkali metal or ammonium thiocyanate. Process according to Claim 5, characterized in that the unsaturated hydrocarbon is chosen from linear or branched olefins, oligomers of propylene, butene and isobutene, C 4 -C 24 alpha-olefins and hydrocarbons. terpene. 7 Process according to claim 5, characterized in that the esters of the carboxylic acids or of the carbonic acid are chosen from the derivatives of the oil of jujube oil, the lard oil, the allylalkylcarbonates and the oléylalkylcarbonates. Process according to Claim 5, characterized in that in the preparation of the sulphochlorinated intermediate the reaction temperature is 0 to 100 ° C and is preferably 20 to 80 ° C. 10 hours. Process according to Claim 5, characterized in that the reaction between the sulphochlorinated intermediate product and the alkali metal thiocyanate or ammonium thiocyanate is carried out at a temperature of between 0 and 200 ° C for a period of time between 1 and 10 hours.