CA1047476A - Lubricant additives - Google Patents
Lubricant additivesInfo
- Publication number
- CA1047476A CA1047476A CA197,455A CA197455A CA1047476A CA 1047476 A CA1047476 A CA 1047476A CA 197455 A CA197455 A CA 197455A CA 1047476 A CA1047476 A CA 1047476A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- group containing
- lubricating composition
- compound
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
- C10M135/04—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/34—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for preparing an oil-soluble metal-free phosphorus-free substance for use as a lubricating additive, which comprises sulphurising a compound having the general formula:
A process for preparing an oil-soluble metal-free phosphorus-free substance for use as a lubricating additive, which comprises sulphurising a compound having the general formula:
Description
1~7g76 This invention relates to sulphurised products having utility as lubricant ad~itives and lubricating compositions containing them. The invention also relates to a process for preparing sulphurised products, the . .
products so prepared and lubricating compositions containing such products.
Antioxidant additives used in lubricating oils, particularly, but not exclusively, automotive lubricants, require a combination of properties which is dif~icult ; 10 to meet in practice. Such additives must, of course, impart a high degree of resistance to oxidation to the ~- lubricant, but in addition must be reasonably inexpensive, must be compatible with various other additives commonly used in lubricants, must have adequate thermal stability and must satisfy various other criteria of suitability, such as the ability to protect copper-lead bearings from corrosion. Very many different types of antioxidants have been proposed, and in some cases have been commercially used on a comparatively small scale. However, for many years the type of antioxidants which have been very widely used as the most suitable general purpose antioxidants for automotive and other lubricants are metal, particularly zinc, salts of di-hydrocarbyl dithiophosphoric acids.
Ho-~!ever, the need for lubricant developments to keep pace with engine developments has given rise recently -to difficulties in the use of metal dithiophosphate salts as antioxidant. The metal content of these additives is a source of ash and there is a growing tendency for the quality standards laid do~n by manufacturers and other 3o interested organisations to specify low-ash lubricant formulations for modern engines. Attempts have been made to develop dithiophosphate derivatives, which do not contain
products so prepared and lubricating compositions containing such products.
Antioxidant additives used in lubricating oils, particularly, but not exclusively, automotive lubricants, require a combination of properties which is dif~icult ; 10 to meet in practice. Such additives must, of course, impart a high degree of resistance to oxidation to the ~- lubricant, but in addition must be reasonably inexpensive, must be compatible with various other additives commonly used in lubricants, must have adequate thermal stability and must satisfy various other criteria of suitability, such as the ability to protect copper-lead bearings from corrosion. Very many different types of antioxidants have been proposed, and in some cases have been commercially used on a comparatively small scale. However, for many years the type of antioxidants which have been very widely used as the most suitable general purpose antioxidants for automotive and other lubricants are metal, particularly zinc, salts of di-hydrocarbyl dithiophosphoric acids.
Ho-~!ever, the need for lubricant developments to keep pace with engine developments has given rise recently -to difficulties in the use of metal dithiophosphate salts as antioxidant. The metal content of these additives is a source of ash and there is a growing tendency for the quality standards laid do~n by manufacturers and other 3o interested organisations to specify low-ash lubricant formulations for modern engines. Attempts have been made to develop dithiophosphate derivatives, which do not contain
2.
~ ~047476 . .
metal, in order to meet these requirements. However, such developments have been forestalled, at least to some extent, by yet another development in engine design, namely the use of catalytic devices in engine exhausts to minimise pollution caused by vehicle emissions. The catalysts used in such devices are sensitive to phosphorus compounds and can become poisoned and ineffective if exposed ,;
to s.uch compounds. Consequently, the need has arisen G for antioxidants which do not contain metal or phosphorus, and yet still meet all the requirements for antioxidants formerly satisfied by the metal dithiophosphates.
We have now found certain sulphurised products which are, at least in the preferred embodiments, very effective antioxidants in lubricating compositions such as crankcase lubricants. The sulphurised products are also useful for other purposes, for example as load-carriers in gear oil formulations.
Accordingly in one aspect of the present invention there is provided a lubricating composition containing a major amount of lubricating oil and a minor amount of a ~ulphur containing additive wherein said additive is a sulphur containing norbornenyl compound having the general - formula:
~ R
(h~
R
wherein:
- ~047476 (a) each of R, R2 and R4 when taken singly is a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms or : .
a cycloalkyl group containing from 4 to about 10 carbon atoms;
(b) each of R1 and R3 when taken singly is a hydrogen atom, an alkyl group containing from 1 . . .
to about 15 carbon atoms; an aryl group containing -~ 10 from 6 to about 15 carbon atoms; a cycloalkyl group .
~ containing from 4 to about 10 carbon atoms or ., .
an alkenyl group containing from 2 to about 10 carbon atoms or Rl and R3 taken together form the group -CHY.CY=CY- in which Y is a hydrogen atom or a methyl group or R1 together with R2 form an alkylidene group containing from 1 to ~-about 6 carbon atoms; and -(c) R5 is a hydrogen atom or an alkyl group containing from 1 to about 15 carbon atoms; or, - : .
wherein said additive is the oil-soluble .. . . . . .
. sulphur containing norbornenyl product resulting from sulphurising a compound having the general -: formula:
. R
~ 3 ~ ~O
wherein R, Rl, R2, R3, R and R5 are as hereinbefore 4.
- .
'' - 1047~76 defined at a temperature of up to 180 C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar ~; solvent.
The foregoing compcunds of formula (A) are known compounds and are described in United States Patent No. 3586700, which also describes the preparation of the compounds by sulphurisation of norbornenyl compounds to form the trithiolan derivatives depicted above. The sulphurisation reaction of United States Patent No. 3586700 is carried out necessarily in tne presence of certain highly polar organic solvents.
However, in a very important aspect of the present invention there is prGvided a process for preparing an oil-soluble, metal-free, phosphorus-free substance suitable for use as a lubricant additive, which process comprises sulphurising a compound having the general formula:-R
(O
R Rl R2 R3 R4, and R5 are as hereinbefore defined, at a tempera~lire of up to 180C., said sulpnurisation being carried out in the absence of a solvent or in she presence of a non-polar sovent, and thereafter removing any oil-insoluble constituents from the resulting ~ulphurised product.
, .,. ,.1 .
~.
' ': , ~047476 Examples of compounds which may ~e sulphurised in the process of the present invention are norbornene, 5-vinylnor~ornene, dicyclopentadiene and methyl cyclopentadiene dimer of which dicyclopentadiene and methyl cyclopentadiene dimer are especially preferred.
If desired the process of the present invention may be carried out in the presence of a catalyst of the type common;y used in sulphurisation reactions, for example tertiary amines such as triethylamine or pyridine, secondary amines such as di-isopropylamine, di-butylamine, and di-cyclohexylamine and primary amines such as cyclo- -hexylamine and the~, ~-dimethyl tertiary alkyl primary amines available commercially under such trade names as :~ Primene JM-T and Primene 81-R. Other catalysts which may be used include:-2,5 - Dimercapto - 1,3,4,- thiadiazole 2,5 - Dimercapto 1,2,4- thiadiazole 2,5 - Bis(t-octyldithio) - 1,3,4- thiadiazole Mercaptobenzothiazole Sulphide ions, e.g. provided by sodium sulphide - Alkanolamines Diphenyl guanidine - A Mixture o~ NaOH and mercaptobenzothiazole peroxide such as the material marketed as ter~iary butyl hydroperoxide consisting of about 70% of that - peroxide together with about 30% di-t-butyl peroxide Farti.^ular]y preferred catalysts are combinations of an amine and a thiadiazole derivative.
m e amount of catalyst used is not critical, but normally will be about 0.1 to 20%, for example, from 2 to 10%
more preferabiy 0.1 to 10% and most preferably 0.3 to 2%, , . . , ,-....
J
: ~047~'7~;
by weight based on the weight of the compound to be sulphurised.
The process of the present invention may also be carried out in the presence of a small amount, e.g. not ~ore than 25 molar percent based on the compound to be sulphurised, of a solubilising agent. Examples of solubilising agents which may be used are:-Conjugated d -or poly-olefins such as alloocimene (1,5-dimethyl-2,4,6-octatriene) Non-conjugated di-or poiy olefins such as 1,5,9-., .
cyclododecatriene and 1,s-cyclooctadiene Dialkyl ma'eates, preferably containing from 1 to 12, more preferably 4 to 8, carbon atoms in each alkyl group, e.g. dibutyl maleate Alkenyl succinic acids or anhydrides thereof, preferably containing 8 to 12 carbon atoms in the alkenyl group, such as dodecenyl succinic acid Alkyl mercaptans, preferably containing 8 to 12 ,. . .
carbon atoms such as t-dodecyl mercaptan Polyisobutenyl succinimides Mercaptobenzothiazole Benzothiazole disulphide ~- Alkenoic acids, preferably containing ~rom 8 to 18 carbon atoms such as oleic acid Alkyl esters of alkenoic acids such as octyl methacrylate Ethoxylated amines such as the material available comrr.e-cially lmde~ the trade name Ethomeen T15 Dimerised alkenoic acids, preferably containing from 18 to 36 carbon atoms Dicyclopentadiene hydrate Alkanols, such as isodecanol.
7~76 Such solubilising agents may assist in increasing the proportion of oil-soluble constituents in the product of the sulphurisation reaction and, when used, will normally be present in an amount of 1 to 25, preferably 2 to 15, molar percent. Within this range it is preferred to use as small an amount of solubilising agent as possible consistent with obtaining a reasonable amount of oil-soluble product (for example not more than 25-30/o by weight, preferably less, of the product should be oil-insoluble). The effectiveness of the solubilising agent has been found to be dependent in part on the proportion of sulphur used in the sulphurisation reaction, effectiveness decreasing with increasir.g proportions of sulphur used. Moreover, as exemplified -hereinafter some solubilising agents are more effective than others and solubilising agentssuch as alloocimene, dibutyl maleate, dodecenyl succinic acid, t-dodecyl B mercaptan, Ethomeen T15, oleic acid and mercaptobenzothiazole are most preferred.
In the process of the present invention the sulphur - 20 is preferably used in an amount of from 0.1 to 4 moles per mole of compound to be sulphurised, with an amount cf about 1 to 2 mcles per mole of compound to be sulphurised ; being most preferred. m e sulphurisation can be conveniently carried out by merely mixing the reactants, including any catalyst, and/or solub lising agent used, and heating. Alternatively, the compound to be sulphurised can be added to hot sulphur. However, when using a rel~t,ively high amount of sulphur, i.e. an amount in the upper end of the preferred range, it is preferred to add the
~ ~047476 . .
metal, in order to meet these requirements. However, such developments have been forestalled, at least to some extent, by yet another development in engine design, namely the use of catalytic devices in engine exhausts to minimise pollution caused by vehicle emissions. The catalysts used in such devices are sensitive to phosphorus compounds and can become poisoned and ineffective if exposed ,;
to s.uch compounds. Consequently, the need has arisen G for antioxidants which do not contain metal or phosphorus, and yet still meet all the requirements for antioxidants formerly satisfied by the metal dithiophosphates.
We have now found certain sulphurised products which are, at least in the preferred embodiments, very effective antioxidants in lubricating compositions such as crankcase lubricants. The sulphurised products are also useful for other purposes, for example as load-carriers in gear oil formulations.
Accordingly in one aspect of the present invention there is provided a lubricating composition containing a major amount of lubricating oil and a minor amount of a ~ulphur containing additive wherein said additive is a sulphur containing norbornenyl compound having the general - formula:
~ R
(h~
R
wherein:
- ~047476 (a) each of R, R2 and R4 when taken singly is a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms or : .
a cycloalkyl group containing from 4 to about 10 carbon atoms;
(b) each of R1 and R3 when taken singly is a hydrogen atom, an alkyl group containing from 1 . . .
to about 15 carbon atoms; an aryl group containing -~ 10 from 6 to about 15 carbon atoms; a cycloalkyl group .
~ containing from 4 to about 10 carbon atoms or ., .
an alkenyl group containing from 2 to about 10 carbon atoms or Rl and R3 taken together form the group -CHY.CY=CY- in which Y is a hydrogen atom or a methyl group or R1 together with R2 form an alkylidene group containing from 1 to ~-about 6 carbon atoms; and -(c) R5 is a hydrogen atom or an alkyl group containing from 1 to about 15 carbon atoms; or, - : .
wherein said additive is the oil-soluble .. . . . . .
. sulphur containing norbornenyl product resulting from sulphurising a compound having the general -: formula:
. R
~ 3 ~ ~O
wherein R, Rl, R2, R3, R and R5 are as hereinbefore 4.
- .
'' - 1047~76 defined at a temperature of up to 180 C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar ~; solvent.
The foregoing compcunds of formula (A) are known compounds and are described in United States Patent No. 3586700, which also describes the preparation of the compounds by sulphurisation of norbornenyl compounds to form the trithiolan derivatives depicted above. The sulphurisation reaction of United States Patent No. 3586700 is carried out necessarily in tne presence of certain highly polar organic solvents.
However, in a very important aspect of the present invention there is prGvided a process for preparing an oil-soluble, metal-free, phosphorus-free substance suitable for use as a lubricant additive, which process comprises sulphurising a compound having the general formula:-R
(O
R Rl R2 R3 R4, and R5 are as hereinbefore defined, at a tempera~lire of up to 180C., said sulpnurisation being carried out in the absence of a solvent or in she presence of a non-polar sovent, and thereafter removing any oil-insoluble constituents from the resulting ~ulphurised product.
, .,. ,.1 .
~.
' ': , ~047476 Examples of compounds which may ~e sulphurised in the process of the present invention are norbornene, 5-vinylnor~ornene, dicyclopentadiene and methyl cyclopentadiene dimer of which dicyclopentadiene and methyl cyclopentadiene dimer are especially preferred.
If desired the process of the present invention may be carried out in the presence of a catalyst of the type common;y used in sulphurisation reactions, for example tertiary amines such as triethylamine or pyridine, secondary amines such as di-isopropylamine, di-butylamine, and di-cyclohexylamine and primary amines such as cyclo- -hexylamine and the~, ~-dimethyl tertiary alkyl primary amines available commercially under such trade names as :~ Primene JM-T and Primene 81-R. Other catalysts which may be used include:-2,5 - Dimercapto - 1,3,4,- thiadiazole 2,5 - Dimercapto 1,2,4- thiadiazole 2,5 - Bis(t-octyldithio) - 1,3,4- thiadiazole Mercaptobenzothiazole Sulphide ions, e.g. provided by sodium sulphide - Alkanolamines Diphenyl guanidine - A Mixture o~ NaOH and mercaptobenzothiazole peroxide such as the material marketed as ter~iary butyl hydroperoxide consisting of about 70% of that - peroxide together with about 30% di-t-butyl peroxide Farti.^ular]y preferred catalysts are combinations of an amine and a thiadiazole derivative.
m e amount of catalyst used is not critical, but normally will be about 0.1 to 20%, for example, from 2 to 10%
more preferabiy 0.1 to 10% and most preferably 0.3 to 2%, , . . , ,-....
J
: ~047~'7~;
by weight based on the weight of the compound to be sulphurised.
The process of the present invention may also be carried out in the presence of a small amount, e.g. not ~ore than 25 molar percent based on the compound to be sulphurised, of a solubilising agent. Examples of solubilising agents which may be used are:-Conjugated d -or poly-olefins such as alloocimene (1,5-dimethyl-2,4,6-octatriene) Non-conjugated di-or poiy olefins such as 1,5,9-., .
cyclododecatriene and 1,s-cyclooctadiene Dialkyl ma'eates, preferably containing from 1 to 12, more preferably 4 to 8, carbon atoms in each alkyl group, e.g. dibutyl maleate Alkenyl succinic acids or anhydrides thereof, preferably containing 8 to 12 carbon atoms in the alkenyl group, such as dodecenyl succinic acid Alkyl mercaptans, preferably containing 8 to 12 ,. . .
carbon atoms such as t-dodecyl mercaptan Polyisobutenyl succinimides Mercaptobenzothiazole Benzothiazole disulphide ~- Alkenoic acids, preferably containing ~rom 8 to 18 carbon atoms such as oleic acid Alkyl esters of alkenoic acids such as octyl methacrylate Ethoxylated amines such as the material available comrr.e-cially lmde~ the trade name Ethomeen T15 Dimerised alkenoic acids, preferably containing from 18 to 36 carbon atoms Dicyclopentadiene hydrate Alkanols, such as isodecanol.
7~76 Such solubilising agents may assist in increasing the proportion of oil-soluble constituents in the product of the sulphurisation reaction and, when used, will normally be present in an amount of 1 to 25, preferably 2 to 15, molar percent. Within this range it is preferred to use as small an amount of solubilising agent as possible consistent with obtaining a reasonable amount of oil-soluble product (for example not more than 25-30/o by weight, preferably less, of the product should be oil-insoluble). The effectiveness of the solubilising agent has been found to be dependent in part on the proportion of sulphur used in the sulphurisation reaction, effectiveness decreasing with increasir.g proportions of sulphur used. Moreover, as exemplified -hereinafter some solubilising agents are more effective than others and solubilising agentssuch as alloocimene, dibutyl maleate, dodecenyl succinic acid, t-dodecyl B mercaptan, Ethomeen T15, oleic acid and mercaptobenzothiazole are most preferred.
In the process of the present invention the sulphur - 20 is preferably used in an amount of from 0.1 to 4 moles per mole of compound to be sulphurised, with an amount cf about 1 to 2 mcles per mole of compound to be sulphurised ; being most preferred. m e sulphurisation can be conveniently carried out by merely mixing the reactants, including any catalyst, and/or solub lising agent used, and heating. Alternatively, the compound to be sulphurised can be added to hot sulphur. However, when using a rel~t,ively high amount of sulphur, i.e. an amount in the upper end of the preferred range, it is preferred to add the
3 , sulphur in portions over an initial period to the compound to be sulphurised maintained at the reaction temperature and then to continue maintaining the reaction temperature ~rc~Jer~ark 8.
for a further period.
In general a reaction temperature of at least 60C. is preferred, with at least 90C. or 100C. being ; most preferred for providing the preferred sulphurised materials as hereinbefore described. Also, a reaction temperature no greater than 160C is preferred.
Sulphurisation is normally completed in from 0.5 to 24 hours depending on the reaction temperature. At the optimum temperature of about 110C. to 140C. a reaction time of about 2 hours is generally found to be most satisfactory, the co-reactants either being mixed and heated for 2 hours or the sulphur being added to the compound to be sulphurised in portions over, for example 1 hour at 120C and thi~ temperature then being rnaintained for a further hour.
The sulphurisation may, if desired, be carried out in an inert atmosphere such as a nitrogen blanket.
The-pressure at which the sulphurisation is carried out i8 not critical, but is preferably not reduced to a level at which significant amounts of the compound being sulphurised are lost from the reaction system by distillation.
Although it is preferred to carry out the ~-sulphurisation in the absence of a solvent .it is also possible to carry out the reaction in the presence of a non-polar solvent, examples of the latter being petroleium ether, toluene, benzene,XYlene and mineral oil (especially a mineral lubricating oil).
After comp~ef ' on of the sulphu isatior. any oi;-insoluble constituent of the product may be remove~ by ~-any convenient method using well known-techniques such as solvent exbraction or dissolving in oil followed by filtration.
9.
.' . '' ~o474 ~6 However, if the reaction ;s carried out under careful , control at the optimum conditions the whole product is frequently oil-soluble and removal of oil-insoluble constituents is not necessary. Accordingly, reference made herein and in the appended claims to removal of oil-insoluble constituents is to be understood to mean, unless the context denotes otherwise, removal of oil-insoluble constituen~s if, and as, necessary.
- A preferred technique for removal of oil-insoluble ' 10 by products is to initially strip off excess olefin which ~; would otherwise solubilize the insoluble component and to then add excess petroleUm ether to precipitate an . insoluble phase which can be removed. The petroleum ether is then stripped off co yield a~otallyoil-soluble product.
In a preferred embodiment of the invention dicyclopentadiene is sulphurised using 2 moles of sulphur per mole of dicyclopentadiene at a temperature of about ~- 120C using di-isopropylamine and 2,5- bis(t-octyl-dithio)-1,3,4- thiadiazole as catalysts, and, optionally, one Or the most preferred solubilisers listed above.
In a further aspect the present invention also includes the oil-soluble, metal-free, phosphorus-free products prepared by the process of the present invention.
It is to be understood that as with all chemical substances purity, in an absolute sense, is impossible to achieve and the sulphurised olefins of the present invention may contain, as a result of contaminants present in the starting materials, a trace of metal and'or pnosphorus.
However, such traces should be present in such minute quantities as to be of no practical significance and it is to be understood that the starting materials should not be grossly contamin~ted with metal and/or phosphorus compounds.
10 .
, .
However, commercially available grades of starting materials are normally completely adequate in this respect and any contamination arising therefrom is far . .
below any level of practical significance.
The products of the process of the present invention preferably contain from about 15 to 40% by weight of sulphur and reaction conditions and proportions of co-reactants may be adjusted in order to vary the sulphur content of the product. Further the products of the process of the present invention are believed to contain substantial amounts of the trithiolan derivatives hereinbefore depicted in formula (A).
Preferably the lubricating compositions of the present invention comprise from 0.1% to 10%,more preferably 0.25% to 5%, by weight of the oil-soluble, metal-free, phosphorus-free products and/or compounds of foregoing formula (A) and the Iubricating oil may be any of the ~ell known mineral or synthetic oils of appropriate viscosity characteristics.
It will be understood that the lubricating compositions of the present invention may also contain, if desired, conventional lubricant additives such as ancillary antioxidants and anti-wear additives (preferably ashless), corrosion inhibitors, dispersants, particLlarly dispersants f the succinimide type, detergents, thickeners, pour-point depressants and viscosity index improvers. A particularly useful additive to be used in conjunction with the additives of the present invention is benzotriazole whic~ has been found to reduce lacquer formation and improve the appearance of bearings in test engines lubricated with compositions of the present invention. The benzotriazole may, if desired, , 11 . ' - .
i :~
~047476 be incorporated prior to the sulphurisation reaction of the present invention or after sulphurisation but either before or after the removal of any oil-insoluble ` constituents.
.
The additlves of the present invention may also be conveniently prepared as a concentrate consisting of a concentrated solution of a major amount of the :
~- additives and a minor amount of mineral oil, or as an .
additive package consisting of a concentrated solution , 10 in mineral oil of a major amount of a combination of the additives with one or more conventional additives. Such concentrates and packages are frequently very convenient ~orms in which to handle and transport additives and are diluted with further quantities of oil, and optionally blended with further additives, before use.
Hence in accordance with another aspect of the ` invention there is provided a solution comprising a -L major amount of one or more compounds having the formula (A) or one or more of the oil-soluble metal free, phosphorus-free products of the process of the invention and a minor amount of a lubricating oil.One or more conventional additives may be combined with the compounds of formula (A) or the oil soluble, metal-free, phosphorus-free products.
The present invention will now be illustrated with reference to the following examples:-A mixture of dicyclopentadiene (264g.;n 2.0m) and triethylamine catalyst (13.2g) was added dropwise over a period of one hour to sulphur (128g., 4.0m) maintained at a temperature of about 140C. About half-way through this .. . .
` ~047476 addition an exotherm to 155C. was noticed and this was quickly controlled by air blast cooling and no further problems were encountered during the remainder of the addition. After completion of the ~ddition the resulting reaction mixture was maintained at 140-145C. for a further one hour, whereafter about 0.2g hydroquinone was added to the resulting crude product.
me crude product was stripped under high vacuum (0.2mm. Hg) to a base temperature of 160C. (internal temperature 140C.) to yield 33.0g (8.4% by weight) of a distillate (predominantly unreacted dicyclopentadiene).
:~,s i The residue was placed in a 1 litre separating funnel together with an amount of petroleum ether (B.Pt. 62-68C.) 7~ sufficient to substantially fill the funnel resulting in 15 a viscous, oily, petroleum ether-insoluble layer (yield 212.1g., 54.1% by weight) anl a petroleum ether layer.
The latte. was separated and the petroleum ether stripped off to yield 149.2g. (38.2% by weight) of the final, oil-soluble product containing 32.5% sulphur.
;; 20 EXAMPLE 2 Dicyclopentadiene (264g., 2.m) was added dropwise over a period of 40 minutes to sulphur (64g.2.Om) - at 145C. The resulting reaction mixture was maintained at 145C. for a further hour and about ~.2g. hydroquinone added to the resulting crude product which was cooled and then stripped under high vacuum to a base temperature of 140C. to yield 180g (55.0% by weight) of unreacted dicyclopentadiene as distillate. The residue was wcrked up in the same manner as in Example 1 to yield 66.3g.
(20.2% by weight) of soluble material containing 31.0%
sulphur and 18.9g (5.8% by weight) of oil insoluble product.
' 1047~76 Dicyclopentadiene ~64g., 2.0m), sulphur(64g., 2.0m) and triethylamine catalyst (13.2g.) were mixed - and heated to 145C. for 2 hours. The resulting crude product was cooled slightly and about 0.2g hydroquinone . added thereto. The crude product was then cooled and worked up in the same manner as in Example 2 to yield ; 116.7g (35.6% by weight) distillate, 53.2g (16.2% by weight) insoluble material and 155.0g (47.4% by weight) oil-soluble product containing 27.7% sulphur.
..
Dicyclopentadiene ~238g., 1.8m) sulphur (64g., 2.0m), triethylamine catalyst (14.2g.) and, as solubilising agent, dibutyl maleate (45.6g 0.2m) were mixed and heated to 140-150C. for 2 hours. Hydroquinone (about 0.2g) was added to the crude product which was then stripped to - 120C. at 0.2mm Hg. to yield 83g. (23.9% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield about lg. insoluble material and 250.3g (72.0% by weight) oil-soluble product containing 24.7% sulphur.
Further preparations were carried out in the -mannér of Exa~ple 4 and details thereof are given in the following Table 1.
.'~ mixture of dicyGlopentadiene (178g., 1;35m) dibutyl maleate (34.2g., 0.15m.) and triethylamine (10.6g.) was heated to 140C. and suiphur (72g., 2.25m) was added thereto over a period of 50 minutes during which the temperature was maintained at 140C. The temperature was 14.
- !
:
1~47~76 )t maintain~d at 140C. for a further 70 minutes whereafter 0.2g. hydroquinone was added and the crude product stripped to 150C. (140C. internal temperature) at O.lmm Hg. to yield 57g. (20.1% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield 32.6g. (11.5% by weight) insoluble material and 184.3g.
;, (64.8% by weight) oil-soluble product containing 28.4%
sulphur.
,; . .
EXAMPLE 16 to 30 - 10 ~urther preparations were carried out in the -manner of Example 15 and details thereof are given in the following Table 2.
Sulphur (144g. 4.5m.) was added incrementally over a period of 1 hour to a mixture of dicyclopentadiene (356g., 2.7m.) dibutyl maleate (68.4g., 0.3m.) triethylamine (21.2g.) and 2,5-dimercapto -1,3,4- thiadiazole (4.2g.) at a temperature of 160C. The reaction mixture was then ,' .
maintained at 160C. for a further hour, whereafter it was stripped up to 110C. on a rotary evaporator under .
water pump vacuum (about 30mm Hg) to yield 2g. of distillate ~excess dicyclopentadiene). The product was extracted with three times its volume of petroleum ether (boiling point 62-68C.) yielding 75.1g. (13.7%) of insoluble material and petroleum ether stripped off the extract to yield 472.3g. (83%) of soluble material containing 25.0%S.-Example 31 was repeated except in tha~ the reaction temperature was kept at 90C. and extraction with petroleum ether was nct carried out to yield 184g. (50.4%) excess cyclorentadiene, no insoluble material and 386g. (68.o%) soluble product containing 35.5%S.
15.
"
)47~76 , Example 32 was repeated, except in that the .
,, reaction temperature was kept at 120 C., to yield 120g ^ excess cyclopentadiene, no insoluble material and 455g.
t 5 (80%) soluble product containing 31.9%S.
EXAMPLE 34 to 42 Further preparations were carried out in the manner of Example 33 and details thereof are given in the , following Table 3.
Sulphur (172.8g., 5.4m.) was added incrementally over 1' hours, at a temperature of 90 C., to a mixture of dicyclopentadiene (356g., 2.7m.), dibutyl maleate (68.4g., O. 3M. ) di-isopropylamine (5g.) and sodium sulphide powder (5g.). The reaction mixture was then stirred for a further 2 hours with the reaction temperature maintained in the range of 85-90C. me resulting product was then filtered and stripped to 120 C. under water pump vacuum to yield 83g. distillate (excess dicyclopentadiene). The ;.20 stripped product (462g.) was not fully oil soluble and was therefore boiled with 1~ litres petroreum ether to yield 350g. (59%) of soluble product containing 33.8%S.
EXAMPLE _44 Dic-lclopentadiene (356g., 2.7m), dibutyl maleate (68.4g., 0.3m), diisopropylamine (4g) and 2,5-bis (t-octyldithio) -1,3,4,-thiadiazole were dissolved in toluene (500ml) and sulphur (172. 8g., 5.4m) added thereto incrementally over 1 hour while maintaining a reaction temperature of 120 C. The reaction mixture was then stirred 3 for a further 1 hour at 120 C. and vacuum stripped (removing toluene at 100 C. and excess dicyclopentadiene at 120C.) 16.
~4747~
to yield 461g. (76.7%) soluble product containing 34.1%S, Example 44 was repeated using 500 ml petroleum ether (boillng point 80-100C.) in place of the toluene.
- 5 The reaction temperature was maintained in the range of 100-110C. throughout due to the volatility of the solvent.
In this way was obtained 469.9g. (78.2%) of soluble product containing 36.2%S.
Dicyclopentadiene (178g. 1.35m), dibutyl maleate (34.2g., 0.15m), di-isopropylamine (2g.) and 2,5-bis (octyldithio) -1,3,4-thiadiazole (2g) were dissolved in 200g. of high viscosity index 100 Solvent Neutral mineral oil. Sulphur (86.4g., 2.7m) was added incrementally over 1 hour at 110-120C. and the reaction ~emperature maintained at 120C. for a further 1 hour. The product was vacuum stripped and filtered to yield 461g. (92.4%) of oil soluble product containing 19.0%S.
Dicyclopentadiene (178g., 1.35m), dibutyl maleate (34.2g., 0.15m) di-isopropylamine (2g) were dissolved in 250ml toluene. Sulphur (129.6g. 4.05m) was added thereto over ~ hour at 110-120C. and the resulr,ing mixture stirred for a further 1~ hours at 120CC. After vacuum ?5 stripping and filtration 300g (88%) of product containing 39.9%S was obtained. This gave a hazy solution in mineral oil indicating the presence of a very low level of insoluble material.
3C Example 44 was repeated except in that 172.8g.
(5.4m) sulphur was used and a reaction temperature of 110C.
:::
~;
: was used. There was obtained 191.4g. (49.9%) soluble . product and 138.6g (36.1%) insoluble product. -3: EXAMPLE 49 ~$ 5-Vinylnorbornene (84g. 0.7m), di-isopropylamine (4.0g.) and 2,5-bis (t-octyldithio) -1,3,4,-thiadiazole :,:
(o.8g.) were mixed, heated to 130C. and sulphur (22.4g., -` 0.7m) added thereto portionwise over 1 hour. The -temperature was maintained at 130C. for a further 1 hour and the reaction mixture was stripped to 100C. at O.lmm Hg. to remove 20.8g. (19.6%) unreacted 5-vinylnorbornene.
The product was extracted with 250ml petroleum ether (boiling point 62-68C.) and filtered to remove a small ` quantity of insoluble material. The petroleum ether was i stripped frotn the extract to yield 51g (48%) of soluble ~- 15 product , . . .
,..:
~- In some of the foregoing examples (1 to 5, 9 11 and 18) a small quantity of hydroquinone was added to the crude product of the sulphurisation reaction since it was thought that the reaction proceeded by a free radical mechanism and that continuation of a free radical reaction during working up of the crude product could lead to some degradation. The hydroquinone was therefore used ~-to suppress free radical reaction. However, subsequent .,, ~.
experiences ~ndicated that the use of hydroquinone did not materially improve the additive preparation.
Various products of the foregoing examples were s tested to determine their suitability as lubricant additives.
Petter WI Engine testr were carried out by the Institute of Petroleum's method IP 176/69 using an ashless blend consisting of a commercially available succinimide-type dispersant, a secondary aromatic amine antioxidant and a 18.
~.V47~ :
combination of corrosion inhibitors together with 1.0%
by weight of the test additive all dissolved in a 500 l-Solvent Neutral mineral oil. Bearing weight losses afte a 36 houF test were measured and were as follows:
; Test AdditiveBearing Test Bearing [
~ Weight Additive Weight Loss (mg) Loss (mg.) 1.
Product of Example 1 9 Product of EY.ample 15 12 " 3 17.4 " n - 16 -8 " " " 4 9 " " '' 19 8 ~-" "' 5 75 ~ t n 21 3 ~-" " " 6 8 22 -17 i " " " 8 7 " " " 24 19 l~
11 5 " " " 30 9 - " " " 12 5 '' " " 37 13 i' " " 14 10 Extended WI tests were carried out for typical test / additives (in the same blends) by the same method except _ that oil samples removed from time to time were not replaced.
~04 ;~'76 :
. Bearing Weight Losses were as follows:-" . .
Test Additive Bearing Weight Loss (mg.) 36 hours 72 hours 108 hours Product of Example 29 10 19 28 " " " 30 22 28 51 .: " " " 42 10 17 20 In comparison a typical fully-formulated .; commercially available lOW/50 oil containing a zinc dialkyl :.
dithiophosphate as antioxidant, a succinimide-type dispersant, a metal sulphonate detergent, a polymethacrylate viscosity index improver and a combination of corrosion inhibitors gave bearing weight losses in this test of 15mg, 27mg and 68mg at 36,72 and 108 hours respectively.
; 15 Load carrying properties were determined using the Timken OK load test according to the IP240/69T method (except in that results are quoted in lbs.) The test blends con8isted of test additive diæsolved in 150 Solvent Neutral mineral oil, the former being in amount to provide 0.3% by weight sulphur in the test blend and the results were as follows:-Test Additive ~i~kln OK Load (lbs) None (h~se oil only) 12 Product o~ Example 5 ~ 30 / " " " 6 ~5-" ,. ~ 8 20.
-~ 7~6 :
: , , . ll " 19 45 ~` " " " 23 40 " " " 33 40 .
. .
.,~ , .
In comparison commercially available zinc dialkyl dithiophosphates usually give Timken OK loads of 35-40 lbs in this test.
.,, :, . .
Rotary Bomb TestScarried out by the IP229/68T
.. 5 method on blends consisting of 2.0% by weight test additive dissolved in 500 Solvent Neutral mineral oil gave the following induction periods:-. ' , .
Test Additive Induction Period (minutes) i 10 None (base oil only) 35 Product of Example 5 99 " " " 11 178 ~ " " 1 190 (25 p.s.i. loss~
.. " " 19 216 (25 " "
. " " " 23 112 (25 " "
Copper strip tests were carried out by the ASTM
method except in that a temperature of 120C. was used. The blends tested consiS~e~ of sufficient test additive to provide a blend containing 0.15%S dissolved in a 500 Solvent Neutral or a 150 Solven'c Neutral mineral oil. ASTM ratings after 3 hours were as follows:-21, 1~3~ 6 , Test Additive RatingTest Additive Rating .; , ~ , ~
None (bace oil only) 2bProduct of Example 18 2e Produc~ of Exa~ple 1 2a 19 2e " " " 4 2e " " " 21 1b ' " " " 5 2e " " ~ 22 2e " " " 6 1b n ~ ~ 23 3b " " " 8 1b " " " 24 1b " " " 11 2e " " " 30 1b " " " 12 2e " " " 33 1b " " " 14 2b/c " " " 37 2c/3a n n n 15 1b/3a 42 1b " " " 16 3b " " " 49 2a From the foregoing test results it can be seen that the additives of the present invention impart antioxidant properties (Rotary Bomb Test) and yet have a low level of corrosiveness (Copper Strip Test) despite the high sulphur content. Furthermore in the standard tests the additives demonstrate load carrying abilities (~imken OX load Test) and test engine performance (Peter WI Tests) in fully formulated blends similar to those exhibited by the zinc dialkyl dithiophosphateSnormally used in premium grade -~ crank~se lubricants.
, 22, ~3~7~76 ; The suitability of the additives of the present invention for use in gear oil formulations was determined - by use of the S.A.E. test~ in which two parallel shafts are provided with interengaging surfaces lubricated with . . .
the test blend and are driven at speeds in a ratio of 14.6:1. After a short running period the load on the interengaging surface is incrementally increased until scurfing occurs. With a blend consisting of an S.A.E.
90 base oil, 4.5% by weight of an additive in accordance with the present invention (containing 30.3%S) and 0.5%
by weight di-isopropyl phosphite scuffing resulted at 2451b and 2301b (duplicate tests) at a drive shaft speed of 1,000 r.p.m. Under the same condition a blend consisting of the same base oil containing 4.5% by weight sulphurised isobutylene (a commercially available gear oil additive containing 45%S) and 0.5% by weight di-isopropyl - phosphite resulting in scuffing at 2651b and 310 lb. Thus , the blend containing the additive according to the present invention produced similar test results even though the sulphur content was substantially less than in the comparison blend.
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for a further period.
In general a reaction temperature of at least 60C. is preferred, with at least 90C. or 100C. being ; most preferred for providing the preferred sulphurised materials as hereinbefore described. Also, a reaction temperature no greater than 160C is preferred.
Sulphurisation is normally completed in from 0.5 to 24 hours depending on the reaction temperature. At the optimum temperature of about 110C. to 140C. a reaction time of about 2 hours is generally found to be most satisfactory, the co-reactants either being mixed and heated for 2 hours or the sulphur being added to the compound to be sulphurised in portions over, for example 1 hour at 120C and thi~ temperature then being rnaintained for a further hour.
The sulphurisation may, if desired, be carried out in an inert atmosphere such as a nitrogen blanket.
The-pressure at which the sulphurisation is carried out i8 not critical, but is preferably not reduced to a level at which significant amounts of the compound being sulphurised are lost from the reaction system by distillation.
Although it is preferred to carry out the ~-sulphurisation in the absence of a solvent .it is also possible to carry out the reaction in the presence of a non-polar solvent, examples of the latter being petroleium ether, toluene, benzene,XYlene and mineral oil (especially a mineral lubricating oil).
After comp~ef ' on of the sulphu isatior. any oi;-insoluble constituent of the product may be remove~ by ~-any convenient method using well known-techniques such as solvent exbraction or dissolving in oil followed by filtration.
9.
.' . '' ~o474 ~6 However, if the reaction ;s carried out under careful , control at the optimum conditions the whole product is frequently oil-soluble and removal of oil-insoluble constituents is not necessary. Accordingly, reference made herein and in the appended claims to removal of oil-insoluble constituents is to be understood to mean, unless the context denotes otherwise, removal of oil-insoluble constituen~s if, and as, necessary.
- A preferred technique for removal of oil-insoluble ' 10 by products is to initially strip off excess olefin which ~; would otherwise solubilize the insoluble component and to then add excess petroleUm ether to precipitate an . insoluble phase which can be removed. The petroleum ether is then stripped off co yield a~otallyoil-soluble product.
In a preferred embodiment of the invention dicyclopentadiene is sulphurised using 2 moles of sulphur per mole of dicyclopentadiene at a temperature of about ~- 120C using di-isopropylamine and 2,5- bis(t-octyl-dithio)-1,3,4- thiadiazole as catalysts, and, optionally, one Or the most preferred solubilisers listed above.
In a further aspect the present invention also includes the oil-soluble, metal-free, phosphorus-free products prepared by the process of the present invention.
It is to be understood that as with all chemical substances purity, in an absolute sense, is impossible to achieve and the sulphurised olefins of the present invention may contain, as a result of contaminants present in the starting materials, a trace of metal and'or pnosphorus.
However, such traces should be present in such minute quantities as to be of no practical significance and it is to be understood that the starting materials should not be grossly contamin~ted with metal and/or phosphorus compounds.
10 .
, .
However, commercially available grades of starting materials are normally completely adequate in this respect and any contamination arising therefrom is far . .
below any level of practical significance.
The products of the process of the present invention preferably contain from about 15 to 40% by weight of sulphur and reaction conditions and proportions of co-reactants may be adjusted in order to vary the sulphur content of the product. Further the products of the process of the present invention are believed to contain substantial amounts of the trithiolan derivatives hereinbefore depicted in formula (A).
Preferably the lubricating compositions of the present invention comprise from 0.1% to 10%,more preferably 0.25% to 5%, by weight of the oil-soluble, metal-free, phosphorus-free products and/or compounds of foregoing formula (A) and the Iubricating oil may be any of the ~ell known mineral or synthetic oils of appropriate viscosity characteristics.
It will be understood that the lubricating compositions of the present invention may also contain, if desired, conventional lubricant additives such as ancillary antioxidants and anti-wear additives (preferably ashless), corrosion inhibitors, dispersants, particLlarly dispersants f the succinimide type, detergents, thickeners, pour-point depressants and viscosity index improvers. A particularly useful additive to be used in conjunction with the additives of the present invention is benzotriazole whic~ has been found to reduce lacquer formation and improve the appearance of bearings in test engines lubricated with compositions of the present invention. The benzotriazole may, if desired, , 11 . ' - .
i :~
~047476 be incorporated prior to the sulphurisation reaction of the present invention or after sulphurisation but either before or after the removal of any oil-insoluble ` constituents.
.
The additlves of the present invention may also be conveniently prepared as a concentrate consisting of a concentrated solution of a major amount of the :
~- additives and a minor amount of mineral oil, or as an .
additive package consisting of a concentrated solution , 10 in mineral oil of a major amount of a combination of the additives with one or more conventional additives. Such concentrates and packages are frequently very convenient ~orms in which to handle and transport additives and are diluted with further quantities of oil, and optionally blended with further additives, before use.
Hence in accordance with another aspect of the ` invention there is provided a solution comprising a -L major amount of one or more compounds having the formula (A) or one or more of the oil-soluble metal free, phosphorus-free products of the process of the invention and a minor amount of a lubricating oil.One or more conventional additives may be combined with the compounds of formula (A) or the oil soluble, metal-free, phosphorus-free products.
The present invention will now be illustrated with reference to the following examples:-A mixture of dicyclopentadiene (264g.;n 2.0m) and triethylamine catalyst (13.2g) was added dropwise over a period of one hour to sulphur (128g., 4.0m) maintained at a temperature of about 140C. About half-way through this .. . .
` ~047476 addition an exotherm to 155C. was noticed and this was quickly controlled by air blast cooling and no further problems were encountered during the remainder of the addition. After completion of the ~ddition the resulting reaction mixture was maintained at 140-145C. for a further one hour, whereafter about 0.2g hydroquinone was added to the resulting crude product.
me crude product was stripped under high vacuum (0.2mm. Hg) to a base temperature of 160C. (internal temperature 140C.) to yield 33.0g (8.4% by weight) of a distillate (predominantly unreacted dicyclopentadiene).
:~,s i The residue was placed in a 1 litre separating funnel together with an amount of petroleum ether (B.Pt. 62-68C.) 7~ sufficient to substantially fill the funnel resulting in 15 a viscous, oily, petroleum ether-insoluble layer (yield 212.1g., 54.1% by weight) anl a petroleum ether layer.
The latte. was separated and the petroleum ether stripped off to yield 149.2g. (38.2% by weight) of the final, oil-soluble product containing 32.5% sulphur.
;; 20 EXAMPLE 2 Dicyclopentadiene (264g., 2.m) was added dropwise over a period of 40 minutes to sulphur (64g.2.Om) - at 145C. The resulting reaction mixture was maintained at 145C. for a further hour and about ~.2g. hydroquinone added to the resulting crude product which was cooled and then stripped under high vacuum to a base temperature of 140C. to yield 180g (55.0% by weight) of unreacted dicyclopentadiene as distillate. The residue was wcrked up in the same manner as in Example 1 to yield 66.3g.
(20.2% by weight) of soluble material containing 31.0%
sulphur and 18.9g (5.8% by weight) of oil insoluble product.
' 1047~76 Dicyclopentadiene ~64g., 2.0m), sulphur(64g., 2.0m) and triethylamine catalyst (13.2g.) were mixed - and heated to 145C. for 2 hours. The resulting crude product was cooled slightly and about 0.2g hydroquinone . added thereto. The crude product was then cooled and worked up in the same manner as in Example 2 to yield ; 116.7g (35.6% by weight) distillate, 53.2g (16.2% by weight) insoluble material and 155.0g (47.4% by weight) oil-soluble product containing 27.7% sulphur.
..
Dicyclopentadiene ~238g., 1.8m) sulphur (64g., 2.0m), triethylamine catalyst (14.2g.) and, as solubilising agent, dibutyl maleate (45.6g 0.2m) were mixed and heated to 140-150C. for 2 hours. Hydroquinone (about 0.2g) was added to the crude product which was then stripped to - 120C. at 0.2mm Hg. to yield 83g. (23.9% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield about lg. insoluble material and 250.3g (72.0% by weight) oil-soluble product containing 24.7% sulphur.
Further preparations were carried out in the -mannér of Exa~ple 4 and details thereof are given in the following Table 1.
.'~ mixture of dicyGlopentadiene (178g., 1;35m) dibutyl maleate (34.2g., 0.15m.) and triethylamine (10.6g.) was heated to 140C. and suiphur (72g., 2.25m) was added thereto over a period of 50 minutes during which the temperature was maintained at 140C. The temperature was 14.
- !
:
1~47~76 )t maintain~d at 140C. for a further 70 minutes whereafter 0.2g. hydroquinone was added and the crude product stripped to 150C. (140C. internal temperature) at O.lmm Hg. to yield 57g. (20.1% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield 32.6g. (11.5% by weight) insoluble material and 184.3g.
;, (64.8% by weight) oil-soluble product containing 28.4%
sulphur.
,; . .
EXAMPLE 16 to 30 - 10 ~urther preparations were carried out in the -manner of Example 15 and details thereof are given in the following Table 2.
Sulphur (144g. 4.5m.) was added incrementally over a period of 1 hour to a mixture of dicyclopentadiene (356g., 2.7m.) dibutyl maleate (68.4g., 0.3m.) triethylamine (21.2g.) and 2,5-dimercapto -1,3,4- thiadiazole (4.2g.) at a temperature of 160C. The reaction mixture was then ,' .
maintained at 160C. for a further hour, whereafter it was stripped up to 110C. on a rotary evaporator under .
water pump vacuum (about 30mm Hg) to yield 2g. of distillate ~excess dicyclopentadiene). The product was extracted with three times its volume of petroleum ether (boiling point 62-68C.) yielding 75.1g. (13.7%) of insoluble material and petroleum ether stripped off the extract to yield 472.3g. (83%) of soluble material containing 25.0%S.-Example 31 was repeated except in tha~ the reaction temperature was kept at 90C. and extraction with petroleum ether was nct carried out to yield 184g. (50.4%) excess cyclorentadiene, no insoluble material and 386g. (68.o%) soluble product containing 35.5%S.
15.
"
)47~76 , Example 32 was repeated, except in that the .
,, reaction temperature was kept at 120 C., to yield 120g ^ excess cyclopentadiene, no insoluble material and 455g.
t 5 (80%) soluble product containing 31.9%S.
EXAMPLE 34 to 42 Further preparations were carried out in the manner of Example 33 and details thereof are given in the , following Table 3.
Sulphur (172.8g., 5.4m.) was added incrementally over 1' hours, at a temperature of 90 C., to a mixture of dicyclopentadiene (356g., 2.7m.), dibutyl maleate (68.4g., O. 3M. ) di-isopropylamine (5g.) and sodium sulphide powder (5g.). The reaction mixture was then stirred for a further 2 hours with the reaction temperature maintained in the range of 85-90C. me resulting product was then filtered and stripped to 120 C. under water pump vacuum to yield 83g. distillate (excess dicyclopentadiene). The ;.20 stripped product (462g.) was not fully oil soluble and was therefore boiled with 1~ litres petroreum ether to yield 350g. (59%) of soluble product containing 33.8%S.
EXAMPLE _44 Dic-lclopentadiene (356g., 2.7m), dibutyl maleate (68.4g., 0.3m), diisopropylamine (4g) and 2,5-bis (t-octyldithio) -1,3,4,-thiadiazole were dissolved in toluene (500ml) and sulphur (172. 8g., 5.4m) added thereto incrementally over 1 hour while maintaining a reaction temperature of 120 C. The reaction mixture was then stirred 3 for a further 1 hour at 120 C. and vacuum stripped (removing toluene at 100 C. and excess dicyclopentadiene at 120C.) 16.
~4747~
to yield 461g. (76.7%) soluble product containing 34.1%S, Example 44 was repeated using 500 ml petroleum ether (boillng point 80-100C.) in place of the toluene.
- 5 The reaction temperature was maintained in the range of 100-110C. throughout due to the volatility of the solvent.
In this way was obtained 469.9g. (78.2%) of soluble product containing 36.2%S.
Dicyclopentadiene (178g. 1.35m), dibutyl maleate (34.2g., 0.15m), di-isopropylamine (2g.) and 2,5-bis (octyldithio) -1,3,4-thiadiazole (2g) were dissolved in 200g. of high viscosity index 100 Solvent Neutral mineral oil. Sulphur (86.4g., 2.7m) was added incrementally over 1 hour at 110-120C. and the reaction ~emperature maintained at 120C. for a further 1 hour. The product was vacuum stripped and filtered to yield 461g. (92.4%) of oil soluble product containing 19.0%S.
Dicyclopentadiene (178g., 1.35m), dibutyl maleate (34.2g., 0.15m) di-isopropylamine (2g) were dissolved in 250ml toluene. Sulphur (129.6g. 4.05m) was added thereto over ~ hour at 110-120C. and the resulr,ing mixture stirred for a further 1~ hours at 120CC. After vacuum ?5 stripping and filtration 300g (88%) of product containing 39.9%S was obtained. This gave a hazy solution in mineral oil indicating the presence of a very low level of insoluble material.
3C Example 44 was repeated except in that 172.8g.
(5.4m) sulphur was used and a reaction temperature of 110C.
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: was used. There was obtained 191.4g. (49.9%) soluble . product and 138.6g (36.1%) insoluble product. -3: EXAMPLE 49 ~$ 5-Vinylnorbornene (84g. 0.7m), di-isopropylamine (4.0g.) and 2,5-bis (t-octyldithio) -1,3,4,-thiadiazole :,:
(o.8g.) were mixed, heated to 130C. and sulphur (22.4g., -` 0.7m) added thereto portionwise over 1 hour. The -temperature was maintained at 130C. for a further 1 hour and the reaction mixture was stripped to 100C. at O.lmm Hg. to remove 20.8g. (19.6%) unreacted 5-vinylnorbornene.
The product was extracted with 250ml petroleum ether (boiling point 62-68C.) and filtered to remove a small ` quantity of insoluble material. The petroleum ether was i stripped frotn the extract to yield 51g (48%) of soluble ~- 15 product , . . .
,..:
~- In some of the foregoing examples (1 to 5, 9 11 and 18) a small quantity of hydroquinone was added to the crude product of the sulphurisation reaction since it was thought that the reaction proceeded by a free radical mechanism and that continuation of a free radical reaction during working up of the crude product could lead to some degradation. The hydroquinone was therefore used ~-to suppress free radical reaction. However, subsequent .,, ~.
experiences ~ndicated that the use of hydroquinone did not materially improve the additive preparation.
Various products of the foregoing examples were s tested to determine their suitability as lubricant additives.
Petter WI Engine testr were carried out by the Institute of Petroleum's method IP 176/69 using an ashless blend consisting of a commercially available succinimide-type dispersant, a secondary aromatic amine antioxidant and a 18.
~.V47~ :
combination of corrosion inhibitors together with 1.0%
by weight of the test additive all dissolved in a 500 l-Solvent Neutral mineral oil. Bearing weight losses afte a 36 houF test were measured and were as follows:
; Test AdditiveBearing Test Bearing [
~ Weight Additive Weight Loss (mg) Loss (mg.) 1.
Product of Example 1 9 Product of EY.ample 15 12 " 3 17.4 " n - 16 -8 " " " 4 9 " " '' 19 8 ~-" "' 5 75 ~ t n 21 3 ~-" " " 6 8 22 -17 i " " " 8 7 " " " 24 19 l~
11 5 " " " 30 9 - " " " 12 5 '' " " 37 13 i' " " 14 10 Extended WI tests were carried out for typical test / additives (in the same blends) by the same method except _ that oil samples removed from time to time were not replaced.
~04 ;~'76 :
. Bearing Weight Losses were as follows:-" . .
Test Additive Bearing Weight Loss (mg.) 36 hours 72 hours 108 hours Product of Example 29 10 19 28 " " " 30 22 28 51 .: " " " 42 10 17 20 In comparison a typical fully-formulated .; commercially available lOW/50 oil containing a zinc dialkyl :.
dithiophosphate as antioxidant, a succinimide-type dispersant, a metal sulphonate detergent, a polymethacrylate viscosity index improver and a combination of corrosion inhibitors gave bearing weight losses in this test of 15mg, 27mg and 68mg at 36,72 and 108 hours respectively.
; 15 Load carrying properties were determined using the Timken OK load test according to the IP240/69T method (except in that results are quoted in lbs.) The test blends con8isted of test additive diæsolved in 150 Solvent Neutral mineral oil, the former being in amount to provide 0.3% by weight sulphur in the test blend and the results were as follows:-Test Additive ~i~kln OK Load (lbs) None (h~se oil only) 12 Product o~ Example 5 ~ 30 / " " " 6 ~5-" ,. ~ 8 20.
-~ 7~6 :
: , , . ll " 19 45 ~` " " " 23 40 " " " 33 40 .
. .
.,~ , .
In comparison commercially available zinc dialkyl dithiophosphates usually give Timken OK loads of 35-40 lbs in this test.
.,, :, . .
Rotary Bomb TestScarried out by the IP229/68T
.. 5 method on blends consisting of 2.0% by weight test additive dissolved in 500 Solvent Neutral mineral oil gave the following induction periods:-. ' , .
Test Additive Induction Period (minutes) i 10 None (base oil only) 35 Product of Example 5 99 " " " 11 178 ~ " " 1 190 (25 p.s.i. loss~
.. " " 19 216 (25 " "
. " " " 23 112 (25 " "
Copper strip tests were carried out by the ASTM
method except in that a temperature of 120C. was used. The blends tested consiS~e~ of sufficient test additive to provide a blend containing 0.15%S dissolved in a 500 Solvent Neutral or a 150 Solven'c Neutral mineral oil. ASTM ratings after 3 hours were as follows:-21, 1~3~ 6 , Test Additive RatingTest Additive Rating .; , ~ , ~
None (bace oil only) 2bProduct of Example 18 2e Produc~ of Exa~ple 1 2a 19 2e " " " 4 2e " " " 21 1b ' " " " 5 2e " " ~ 22 2e " " " 6 1b n ~ ~ 23 3b " " " 8 1b " " " 24 1b " " " 11 2e " " " 30 1b " " " 12 2e " " " 33 1b " " " 14 2b/c " " " 37 2c/3a n n n 15 1b/3a 42 1b " " " 16 3b " " " 49 2a From the foregoing test results it can be seen that the additives of the present invention impart antioxidant properties (Rotary Bomb Test) and yet have a low level of corrosiveness (Copper Strip Test) despite the high sulphur content. Furthermore in the standard tests the additives demonstrate load carrying abilities (~imken OX load Test) and test engine performance (Peter WI Tests) in fully formulated blends similar to those exhibited by the zinc dialkyl dithiophosphateSnormally used in premium grade -~ crank~se lubricants.
, 22, ~3~7~76 ; The suitability of the additives of the present invention for use in gear oil formulations was determined - by use of the S.A.E. test~ in which two parallel shafts are provided with interengaging surfaces lubricated with . . .
the test blend and are driven at speeds in a ratio of 14.6:1. After a short running period the load on the interengaging surface is incrementally increased until scurfing occurs. With a blend consisting of an S.A.E.
90 base oil, 4.5% by weight of an additive in accordance with the present invention (containing 30.3%S) and 0.5%
by weight di-isopropyl phosphite scuffing resulted at 2451b and 2301b (duplicate tests) at a drive shaft speed of 1,000 r.p.m. Under the same condition a blend consisting of the same base oil containing 4.5% by weight sulphurised isobutylene (a commercially available gear oil additive containing 45%S) and 0.5% by weight di-isopropyl - phosphite resulting in scuffing at 2651b and 310 lb. Thus , the blend containing the additive according to the present invention produced similar test results even though the sulphur content was substantially less than in the comparison blend.
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. ' a)- .
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.
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.
:
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.. I ,. ~
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~-~rl _I h t~
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'~ ¦ ~ t~ rl S ~ W ~d . ~1 _~ t~) .C ~
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,~ _._ ~ .
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46.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A lubricating composition containing a major amount of lubricating oil and a minor anti-oxidant or load-carrying amount of a sulphur-containing additive selected from the group consisting of (1) sulphurised norbornenyl compound having the general formula:
(A) wherein: a. each of R, R2 and R4 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about 10 carbon atoms; b. each of R1 and R3 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms; c. R1 and R3 when taken together from the group -CHY.CY = CY-in which Y is a hydrogen atom or a methyl group; d. R1 when taken together with R2 forms an alkylidene group containing from 1 to about 6 carbon atoms;
and e. R5 is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulfurising a compound having the general formula:
(B) wherein R, R1, R2, R3, R4 and R5 are as hereinbefore defined at a temperature of up to 180°C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
(A) wherein: a. each of R, R2 and R4 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about 10 carbon atoms; b. each of R1 and R3 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms; c. R1 and R3 when taken together from the group -CHY.CY = CY-in which Y is a hydrogen atom or a methyl group; d. R1 when taken together with R2 forms an alkylidene group containing from 1 to about 6 carbon atoms;
and e. R5 is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulfurising a compound having the general formula:
(B) wherein R, R1, R2, R3, R4 and R5 are as hereinbefore defined at a temperature of up to 180°C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
2. A lubricating composition according to claim l wherein the additive is a compound having the Formula (A) as hereinbefore defined.
3. A lubricating composition according to claim 2 which comprises from 0.1 to 10 by weight of the additive.
4. A lubricating composition according to claim 1 which incorporates a minor amount of benzotriazole therein.
5. A lubricating composition according to claim 4 wherein the benzotria-zole is present in an amount of from 0.0025 to 0.1% by weight.
6. A lubricating composition according to claim 1 wherein the additive is an oil soluble sulphurized norbornenyl product resulting from sulphurizing a compound having the formula (B).
7. A lubricating composition according to claim 6 which comprises from 0.1 to 10% by weight of the additive.
8. A lubricating composition according to claim 6 wherein the compound having the formula (B) is dicyclopentadiene or an alkyl substituted dicyclopen-tadiene and said sulphurization has been carried out at a temperature of from 90° to 180°C.
9. A lubricating composition according to claim 8 which comprises from 0.25 to 5 percent by weight of the additive.
10. A lubricating composition according to claim 8 wherein said sulphuri-zation has been carried out in the presence of an amine sulphurization catalyst.
11. A lubricating composition according to claim 6 wherein said sulphurized norbornyl product is that resulting from sulphurizing a compound having the formula (B) with from about 1 to 2 moles of sulphur per mole of compound.
12. A lubricating composition according to claim 10 wherein said sulphuri-zation has been carried out in the presence of a solubilizing agent selected from the group consisting of alloocimene, dibutyl maleate, dodecenyl succinic acid, t-dodecyl mercaptan, ethoxylated tallow amine having an average mole-cular weight of 482 and containing an average of 5 ethylene oxideresidues per molecule, oleic acid, 1,5,9-cyclododecatriene and mercaptobenzothiazole.
13. A concentrate for addition to a lubricating composition, said concen-trate comprising a minor amount of a mineral oil and a major amount of a sul-phur-containing additive selected from the group consisting of (1) sulphurised norbornenyl compound having the general formula:
(A) wherein: a. each of R, R2 and R4 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about 10 carbon atoms; b. each of R1 and R3 when taken singly is selected from the group consisting of a hydrogen atom, and alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms; c. R1 and R3 when taken together from the group -CHY.CY=CY-in which Y is a hydrogen atom or a methyl group; d. R5 when taken together with R2 forms an alkylidene group containing from 1 to about 6 carbon atoms;
and e. R5 is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulphurising a compound having the general formula:
(B) wherein R, R1, R2, R3, R4 and R5 are as hereinbefore defined at a temperature of up to 180°C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
(A) wherein: a. each of R, R2 and R4 when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about 10 carbon atoms; b. each of R1 and R3 when taken singly is selected from the group consisting of a hydrogen atom, and alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms; c. R1 and R3 when taken together from the group -CHY.CY=CY-in which Y is a hydrogen atom or a methyl group; d. R5 when taken together with R2 forms an alkylidene group containing from 1 to about 6 carbon atoms;
and e. R5 is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulphurising a compound having the general formula:
(B) wherein R, R1, R2, R3, R4 and R5 are as hereinbefore defined at a temperature of up to 180°C., said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA313,946A CA1066270A (en) | 1973-04-12 | 1978-10-23 | Lubricant additives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1772873A GB1470649A (en) | 1973-04-12 | 1973-04-12 | Sulphurised norbornyl derivatives and their use as lubri cant additives |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1047476A true CA1047476A (en) | 1979-01-30 |
Family
ID=10100199
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA197,455A Expired CA1047476A (en) | 1973-04-12 | 1974-04-11 | Lubricant additives |
Country Status (14)
Country | Link |
---|---|
US (1) | US3882031A (en) |
JP (2) | JPS5347124B2 (en) |
AR (1) | AR208174A1 (en) |
AT (1) | AT341537B (en) |
BE (1) | BE813603A (en) |
BR (1) | BR7402912D0 (en) |
CA (1) | CA1047476A (en) |
DE (1) | DE2417864C3 (en) |
FR (1) | FR2225431B1 (en) |
GB (1) | GB1470649A (en) |
IT (1) | IT1007869B (en) |
NL (2) | NL159136B (en) |
SE (1) | SE7711154L (en) |
ZA (1) | ZA742357B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1518102A (en) * | 1974-07-25 | 1978-07-19 | Cooper Ltd Ethyl | Trithiolan derivatives and lubricating compositions containing them |
GB1560667A (en) * | 1976-09-24 | 1980-02-06 | Cooper & Co Ltd Edwin | Sulphurize olefins and their use as lubricant additives |
US4389221A (en) * | 1982-07-23 | 1983-06-21 | Shell Oil Company | Gasoline composition and method for reducing fuel consumption |
US4493927A (en) * | 1983-12-22 | 1985-01-15 | The Dow Chemical Company | Condensation polymers of sulfur compounds and norbornenyl compounds |
US4639324A (en) * | 1985-07-08 | 1987-01-27 | Ethyl Petroleum Additives, Inc. | Lubricating compositions |
US4876375A (en) * | 1988-05-02 | 1989-10-24 | Ethyl Petroleum Additives, Inc. | Norbornyl dithiocarbamates |
US4927552A (en) * | 1988-05-02 | 1990-05-22 | Ethyl Petroleum Additives, Inc. | Lubricating oil composition |
US4836942A (en) * | 1988-06-06 | 1989-06-06 | Ethyl Petroleum Additives, Inc. | Lubricant composition |
FR2712824B1 (en) * | 1993-11-26 | 1996-02-02 | Inst Francais Du Petrole | Catalyst regeneration process. |
EP0714970A1 (en) * | 1994-11-28 | 1996-06-05 | Institut Français du Pétrole | Olefinic hydrocarbons sulfurized with elemental sulfur in the presence of alkali on alkaline earth metal hydroxides and glycols, polyglycols or their alkyl ethers and/or water |
FR2729154A1 (en) * | 1995-01-10 | 1996-07-12 | Inst Francais Du Petrole | ETHYLENIC HYDROCARBONS SULFURATED BY ELEMENTARY SULFUR IN THE PRESENCE OF ALKALINE CARBONATE OR HYDROGENOCARBONATE, THEIR PREPARATION AND THEIR USES |
GB2623137A (en) * | 2022-11-10 | 2024-04-10 | Afton Chemical Corp | Corrosion inhibitor and industrial lubricant including the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1195749A (en) * | 1966-12-19 | 1970-06-24 | Lubrizol Corp | Sulfur-Containing Cycloaliphatic Reaction Products and their use in Lubricant Compositions |
US3586700A (en) * | 1969-02-19 | 1971-06-22 | Union Carbide Corp | 3,4,5-trithiatricyclo(5.2.1.0**2,6)decanes and derivatives |
US3793203A (en) * | 1971-05-17 | 1974-02-19 | Sun Oil Co | Lubricant comprising gem-structured organo compound |
-
0
- NL NL159136D patent/NL159136C/xx active
-
1973
- 1973-04-12 GB GB1772873A patent/GB1470649A/en not_active Expired
-
1974
- 1974-01-01 AR AR253275A patent/AR208174A1/en active
- 1974-04-10 JP JP4160874A patent/JPS5347124B2/ja not_active Expired
- 1974-04-10 BR BR2912/74A patent/BR7402912D0/en unknown
- 1974-04-11 CA CA197,455A patent/CA1047476A/en not_active Expired
- 1974-04-11 AT AT304674A patent/AT341537B/en not_active IP Right Cessation
- 1974-04-11 FR FR7412738A patent/FR2225431B1/fr not_active Expired
- 1974-04-11 BE BE143102A patent/BE813603A/en not_active IP Right Cessation
- 1974-04-11 IT IT21301/74A patent/IT1007869B/en active
- 1974-04-11 DE DE2417864A patent/DE2417864C3/en not_active Expired
- 1974-04-11 ZA ZA00742357A patent/ZA742357B/en unknown
- 1974-04-11 US US459938A patent/US3882031A/en not_active Expired - Lifetime
- 1974-04-11 NL NL7405010.A patent/NL159136B/en not_active IP Right Cessation
-
1977
- 1977-01-12 JP JP281377A patent/JPS52107009A/en active Granted
- 1977-10-05 SE SE7711154A patent/SE7711154L/en unknown
Also Published As
Publication number | Publication date |
---|---|
ZA742357B (en) | 1975-11-26 |
SE7711154L (en) | 1977-10-05 |
FR2225431A1 (en) | 1974-11-08 |
DE2417864A1 (en) | 1974-10-31 |
DE2417864B2 (en) | 1978-10-05 |
BE813603A (en) | 1974-07-31 |
FR2225431B1 (en) | 1978-11-17 |
GB1470649A (en) | 1977-04-14 |
DE2417864C3 (en) | 1979-06-07 |
NL7405010A (en) | 1974-10-15 |
JPS5347364B2 (en) | 1978-12-20 |
IT1007869B (en) | 1976-10-30 |
NL159136B (en) | 1979-01-15 |
BR7402912D0 (en) | 1974-11-19 |
ATA304674A (en) | 1977-06-15 |
JPS5076103A (en) | 1975-06-21 |
AR208174A1 (en) | 1976-12-09 |
NL159136C (en) | |
AU6775274A (en) | 1975-10-16 |
AT341537B (en) | 1978-02-10 |
JPS5347124B2 (en) | 1978-12-19 |
JPS52107009A (en) | 1977-09-08 |
US3882031A (en) | 1975-05-06 |
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