AU609075B2

AU609075B2 - Alkaline earth metal hydrocarbyl phenates, their sulphurised derivatives, their production and use thereof

Info

Publication number: AU609075B2
Application number: AU82372/87A
Authority: AU
Inventors: Charles Cane; John Crawford; Sean Patrick O'connor
Original assignee: BP Chemicals Additives Ltd
Current assignee: Lubrizol Adibis Holdings UK Ltd
Priority date: 1986-11-29
Filing date: 1987-11-26
Publication date: 1991-04-26
Anticipated expiration: 2007-11-26
Also published as: FI883503A0; JPH0631383B2; FI93654C; SG101192G; AU8238087A; DE3781118D1; GR3006112T3; FI883503A; CN1015642B; EP0273588B2; DE3781118T2; NO883349L; KR890700159A; JPH01501400A; WO1988003944A1; EP0273588A1; ES2051751T3; SG101092G; DK175287B1; FI883502A0

Abstract

An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: (a) a lubricating oil, (b) a lubricating oil soluble sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to 35% by weight based on the weight of the composition of either (i) at least one carboxylic acid having the formula:- R - @@ - COOH (I) wherein R is a C10 to C24 alkyl or alkenyl group and R<1> is either hydrogen, as C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition having a TBN greater than 300.

Description

.1~ AU-AlI-823 72/87 WORLD INTELLECTUAL PROPERTY ORGANIZATION PIC6TOwqI!.7T COOPEATW= INTERNATIONAL APPLICATION P6' 7T COEAINTREATY (PCT) (51) International Patent Classification 4 (11) lnternatlunal Publien'lon Number: WO 88/ 03944 ClOM 159/22 jAl (43) Internationgi Publication Date: 2 June 1988 (02.06.88) (21) International Appli;-ation Number: PCT/GB87/00847 (74) Agept: FAWCETT, Richard, Fennelly; BP International Limited, Patents Agreements Division, Chertsey (22) International Fihig Date: 26 November 1987 (26.11.87) Road, Sunbury-on-Thames, Middlesex TWl6 7LN

(GB).

(31)Pririt AplictionNumer:862609(81) Designated States: AU, BR, DK, FI, JP, KR, NO, US.

(32) Priority Date: 29 November 1986 (29.11.86) (33) Priority Country: GB Published With international search report.

Before the expiration of the time limit for amending the (71) Applicant (for all designated States except US): BP claims and to bc republished in the event of the receipt CHEMICALS (ADDITIVES) LIMITED [GB/GB]; of amendments.

Beigrave House, 76 Buckingham Palace Road, London SWI'W OSU -J-P 2 1 JUL 1988 S72) Inventors; and Inventors/Applicants (for US only) ,CANE, Charles [GB/GB]: 39 Loxley Green, West Borough Way, Anlaby Common, Hull, North Humberside HU4 7SJ LRLA CRAWFORD, Johri (GB/Gfl]1; Southcott, 13 Loxford AUST RALA RoadW, Caterham, 'Surrey CR3 6B3H O'CON- 1 UN 1988 NOR, Sean, Patrick 31 St. Martin's Court,16JN98 Beverley, North Humberside

VC

PENT OfFC (54) Title: ALKALINE E\ RTH METAL HYDROCARBYL PHENATES, THEIR SULPHURISED) DERIVATIVES, THEIR PRODUCTION AND USE rHEREOF This document contains Ow~ amiendmentS MaidC Lnc~r Section 49 and is correct for R CHi COOH (537) Abstract An additivwc concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: a) a lubricating fill, b) a lubricating oil soluble sulphurised or non-suiphurised alkaline earth metal hy.

drocarbyl phenate modified by Incorporation of from greater than 2 to legs than 40 by weight based on the Weight of the composition of either at least onie carboxylic. aclJ lnavl'g formula wherein R is a CI to C2 4 alkyl or ialkenyl group and RI is either hydrogen, a CI to C 4 alkyl group ur a -CI-1-COOH group, or an anhydride, acid chloride or cster thereof or (1i) a, di. or polycartxoxylic. acid, containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition, halving a TBN greate than 300.

,'WO 88/03944 PCT/GB87/00847 1 ALKALINE EARTH METAL HYDROCARBYL PHENATES. THEIR SULPHURISED DERIVATIVES, THEIR PRODUCTION AND USE THEREOF The present invention relates in general to alkaline earth metal hydrocarbyl phenates and their sulphurised derivatives, their production and use thereof as lubricating oil additives. In particular the present invention relates to concentrate additive compositions comprising alkaline earth metal hydrocarbyl phenates and their sulphurised derivatives having both a high total base number (TBN) and an acceptable viscosity, to their production and to their use as lubricating oil additives.

In the internal combustion engine, by-products from the combustion chamber often blow by the piston and admix with the lubricating oil. Many of these by-products eorm 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 ccmbustion chamber. Such 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.metal alkyl phenates and sulphurised metal alkyl phenates, wherein the metal is an alkaline earth metal such as calcium, WO 88/03944 PCT/GB87/00847 2 magnesium or barium. Both "normal" and "overbased" alkaline earth metal alkyl phenates have been employed. The term "overbased" is used to describe those alkaline earth metal alkyl phenates in which the ratio of the number of equivaldnts 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 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" 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" metal alkyl phenates. One such method for preparing "overbased" alkyl phenates generally referred to as the "single lime addition" process comprises reacting an alkyl phenol, in the presence or absence of sulphur, lubricating oil, 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 3 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 88/)3944 PCT/GB87/00847 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. Another 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), expressed 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 produce an additive concentrate comprising alkaline earth metal alkyl phenates or sulphurised derivatives thereof having a high TBN, that is a TBN greater than 300, and preferably greater than 350. 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 viscous products which, rather than being 'thinned' by subsequent carbonation attempts using excess carbon dioxide, are rendered insoluble. We have achieved this objective and thereby obtained products having a TBN in excess of 300, and in some cases greater than 350, whilst retaining an acceptable viscosity, that is a viscosity at 100'C of less than 1,000 cSt and avoiding insolubility by incorporating into the..reaction mixture 4 defined amount of certain carboxylic acids having at least 10 carbon atoms in the molecule or acid derivatives.

The use of carboxylic acids either in the production of alkaline earth metal alkyl phenates and their sulphurised derivatives or An association therewith in lubricating oil compositions is not new, see for example US-A-3,372,116; GB-A-1440261; US-A-4049560 and EP-A-0094814.

US-A-3,372,116 discloses an improvement in the method for preparing a basic metal phenate by reacting at a temperature between about 25*C and the reflux temperature a hydrocarbon-substituted phenol having at least 6 carbon atoms in the hydrocarbon WO 88/03944 PCT/GB87/00847 4 substituent, a mixture of said phenol with up to an equivalent amount of a hydrocarbon-substituted succinic acid or anhydride having at least about 6 carbon atoms in the hydrocarbon substituent, or a substantially neutral alkali metal or alkaline earth metal salt or either of the foregoing, about 1-10 equivalents, per equivalent of of a calcium or strontium base, and carbon dioxide, which improvement comprises carrying out the reaction in the presence of about 0.002-0.2 equivalent, per equivalent of said calcium or strontium base, of a carboxylic acid having up to about 100 carbon atoms or an alkali metal, alkaline earth metal, zinc or lead salt thereof. The preferred carboxylic acids are those containing up to about 10 carbon atoms, more preferred being monocarboxylic acids containing up to 10 carbon atoms and alkaline earth metal salts thereof. In many of the Examples water and a carboxylate salt are employed. Not only do we wish to avoid the presence of water but we also find that carboxylate salts can not be used in the process of the present invention because of their inherent insolubility in the system. The process of US-A-3,372,116 does not employ phenol to alkaline earth metal base ratios sufficient to produce phenates having TBNs in excess of 300.

GB-A-1440261 discloses a lubricating oil composition comprising a lubricating oil, a detergent or dispersant additive and a mixture of at least two carboxylic acids, one acid having a melting point of at least 20*C and not more..than 30 carbon atoms per molecule, and another acid having a melting point of below 20*C, the weight proportion of low melting point acid to high melting point acid being between 1.5:1 and 8:1. The detergent may be an overbased phenate, those having a TBN of 50 to 100 being considered very suitable. In the lubricating oil composition the mixture of acids is present in an amount of 0,05 to 2.0 wt 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: 15-40 wt of a sulphurised phenol or thiophenol containing one or more hydrocarbyl substituents, or a phenol or thiophenol WO 88/03944 PCT/GB87/00847 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 of a glycol, a C i to C 5 monohydric alkanol or C 2 to

C

4 ailkoxy alkanol, 2-15 wt of a magnesium hydroxide or active magnesium oxide, at least 0.1 wt X of a C l 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 Cig carboxylic acid, and at least 101 by weight of a diluent oil (including any present in components and The amount of carboxylic acid (component is preferably in the range 045 to 2,0% by weight. The product prepared by this reaction is said to have a TBN of about 200 to 250, e.g. 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 forulai CH COOH (I) R1 (wherein R is a CIO to C 24 unbranched alkyl or alkenyl group, and RI s is hydrogen, a C 1 to C 4 alkyl group or a -CH 2 -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 problzms. The problem of EP-A-0094814 is not that of producing phenate additive concentrates having a TBN of greater than 300 and indeed the phenate additive concentrates produped by the process of the 1, 1s WO 88/03944 PCT/GB87/00847 6 invention, although demonstrating 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 ire employed does not address the problem of producing additive concentrates comprising overbased alkaline earth metal hydrocarbyl phenates having a TBN of greater than 300 and an acceptable viscosity.

Accordingly, in one aspect the present invention provides an additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: a lubricating oil, a lubricating oil soluble sulphurised or non-sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to less than 40% by weight based on the weight of the composition of either at least ne carboxylic acid having the formula:- R CH COOH (I) R1 wherein R is a C 10 to C 24 alkyl or alkenyl group and R i is either hydrogen, a C 1 to C 4 alkyl group or a -CH 2 -COOH group, or an anhydride, acid chloride or ester thereof or (ii) a dior polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition having a TBN greater than 300.

Component of the composition is a lubricating oil. The lubricating 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 adi'pate, di'-octyl sebacate and tridecyladipate, or polymeric hydrocarbon lubricating jtils, for r r .WO 88/03944 PCT/GB87/00847 7 example liquid polyisobutenes and poly-alpha olefins. The lubricating oil may suitably comprise from 10 to 90%, preferably from 10 to 70%, by weight of the composition.

Component is a lubricating oil soluble sulphurised or non-sulphurised, preferably sulphurised, alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to less than 40% by weight based on the weight of the composition of either or Suitably the alkaline earth metal may be strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, more preferably calcium. The hydrocarbyl phenate moiety of the alkaline earth metal hydrocarbyl phanate is preferably derived from at least one alkyl phenol. The alkyl groups of the alkyl phenol may be branched or unbranched. Suitable alkyl groups contain from 4 to 50, preferably from 9 to 28 carbon atoms. A particularly suitable alkyl phenol is the C 1 2 -alkyl phenol obtained by alkylating phenol with propylene tetramer.

The alkaline earth metal hydrocarbyl phenate is modified by incorporation of either or As regards this is at least one carboxylic acid having the formula or an acid anhydride, acfi chloride or ester thereof. Preferably R in the formula io an unbranched alkyl or alkenyl group. Preferred acids of formula are those wherein R is a CI 0 to C 24 more preferably C 18 to C 24 straight chain alkyl group and RI is hydrogen. Examples of 'kitab.e saturated carboxylic acids of formula include capric acia, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric aoid. Examples of suitable unsaturated acids of S formula include lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid and linolenic acid. Mixtures of acids may also be employed, for 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. Such mixtures may be obtained synthetically or may be derived from r WO 88/03944 PCT/GB87/00847 8 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 of carboxylic acids. A preferred carboxylic acid of formula is stearic acid.

Instead of, or in addition to the alkaline earth metal hydroca;byl phenate may be modified by incorporation of which is a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride, acid chloride or ester derivative thereof, preferably an acid anhydride thereof. Preferably (ii) is a polyisobutene succinic acid or a polyisobutene succinic anhydride.

Preferably the carboxylic acid(s) having the formula the di- or polycarboxylic acid, or the acid anhydride, acid chloride or ester thereof is incorporated in an amount from greater than 10% to 35%, more preferably from 12 to 20%, for example about 16% by weight based on the weight of the composition. An advantage of incorporating greater than 10% of the iarboxylic acid or derivative thereof is generally a relativelylower concentrate viscosity.

Suitably the alkalie- earth metal may be present in the composition in an amount in the range from 10 to 20% by weight based on the weight of the composition.

The alkaline earth metal hydrocarbyl phenate may be either Ssulphurised or non-sulphurised, preferably sulphurised, Suitably sulphur may be present in the composition in an amount in the range from 1 to 6, preferably from 1.5 to 3% by weight based on the weight of the compos4ition, Suitably carbon dioxide may be present in the composition in an amount in the range from 5 to 20, preferably from 9 to 15% by weight based on thae vight of the eompoasition.

Preferably the TBN df the coaposition is greater than 350, more

I

r preferably greater than 400.

Suitably the composition may have a viscosity measured at 100"C of less than 1000 cSt, preferably less than 750 cSt, more preferably less than 500 cSt.

In another aspect the present invention provides a process for the production of an additive concentrate which process comprises reacting at elevated temperature (A) either a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, 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 .r 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 less than 40% by weight based on the i o0 weight of the concentrate of either a carboxylic acid having the formula or an acid anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid contai. 'ng from 36 to 100 carbon atoms or an acid anhydride, acid cih.oride or ester thereof, the weight ratios of components to being such as to produce a concentrate having a TBN greater than 300, SComponent of the reaction mixture is either a S. hydrocarbyl phenol or (ii) a hydrocarbyl phenol and 30 sulphur. Using component the product is an alkaline S earth metal hydrocarbyl phenate and using component (ii) the product is a sulphurised alkaline earth metal hydrocarbyl phenate. The hydrocarbyl phenol employed is that alkyi phenol from which is derived the desired hydrocarbyl phenate moiety as hereinbefore described.

-9- Sr WO 88/03944 PCT/GB87/00847 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 moie preferred is calcium. The alkaline earth metal base must bo 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 amount will depend on a number of factors including the nature of the sulphurised alkyl phenol and will be higher than the amounts generally employed in prior art processes.

Typically, the weight ratio of component to component may suitably be in the range from 0.2 to 50, preferably from 0.4 to 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. In order to produce an additive concentrate having a TBN greater than about 350 and a viscosity at 100'C of less than 1000 cSt it is particularly desirable to add component in at least two, and preferably more additions and to add component in an amount greater than 10 by weight based on the weight of the additiv concentrate product, component is either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C 2 to C 4 glycol alkyl ether. The polyhydric alcohol may suitably be either a dihydric alcohol, for example 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:- R (ORl)xOR 2 wherein R is a C I to C 6 alkyl group, R 1 is an alkylene group, R 2 is hydrogen or C1 to C6 alkyl and x is an integer in the range from I to 6, Suitable solvents having the formula (tI) include the monomethyl or dimethyl ethers of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol, A particularly suitable WO 88/03944 PCT/GB87/00847 solvent is methyl digol (CH 3

OCH

2

CH

2

OCH

2

CH

2 0H). Mixtures of glycol~s and glycol ethers of formula (II) may also be employed. Using a glycol or glycol ether of formula (11) as solvent it is preferred to use in combination therewith an inorganic halide, for example ammionium 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.

Comnponent is a lubricating oil as hereinbefore described with reference to the additive concentrate, Component is carbon dioxide, which may be added in the form of a gas or a solid, preferably Jn 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 In order to produce a conco 4 ,arate having a TBNI greater ttan about 350 the carbon dioxide is preferably added subsequent to, each of two or preferably more additions of componient Component 14s either a carboxylic acid of formula, a dior polycarboxylic. acid containing from 36 to 100 carbon atoms, or an acid anhydride, an acid chloride or ester thoreoe Ad horainbeforpdescribed with refeqrqnce to the additive concenvrato omposition,, The amount of the aforesaid required to provide from greater than 2, to less than 40% by weiglt based on the Weight of 0o e ncentratO will be to a first, approximation the amount desired in the concontrate, In calaulating this amount ai4lowAnde should be made for loss of water from, carboxylic acids, for exAmp ,e The reaction may be performed in, the PE405d of A diluent.

Suitab.. diluents are. liquids having A, volatility consistent wth operation of the procesaf i,e. having a volatility such that th'oy" are readily strippabie from the fdidtion mixture at the coct~aoj of the reaction. Examples of suitable diluents ineilu.ds Z-othyl hexanoll iso-octanql, is*-hoptanol and tri-decanol.

PreferAkly the reaction is carried out in the presence eE further efpdnnt which i! a catalyst for the roaction.4 An q~taliyst,

II-

WVO 88/03944 PCT/GB87/00847 12 there may be used an inorganic halide which may suitably be either a hydrogen halide, an ammonium halide or a metal halide. Suitably the metal moiety of the metal halide may be ,nc, aluminium or an alkaline earth metal, preferably calcium. Of the halides, the chloride is preferred. Suitable catalysts include hydrogen chloride, calcium chloride, ammonium chloride, aluminium chloride and zinc chloride, preferably calcium chloride. Suitably the amount of catalyst employed may be up to 2.0% wt/wt.

Suitably the reaction of components and also the carbonation reaction may be carried out at elevated temperatures in the range from 120 to 200, preferably from about 130 to 165'C, though the actual temperatures chosen for the reaction f components and the carbonation may differ if desired. The pressure may be atmospheric, subatmospheric or superatmospheric, The concentrate may be recovered by conventional means, for example by distillative stripping of component and diluent (if 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, that 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 propierties.

Such viscometric properties are advantageous because they facilita, 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 TBN levels. Filtration of such concentrates presents a problem, which may be overcome by adding a diluent prior to filtration and stripping the diluent off after giltration, Aiternatively, high viscosity concentrates, for example concentrates having a viscosity at 100'C greater than 1000 cSt, and also having a high TBN, for example greater than 350, may be diluted by addition of further lubricating oil whilst Faintaiining a TB greater than 300, thereby facilitating filtration.

In a final aspect the present invention provides a finished 'WO 88/03944 PCT/GB87/00847 13 lubricating oil composition which composition comprises a lubricating oil and sufZ cient 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 contains sufficient of the additive concentrate to provide a TBN in the range from 0.5 to 100.

The amount of additive concentrate present in the finished lubricating oil will depefnd on thb nature of the final use. Thus, for marine lubricating oils the amount of additive concentrate present may suitably be sufficient to provide a TBN in the range from 9 to 100 and for automobile engine lubricating oils the amount ay suitably be sufficient to provide a TBN in tiie range from 4 to The finished lubricating oil may also contain effective amounts of one or more other types of conventional lubricating oil additives, for example viscosity index improvers, anti-wear agents, 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 additive concentrate 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 KOHW as measured by the method of ASTM D2896.

The viscosity was measured by the method of ASTM D445.

In all the Examples, except otherwise expressly stated, a commercially available C1 2 -alkyl phenol obtained by alkylating phenol with propylene tetramer was employed.

Eramp*e I.

WO 88/03944 PCT/GB87/00847 14 Charge: C 12 -alkyl phenol 75 g Lubricating oil (100 SN) 131 g Lime 82 g Sulphur 23 g Stearic acid 70 g Calcium chloride 4 g 2-Ethyl hexanol 112 g Method The charge was heated to 145-'1-65'C/700 mm Hg whilst adding ethylene glycol (36 g), The mixture was heated at 165*C/700 mm Hg for one hour, Carbon dioxide (40 g) was added at 165*C/l bar, The mixture was cooled to 125*C/700 mm Hg, Lime (35 g) was added at 1254C/700 mm Hg, The mixture was heated at 165°C/700 mm Hg for one hour, Carbon dioxide (20 g) was added at 165"C/l bar, The product was then stripped of solvent at 200*C/10 mm Hg, and The product was filtered. The filtration rate was fast.

Product Weight Crude Product 436 g Distillate 169 g Product Composition After Fil ration Calcium 14.1% w/ Sulphur 2.9% w/w

CO

2 12.4% w/w TBN 396 VI00 308 cSt BPHV 150 1 Stearic acid 16.1%X w/w This Example demonstrates that a high TBN additive concentrate of acceptable viscosity can be produced in a "double lime addition" process according to the present invention.

Example 2 Charg%: As for Example I, except that the amount of lime in tha charge was increased from 82 g to 117 g corresponding to

I

WO 8/03944 PCT/GB87/00847 the total amount of lime added in Example 1 in two additions.

Method As for Example I except that the amount of carbon dioxide added in step was increased from 40 g to 60 g and steps (f) and were omitted. The filtration rate in the final step was slow.

Product Weight Crude Product Product Composition After Filtration 514 g Calcium 14.1% w/v Sulphur 3.0% w/w

CO

2 12.3% w/w TBN 390

V

100 7600 cSt Stearic acid 13,6X w/w This Example demonstrates that an additive concentrate phenate having a high TBN can be produced in a single lime addition process but under the conditions of the Example the viscosity of the product is unacceptable for commercial operation without dilution with lubricating oil.

Example 3 Charge; As for Example 1.

Method As for Example 1, except that in step the amount of carbon dioxide was increased from 20 g to 40 g and the following steps were added after step and before steps and The mixture was cooled to 120*C, Lime (35 g) was added at 120'C, The mixture was heated at 165*C/700 mm Hg, and Carbon dioxide (50 g) was added to the mixture.

Product Weights Crude Product Distillate 484 g 169 g

J

I .i 1~ I, WO 88/03944 PCT/GB87/00847 Product Composition After Filtration Calcium 15.8% v/w Sulphur 2.6% w/v

CO

2 15.0% w/w TBN 439

V

100 506 cSt Stearic acid 14.5% w/w This Example demonstrates that high TSN additive concentrates can be produced by the process of the invention by a triple lime addition.

Example 4 Charge: As for Example 1 except that the amount of lubricating oil was reduced from 131 g to 158 g and the acid was reduced from 70 g to 43 g.

amount of stearic Method As for Example 1 except that in to 135'C instead of 125'C.

Product Weights Crude Product Distillate Product Composition After Filtration step the mixture was cooled 442 g 155 g Calcium 14.1% w/w Sulphur 2.9% w/w C0 2 11.9% w/w TBN :393 Vl 00 t 3440 cSt Stearic acid 9.8% w/w This Example demonstrates by comparison with Example I that although a high TBN product can be produced at an acid level less than 10% w/w the viscosity of the product is high.

Example Charge; C 12 -alkylphenol 35.3 g Lubricating oil (SN 100) 131 g Sulphur :14.7 g Calcium chloride 4.0 g j j 1 o WO 88/03944 PCT/GB87/00847 Stearic acid 2-Ethyl hexanol 109.1 g 224 g Method The mixture was heated to 120*C, Lime (82 g) was added at 120*C/2" Hg vacuum, Ethylene glycol (36 g) was added at 145 165*C/2" Hg, The mixture was held at 165'C/2" Hg for 1 hour, Carbon dioxide (40 g) was added, The mixture was cooled to 130'C and lime (35 g) added at 130*C/2" Hg, The mixture was held at 165*C/2" Hg for 1 hour, Carbon dioxide (20 g) was added at 1650C, Solvent was stripped from the product at 200'C/30" Hg, and The product was filtered.

Product Weights Crude Product Distillate Product Composition After 'iltration Calcium Sulphur CO2

TEN

397 g 245 g 13.6% w/w 1.2% w/w 13.9% w/w 376

V

10 0 142 cSt

V

4 0 1881 cSt VI 180 Carboxylic acid 27.5% w/w This Example demonstrates that a high TBN product having an acceptable viscosity can be obtained using a stearic acid addition of 27.5% w/w based on the weight of the final product.

Example 6 Chirage: As for Example 5 except that the amount of C 12 -alkylphenol was reduced from 35.3 g to 15.6 g and the amount of stearic acid was increased from 109.1 g to 128.7 g.

Method As for Example r i: V I WO 88/03944 PCT/GB87/00847 Product Weights Crude Product Distillate Product Composition After Filtration 416 g 242 g Calcium Sulphur C02 TBN (mg KOH/g)

V

100

V

40 14.5% 1.OX 13.6% 395 255 cSt 3100 cSt VI 221 Stearic acid 30.9% w/w This Example demonstrates that a high TBN product can be obtained at a stearic acid content of 30.9% w/w.

Examples 7 to 13 Charge: As ahown in the Table.

Method A mixture of alkyl phenol, 'lubricating oil, calcium chloride, stearic acid and 2-ethyl hexanol was heated to 120"C/700 mm Hg, Lime was added at 120*C/700 mm Hg, Ethylene glycol was added at 145 to 165*C/700 mm Hg and the mixture was held at 165*C/700 mm Hg for one hour, Carbon dioxide was added at 165*C/1 bar, Solvent was recovered at 200'C/10 mm Hg, and The product was filtered.

Product Weights As shown in the Table.

Product Composition After Filtration As shown in the Table.

The Examples demonstrate that an additive concentrate having a TEN greater than 300 can be produced in a single lime addition process over a range of stearic acid contents from 2.6 to 29.7% w/w based on the weight of the concentrate.

WO 89/03944 PCT/GB87/00847

TABLE

Example 7 81 9 10 11 12 i Stearic Acid Content of Product 2.6 7.7 12.9 18.2 18.0 23.0 29.7 (Z W/i,) Charge Weights (R) Lube oil 131 131 131 131 131 131 131

C

12 Alkyl Phenol 135 115 95 75 75 55 36 Lime 82 82 82 82 82 82 Sulphur 23 23 23 23 23 23 Stearic Acid 10 30 50 70 70 90 113 CaC1 2 4 4 4 4 4 4 4 2-EH 112 t12 112 112 112 112 112 Ethylene Glycol 36 36 36 136 36 36 36 ~C0 2 28 28 28 148 40 140 Product wt g)389 391 386 385 389 391 382 Distillate wt g)158 159 Composition After Filtration Suipii~r 3.6 3.4 3.0 3.0 2.7 1,~6 C0 2 M% 6.5 6.9 7.1 6.5 8.2 10.8 10.2 TEN 314 310 311 310 308 312 302

V

100 (cSt) 286 190 163 160 109 128 84 Example 14 Charge: C 12 -alkyl phe~o1 64 g Lubricating oil (SN 100) 1 111 g Sulphur Stoaric acid Calcium chloride 2-Ethyl hexanol 59 g 4 g 190 g Method The charge was heated to 120*C/700 mm Hg, Lime (70 g) was addedo The mixture was heated from 145'C to 1659C/700 mm Hg Vhilst adding ethylene glycol (32 g), WO 88/03944 WO 8/0944PCT/GR-7/0)0847 The mixture was held at 165*C/700 tmm H& for 5 minutes, Carbon dioxide (44 g) was added at 1656C/1 bar, The mixture was cooled to 120.C and lime (60 S) was added, The mixture was held at 165*C/700 mm Hg for 5 minutes, Carbon dioxide (44 g) was added at 165*C/l bar, Solvent was recovered frona the product by stripping at 2006C/10 mm Hg, and The product was filtered.

Product Weights Crude Product Distillate Product Composition After Filtration.

Calcium Sulphur C0 2

TBN

V

100 Stearic acid This Example demonstrates that TBN as high as 450 and an acceptable the process of the invention.

Example Charge: C 12 -alkyl phenol Lubricating oil (SN 100) Sulphur Stearic acid Acetic acid Ammonium chloride Methyl diglycol 40,1 g 245 g 16.0% w/w w/w 14.61% w/w 450 488 cSt 14. 5% w/w an additive concentrate having viscosity can be produced by Method The charge was heated to 120*C/l00 mm Hg, Lime (70 g) was added, The mixture was heated from 145*C to 165*C/700 mm Hg whilst adding methyl diglycol (90 g), The mixture vas held at 165*C/700 mm Hg for 1 hour, WO 88/03944 PCT/GB87/00847 21 Carbon dioxide (34 g) was added, The mixture was cooled to 120*C azr lime (30 g) was added, The mixture was held at 165*C/700 tm Hg for 1 hour, Carbon dioxide (17 g) was added, Solvent was recovered by stripping at 200*C/10 mm Hg, and The product was filtered.

Product Weights Crude Product 361 g Distillate 146 g Product .omposition After Filtration Calcium 4.1% w/w Sulphur 2.7% w/w

CO

2 12.4% w/w TBN 394

V

100 164 cSt Stearic acid w/w This Example demonstrates that methyl diglycol can be used as component and that ammonium chloride can be used as the catalyst in the process of the invention.

Examole 16 Charge: C 1 2 -alkyl phenol 64 g Lubricating oil (SN 100) 73 g

C

1 8 -linear alpha-olefin 38 g Sulphur 23 g Stearic acid 59 g Calcium chloride 3 g 2-Ethyl hexanol 190 g Method As for Example 15 except that in step instead of methyl diglycol (90 g) there was used ethylene glycol (31 g) and in steps and the mixture was held at 165'C/700 mm Hg for minutes instead of I hour.

Product Weights Crude Product 373 g Distillate 239 g WO 88/03944 wo 8/0944PCT/GB87/00847 22 Product Composition After Filtration Calcium Sulphur C0 2

TBN

14.4% w/w 2.3% v/v 13. 3% v/v *405

V

100 ,460 cSt Stearic acid 15.8% w/v This Example demonstrates that a long carbon-chain alpha-ol can be incorporated in the reaction, Example 17 Chargei As for Example 16 except that instead of the

C

18 -alpha-olefin (38 g) there was used a polyisobutene having an Mn Of 500 (38 g).

Method ef in As for Example 16.

Product Weights Crude Product Distillate Product Composition After Filtratic Calciu~m Sulphur C0 2

TBN

V

1 0 0

V

4 0

VI

363g 246 g In 14, 3X w/w 2. 8% w/w 13.8% W/w 406 697 cSt 26,600 cSt 175 Stearic acid 16.3: This Excample demonstrates that a polyisol incorporated in the reaction, Example 18 Charae: C 12 -alkyl phenol 1 55.2 g LtbricatIng oil (SbN 100) 1 131. a Sulphur 3 23 g Celcim 'iaride 4 g r atty Acid 89.8 g 2-Ithyl hexanol :112 g w/w41 butene can~ be WO 88/03944 PCT/GB87/00847 Method As for Example 5 except that steps and wera omitted, i.e. a single lime addition process.

Product Weipghts Cruide Product Distillate Product Composition After Filtration Calcium Sulphur C0 2

TBN

396g 151 10.8% 3.1% 11.3% 305 388 cSt 20,000 cSt

V

1 0 0

V

4 v/v v/v v/v additive concentrate VI 101 Carboxylic acid 22.7% This Example dernongtrates that a high TBbN can be obtained using a Tallow Fatty Acid.

Comparison Test Charge: C 12 -alkyl phenol :75 g Lubricating oil 100) 131 g Sulphur t 23 g Calcium chloride 14 4 g Acetic acid 2-Ethyl hexan6: 15 g 12g Methd As for Example 5 (d)o Thereafter the mixture became 4, thick heterogeneous mass, Stirring was ineffective and the mixture gelled on cooling. The reaction was discontinued.

This Test demonstrates that acetic acid can not be used as the carboxylic acid in the process of the invention.

Example 19 Charges C 12 -alkyl phenol :135 Lubricating oil (SN 100) Lime Sulphur s131 g 82 g 1 23 g

I

WO 88/03944 PCT/GB87/00847 Stearic acid Calcium chloride 4g Method The charge was heated to 145*C/700 mm Hg and iso-octanol (112 g) was added, The mixture was heated from 145*C to 165'C/700 imm Hg and ethylene glycol (36 g) was added, The mixture was held at 165*C/700 mm Hg for I hour, Carbon dioxide (28 g) was added at 165'C/1 bar, Solvent was recovered by stripping at 210*C110 imm Hg, and The product was filtered.

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

TBN

V

1 0 0 Stearic acid 380 g 144 g 10.8% w/W 3. 6% w/w w/w 301 2.16 cSt, 2 46% w/w

Claims

4. An additive concentrate according to claim 3 wherein the alkaline earth metal is calcium. An additive concentrate according to any one of the previous claims wherein the alkaline earth metal hydrocarbyl phenate is a sulphurised alkaline earth matal hydrocarbyl phenate. 6, An additive concentrAce according to any one of the preceding claims wherein the hydrocarbyl phenate moiety of the oil soluble alkaline earth metal hydrocarbyl phenate is derived from at least one alkyl phenol, the alkyl group or groups of the alkyl phenol or phenols contain!.), F r om 9 to 28 carbon atoms.
7. An additis :entrate according to claim 5 wherein the hydrocarbyl phe .noiety is derived from a C 1 2 -alkyl phenol obtained by alLylati.._ phenol with propylene tetramer,
8. An additive concentrate according to any one of the preceding 15 claims wherein there is incorporated at least one carboxylic acid having the formula wherein R is an unbranched alkyl or alkenyl grcup.
9. An additive concentrate according to claim 8 wherein in the carboxylic acid of formula R is a CIO to C 2 4 straight chain 20 alkyl group and R I is hydrogen.
10. An additive concentrate according to any one of claims 1 to 7 wherein there is incorporated a mixture of carboxylic acids of formula which mixture is a commercial grade containing a range of acids, including both saturated and unsaturated acids.
11. An additive concentrate according to any one of claims I to 7 wherein there is incorporated stearic acid,
12. An additive concentrate according to any one of claims I to 7 wherein there is incorporated a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride thereof,
13. An additive concentrate according to claim 12 wherein there is incorporated either a p-lyisobutene succinic acid or a polyisobutene succinic anhydride. 14, An additive concentrate according to any one of the preceding claims wherein there is incorporated either component or component (ii) in an amount from greater than 10 to 35% by 26 F I S *0i 00 S S. 0 0 j 0 i 9 S S. 0 @0 00 S 0 I weight based on the weight of the concentrate. An additive concentrate according to claim 14 wherein components or (ii) are incorporated in an amount in the range from 12 to 20% by weight based on the weight of the concentrate.
16. An additive concentrate according to any one of the preceding claims wherein the TBN of the composition is greater than 350.
17. An additive concentrate according to claim 15 wherein the TBN of the composition is greater than 400.
18. An additive concentrate according to any one of the preceding claims having a viscosity at 100'C of less than 1000 cSt.
19. An additive concetrate according to claim 18 wherein the viscosity at 100*C is less than 500 cSt.
20. A process for the production of an additive concentrate as claimed 15 in any one of claims 1 to 19 which process comprises reacting at elevated temperature either a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, 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 ?)mponent and (F) sufficient to provide from greater than 2 to less than 40% by weight based on the weight of the concentrate of either a carboxylic acid having the formula 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 weight ratios of components to being such as to 3b prodl!e a concentrate having a TBN greater than 300.
21. A process according to claim 20 wherein component is lime,
22. A process according to either claim 20 or claim 21 wherein the weight ratio of component to component is in the range from 0.4 to
23. A process according to any one of claims 20 to 22 wherein 27 i, F I I 'I'd component is ethylene glycol.
24. A process according to any one of claims 20 to 22 wherein component is methyl digol. A process according to any one of claims 20 to 24 wherein the carbon dioxide (component E) is added subsequent to each of two or more additions of component
26. A process according to any one of claims 20 to wherein a diluent is present.
27. A process according to any one of claims 20 to 26 wherein the reaction is carried out in the presence of a catalyst. 0 0 S go 0000 125 go goe S S S 0 SO :i: C S .3
28. A process according to claim 27 wherein the catalyst is calcium chloride.
29. A process as claimed in claim 20 substantially as herein described with reference to any non-comparative Example.
30. An additive concentrate prepared by a process as claimed in any one of claims 20-29.
31. An additive concentrate as claimed in claim 1 substantially as herein described with reference to any non-comparative Example.
32. A finished lubricating oil composition which composition comprises a lubricating oil and sufficient of an additive concentrate as claimed in any one of claims 1 to 19, 30 or 31 to provide a TBN (as hereinbefore defined) in the range from 0.5 to 120.
33. A finished lubricating oil composition according to claim 32 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.
34. A finished lubricating oil composition according to claim 32 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 21st day of January 1991 BP CHEMICALS (ADDITIVES) LIMITED By their Patent Attorneys SGRIFFITH HACK CO. -28- INTERNATIONAL SEARCH REPORT International Avolication No P CT /GB 87/ 00 84 7 1. CL.ASSIFICATION OF SUIJICT MATTER (it several ciassificition symoola apply, Indicate all) According to Interrnation,11 Patent Classification (119C) or to both National Classification and 11C XPC 4 C 10 M 159/22 it. P111.05 SKARCNO I ~Minimum Documentation Searched classificationi System IClassification Symbols 1Pc 4 Cl10M; C07 c Documenttion~ Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched 0 Ill. DOCUMENTS CONSIDERED TO 01 RKLIVANTO Category I Citation of Document. 11 with Indication. where appropriate. of the reievant passages 'I Reievant to Claim No. iS EP, A, 0095322 (OROBIS LTD) November 1983 see pages 5-8; examples 10-12; claims 1,3-6,8,11-13 US, A, 4328111 WATSON) 4 May 1982 see column 2, lines 21-68, column 3; column 4, lines 5-24; column 6, line column 8, line 10; column 9, examples 11,12 1-16 ,18- 32 1- 16 ,18 32 *Special categorlas of cited documents, Is I" satar document Published after the International filing date document defining the general state of the art which io not or priority date and not In conflict with the application but considered to be of particular relevance Cited to understand the principle or theory underlying the Invention earlier document but published on or altar the International Ix" document of particular relevance;, the claimed invention filing date cannot be considered novel or cannot be considered to *L document which may throw doubts on priority cilm~s) or Involve an inventive step which Ie cited to establish the publicationl date Of another document of particular relevanice;, the claimed finvention citation or other special reason (as specifled) Cannot be considered to Involve an Inventive step when the document referring to an oral diloaure141, usisa ehibitlon or document is comaiined with one or More other such do'Cti" other means ments, such combination being obvious to a person skilled 110" document published prior to the International filing date but In the art. ister than the priority date claimed "ll" documtent member of the same patent family IV. Datef of the Actual Completion of the international Seawch Dale of Maliling of this lntairallenal Search Reortn February 1988 0 7 AR I8 International Searching Authority 1-41 thrm Ofcr~ EUROPEAN PATENT OFFICE ANMPM1 Form PCTIISA1210 (second shet (JanurY 1111111 *1 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. GB 8700847 SA 19583 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are contained in the European Patent Office EDP ile on 16/03(88 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document PulctoPatent family Publication cited in search report date Tmember(s) date EP-A- 0095322 30-11-83 AU-A- 1482883 24-11-83 JP-A- 59025343 09-02-84 AU-B- 556650 13-11-86 US-A- 4328111 04-05-82 None :6. w For more details about this annex set official Journal of the European Patent Office, jo, 12/82