AU608792B2 - Sulphurised alkaline earth metal hydrocarbyl phenates, the production and use thereof - Google Patents

Sulphurised alkaline earth metal hydrocarbyl phenates, the production and use thereof Download PDF

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Publication number
AU608792B2
AU608792B2 AU82380/87A AU8238087A AU608792B2 AU 608792 B2 AU608792 B2 AU 608792B2 AU 82380/87 A AU82380/87 A AU 82380/87A AU 8238087 A AU8238087 A AU 8238087A AU 608792 B2 AU608792 B2 AU 608792B2
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AU
Australia
Prior art keywords
lubricating oil
tbn
acid
alkaline earth
earth metal
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Charles Cane
John Crawford
Sean Patrick O'connor
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Lubrizol Adibis Holdings UK Ltd
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BP Chemicals Additives Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Description

AU-Al-82380/ 87 WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau

PCT

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) Internatioral Patent Classification 4 1 In~ ~rternatinal Publication Number-, WOv 38 03941 ClOM 159/22 Al(43) Internationmal Publicati~n Date: 2 June 1988 (02.06.88) (21) lNternational Application Number: PCT/GB87/00848{ (22) International Filing Date: 26 November 1987 (26.11.87) (31) Priority Application Number: 8628609 (32) Priority Date- (33) Priority Country: 29 November 1986 (29.11,86)

GB

(71) Applicant (for all designated S'tates except US). BPI CHEMICALS (ADDITIVES) LIMITED [GB/GB]; Belgrave House, 76 B~uckingham Palace Road, London SWIW OSU (GB), (72) Inventors; and Inventors/Applicnt (for US onivi CANE, Charles [GB/GB]; 39 Loly Green, West, Borough Way, Anlaby Common, Hull, N-'orth Humberside HU4 7SJ (GB).

CRAWFORD, John Southcott, 13 Loxford Road, Caterham, Surrey CR3 61H O'CON- NOR, Sean, Patrick [GB/GB]; 31 St, Martin's Court, Beverley, North Humberside (GB).

AU e 3Pv~z1 R/h a r nnf ;B P Internation- 60rd,58nts Agre ient vision, Chertsey Road, Sunbury-on-Thames, Middlesex TWI6 7LN

(GB).

(81) Designated States: AU, BR, DK, FI, JP, KR, NO, US.

Published With international search report.

Before i/c ca-piration of the time limit for amending the claims and to b e republished in the event of the receipt of amendinents, 2 1 JUL 1988

AUSTRALIAN

16 JUN 1988 PATENT OFFICE

I

(54) Title: SULPHUR.SED ALKALINE EARTH M'VETAL HYDROCARBYL PH-ENATES, THEIR PRODUCTION AND USE THEREOF Tis document contains the amnnments madfe undcr ,;ction 49 and is correct for printi~ng.

R CH COOH (57) Abstract An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: a lubricating oil; a lubricating oil soluble suiphurised alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 35 by Weight based on the weight of the composition of either at least one carboxylic acid having formula whorein R is CIO to C 24 alkyl or alkenyl group and R' is either hydrogen, a C, to C 4 alkyl group or a -CH- 2 -COOH group, or an anhydride, acid chiuride or ester thereof or (ii) a di- or polycairboxylic acid containing from 65 to 100 carb~on atoms or an anhydride, acid chloeide or ester thereof, the composition having a TBN greater than 300, Md wWO 88/03945 PCT/GB87/00848 SULPHURISED ALKALINE EARTH METAL HYDROCARBYL PHENATES, THEIR PRODUCTION AND USE THEREOF The present invention relates in general to sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof as lubricating oil additives. In particular the present invention relates to sulphurised alkaline earth metal hydrocarbyl phenate-containing compositions having a high total base number (TBN) and an acceptable viscosity and to their production from sulphurised alkaline earth metal hydrocarbyl phenates having lower TBNs.

In the internal combustion engine, by-products from the combustion chamber often blow by the piston akd admix with the lubricating oil. Many of these by-products form acidic materials within the lubricating oil. This is particularly marked in diesel engines operating on low-grade fuels of high sulphur content wherein corrosive acids are produced by combustion. The acids thereby incorporated in the lubricating oil can include sulphur acids produced by oxidation of sulphur, hydrohalic acids derived from halogen lead scavengers in the fuel and nitrogen acids produced by the oxidation of atmospheric nitrogen within the combustion chamber. Sucn acids cause deposition of sludge and corrosion of the bearings and engine parts leading to rapid wear and early breakdown of the engine.

One class of compounds generally employed to neutralise the acidic materials and disperse sludge within the lubricating oil are the sulphurised metal alkyl phenates, wherein the metal is an alkaline earth metal such as calcium, magnesium or barium. Both I II- WO 88/03945 PCT/GB87/00848 2 "uormal" and "overbased" sulphurised alkaline earth metal alkyl phenates have been employed. The term "overbased" is used to describe those sulphurised alkaline earth metal alkyl phenates in which the ratio of the number of equivalents of the alkaline earth metal moiety to the number of equivalents of the phenol moiety is greater than one, and is usually greater than 1.2 and may be as high as 4.5 or greater. In contrast, the equivalent ratio of alkaline earth metal moiety to phenol moiety in "normal" alkaline earth metal alkyl phenates is one. Thus, the "overbased" material contains greater than 20% in excess of the alkaline earth metal present in the corresponding "normal" material. For this reason "overbased" sulphurised alkaline earth metal alkyl phenates have a greater capability for neutralising acidic matter than do the corresponding "normal" alkaline earth metal alkyl phenates.

The prior art teaches many methods for preparing both "normal" and "overbased" sulphurised metal alkyl phenates. One such method for preparing "overbased" sulphurised alkyl phenates generally referred to as the "single lime addition" process comprises reacting an alkyl phenol, in the presence of lubricating oil, sulphur, a hydroxylic compound and excess alkaline earth metal hydroxide (above the stoichiometric proportion required to neutralise the alkyl phenol), to form an intermediate product, followed by carbonation, a heading distillation (to remove unreacted hydroxylic compound) and filtration. The production of intermediate product is accompanied by a marked increase in viscosity while the subsequent carbonation reduces the viscosity to a relatively low level. The increase in viscosity accompanying the formation of the intermediate product is undesirable because the reaction mixture becomes difficult to agitate to the detriment of subsequent reactions. Whilst this increase in viscosity may be controlled to an acceptable level by incorporation of less alkaline earth metal hydroxide in the reaction, the overbased alkyl phenate product necessarily possesses a reduced neutralisation capacity. In order to achieve a high neutralisation capacity product and at the same time control the viscosity of the intermediate product within acceptable limits, the WO 8/03945 PCT/GB87/00848 3 alkaline earth metal hydroxide may be added in two, (generally referred to as the "double lime addition" process) or three separate reaction steps, with sequential carbonation steps. However, this method involves relatively long batch times, A.cther alternative is to use viscosity depressants, such as tridecanol, 2-ethylhexanol, or similar boiling range hydroxylic solvent, in the production of the intermediate product but such an expedient increases the raw material cost of the process. The highest total base number (TBN), as measured in mg KOH/g, consistent with an acceptable viscosity, generally achievable by prior art processes is about 300, though generally prior art TBNs are in the range from 200-300. It would clearly be a desirable objective to produc- sulphurised alkaline earth metal alkyl phenate compositions having a high TBN that is a TBN greater than 300, and preferably greater than 350. It would also be a desirable objective to produce such materials from sulphurised alkaline earth metal alkyl phenates having a lower TBN.

To date it has not been found possible to achieve products of such high TBN because the use of larger concentrations of alkaline earth metal base leads to highly ?iscous products which, rather than being 'thinned' by subsequent carbonation attempts using excess carbon dioxide, are rendered insoluble. We have achieved these objectives and thereby achieved compositions having a TBN in excess of 300 and in some cases greater than 350 whilst retaining an acceptable viscosity, that is a viscosity of less than 1000 cSt, and avoiding insolubility by incorporating into a reaction mixture containing a sulphurised alkaline earth metal alkyl phenate at least one carboxylic acid or acid derivative thereof having at least 10 carbon atoms in the aolecule.

The use of carboxylic acids in the production of sulphurised alkaline earth metal alkyl phenates is not new, see for example US-A-4049560 and EP-A-0094814.

US-A-4049560 describes the production of an overbased magnesium detergent by a process in which carbon dioxide is introduced into a reaction mixture which comprises:

I

WO 88/03945 PCT/GB87/00848 4 15-40 wt Z of a sulphurised phenol or thiophenol containing one or more hydrocarbyl substituents, or a phenol or thiophenol containing one or more hydrocarbyl substituents, or said phenol or thiophenol containing one or more hydrocarbyl substituents together with sulphur, 5-15 wt of an organic sulphonic acid, an organic sulphonate or an organic sulphate, 5-15 wt X of a glycol, a C 1 to C 5 monohydric alkanol or C 2 to

C

4 alkoxy alkanol, 2-15 wt of a magnesium hydroxide or active magnesium oxide, at least 0.1 wt of a C 1 to C 18 carboxylic acid, an anhydride thereof, or an ammonium, an amine salt, a Group I metal or a Group II metal salt of said C 1 to C 18 carboxylic acid, and at least 10% by weight of a diluent oil (including any present in components and The amount of carboxyliq acid (component is preferably in the range 0.5 to 2.0% by weight. The product prepared by this reaction is said to have a TBN of about 200 to 250, eg. about 225.

EP-A-0094814 discloses an additive concentrate for incorporation in a lubricating oil composition comprising lubricating oil, and from 10 to 90 wt of an overbased alkaline earth metal hydrocarbyl sulphurised phenate which has been treated, either during or subsequent to the overbasing process, with from 0.1 to 10, preferably 2 to 6, wt (based on the weight of additive concentrate) of an acid of the formula: R CH COOH (I)

RI

(wherein R is a C 10 to C 24 unbranched alkyl or alkenyl group, and R

I

is hydrogen, a C 1 to C 4 alkyl group or a -CH2-COOH group) or an anhydride or a salt thereof. The object of the invention of EP-A-0094814 is to overcome problems encountered with many additive concentrates containing overbased additives, namely lack of stability giving rise to sedimentation and foaming problems. The problem of EP-A-0094814 is not that of producing phenates having a i TBN of greater than 300 and indeed the phenates produced by the process of the invention, although overcoming the problems of stability and foaming, have TBN values of less than 300.

It can be concluded that the prior art in which carboxylic acids are employed does not address the problem of producing overbased sulphurised alkaline earth metal alkyl phenates having a TBN of greater than 300 and an acceptable viscosity.

In a first aspect the present invention provides an additive concentrate suitable for incorporation into a Sfinished lubricating oil which concentrate is obtainable by S. reacting at elevated temperature a sulphurised alkaline earth metal hydrocarbyl phenate having a TBN less than that of the final additive concentrate, an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during the reaction, either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C 2 to C 4 glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, a lubricating oil, carbon dioxide added subsequent to the, or each, addition of coimponent and sufficient to provide from greater than 2 to 35% by 0 weight based on the weight of the concentrates of either (i) -5 a carboxylic acid having the formula: R CH COOH

(I)

(1) 1

R

wherein R is a C10 to C 2 4 alkyl or alkenyl group and R is either hydrogen, a C 1 to C 4 alkyl group or a -CH -COOH group, or an acid anydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride, acid chloride or ester thereof, the weight ratio of components to being such as to produce a concentrate having a TBN greater than 300.

I_-~LLL_ In a second aspect the present invention provides a process for the production of an additive concentrate for incorporateion into a finished lubricating oil which process comprises reacting at elevated temperature components to as hereinbefore described, the weight ratios of components to being such as to produce a concentrate having a TBN greater than 300.

The process of the invention is advantageous because it affords a method for up-grading low TBN products of the prior art or off-specification products into high TBN 'oo products having an acceptable viscosity. Moreover, because 00o0 hydrogen sulphide is not evolved during operation of the process of the invention, in contrast to processes for producing sulphurised alkaline earth metal alkyl phenates Sinvolving the reaction of an alkyl phenol an sulphur, by the more conventional routes, the hydrogen sulphide disposal problem is avoided, thereby allowing manufacture in *Go o0 0 -6- I r I 1j1 WO 88/03945 PCr/GB87/00848 environmentally sensitive locations and the use of less sophisticated plant.

Component of the reaction mixture is a sulphurised alkaline earth metal hydrocarbyl phenate having a TBN lower than that of the final product, i.e. generally less than 300. Any sulphurised alkaline earth metal hydrocarbyl phenate may be employed. The sulphurised alkaline earth metal hydrocarbyl phenate may be carbonated or non-carbonated. The alkaline earth metal moiety and the hydrocarbyl phenate moiety of the sulphurised alkaline earth metal hydrocarbyl phenate may suitably be as hereinbefore described. Methods for preparing sulphurised alkaline earth metal hydrocarbyl phenates are well known in the art. Alternatively, the precursors of a sulphurised alkaline earth metal hydrocarbyl phenate in the form of a non-sulphurised alkaline earth metal hydrocarbyl phenate and sulphur may be employed, The alkaline earth metal base (component B) may suitably be an alkaline earth metal oxide or hydroxide, preferably the hydroxide, Calcium hydroxide may be added for example in the form of slaked lime. Preferred alkaline earth metals are calcium, magnesium and barium and more preferred is calcium. The alkaline earth metal base must be added in an amount relative to component sufficient to produce a product having a TBN in excess of 300, preferably in excess of 350. This mount will depend on a number of factors including the nature of the sulphurised alkaline earth metal hydrocarbyl phenate. Typically, the weight ratio of component (B) to comporent may suitably be in the range from 0.1 to preferably from 0.2 to 5. The alkaline earth metal base may be added in whole to the initial reactants, or in part to the initial reactants and the remainder in one or more portions at a subsequent stage or stages in the process, Preferably conponent is added in a single addition to the initial reactants.

Component is either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C 2 to C 4 glycol, an alkylene glycol S" alkyl ther or a polyalkylene glycol alkyl ether. Thepolyhydric 1 35 alcohol may suitably be either a dihydric alcohol, for example YUr ethylene glycol or propylene glycol, or a trihydric alcohol, for example glycerol. The di- or tri- (C 2 to C 4 glycol may suitably be either diethylene glycol or triethylene glycol. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether may suitably be of the formula:- J (OR) xOR 2

(II)

wherein R is a C 1 to C 6 alkyl group, R i is an alkylene group, R is hydrogen or C 1 to C 6 alkyl and x is an integer in the range from 1 to 6. Suitable solvents having the formula (II) include the monomethyl or dime.thyl ethers of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol, A particularly suitable solvent is 1 5 methyl digol (CH30OCHCHOCH 2

CH

2 OH). Mixtures of glycols and glycol ethers of formula (II) may also be employed. Using a glycol or glycol ether of formula (II) as solvent it is preferred to use in combination therewith an inorganic halide, for example ammonium chloride, and a lower, i.e. C 1 to C 4 carboxylic acid, for example acetic acid. Preferably the component is either ethylene glycol or methyl digol, the latter in combination with ammonium chloride and acetic acid.

Component is a lubricating oil. The lubricating -*25 oil may suitably be either an animal oil, a vegetable oil or a mineral oil. Suitably the lubricating oil may be a petroleum-derived lubricating oil, such as a naphthenic base, paraffin base or mixed base oil. Solvent neutral oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl scbacate and tridecyladipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutenes and poly-alpha olefins.

8345S/as -8- 1 Component is carbon dioxide, which may be added in the form of a gas or a solid, preferably in the form of a gas. In gaseous form it may suitably be blown through the reaction mixture. We have found that generally the amount of carbon dioxide incorporated increases with increasing concentrations of component The carbon dioxide is preferably added subsequent to a single addition of component at the conclusion of the reaction between component and Component is either a carboxylic acid of formula a di- or polycarboxylic acid containing from 36 to 100 carbon atoms, or an acid anhydride, an acid chloride or ester thereof. Preferably R in the formula is an unbranched alkyl or alkenyl group. Preferred acids of formula are those wherein R is a Cl to C2, more preferably C18 to C24 straight chain alkyl groups and 1. 8 24 R is hydrogen. Examples of suitable saturated carboxylic acids of formula include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, z0 behenic acid and lignoceric acid. Examples of suitable unsaturated acids of formula include lauroleic acid, myi -toleic acid, palmitoleic acid, oleic acid, gadoleic acik, erucic acid, ricinoleic acid, linoleic acid and linolenic acid. Mixtures of acids may also be employed, for 25 example rape top fatty acids. Particularly suitable mixtures of acids are those commercial grades containing a range of acids, including both saturated and unsaturated acids. Sucn mixtures may be obtained synthetically or may be derived from natural products, for example cotton oil, ground nut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, soyabean oil, sunflower oil, herring oil, sardine oil and tallow.

Sulphurised acids and acid mixtures may also be employed.

Instead of, or in addition to, the carboxylic acid there may be used the acid anhydride, the acid chloride or the ester derivatives of the acid, preferably the acid anhydride. It is preferred however to use a carboxylic acid or a mixture -9-

IIII

of carboxylic acids. A preferred carboxylic acid of formula is stearic acid. The amount of the aforesaid components required to provide from greater than 2 to 35% by weight based on the weight of the concentrate will be to a first *09 9

S

S.

S S S S

S.

5 *1~ 5 9 5 S. S

S.

S

SS

S S 95

*OS*

5955 S S I~ a

S

S

S

S

S

0 5055

*S

$345E$/as 0- W6,88/03945 WO ~88O3945PCT/GB87/00848 11 approximation the amount derived in the concentrate. In calculating this amount allowance should be made for loss of water from carboxylic acids, for example.

The reaction may be performed in the presence of a diluent, Suitabls diluents are liquids having a volatility consistent with operation of the process, i.e, having a volatility such that they are readily strippable from the reaction mixture at the conclusion of the reaction. Examples of suitable diluents include 2-ethyl hexanol, iso-octanol, iso-heptanol and tri-decanol.

Further sulphur, that is sulphur additional to that already present by way of component may be added to the reaction mixture. An advantage of adding .urther sulphur is that it increases the amount of sulphur In the concentrateo which may be desirable for certain applications. On the other hand sulphur addition leads to 0t~ evolution of hydrogen sulphide, thereby to some extent. detracting frqm the advantage of the invention as hereinbefore mentioned, Proferably the reaction is carried out In the p es1ende, of 4 further component which is a catalyst for the roaction, As catalyst there may be used an inorganic halide which may suitaball be either a hydrogen halide, an amonium halide or a mattal i,',Aide, Suitably~ the metal moiety of the Metal halide may be z.inct atIAnrium, or an alkaline earth metal, preferably calcium. Of the halidess the chloride is preferred, Suitable catalysts incolude hydrogen chloride, calcium chloridet ammoium, chloride, aluminium. chloride and zinc chloride) preferably calcium chlorido, Suitaby, the amount of catalyst employed m-ay be up to 2,0% wt/wt, Suitably the reaction of components and alsai the carbonation reaction may be carried out at elevated temperatures In the range from 120 to 200, preforably from about 1430 to 104Ct though the actual temperatures chosen for the reaction at componotaz and the carbonation may differ if desired, the peodtg mnay be atmosphorial dubatmospheric or superatmospharic.

TMq conleentrato may, bq recoverad by conventional m~eans, tor exaimple by di~tillat-00 #ttppih4 of domponent and diludnt~ (19

U

WO 88/03945 PCT/GB87/00848 12 any) Finally, it is preferred to filter the concentrate so-obtained, Generally, the process of the invention will produce a concentrate having an acceptable viscosity, '~hat is a viscosity of less than 1000 cSt at 100'C, and can produce concentrates having a viscosity less than 750 or 500 cSt at 100'C. Moreover, the concentrates generally have desirable viscosity index properties, Such viscometric properties are advantageous because they facilitate processing (including filtration) of the concentrate. However, it is also possible to produce concentrates having a higher viscosity than 1000 cSt at 100'C, generally at higher TEN levels. Filtration of such concentrates presents a problem, which may be: overcome by adding a diluent prior to filtration and strippiL t.he diluent off after filtration. Alternatively, or in addition, the concentrate may be diluted with lubricating oil and still retain a TBN in excess of 300, particularly if the TEN of the concentrate as produced is high, for example above 400.

In a final aspect the present invention provides a finished lubricating oil composition which composition comprises a 2Q lubricating oil and sufficient of the additive concentrate as hereinbefore described to provide a TBN in the range from 0.5 to 120.

Preferably the finished lubricating oil composition co,,taits sufficient of the concentrate composition to provide a TBN in ,e range from 0,5 to 100.

The amount of concentrate composition present in the finished lubricating oil will depend on the nature of the final use. Thus, for marine lubricating oils the amount of concentrate composition present may suitably be sufficient to provide a TBN in the range from 9 to 100 and for automobile engine lubricating oils the amount may suitably be sufficient to provide a TBN in the range from 4 to The finished lubricating oil may also contain effective amounts of one or moire other types of conventional lubricating oil additives$ for example viscosity index improvers, anti-wear agents, rr I W0O88/03945 PCT/GB87/00848 13 antioxidants, dispersants, rust inhibitors, pour-point depressants, or the like, which may be incorporated into the finished lubricating oil composition either directly or through the intermediacy of the concentrate composition.

In addition to their use as additives for incorporation into lubricating oil compositions, the concentrate compositions of the present invention may also find application as fuels additives.

The invention will now be further illustrated by reference to the following Examples.

In all the Examples the term "TBN" is used. The TBN is the Total Base Number in mg KOH/g as measured by the method of ASTM D2896.

In all the Examples, except otherwise expressly stated, a commercially available sulphurised calcium alkyl phenate derived from a C12-alkyl phenol was employed. The phenate is supplied as a solution in lubricating oil, which forms from 36-40% w/w of the composition. The composition has a TBN of 250 and a composition as follows;- calcium (9,25% sulphur (3,25% w/w) and carbon dioxide Where the "Charge" for any Example includes lubricating oil, this is additional to that already present in the phenate composition.

The viscosity was measured by the method of ASTM D445.

Example 1 Up-grading of Sulphurised Calcium Alkyl Phenate Charge: Lubricating oil (57 g) Sulphurised calcium alkyl phenate (206 g) Lime (49 g) Stearic acid (70 g) Calcium chloride 4 g) 2-ethyl hexanol (112 g) The charge was heated to 145-165*C/700 mm Hg whilst adding 36 g ethylene glycol. It was then maintained for one hour at 165'C/700 mg Hg. Carbon dioxide (50 g) was added at 165'C over 1 hour. The product was cooled to 115'C/700 rA Hg. Lime (33 g) was

I

An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: a lubricating oil; a lubricating oil soluble sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 35 by weight based on the weight of the composition of either at least one carboxylic acid having formula wherein R is Clo to C 24 alkyl or alkenyl group and R' is either hydrogen, a C to C 4 alkyl group or a -CH 2 -COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 2 to 100 carbon atoms or an anhydride, acid chloide or ester thereof, the composition having a TBN greater than 300.

s *WA WO 88/03945 PCT/GB87/00848 added. The temperature was raised to 165"C/700 mm Hg and held at this temperature for one hour. Carbon dioxide (25 g) was added at 165'C over one hour. The product was then stripped at 200'C/10 mm Hg. Finally the product was filtered. It was observed that the filtration rate was very fast. 437 g product and 167 g distillate were obtained.

The product was analysed for calcium, sulphur and carbon dioxide. Its TBN, BPHVI50 and Viscosity at 100'C were determined.

The BPHV150 determination is a solubility test. Results of the test are expressed on the scale 1 (highly soluble; pass), 2 (borderline) and 3 (fail).

Results Calcium 13.9% w/w (corresponding to 96% retention in Sulphur the product of the calcium charged.

1,5% w/w (corresponding to 100% retention in the product of the sulphur charged), 12.3% w/w (corresponding to 62% retention in the product of the CO 2 charged).

Carbon Dioxide TBN 395

V

100 228 cSt

A

Stearic acid 16% w/w This Example demonstrates that a low TBN product can be converted to a high TBN product having an acceptable viscosity by the process of the invention.

Example 2 Charge: Sulphurised Calcium alkyl phonate 230 g Lubricating oil Calcium chloride 26 g 3 g Method The charge was heated to 100*C/700 mm Hg. Stearic acid (63 g) was added and the mixture stirred for 15 minutes, 2-Ethyl hexanol (190 g) was added at 100 110*C/700 mm Hg, Lime (66 g) was added at 110OC/700 mm Hg, The mixture was heated to 165*C/700 mm Hg and ethylene glycol (32 g) was added quickly (one minute), acidic matera-Lz the suiphurised metal alkyl phenates, wherein the metal is an alkaline earth metal such as calcium, magnesium or barium. Both I WO 88/03945 PCT/GB87/00848 The mixture was held for 5 minutes at 165*C/700 mmn Hg, Carbon dioxide (66 g) was then added at 165*C/l bar, The solvent was recovered at 200*C/1O mm Hg, and atripped product was filtered.

Product Weights Crude Product Distillate iAfter Filtratio Product Comoositior The filtration rate was fast.

Calcium Sulphur C0 2

TBN

V

100 Stearic acid 398 g 236 g 14. 1% v/v 2. 0% v/w 12.9% w/v 399 825 cSt 15.8% v/v Exaple 3 Charge: As for Example 2.

Met hod As for Example 2 except that the of l65*C in steps and (if).

Product Weights temperature was 145*C instead Crude Product Distillate i After Filtration Product Compositior Calcium SulphurI

CO

2

TBN

V

1 0 0 Stearic acid 402 g 239 g 13. 9; v/v 1. 9% v/v 13. 9% v/v 392 206 cSt 15. 7Z v/v Example 4 Charge: As for Example 2 Method As for Example 2 except that the temperature was 130'C instead of 165*C in steps and a reduced neutralisation capacity. In order to achieve a high neutralisation capacity product and at the same time control the viscosity of the intermediate product within acceptable limits, the WO 88/03945 PCT/GB87/00848 16 Products Weights Crude Product 377 g Distillate 236 g Prod a. Composition After Filtration Calcium 13.7% v/w Sulphur 2.1% w/w

CO

2 13.2% w/w TBN 380

V

100 99 cSt Stearic acid :16.7 w/w Example Charge: As for Example 3 except that calcium chloride was omitted, Method As for Example 3.

Product Weights Crude Product 388 g Distillate 239 g Product Composition After Filtration Calcium 11,9% w/w Sulphur 2.1% w/w C02 9.0% w/w TBN 331

V

100 98 cSt

V

40 1490 cSt VI 148 Stearic acid 16.2% w/w The filtration step was very difficult, This Example, as compared with Example 3 demonstrates the desirability of using a catalyst in the process of the invention.

In the absence of catalyst, although a lower V 100 was obtained, this was achieved at the expense of reduced incorporation of calcium and carbon dioxide, and moreover filtration was difficult.

Example 6 Charge: Sulphurised calcium alkyl phenate 253 g Lubricating oil (100 SN) 26 g reaction mixture which comprises: e I i I ID Wa-- WO 88/03945 PCT/GB87/00848 Calcium chloride 2-Ethyl hexanol Stearic acid 4 g 190 g 40 g Method The charge was heated to 120*C/700 mm Hg and lime (36 g) was then added, The mixture was heated to 145 165'C whilst adding ethylene glycol (32 g), The mixture was held for one hour at 165*C/700 mm Hg, Carbon dioxide (44 g) was added at 165*C/1 bar, The mixture was cooled to 120'C and lime (25 g) was added, The mixture was held at 165'C/700 mm Hg for one hour, Carbon dioxide (22 g) was added at 165'C/1 bar, The solvent was stripped off at 200*C/10 mm Hg, and The product was filtered. The filtration rate was fast.

Product Weights Crude Product Distillate Product Composition After Filtration Calcium Sulphur C02 401 g 239 g 14.3% w/w 2.1% w/w 11.3% w/w TBN 405

V

100 1483 cSt Stearic acid 10% w/w This Example demonstrates that it is possible to produce a high TBN concentrate, though the viscosity is relatively high, by incorporating 10% w/w stearic acid.

Example 7 Charge: As for Example 6 except that the phenate was increased from 250 g to 268 g and the stearic acid was increased from 40 g to 51 g.

thodAs for Exampl 6.

As for Example 6.

I r r i I I concentrates containing overbased additives, namely lack of stability giving rise to sedimentation and foaming problems. The problem of EP-A-0094814 is not that of producing phenates having a I WO 88/03945 PCT/GB87/00848 Products Weights Crude Product 396 g Distillate 234 g Product Composition After Filtration Calcium 14.5% w/w Sulphur 2.2% w/w

CO

2 13.1% w/w TEN 399

V

100 706 cSt Stearic acid 12.9% w/w This Example demonstrates that a high TBN concentrate having a lower viscosity as compared with Example 6 can be produced at a stearic acid content of 12.9% w/w based on the weight of the concentrate.

Example 8 Charge: Sulphurised calcium alkyl phenate 230 g Lubricating oil (SN 100) Calcium chloride 0 g Method The charge was heated to 100'C, stearic acid (99 g) was then added and the mixture was stirred for 15 minutes, 2-Ethyl hexanol (190 g) was added at 100 110C, Lime (66 g) was added at 110*C/2" Hg vacuum, The mixture was heated to 145'C/10" Hg and ethylene glycol (32 g) was added over 20 minutes, The mixture was held for 5 minutes at 145'C/10" Hg, Carbon dioxide (66 g) was added at 145'C, The product was stripped at 200*C/30" Hg, and The product was filtered. The filtration rate was slow.

Product Weights Crude Product Distillate 398 g 209 g thereof, the weight ratio of components to being such as to produce a concentrate having a TBN greater than 300.

/as

I

L WO '89/O3945 PCT/GB87/00848 Product Composition After Filtration Calcium Sulphur C02

TBN

V

100 Vloo

V

40 Stearic acid This Example demonstrates that TBN concentrate having a low viscosi 24.9% w/w,.

Comparison Test I Charge; As for Example 3.

Method As for Example 3 except that th step was omitted.

Product Weights Crude Product Distillate Product Composition After Filtration 11.95% w/w 1.65% w/w 11.6% w/v S 349 S 100 cSt S 974 cSt 24.9% w/w it is possible to produce a high ty at a stearic acid content of ie addition of ethylene glycol in 332 g 200 g

I

Calcium 8,4% w/w Sulphur 2.3% w/w

CO

2 4.4% w/w TBN 239

V

1 0 0 41 cSt The filtration rate in step was slow.

This is not an example according to the present invention and is included for the purpose of demonstrating that the presence of a component is essential to the performance of the process of the invention.

Example 9 Charge: As for Example 3.

Method As for Example 3 except that the ethylene glycol addition in step was reduced from 32 g to 16 g.

e F ._i -6-

I

WO 88/03945 PCT/G B87/00848 Product Weiphts Crude Product Distillate After Filtration 399 g 225 g Product Composition Calcium 13.7% w/v Sulphur 2.0% w/w

CO

2 13.5% v/v TBN 1195

V

100 182 cSt Stearic acid 15.8% v/v The filtration rate in step was slow.

This Example demonstrates that the addition of ethylene glycol can be reduced by 50% as compared with Example 3.

Example Charget Sulphurised qalcium alkyl phenate Lubricating oil (100 SN) Ammonium chloride Acetic acid 230 g 26 g 4g Zg Method As for Example 3 except that in step instead of 2-ethyl, hexanol (190 g) there was added methyl dlglycol (130 g) and in step the addition of ethylene glycol was omitted.

Product Wegt Product Compositioi Crude Product Distillate i After Filtration Calcium Sulphur C0 2

TBN

V

100

V

40

VI

Stearic acid 390 g 166 g 14. 1% v/w 2. 0% v/w 14. 2% v/v 19 8 210 cSt 3821 cSt 170 16.2% v/w

I

compolefL r r (2,t O gyoa lyeegyo carbon atoms, a di- orti (C toC) lyla alleegcl alkyl ther or a polyalicylefle glycol alkyl ether. ThepOlyhydri. alcohol may suitably be either a dihydric alcohol, for example El ,WO 88/03945 PCT/GB87/00848 The filtration rate in step -*as rapid.

This Example demonstrates that LNthyl diglycol is effe .tive as component Example 11 Charge,: As for Example 3.

Met hod As for Example 3 except that in 270 mm Hg.

P:rodu... Weig~ht Crude Product Distillate iAfter Filtration Product Compositior Calcium Sulphur C0 2

TBN

V

1 0 0 Stearic acid step the pressure was 402 g 238 g 14. 0% w/v 1. 9% W/w 14,4% w/w 392 288 oSt 15,7% W/W ExaPle 12 Charve: As for Example 3.

Method As or Example 3 except that there was u4sed 40 g.

Product.Weights instead of 190 g 2-ethyl hexanol Crude Product Distillate iAfter Filtratlo Product Comositior Calcium Sulphur C0 2

TBN

V

1 0 0

V

4 0 vi 399 g 90 g n 13. 9% v/v 1. 9% v/v 12,.1; v/v 387 cSt t7980 cSt 193 15.8% v/v Stearic acid 8345S/as -8- I WO 88/03945 PCT/GB87/00848, Example 13 Charge: Suiphurised calcitl alkyl phenate Stearic acid Calcium chloride

C

18 linear aipha-olefin 2-ethyl hexanol 230 63 g 4 g 26 g 90 g Method The mixture was heated to 145 165*C/700 mm, Hg whilst adding ethylene glycol (32 g), The mixture was held for 30 minutes at 165'C/700 rmm Hg,

CO

2 (38 g) was added at 165*C/1 bar, The mixture was cooled to 120*C and 2-ethyl hexanol (100 g) added, Lime (66 g) was added, The mixture was held at 165'C/100 mm Hg for 5 mliutes, Carbon dioxide (66 g) was added, The solvent was recovered by stripping at 200*C/1O ig The product was filtered.

Product Weights Crude Product I Distillate 1 kAfter Filtration 385 g 256 g Product Comnositiox.

Calcium 14,18% w/w Sulphur 1.9; w/w C0 2 13,4% w/w TBN 424

V

100 583 cSt

V

40 i 13,080 cSt VI 209 Stearic acid 1 6.4Z w/w The filtration rAte ini step was rapid, This S.xamrple demoriatra),es that a lubricating oil can be replaced by a lot%& carbon i-phain aipha-olefin (in this case C 18 derivatives or tne acia, preteraniy tcne acia annyariae. i T.

is preferred however to use a carboxylic acid or a mixture ""34 5S/as -9- WO 88/03945 PCT/GB87/00848 23 Example 14 Charge: Suiphurised calcium alkyl phenate (250 TBN) derived from a mixture Of C 12

/C

22

/C

24 alkyl phenols 233.5 g Lubricating oil (SN 100) :26 g Calcium chloride 3 3g Method The mixture was heated to 1001CO stearic acid (63 g) was added and the mixture was stirred for 15 minutes# 2-Ethyl hexanol (194 g) was added at 100 110C, Lime (66 g) was added at 110*C/2" Hg vacuum, The ixture was heated to 145*C/10 1 Hg and ethylene Zlycol (32 g) added over 20 minutes, The mixture was held for 5 4nnutes at 145*C/10" Hgt Carbon dioxide (66 g) was added, The product was stripped at 200'C/30" Hg, The product was filtered.

Product Weights Crude Product 385 g Distillate 250 g Product Composition After Filtration Calcium 14,0% '41w Sulphur I .Q4X V/W

CO

2 :1249% w/v TBN 401

V

100 I Al8 cSt

V

40 8385 cSt VI 186 Stearic acid :16.4 w/w This Example demonstrates that sulphurised calcium alkyl phenates derived from a mixture Of C 1 2

/C

2

!/CZ

4 alkyl phenols can be upgraded.

Example Charge: Sulphurised calcium alkyl phonate t 181 834 5S/as

WT

WO 88/03945 PCT/GB87/00848 Lubricating oil (SN 100) Calcium chloride Rape Top Fatty Acid 2-Ethyl hexanol 4 62 190 Method The mixture was heated to 120*Cs Lime (43 g) was added at 120'C/2" Hg vacuumt Ethylene glycol (32 g) was added at 145 165*C/2" Hg, The mixture was held at 165'C/2" Hg for I hour, Carbon dioxide (44 g) was acded, ()The mixture was cooled to 130'C and lime (Z9 g) was ad 130-C/2" Jg The mixture was held at 165'C/2" Hg for 1 hour, Lime (22 g) was added at 165"C, The product was stripped at 200'Q/304 1Igj (j The product was filterad, Product Weights ded at Cru.de Product 1 82 i4 Distillate 1 230 g Product Composition Aftemr Filtration Calcium 1 14j0% w/w Sulphur 1.8% v/w C0 2 12.3% v/v TBN 374

V

10 6 176 -St,

V

40 120:~ 43t VI 172 Carboxylic Acid content t 1641 This Example dem~onstrates that Rakpe Ti p Fatty Acid can be use, In the process of t~he invention, EXample16I Charge: Sulphurised calcium alkyl.

phonate Lubricating oil (SN 100) Calcium chloride 26 t 3 &g WO,88/O3945 PM 71B81108 Method As for Example 2 except that in step Irtemi of stworic acid (63 g) there was used Tall Oil Fatty Acid (63 g).

Product Weights Crude Product Distillate Product Composition After Filtration Calcium Sulphur C0 2

TBN

380 g 223 g 14. 0% v/w 2.09% v/w 9,7% w/lw 380 V100 ;263 cSt CarboXylic acid content 16,6 Z w/w based on the weight of product, This Excample demonstrates that Tal~l Oil fatty Acid can be used in the process of the Tnvention4 Example 17 Charget As for E.=amp 16, Method As for Excamnple 16 except that instead of Tall Oil Fatty Acid (63 g) there was used a mixture of 52 g polyisobutene succinic anhydri~de (PIDSA) in SN 100 lubricating oil (TBN 6 0 mg KOH/g), and stearic acid (47 g).

Product Weights Crude Product Distillate t Pr ,oduct Composition After Filtration 390 Calcium sulphur C0 2

TBN

V

100

V

4 0 13,1% v/v 1. 8; v/v 12.5% v/v a6O 416 cSt 1,4,690 cst 1614 12.1 v bastd on the 7.2 v,/w wei~ght of product P;arboxylic acid content Anhydride content of one or mozre other types of conventional lubricating oil additives, for example viscosity index improvers, anti-wear agents, WO 88/03945 PCT/GB87/00848 26 This Example demonstrates that the carboxylic acid can be replaced in part by PIBSA in the process of the invention.

Example 18 Chge: As! f or Example 16.

M'ethod As for Example 16 except that instead of Tall Oil Fatty Acid (63 g) there was used behenic acid (63 g).

Product Weights Crwie Product 402 g Distillate 247 g Pro.. 'ct Composition After Filtration Calc ium 12.4v^ wlA Sulphur 1.9% w/w

CO

2 i.4% w/w BN354 1I00 141 cSt qehenic acid 5.7 V/w This '-t.uapla dtimonstrates that behatli- acid can be used as carboxylic L:id in the pro-less of the invention, Example 19 Charge.- As for Exainpla 15 except that In.-ead of R~ape Top Fatty Acid (62 g) there was used palmitic acid (56.2 g).

Method As for Example 15 except that steps and were omitted.

Pro~uct Weiphts Crude Product 312 g Distillate 1 222 g Product Composition After Filtratioi Calcium 11.7% w/w Sulphur 1.9% v/w C0 2 8#2% v/w TBN 332

V

100 70 cSt V4 8% cSt 165*C/700 mg Hg. Carbon dioxide (50 g) was added at 165'C over 1 hour. The product was cooled to 125*C/700 r= Rg. Lime (33 g) was 0O 88/03945 PCT/GB87/00848 VI 156 Falmitic, acid 18.0 W/w This Example demonstrates that palmitic acid can be used in the process of the invention.

Example Charge: As for Example Method As f or Exzrle 15 except that steps and were omritted.

13 Product Weight, ie Product Distillate Product Composition After Filtration Calc ium Sulphur C0 2

TBN

V

1 0 0

V

4 0

VI

Carboxylic acid content Comarison Test 2 Charge- Sulphurised calcium alkyl phenate Lu.bricating oil Calcium chloride Met hod 334 g 234 g 11,8% w/w 1, 8Z W/w 10. 9z W/w 321 168 cSt 1009 cSt 286 18.6 ~w/w based on the weight of product.

i230 g 26g 3g, and 2-ethyl hexanol (190 g) was The mixture wLs heated to 100*C added, Acetic acid (14 g) was added, The mixture became thick and heterogeneous and assumed a green colouration. Stirring was ineffective. The reaction was discontinued.

This Test is not an example according to the present invention 2-Ethyl hexanol (190 g) was added at 100 110C/700 mm Hg, Lime (66 g) was added at 110'C/700 mm Hg, The mixture was heated to 165'C/700 mm Hg and ethylene glycol (32 g) was added quickly (one minute), WO 88/03945 PCT/GB87/00848 28 and is included only for the purpose of demonstrating that lower carboxylic acids, in this case acetic acid, can not be used in the process of the invention.

Example 21 Charge: As for Example 16 except that instead of the commercially available sulphurised calcium alkyl phenate there was used an uncarbonated commercially available sulphurised calcium

C

12 -alkyl phenate (145 TBN).

Method As for Example 16 except that in step the amount of lime was increased from 66 g to 83 g and in step the amount of carbon dioxide was increased from 66 g to 83 g.

Product Weights Crude Product 421 g Distillate 246 g Product Composition After Filtration Calcium 13.7% w/w Sulphur 1.9% w/w

CO

2 10.3% w/w TBN 383

V

10 0 137 cSt

V

4 0 2119 cSt VI 163 Carboxylic acid 15.0% w/w This Example demonstrates that an uncarbonaed sulphurised salcium alkyl phenate of low initial TBN can be used in the process )f the invention.

E IaDle 22 Charge! A carbonated sulphurised calcium alkyl phenate (150 TBN) i 253 g Stearic acid 40 g 2-Ethyl hexanol 90 g Calcium chloride 4 g Method The mixture was heated from 145 to 165*C/700 mn Hg whilst t

CLIII-

WO 88/03945 PCT/GB87/00848 29 adding ethylene glycol (32 g), The mixture was held at 165'C/700 mm Hg for 30 minutes, Carbon dioxide (38 g) was added at 165'C/1 bar, The mixture was cooled to 120*C and there was added 2-ethyl hexanol (100 g) and lime (76 g), The mixture was held for 60 minutes at 165'C/700 mm Hg, Carbon dioxide (82 g) was added at 165'C/l bar, Solvent was recovered at 200'C/10 mm Hg, and The product was filtered.

Product Weights Product Weight Product Composition After Filtration Calcium Sulphur CO2

TBN

V

100 Stearic acid This Example demonstrates that a calcium alkyl phenate can be upgraded Example 23 Charge: As for Example 14 except thi 390 g 14.4% w/w' 2.3% w/w 11.6% w/w 402 674 cSt 10,3% v/w low (150) TBN sulphurised to a high TBN product.

at instead of the sulphurised calcium alkyl phenate derived from a mixture of alkyl phenols there was used the commercially available sulphurised calcium alkyl phenate derived from a Cl2-alkyl phenol (250 TBN).

Method As for Example 14 except that in step instead of 2-ethyl hexanol (194 g) there was used iso-heptanol (190 g) and in step (d) the ethylene glycol was added quickly (within 1 minute).

Product Weights Crude Product Distillate S 402 g 239 g WO 88/03945 Product Composition After Filtration Calcium 13.9% v/v Sulphur 1. 9% v/v C0 2 12. 0% v/v TBN :391

V

100 :313 cSt

V

4 0 :6700 cSt VI 177 Stearic acid 15.7% v/v The filtration rate was rapid.

This Example demonstrates thz.-, iso-heptanol solvent in the process of the invention.

PCT/GB87/00848 may be used as

Claims (2)

1. An additive concentrate suitable for incorporation into a finished lubricating oil which concentrate is obtainable by reacting at elevated temperature a sulphurised alkaline earth metal hydrocarbyl phenate having a TBN less than that of the final additive concentrate, an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during the reaction, either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C 2 to C4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, a lubricating oil, o. carbon dioxide added subsequent to the, or each, addition of component and sufficient to provide from greater than 2 to 35% by weight based on the weight of Sthe concentrates of either a carboxylic acid having the formula: formula: @6 r S *.@625 @06656 6 R CH COOH I 1 wherein R is a C10 to C24 alkyl or alkenyl group and R 1 is either hydrogen, a C1 to C 4 alkyl group or a -CH -COOH group, or an acid anydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride, acid chloride or ester thereof, the weight ratio of components to being such as to produce a concentrate having a TBN greater than
300. 2. A process for the production of an additive concentrate which process comprises reacting at elevated temperature a sulphurised alkaline earth metal hydrocarbyl phenate having a TBN less than that of the final additive concentrate, an alkaline earth metal base added in either a single addition or in a plurality of additions -31- As for Example 3 except that the ethylene glycol addition in step was reduced from 32 g to 16 g. at intermediate points during the reaction, either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C 2 to C 4 glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, a lubricating oil, carbon dioxide added subsequent to the, or each, addition of component and sufficient to provide from greater than 2 to 35% by weight based on the weight of the concentrate of either a carboxylic acid having the formula (as hereinbefore defined) or an acid anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride, acid chloride or ester thereof, the S weight ratios of components to being such as to produce a concentrate having a TBN greater than 300. 3. A process according to claim 2 wherein S* component is lime. 4. A process according to either claim 2 or claim 3 wherein the weight ratio of component to component (A) is in the range from 0.2 to 5. A process according to any one of claim 2-4 wherein component is ethylene glycol. 6. A process according to any one of claims 2-4 wherein component is methyl digol. 7. A process according to any one of claims 2-6 :25 wherein the carbon dioxide (component E) is added subsequent to a single addition of component at the conclusion of the reaction between components to and 8. A process according to any one of claims 2-7 wherein a diluent is present. 9. A process according to any one of claims 2-8 wherein sulphur additional to that already present by way of component is added to the reaction mixture. A process according to any one of claims 2-9 wherein the reaction is carried out in the presence of a catalyst. 11. A process according to claim 10 wherein the catalyst is calcium chloride. 83 -32- I I 12. A process as claimed in claim 2 substantially as herein described with reference to any non-comparative Example. 13. An additive concentrate prepared by a process as claimed in any one of claims 2-12. 14. A finished lubricating oil composition which composition comprises a lubricating oil and sufficient of the additive concentrate as claimed in claim 1 or claim 13 to provide a TBN in the range from 0.5 to 120. 15. A finished lubricating oil composition according to claim 14 wherein the lubricating oil is a marine lubricating oil and sufficient of the additive concentrate is present to provide a TBN in the range from 9 to 100. ,15 16. A finished lubricating oil composition according to claim 14 wherein the lubricating oil is an automobile engine lubricating oil and sufficient of the additive concentrate is present to provide a TBN in the range from 4 to DATED this 18th day of December 1990 S BP CHEMICALS (ADDITIVES) LIMITED *51g I *L I CI I S. Sl S SI se* 0 a, 'OS. SO I I S I By their Patent Attorneys GRIFFITH HACK CO. 8345S/as -33- Thisi~'amile emostr t tat a lubricating oil can be replaced b7 a lo11g carbon 'hain alpha-.olefin (in this case C 18 INTERNATIONAL SEARCH IiEPORT ;;%lornatfornal Application No PCT/GB3 87/0i0848 1. CLASSIFICATION OF SUBJECT MATTER (it several aIssI catlaov ilmools oly, indicate all)I According (a Internaion~al Patent Classification (IPC) or to ?join National Clasartication and IPC 4 C 10 MI 159/22 11. FIELDS SEARCHED Minimum Documentation Searched Classiication System Ctessificslion SYMOole IPC 4 C 10QM;C07 C Documentation Searched other than Minimum Documeantation to the Extent that sucih Doctimanta ara Included In the Filds Searched III, DOCUMENTS CONSIDERED TO Of RELEVANT I Cala7gory Citation of Ulcument, -with Indication, whoreo toorooris, of the relevant Vaucagoo 11 Relievant to dCim No, i) X EP, A, 0095322 (OROBIS LIMITED) 1-13117- November 1983 32 see pages 5-8; examples 10-12; A claims 1,3-6,8,11-13 1 A 16 X US, A, 4328111 WATSON) 1-13,17-32 4 May 1982 see column 2, lines 21-68; column3 column 4, lines 5-24; column 6, line 9 column 8, line 10; column 9, examples 1.1,12* Special categories of cited documental, 14 IT~" later document published after the International filing date ocuentdafnin th geera stte f te at w Iis not of Priority dats and not In conflict withtthe applicat:on out A"dcuntida in to e gerala reltae th mlhch0d to understand tMe Principle or theory tinoariring the consderd t be t pll'144lr rlevnceinvention '"earlier document but Published am or atter the International IX document of particular relovanct the claimed iniventian n ng datecannot be considered novel of cannot be coneid4sad to document which may throw doubts on priority ctlm(s) or involve an inventive step which is cited to seablish the puiblication date of another document of ourlicular relevances* the Claimed invention citation or other special reason (as specified) cannot be cornsidered to invoiveam inventive step wnan the document referring to on oral disclosure, use, eahibitlj~i or document is comorned with one or more olhar such docU, other means mrents, such cornolnetion being obvious to a person siled NIX" document published prior to the International fIling date but In the arLt later than the priority date claimed 160 document mamber of the "mm patent family IV. =d11T1FICATION at fin* Actual Completion of 1te lriesnatiorial search February 1988 fo trnational Searohing Authority EUR~OPEAN PATE N OFFICE Form PCTII~21O toocond sheet tisnuisv'v P9IS) I, 1 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. GB 8700848 SA 19584 This annex lists the patent family members relating to the patent documents cited in thle nbove-mentioned international search report, The members are as contained in the Euro0pean Patent Office ED12 ile on 16/03/88 Tile E~uropean Patent Office is in no way liable for these particulars vthich arc merely given for the purpose of information. Poetdocument Publication tetfmyPbicio vie i CorhrPOr date member(s) date EP-A- 0095322 30-11-83 AU-A- JP-A- AU-B- 1482883 59025343 556650 24-11-83 09-02-84 13-11-86 US-A- 4328111 04-05-82 None SFor more details~ about this annex 1 see Official Journal of the Vuropcun I'otgnt 0rnile, No., 12182
AU82380/87A 1986-11-29 1987-11-26 Sulphurised alkaline earth metal hydrocarbyl phenates, the production and use thereof Ceased AU608792B2 (en)

Priority Applications (2)

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GB868628609A GB8628609D0 (en) 1986-11-29 1986-11-29 Lubricating oil additives
GB8628609 1986-11-29

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AU608792B2 true AU608792B2 (en) 1991-04-18

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AU647473B2 (en) * 1990-02-23 1994-03-24 Lubrizol Corporation, The High temperature functional fluids

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GB8628609D0 (en) * 1986-11-29 1987-01-07 Bp Chemicals Additives Lubricating oil additives
GB8814008D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Lubricating oil additives
GB8814010D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Addivites Ltd Lubricating oil additives
GB8814013D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
GB8814009D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Lubricating oil additives
GB8814012D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
EP0385616B1 (en) * 1989-02-25 1994-06-01 Bp Chemicals (Additives) Limited A process for the production of a lubricating oil additive concentrate
GB8917094D0 (en) * 1989-07-26 1989-09-13 Bp Chemicals Additives Chemical process
GB9213723D0 (en) * 1992-06-27 1992-08-12 Bp Chemicals Additives Process for the production of lubricating oil additives
TW277057B (en) * 1993-08-25 1996-06-01 Cosmo Sogo Kenkyusho Kk
JP2737096B2 (en) * 1993-08-25 1998-04-08 コスモ石油株式会社 Overbased sulfurized alkaline earth metal phenate of preparation
GB9318810D0 (en) * 1993-09-10 1993-10-27 Bp Chem Int Ltd Lubricating oil additives
GB9325132D0 (en) * 1993-12-08 1994-02-09 Bp Chemicals Additives Lubricating oil additives
US6008166A (en) * 1994-01-11 1999-12-28 Lubrizol Adibis Holdings Limited Detergent compositions
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