CA1305696C - Alkaline earth metal hydrocarbyl phenates, their sulphurised derivatives, their production and use thereof - Google Patents
Alkaline earth metal hydrocarbyl phenates, their sulphurised derivatives, their production and use thereofInfo
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- CA1305696C CA1305696C CA000552952A CA552952A CA1305696C CA 1305696 C CA1305696 C CA 1305696C CA 000552952 A CA000552952 A CA 000552952A CA 552952 A CA552952 A CA 552952A CA 1305696 C CA1305696 C CA 1305696C
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- lubricating oil
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- acid
- additive concentrate
- component
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concen-trate comprising:
(a) a lubricating oil, (b) 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 concentrate of either (i) at least one carboxylic acid having the formula:- (I) wherein R is a C10 to C24 alkyl ox alkenyl group and R1 is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an an-hydride, acid chloride or ester thereof or (ii) a di- or polycar-boxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the concentrate having a TBN
greater than 300.
An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concen-trate comprising:
(a) a lubricating oil, (b) 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 concentrate of either (i) at least one carboxylic acid having the formula:- (I) wherein R is a C10 to C24 alkyl ox alkenyl group and R1 is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an an-hydride, acid chloride or ester thereof or (ii) a di- or polycar-boxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the concentrate having a TBN
greater than 300.
Description
~3~ Case 6538(2~
ALKALINE EARTH METAL HYDROCARBYL PHENATES, THEIR SULPHURISED
The present invention relates in general to alkaline earth mstal hydrocarbyl phenates and their sulphurised derivatives, their production and use thereo~ a~ lubricating oil additive~. In particular the present invention relates to concentrate additive compositions comprising alkaline sarth metal hydrocarbyl phenate~
and their sulphurised darivativas 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 ~rom the combustion chamber often b1Ow by the piston and admix with the lubricating oil. Many of these by-products form acidic matsrials 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 acid~
produced by oxidation oi sulphur, hydrohalic acids derived from halogen lead scavengers in the fuel and nitrogen acids produced by the oxidation of atmospherlc nitrogen within the combustion chamber. Such acids cause deposition o~ sludge and corrosion of thP
baarings 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 ~ludge within the lubricating oil are the metal alkyl phenates and sulphurised metal alkyl phenates, wherein the metal is an alkaline earth metal ~uch a~ calcium, .
~s~
magnesium or barium. Both "normal" and "overba3ed" alkaline earth metal alkyl phenates have been employed. The term "overbased" is used to describe those alkaline aarth metal alkyl phenates in whLch the ratio o~ tha number of equivalents o~ the alkaline earth metal moiety to the number o~ equivalents of tha phenol moiety i9 graater than one, and is usually greater than 1.2 and ma~ be as high as 4.5 or greater. In contrast, the aquivalent ratio oi alkaline earth metal moiety to phenol moiety in "norntal" alkaline earth metal alkyl phenates is one. Thus, the "overbased" material contains ~reater than 20~ in excess o~ the alkaline earth metal present in the corresponding "nonmal" material. For thi~ reason "overbased"
alkaline earth metal alkyl phenates have a grea~ar capability for neutralising acidic matter than do the corresponding ~normal'~
alkaline earth metal alkyl phenate~.
lS The prior art teachas many methods for preparing both "normal"
and "overbased" metal alkyl phenates. One ~uch method for preparing "overbased" alkyl phenates generally referred to as the "3ingla lime addition" process comprises reacting an alkyl phenol, in the prasence or ab~ence o~ sulphur, lubricating oil, a hydroxylic compound and excess alkaline earth metal hydroxide (above the ~toichiometric 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 produc~ of intermediate product i9 accompanied by a marked increase in viscosity while the subsequent carbonation reduces the viscosity to a relatively low level. The increase in viscosity acco~panying the formation of the intermediate product is undesirable because the reaction mixture becomes dificult 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 raaction, 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 inte~tediate product within acceptable limits, the ~3C~
slkalin~ earth metal hydroxld~ may be added in twol (gcnerally referred to aq the "double lime addition" process) or three 3eparate reaction step~, with ~qu~ntial carbonation 9tCp9. However, this m0thod involves relatively long batch times. Another alt~r~ativa i9 to u~e vi~cosity depr~ant~, ~uch a3 trid~canol, 2-athylhexanol, or 3imilar boiling range hydroxylic aolvent, in the production of th~
intermadiate product but ~uch an expedient increase~ the raw ~aterial cost of th~ proces~. The highsst total base number (TBN), e~pre~ed in mB KOH/g, con~istent with an acceptable vi~c09ity, generally achiavabla by prior art proces3es i3 about 300, though generally prior art TBN~ ars in the range from 200-300. It would clearly be a desirabl~ ob~ective to produce an additiv~ concentrate compri3ing alkaline earth metal alkyl phe~ates or ~ulphuri~ed derivative~ ther~of having a hi8h TBN, that i8 a TBN 8reatQr than 300, ant pr0ferably greater than 350. To dat0 it has not been found po3~ible to achieva products of ~uGh high TBN becau~e tha u~a of larger concentrations o~ alkalin~ earth metal ba~e laads to highly vi~cous product~ which, rathar than being 'thinned' by sub~nqusnt carbonation attempt~ u~ing exces~ carbon dioxide, are rendered inqoluble. We have ach~eved thi3 objectiv0 and thereby obtained products having a TBN in excess of 300, and in ~ome cases 8reater than 350, whilst retaining an acceptable visc03ity, that i~ a vi~cosity at 100C of les3 than 1,000 cSt and avoiding insolubility by incorporating into the re2ction mixtur0 a defined amount of certain carb~xylic scids having at laast 10 carbon atom3 in th0 molecule or acid derivatives.
The u~e o~ carboxylic acid~ either in ~he production of alkaline earth metal alkyl phenates and th~ir sulphurised derivatives or in as~ociatlon therewith in lubricating oil c~mpo3itions i3 not new, see for exampl0 US-A-3,372,116;
GB-A-1440261; US-A-4049560 and EP-A-0094814.
~S-A-3,372,116 disclo~e~ an improvement in tha method for preparing a basic matal phanate by r0acting at a temperature between about 25C and tha reflux temperature (A) a hydrocarbon-~ubstituted phenol havine at least 6 casbon atom~ i~ the h~drocarbon ~3~S~
substituent, a mixture of 3aid phenol with up to an equivalent amount of a hydrocarbon-substituted ~uccinic acid or anhydrida having at least about 6 carbon atoms in th~ hydrocarbon substtuant, or a substantially neutral alkali metal or &lkaline earth metal salt or either of the foregoing, (B) about 1-10 eq~ivalents, per equivalent of (A), of a calcium or strontium bas~, and (C) carbon dioxide, which improvement comprises carrying out tho reaction in the presence of about 0.002-0.2 aqulvalent, per equivalent of Yaid calcium or strontium basa, o a carboxylic ecid 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 pr~ferred being monocarboxylic acid~ containing up to 10 carbon atoms and alkaline earth metal 3alts 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 carbo~ylate salts can not be used in the process o~ the present invention bacause of their inherent insolubility in the system. The procoss of US-A-3,372,116 does not employ phenol to alkaline earth metal base ratios sufficient to produce phenates having TBN~ in excess o~ 300.
GB-A-1440261 discloses a lubricating oil composition comprising a lubricating oil, a detergent or di~persant additive and a mixture of at least two carboxylic acids, one acid having a melting point of at least 20C and not mo~ than 30 carbon atom~ per molecule, and another acid having a melting point of balow 20C, 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 sultable. In the lubricating oil compo~ition the mixture of acids 30 i~ present in an amount of 0.05 to 2.0 wt ~.
US-A-4049560 describes the production of an overba~ed magnesium detergent by a process in which carbon dioYide is introduced into a reaction mixture which comprises:
(a) 15-40 wt % of a sulphurised phenol or thiophenol cont~ining one or more hydrocarbyl sub~tituents, or a phenol or thiophenol ~3~
containing one or more hydrocarbyl substituents, or sald ph~nol or thiophenol containing one or more hydrocasbyl substituents together with sulphur, (b) 5-15 wt ~ o~ an organic sulphonic acid, an organic sulphonate or an organic 3ulphate, ~c) 5-15 wt % of a glycol, a C1 to Cs monohydric alkanol or C2 to C4 alkoxy alkanol, (d) 2-15 wt X of a magncsium hydroxide or active magne~ium oxid~, (e) at least 0.l wt ~ o~ a Cl to Clg carboxylic acid, an anhydride thereof, or an ammonium, an amine salt, a Group I metal or a Group II metal salt of said Cl to Clg carboxylic acid, and (~) at least 10Z by weight of a diluent oil tincluding any present in components (a) and (b).
The amount of carboxylic acit (component (e)) 1s preferably in the range 0.5 to Z.OS by weight. The product prepared by this r~action is said to have a TBN of about 200 to 250, e.g. about 225.
EP-A-0094814 discloses an addit$ve roDcentrate for incorporation in a lubrlcating oil co~position comprising lubricating oil, and from 10 to 91) wt % o~ an overbased alkalina earth metal hydrocarbyl sulphurisod phenate which has bean treated, either during or subsequent to th6~ overbasing process, with from 0.1 to 10, prsferably 2 to 6, wt X (based on the weight of additive concentrate) o~ an acid of the formula:
~ CH - COOH (I) R
(wherein R is a Clo to C~4 unbranched alkyl or alkenyl group, and i9 hydrog~n, a C1 to C4 alkyl group or a -CH2-COOH group) or an anhydride or a ~alt thereof. Th~ ob;ect o~ the invention of EP-A-0094814 is to overcome problems encountered with many additive concentratss containing overbased additives, namely lack of stability giving rise to sedimentation and foaming problems. The problem o~ EP-A-0094814 is not ~hat of producing phenate additive concentrates having a TBN of greater than 300 and indeed the phenate additive concsntrates produced by the process of the invention, although demonstrating overcoming -the problems of stability and ~oaming, have TBN values of less than 300.
It can be concluded that the prior art in which car-boxylic acids are employed does not address the prob~em 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 compositionr the additive concentrate comprising ~a) a lubricating oil, (b) a lubricating oil soluble sulphurised or non-sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation o~ from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) at least one carboxylic acid having the formula:-R - CH - COOH
Il (I) wherein R is a C10 to C24 alkyl or alkenyl group and Rl is either hydrogen, a Cl to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or poly-carboxylic acid containing from 36 to 100 carbon atoms or an anhydride r acid chloride or ester thereof/ the concentrate having a TBN greater than 300.
Component (a) of the composition is a lubricating .~
~ .
:~3~S~
- 6a - 22935-934 oil. The lubricating oil may suitably be ei-ther 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, parafin base or mixed base oil. Solvent neutral oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthe-tic lubricating oils include synthetic ester lubricating oils, which oils in-clude diesters such as di-octyl adipate, di-octyl sebacate and tridecyladipate, or polymeric hydrocarbon lubricating oils, ~or ~' 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 thè composition.
Component (b) is a lubricating oil soluble sulphurised or non-sulphurised, preferably sulphuri~ed, alkaline earth metal hydrocarb~l phenate modified by incorporation of from greater than 2 to less than 40% by weight based on the weight of the composition of either (i) or (ii). Suitably the alkaline earth metal may be strontlum, calcium, magne3ium or barium, preferably calcium, barium or magn2sium, more preferably calcium. The hydrocarbyl phenate moiety of the alkaline earth metal hydrocarbgl phenate is preferably derived from at least one alkyl phenol. The alkyl groups of the alkyl phenol may be branched or unbranched. Suitable a~kyl groups contain from 4 to 50, preferably from 9 to 28 carbon atoms. A
par~icularly suitable alkyl phenol i9 the C12-alkyl phenol obtained by alkylating phenol with propylene tetramQr.
The alkaline earth metal hydrocarbyl phenate is modified by incorporation of either (i) or (ii). As regards ~i), this is at lea~t one carboxylic acld havlng the formula (I) or an acid 2G anhydride, acid chloride or ester thereof. Preerably R in the formula (I) is an unbranched alkyl or alkenyl group. Preferred acid~ of for~ula (I) are those wherein R is a Clo to C24, more preerably Clg to C24 straight chain alkyl group and R1 is hydrogen. Examples of s~table saturated carboxylic ac1ds of formula (I) include capric acid, lauric acid, myri~tic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. Examples of suitable unsaturated acids of formula (I) include lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricineleic acid, linoleic acid and linolenic acid. ~ixtures of acid~ may also be employed, for example rape top fatty acids. Particularly suitable mixtures of acids are those co~mercial grades containing a range of acids, including both saturated and unsaturated acids. Such mixtures may be obtained synthetically or may be derived from ~5~i96 natural products, for exampla cotton oil, ground nut oil, coconut oil, linseed oil, palm karnel oil, olive oil, corn oil, palm oll, castor oil, soyabean oil, sunflo~ar oil, herring oil, sardinQ oil and tallow. Sulphurised acids and acid mlxtures may also ba amployed. 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 (I) is stearic acid.
Instead of, or in addition to (i~, the alkaline earth metal hydrocarbyl phenate may be modified by incorporation of (ii), 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. Praferably (ii) is a polyisobutene succinic acid or a polyi~obutene succinic anhydride.
Prefarably the carboxylic acid(s) having the formula (I), the di- or polycarboxylic acid, or the acid anhydride, acid chloride or ester thereof i~ incorporatHd in an amount from greater than lOX to 35%, more preferably from 12 to 20%, for example about 16Z by weight based on the weight of the composition. An advantage of incorporatine greater than 10% of the carboxylic acid or derivative thereof is generally a relativelylower concentrate viscosity.
Suitably the alkal~`n~-e~rth metal may be present in th~
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 sulphurised or non-~ulphurised, 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 composition.
Suitably carbon dioxide may be present in the composition in an amount in the ranga from 5 to 20, preferably from 9 to lS% by weight based on the weight of the coMposition.
Preferably the TBN of the composition is greater than 350, more ~L3~,~6~6 preferably greater than 400.
Suitably the composition may have a viscosity measured at 100-C
o less than 1000 cStt preferably less than 750 cSt, more preferably less than 500 cSt.
In another aspect the present invention provides an additive concentrate suitable for incorporation into a finished lubricating oll which concsntrate is obtainable by reacting at alevated temperature (A) either ~i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, (B) an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during th~ reaction, (C) either a polyhydric alcohol having from 2 to 4 carbon atomsJ a di- or tri- (C2 to C4) glycol, ~n alkylene ~lycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added subsequent to the, or each, addition of component (B), and (F) sufficient to provide from greater than 2 to less thaD 40% by weight based on the weight of th0 concentrate of either (i) a carboxylic acid having the formula (I) or an acid anhydride, acid chloride or Qster 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 (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
In yet another aspect the present invention provides a process for the production of an`~additive concentrate for incorporation into a ginished lubricating oil which process comprises reacting at elevated temperatura components (A~ to (F) as hereinbefore described, the weight ratios of components (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
Component (A) of khe reaction mixture is either (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur. Usi~g component (A) (i) the product is an alkaline earth metal hydrocarbyl phenate and u~ing component (A) (ii) the product is a ~ulphurised alkaline earth metal hydrocarbyl phenate. The hydrocarbyl phenol employed is that alkyl phenol from which is deri~ed the desired hydrocarbyl phenate moiety as hereinbeiore described.
~31Q~6 lo 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 ~laked lime. Preferred alkaline earth metals ara calcium, magnasiu~ and barium and mora preferred is calcium. The alkaline earth metal base must be added in an amount relative to component (A) suf~icient to produce a product having a TBN in excess of 300, pre~erably in excess of 3S0. This amount will depend on a number of iactors including the natura oi the sulphurised alkyl phenol and will be higher than the amounts generally employ~d in prior art processes.
Typically, the weight ratio o~ componsnt (B) to component (A) may suitably be in the range from 0.2 to 50, preferably fro~ 0.4 to 10. The alkaline earth metal ba3e (~) 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 produc~ an additive concentrate having a TBN greater than about 350 and a viscosity at 100C of less than 1000 cSt it is particularly de~irable to add component (B) in at least two, and preferably more additions and to add component (F) in an amount greater than 10~ by weight based on the weight of the additive concentrate product.
Component (C) i9 eithsr a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C2 to C4) glycol alkyl ether. The polyhydric alcohol may s~itably be either a dihydric alcohol, for example ethylene glycol or propylene glycol, or a trihydric alcohol, for example glycerol. The di- or tri- (C2 to C4) glycol may suitably be either diethylene glycol or triethylene glycol. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether may suitably be of ths ~ormula:-R (ORl)XOR2 (II) wherein R i~ a C1 to C6 alkyl group, Rl is an alkylene group, R2 i9 hydrogen or Cl to C6 alkyl and x i9 an integer in the range from 1 to 6. Suitable solvent~ having the ~ormula (II) include the monomethyl or dimethyl ethers o~ ethylene glycol, diethylene glycol, triethylena glycol or tetra~thylene glycol. A particularly suitable ~56~i solv6llt is methyl digol (CH30CH2CH20CH2CH20H). Mixtures oi glycolsand glycol ethers of formula (II) may also be employed. Using a glycol or glycol ether of fonmula (II) as solvent it is preferred to use in combination therewith an inorganic halide, for example ammoni~m chloride, and a lower, i.e. Cl to C~, carboxylic acid, for example acetic acid. Preferably the component (C) i9 either ethylene glycol or methyl digol, the latter in combination with ammonium chloride and acatic acid.
Component (D) is a lubricating oil as hereinbe~ore described with reference to the additive concentrate.
Component (E) is carbon dioxide, which may be added in the form of a ~as 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 (F). In order to produce a concentrate having a TBN greatsr than about 350 the carbon dioxide is preferably added subsequent to each of two or preferably more additions of component (B).
Component (F) is either a carboxylic acid of formula (I), a di-or polycarboxylic acid containing from 36 to lO0 carbon atoms, or anacid anhydride, an acid chloride or ester thereof as hereinbefore described with reference to the additive concentrate composition.
The amount of the aforesaid required to provide from greater than 2 to less than 40~ by weigh~ bassd on the weight of the concentrate will be to a first approximation the amount desired in the concentrate. In calculating th~s amount allowance should be made for 103g of water from carboxylic acids, for example.
The reaction may be performed in the presence of a diluent.
Suitable 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 re~ction. Examples of suitable diluents include 2-ethyl hexanol, iso-octanol, iso-heptanol and tri-decanol.
Preferably the reaction is carried out in the presence of a further component which is a catalyst for the reaction. As catalyst ~L3a:~S~
there may ba used an inorganic halide which may suitably be eith0r a hydrogen halide, an a~monium halide or a metal halide. Suitably the metal moiety of the metal halide may be zinc, aluminium or an alkaline earth metal, preierably calclum. 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 component~ (A) ~ (F) and also the carbonation reaction may be carried out at elevated temperatures in the range from 120 to 200, preferably from about 130 to 165C, though the actual temperatures cho~en for the reaction of components (A) - (F) and the carbonation may differ if desired. The pressure may be atmospheric, subatmospheric or superatmo~pheric.
The concentrate may be recovered by conventional means, for example by distillative stripping of component (C) and diluent (if any).
Finally, it ic preferred to ~ilter the concentrate so-obtained. Generally, ths 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 prod~ce concentrates having a viscosity less than 750 or 500 cSt at 100C. Moreover, the concentrates generally have desirable viscosity index properties.
Such viscometric propert`~es are advantageous because they facilitate processing ~including filtration) of the concentrate. However, it is also possibla to produce concentrates having a higher visco~ity than 1000 cSt at lOO~C, generally at higher TBN levels. Filtration of such concentrate~ presents a problem, which may be overcome by adding a diluent prior to filtration and stripping the diluent off after filtration. ~lternatiqely, high viscosity concentrates, for example concentrates having a visco~ity at 100C greater than 1000 cSt, and also having a high TBN, ior example greater than 350, may be diluted by addition of further lubricating oil whilst maintaining a TBN greater than 300, thereby facilitating filtration.
In a final aspect the pre~ent invention provides a inished :11 3~:~5~
lubricating oil composltion which composition compri3es a lubricating oil and ~ufficient of the additive concentrate a~
hereinbefore described to provlde a TBN in the range from 0.5 to 120.
Preferably the finishet lubricating oil composition contains sufficient of the additiva concentrate to provide a TBN in the range from 0.5 to 100.
The amount of additiva concentrate presant in the fini~hed lubricating oil will depend on the 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 ~or automobile engine lubricating oils the amount may suitably be sufficient to provids a TBN in the range ~rom 4 to 20.
The finished lubricating oil may also contain effective amounts of one or more other types of conventional lubricating oil additives, for exa~ple visco~ity index improvers, anti-wear agents, antioxidants, di3parsants, rust inhibitors, pour-point depressants, or the like, which may be incorporated into the finished lubricating ?.0 oil composition either directly or through the intermediacy of the concentrata composition.
In addition to their use as additives for incorporation into lubricating oil compo3itions, the additive concentrate of the present invention may al~o find application as fuels additives.
The invention will now be ~urther illustrated by reference to the following Example~.
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 o~
ASTM D2396.
The viscosity was measured by the method of ASTM D445.
In all the Examples, except otherwiqe expressly stated, a comnercially available C12-alkyl phanol obtained by alkylating phenol with propylene tetramer was employed.
Example 1 ~3~5~
Char~: C12 alkyl phenol : 75 B
Lubricating oil (100 SN) : 131 g Lime : 82 g Sulphur : 23 g Stearic acld : 70 g Calcium chloride : 4 g 2-Ethyl hexanol : 112 B
Method (a~ The charge was heated to 145-165C~700 mm Hg whilst adding ethylene glycol (36 g), (b) The m~xture wa~ heated at 165C/700 mm Hg for o~0 hour, (c) Carbon dio~ida (40 g~ wa3 added at 165C/l bar, (d) Tha mixture was cooled to 125C/700 mm H8, (e) Lime ~35 g) was added at 125'C/700 ~m Hg, 15 (f) The mixture was heate~ at 165C/700 mm ~g ~or on0 hour, (g) Carbon dioxide (20 g) wa~ added at 165C/l bar, (h) The product was then ~tripped of solvent at 200C/10 mm Hg, and (i) The product wa3 Pilterad. Ths filtration rats was fast.
Product Wei~ht Crude Product : 436 8 Distillate : 169 g P duct Composition After Filtration Calcium : 14.1~ w/w Sulphur ~ : 2.9~ w/w 25 C2 : 12.42 w/w TBN : 396 VloO : 308 cSt Stearic acid : 16.1~ w~w This Example demon~trate~ that a high TBN additivs concentrate of acceptable vi~cosity can be produced in a "double lime addition"
proce~ acco-ding to the pre~nt invention.
Example 2 Charge: As for Example 1, except that the amount of lime in the charge wa~ increased from 82 g to 117 g corresponding to 1~
::IL3~5~9~
tha total amount of lime added in Example 1 in two additlons.
Method As for Example 1 except that the amount of carbon dioxide added in step (c) was increased from 40 g to 60 8 and ~teps (d), (e), (f) and (g) were omitted. The filtrat~on rate in the final step was slow.
Product Wei~ht Crude Product : 514 g Product Compo~ition After Filtration Calcium : 14.1% w/w Sulphur : 3.0% w/w C2 : 12.3% w/w TBN : 390 Vloo : 7600 c5t Stearic acid : 13.6% w/w This Ex~mple demonstrate3 that an additiva concentrate phenate having a hlgh TBN can be produced in a singlQ 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 Char~e: As ~or Example 1.
Method ~~
As for Example 1, except that in step (8~ the amount o~ carbon dioxide was increased from 20 B to 40 g and the following steps wera added after tep ~g) and before steps (h) and (i):
(j~ The mixture was cooled to 120C, (k) Lime (35 g) was added at 120C, (1) The mixture was heated at 165C/700 mm Hg, and (m) Carbon dioxide (50 g) wa added to the mixture.
Product Wei~hts Crude Product : 484 g ~istillate : 169 g ~3~
Product Composition After Filtration Calcium : 15.8X w/w Sulphur : 2.6~ w/w C2 : 15.0% w/w TBN : 439 Vl~o : 506 cSt Stearic acid : 14.5~ w/w This Example demonstrates that high TBN additive concentrates can be produced by the process of the ~nvention by a tripla lime addition.
Example 4 Charge: As for Example 1 except that the amount of lubricating oil was r~duccd from 131 g to 158 g and the amount of stearic acid was reducad from 70 B to 43 g.
Method As for Example 1 except that in step (d) the mixture was cooled to 135~C instead of 125C.
Product Wei~hts Crude Product : 442 g Distillate : 155 g Product ComPOsition After Filtration Calcium : 14.1% w/w Sulphur : 2.9Z w/w C2 ~-- : 11.9~ w/w TBN : 393 V1OO : 3440 cSt Stearic acid : 9.8Z w/w This Example demonstrates by comparison with Example 1 that although a high TBN product can be produced at an acid level less than lOZ w/w the viscosity of tha product ls high.
E~ample 5 CharRe: C12-alkylphenol : 35.3 g Lubricating oil (SN 100) : 131 g Sulphur : 14.7 g Calcium chloride : 4.0 g 1~
Stearic acid : 109.1 g 2-Ethyl hexanol : 224 g Method (a) The mixture was heated to 120C, (b) Lime (82 B) was added at 120C/2~ Hg vacuum, (c) Ethylene glycol (36 g) was added at 145 - 165C/2" Hg, (d) The mixture was held at 165C/2" Hg for 1 hour, (e) Carbon dioxide (40 g) was added, (f) The mixture was c0012d to 130~C and lime ~35 g~ added at 130C/2" Hg, (g) The mixture was held at 165C/2" Hg for 1 hour, (h) Carbon dioxide (20 g) wa~ added at 165C, (i) Solvent was stripped Erom the product at 200C/30" Hg, and (;) The product was filtered.
~5~9s~ h~e Crude Product : 397 g Distillate : 245 g Product Composition After Filtration Calcium : 13.6% w/w Sulphur : 1.2% w/w C2 : 13.9~ w/w TBN : 376 VloO : 142 cSt V40 ~`- : 18~1 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 oP 27.5% w~w based on the weight of the final product.
Example 6 CharRe: As for Example 5 except that the a~ount of C12-alkylphenol was red~iced from 35.3 g to 15.fi g and the amount oP
stearic acid was increased from 10~.1 g to 128.7 g.
Method As for Example 5.
S6~
1~
Product Weights Crud0 Product : 416 g Distillate : 242 g Prcduct Composition After Filtration Calciu~ : 14.5~ w/w Sulphur : 1.0% w~w C2 : 13.6~ w/w TBN (mg KOH/g) : 395 V100 : 255 cSt V40 : 3100 cSt VI : 221 Stearic acid 5 30.9~ w/w This F~xample demonstrates that a high TBN product can be obtained at a stearic acid content of 30.9% w/w.
Examples 7 to 13 Char~e: As shown in the Table.
Method (a) A mixture of alkyl phenol~ lubricating oll, calcium chloride, stearic acid and 2-ethyl hexanol W~,3 heated to 120C/700 mm Hg, (b) Lime was added at 120C/700 mm Hg, (c) Ethylene glycol was added at 145 to 165~C/700 mm Hg and the mixture was held at 165C/700 mm Hg for one hour, (d) Carbon dioxide was added at 165C/l bar, (e) Solvent was recovered at 200C/10 mm Hg, and (f) The product was filtered.
Product Wel~hts As shown in the Table.
Product Compositlon After Filtrati,on As shown in the Table.
Th~ Examples demonstrate that an additive concentxate having a TBN graater than 300 can be produced in a single lime addition' process over a range of stearic acid contents rom 2.6 to 29.7% w/w based on the weight of the concentrate.
TABL~
_ _ _ _ .
Exampls 7 8 9 10 11 12 13 _ . _ __ 5 Stearic Acid Content of Product 2.6 7.7 12.9 18.2 18.0 23.0 29.7 ... . __ _ _ . ___ Char~e Wei~ht9 (R?
Lube oil 131 131 131 131131131 131 C12 Alkyl Phenol135 115 95 75 75 55 36 Lime 82 32 82 82 82 82 85 Sulphur 23 23 23 23 23 23 15 Stearic Acid 10 30 50 70 70 90 113 CaC12 4 4 4 4 4 4 4 Ethylene Glycol 36 36 36 36 36 36 36 _ _ _ _ _ _ Product wt (g) 389 391 386 385389391 382 Distillate wt (g)158 159 _ _ _ _ . . _ _ . _ . . _ Composition After Filtration Calcium (%) 11.2 11.011.1 11.211.011.111.1 Sulphur (~) 3.7 3.6 3.4 3.03.02.7 1.6 C2 (%) 6.5 6.9 7.1 6.58.210.810.2 Vloo (cSt) 286 190 163 160109128 84 _ __ _ Char~e: C12-alkyl phenol- : 64 g Lubricating oil (SN 100) : 111 B
Sulphur : 20 g Stearic acid : 59 g Calcium chloride : 4 g 2-Ethyl hexanol : 190 g Method (a) The charge was heated to 120C/700 mm ~g, (b~ Lims (70 g) was add~d, (c) The mixture was heated from 145C to 165C/700 mm Hg whilst addinB ethylene glycol (32 g), S~ 6 (d) The mixture was held at 165C/700 mm Hg for 5 minutes, ~e) Carbon dioxide (44 8) was added at 165C/l bar, (f) The mixture was cooled to 120C and l~me (oO g) was added, (g) The mixture was held at 165GC/700 mm Hg for 5 mimltes, (h) Carbon dioxide (44 g) was added at 165C/l bar, (i) Solvent was recovered from the product by stripping at 200C/10 mm Hg, and (;) The product was filtered.
Product We~hts Crude Product : 408 g Distillate : 245 g Product ComPosition After Filtration Calcium : 16.0~ w/w Sulphur : 2.6% w/w 1s C2 : 14.6% w/w TBN : 450 VloO : 488 cSt Stearic acit : 14.5~ w/w This Example demonstr~te~ that an additive concentrate havlng a TBN as high as 450 and an acceptable viscosity can be produced by the process of the invention.
Example 15 C12-alkyl phenol : 64 g Lubricating oi~ (SN 100) : 111 g Sulphur : 20 B
Stearic acid : 59 8 Acetic acid : 2 g AMmonium chloride : 3 B
Methyl diglycol : 40 g Method (a) The charge was heated to 120lC/100 mm H~, ~b) Lime (70 g) was added, (c) The mixture was haated from 145C to 165C~700 mm HB whilst adding methyl diglycol (90 g), (d) The mi~ture was held at 165~C/700 mm H8 for 1 hour, 6~6 (e) Carbon dioxide (34 g) was added, (f) The mixture was cooled to 120C and lime (30 g) wa~ added, (B) The mixture was held at 165C/700 mm Mg for 1 hour, (h) Carbon dioxide (17 8) was added, (i) Solvent was recovered by stripping at 200C/10 mm Hg, and (;) The product was filtered.
Product Weights Crude Product : 361 B
Distillata : 14S g Product Composition A~ter Filtration Calcium : 14.1Z w/w Sulphur : 2.7~ w/w C2 : 12 4% w/w TBN : 394 VloO : 164 cSt Stearic acid : 16.3% w/w Thi~ Example demonstrates that methyl diglycol can be used as component tC) and that ammonium chlorid~ can be used a~ the catalyst in the procas~ of the invention.
Example 16 C4arge: C12-alkyl phenol : 64 g Lubricating oil (SN 100) : 73 g Clg-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 (c~ instead of methyl diglycol (90 g) there wa3 used ethylene glycol (31 g) and ln ~teps (d) and (B) th& mixture was hPld at 165C/700 mm Hg for 10 minutes instead of 1 hour Product Wei~hts Crude Product : 373 g Distillate : 239 g Product Composition After Flltration Calcium : 14.4% w/w Sulphur : 2.3% w/w C2 : 13.3% w~w TBN : 405 VloO : 460 cSt Stearic acid : 15.8% w/w This Example demonstrates that a long carbon-chain alpha-olefln can be incorporated in the reaction.
Example 17 Char~e: As for Example 16 except that instead of the Clg-alpha-olefin (38 g) there was used a polyisobutene having an Nn f 500 (38 g).
Method A3 for Example 16.
~c~
Crude Product : 363 B
Distillate : 246 8 Product Composition After Filtration Calcium : 14.3% w/w Sulphur : 2.8% w/w C2 :13.8% w/w TBN :406 V100 ` :697 cSt V40 : 26,600 cSt VI : 175 Stearic acid : 16.3% w/w This Example demonstrates that a polyisobutene can be incorporated in the reaction.
a8a:E~
Charg~: C12-alkyl phenol : 55.2 Lubricating oil (SN 100) : 131 e Sulphur : 23 g Calcium Chloride ' 4 B
Tallow Fatty Acid : 89.8 B
2-Ethyl hexanol : 112 g ~..3(~ 36 Method As for Example 5 except that staps (f), (g) and (h) were omitted, i.e. a single lime addition proce~s.
Product Wai~hts Crude Product : 396 g Distillate : 151 g Product Composition After Filtration Calcium :10.8~ w/w Sulphur :3.1% w/w C2 :11.3% w~w TBN :305 Vloo :388 cSt V40 : 20,000 cSt VI : 101 Carboxylic acid : 22.7% w/w This Exa~ple demonstrates that a high TBN addit~ve concentrate can be obtained using a Tallow Fal:ty Acid.
Compari on Test CharRe: C12-alkyl phanol : 75 g Lubricating oil (SN 100) : 131 g Sulphur : 23 g Calcium chloride : 4 g Acetic acid : 15 g 2-Ethyl hexano~ : 112 B
~ethod As for Example 5 (a) - (d). Ther~a~ter tha mixture became a thick heterogeneous mas~. Stirring wa~ ineEfectiv0 and the mixture galled on cooling. The reaction ~as discontinued.
This Test demonstr~tes that acetic acid can not be used as the carboxylic acid ln the process of the invention.
Example 19 Char~e: C12-alkyl phenol : 135 8 Lubricating oil (SN 100) : 131 g Lime : 82 g Sulphur : 23 g ~3~5~
Staaric acid : lO g Calcium chlor$de : 4 g Method (a) The charge was heated to 145C/700 m~ Hg and iso-octanol (112 g) was added, (b) The mixtura was heated from 145C to 165Ct700 mm Hg and ethylene glycol (36 g) wa~ added, (c) The mixture was held at 165~C/700 m~ HB for 1 hour, (d) Carbon dioxide (28 g) was added at 165~C/l bar, (e) Solvent wa~ recovered by stripping at 210C/10 mm Hg, and (f) The product was filtered.
Cruda Product : 380 g Dl~tillate : 144 g Product Composition After FiLtration Calcium :10.8X w/w Sulphur :3.6% w/w C2 :6.0% w/w TBN :301 VloO :216 cSt Stearic acld :2.6X w/w
ALKALINE EARTH METAL HYDROCARBYL PHENATES, THEIR SULPHURISED
The present invention relates in general to alkaline earth mstal hydrocarbyl phenates and their sulphurised derivatives, their production and use thereo~ a~ lubricating oil additive~. In particular the present invention relates to concentrate additive compositions comprising alkaline sarth metal hydrocarbyl phenate~
and their sulphurised darivativas 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 ~rom the combustion chamber often b1Ow by the piston and admix with the lubricating oil. Many of these by-products form acidic matsrials 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 acid~
produced by oxidation oi sulphur, hydrohalic acids derived from halogen lead scavengers in the fuel and nitrogen acids produced by the oxidation of atmospherlc nitrogen within the combustion chamber. Such acids cause deposition o~ sludge and corrosion of thP
baarings 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 ~ludge within the lubricating oil are the metal alkyl phenates and sulphurised metal alkyl phenates, wherein the metal is an alkaline earth metal ~uch a~ calcium, .
~s~
magnesium or barium. Both "normal" and "overba3ed" alkaline earth metal alkyl phenates have been employed. The term "overbased" is used to describe those alkaline aarth metal alkyl phenates in whLch the ratio o~ tha number of equivalents o~ the alkaline earth metal moiety to the number o~ equivalents of tha phenol moiety i9 graater than one, and is usually greater than 1.2 and ma~ be as high as 4.5 or greater. In contrast, the aquivalent ratio oi alkaline earth metal moiety to phenol moiety in "norntal" alkaline earth metal alkyl phenates is one. Thus, the "overbased" material contains ~reater than 20~ in excess o~ the alkaline earth metal present in the corresponding "nonmal" material. For thi~ reason "overbased"
alkaline earth metal alkyl phenates have a grea~ar capability for neutralising acidic matter than do the corresponding ~normal'~
alkaline earth metal alkyl phenate~.
lS The prior art teachas many methods for preparing both "normal"
and "overbased" metal alkyl phenates. One ~uch method for preparing "overbased" alkyl phenates generally referred to as the "3ingla lime addition" process comprises reacting an alkyl phenol, in the prasence or ab~ence o~ sulphur, lubricating oil, a hydroxylic compound and excess alkaline earth metal hydroxide (above the ~toichiometric 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 produc~ of intermediate product i9 accompanied by a marked increase in viscosity while the subsequent carbonation reduces the viscosity to a relatively low level. The increase in viscosity acco~panying the formation of the intermediate product is undesirable because the reaction mixture becomes dificult 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 raaction, 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 inte~tediate product within acceptable limits, the ~3C~
slkalin~ earth metal hydroxld~ may be added in twol (gcnerally referred to aq the "double lime addition" process) or three 3eparate reaction step~, with ~qu~ntial carbonation 9tCp9. However, this m0thod involves relatively long batch times. Another alt~r~ativa i9 to u~e vi~cosity depr~ant~, ~uch a3 trid~canol, 2-athylhexanol, or 3imilar boiling range hydroxylic aolvent, in the production of th~
intermadiate product but ~uch an expedient increase~ the raw ~aterial cost of th~ proces~. The highsst total base number (TBN), e~pre~ed in mB KOH/g, con~istent with an acceptable vi~c09ity, generally achiavabla by prior art proces3es i3 about 300, though generally prior art TBN~ ars in the range from 200-300. It would clearly be a desirabl~ ob~ective to produce an additiv~ concentrate compri3ing alkaline earth metal alkyl phe~ates or ~ulphuri~ed derivative~ ther~of having a hi8h TBN, that i8 a TBN 8reatQr than 300, ant pr0ferably greater than 350. To dat0 it has not been found po3~ible to achieva products of ~uGh high TBN becau~e tha u~a of larger concentrations o~ alkalin~ earth metal ba~e laads to highly vi~cous product~ which, rathar than being 'thinned' by sub~nqusnt carbonation attempt~ u~ing exces~ carbon dioxide, are rendered inqoluble. We have ach~eved thi3 objectiv0 and thereby obtained products having a TBN in excess of 300, and in ~ome cases 8reater than 350, whilst retaining an acceptable visc03ity, that i~ a vi~cosity at 100C of les3 than 1,000 cSt and avoiding insolubility by incorporating into the re2ction mixtur0 a defined amount of certain carb~xylic scids having at laast 10 carbon atom3 in th0 molecule or acid derivatives.
The u~e o~ carboxylic acid~ either in ~he production of alkaline earth metal alkyl phenates and th~ir sulphurised derivatives or in as~ociatlon therewith in lubricating oil c~mpo3itions i3 not new, see for exampl0 US-A-3,372,116;
GB-A-1440261; US-A-4049560 and EP-A-0094814.
~S-A-3,372,116 disclo~e~ an improvement in tha method for preparing a basic matal phanate by r0acting at a temperature between about 25C and tha reflux temperature (A) a hydrocarbon-~ubstituted phenol havine at least 6 casbon atom~ i~ the h~drocarbon ~3~S~
substituent, a mixture of 3aid phenol with up to an equivalent amount of a hydrocarbon-substituted ~uccinic acid or anhydrida having at least about 6 carbon atoms in th~ hydrocarbon substtuant, or a substantially neutral alkali metal or &lkaline earth metal salt or either of the foregoing, (B) about 1-10 eq~ivalents, per equivalent of (A), of a calcium or strontium bas~, and (C) carbon dioxide, which improvement comprises carrying out tho reaction in the presence of about 0.002-0.2 aqulvalent, per equivalent of Yaid calcium or strontium basa, o a carboxylic ecid 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 pr~ferred being monocarboxylic acid~ containing up to 10 carbon atoms and alkaline earth metal 3alts 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 carbo~ylate salts can not be used in the process o~ the present invention bacause of their inherent insolubility in the system. The procoss of US-A-3,372,116 does not employ phenol to alkaline earth metal base ratios sufficient to produce phenates having TBN~ in excess o~ 300.
GB-A-1440261 discloses a lubricating oil composition comprising a lubricating oil, a detergent or di~persant additive and a mixture of at least two carboxylic acids, one acid having a melting point of at least 20C and not mo~ than 30 carbon atom~ per molecule, and another acid having a melting point of balow 20C, 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 sultable. In the lubricating oil compo~ition the mixture of acids 30 i~ present in an amount of 0.05 to 2.0 wt ~.
US-A-4049560 describes the production of an overba~ed magnesium detergent by a process in which carbon dioYide is introduced into a reaction mixture which comprises:
(a) 15-40 wt % of a sulphurised phenol or thiophenol cont~ining one or more hydrocarbyl sub~tituents, or a phenol or thiophenol ~3~
containing one or more hydrocarbyl substituents, or sald ph~nol or thiophenol containing one or more hydrocasbyl substituents together with sulphur, (b) 5-15 wt ~ o~ an organic sulphonic acid, an organic sulphonate or an organic 3ulphate, ~c) 5-15 wt % of a glycol, a C1 to Cs monohydric alkanol or C2 to C4 alkoxy alkanol, (d) 2-15 wt X of a magncsium hydroxide or active magne~ium oxid~, (e) at least 0.l wt ~ o~ a Cl to Clg carboxylic acid, an anhydride thereof, or an ammonium, an amine salt, a Group I metal or a Group II metal salt of said Cl to Clg carboxylic acid, and (~) at least 10Z by weight of a diluent oil tincluding any present in components (a) and (b).
The amount of carboxylic acit (component (e)) 1s preferably in the range 0.5 to Z.OS by weight. The product prepared by this r~action is said to have a TBN of about 200 to 250, e.g. about 225.
EP-A-0094814 discloses an addit$ve roDcentrate for incorporation in a lubrlcating oil co~position comprising lubricating oil, and from 10 to 91) wt % o~ an overbased alkalina earth metal hydrocarbyl sulphurisod phenate which has bean treated, either during or subsequent to th6~ overbasing process, with from 0.1 to 10, prsferably 2 to 6, wt X (based on the weight of additive concentrate) o~ an acid of the formula:
~ CH - COOH (I) R
(wherein R is a Clo to C~4 unbranched alkyl or alkenyl group, and i9 hydrog~n, a C1 to C4 alkyl group or a -CH2-COOH group) or an anhydride or a ~alt thereof. Th~ ob;ect o~ the invention of EP-A-0094814 is to overcome problems encountered with many additive concentratss containing overbased additives, namely lack of stability giving rise to sedimentation and foaming problems. The problem o~ EP-A-0094814 is not ~hat of producing phenate additive concentrates having a TBN of greater than 300 and indeed the phenate additive concsntrates produced by the process of the invention, although demonstrating overcoming -the problems of stability and ~oaming, have TBN values of less than 300.
It can be concluded that the prior art in which car-boxylic acids are employed does not address the prob~em 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 compositionr the additive concentrate comprising ~a) a lubricating oil, (b) a lubricating oil soluble sulphurised or non-sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation o~ from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) at least one carboxylic acid having the formula:-R - CH - COOH
Il (I) wherein R is a C10 to C24 alkyl or alkenyl group and Rl is either hydrogen, a Cl to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or poly-carboxylic acid containing from 36 to 100 carbon atoms or an anhydride r acid chloride or ester thereof/ the concentrate having a TBN greater than 300.
Component (a) of the composition is a lubricating .~
~ .
:~3~S~
- 6a - 22935-934 oil. The lubricating oil may suitably be ei-ther 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, parafin base or mixed base oil. Solvent neutral oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthe-tic lubricating oils include synthetic ester lubricating oils, which oils in-clude diesters such as di-octyl adipate, di-octyl sebacate and tridecyladipate, or polymeric hydrocarbon lubricating oils, ~or ~' 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 thè composition.
Component (b) is a lubricating oil soluble sulphurised or non-sulphurised, preferably sulphuri~ed, alkaline earth metal hydrocarb~l phenate modified by incorporation of from greater than 2 to less than 40% by weight based on the weight of the composition of either (i) or (ii). Suitably the alkaline earth metal may be strontlum, calcium, magne3ium or barium, preferably calcium, barium or magn2sium, more preferably calcium. The hydrocarbyl phenate moiety of the alkaline earth metal hydrocarbgl phenate is preferably derived from at least one alkyl phenol. The alkyl groups of the alkyl phenol may be branched or unbranched. Suitable a~kyl groups contain from 4 to 50, preferably from 9 to 28 carbon atoms. A
par~icularly suitable alkyl phenol i9 the C12-alkyl phenol obtained by alkylating phenol with propylene tetramQr.
The alkaline earth metal hydrocarbyl phenate is modified by incorporation of either (i) or (ii). As regards ~i), this is at lea~t one carboxylic acld havlng the formula (I) or an acid 2G anhydride, acid chloride or ester thereof. Preerably R in the formula (I) is an unbranched alkyl or alkenyl group. Preferred acid~ of for~ula (I) are those wherein R is a Clo to C24, more preerably Clg to C24 straight chain alkyl group and R1 is hydrogen. Examples of s~table saturated carboxylic ac1ds of formula (I) include capric acid, lauric acid, myri~tic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. Examples of suitable unsaturated acids of formula (I) include lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricineleic acid, linoleic acid and linolenic acid. ~ixtures of acid~ may also be employed, for example rape top fatty acids. Particularly suitable mixtures of acids are those co~mercial grades containing a range of acids, including both saturated and unsaturated acids. Such mixtures may be obtained synthetically or may be derived from ~5~i96 natural products, for exampla cotton oil, ground nut oil, coconut oil, linseed oil, palm karnel oil, olive oil, corn oil, palm oll, castor oil, soyabean oil, sunflo~ar oil, herring oil, sardinQ oil and tallow. Sulphurised acids and acid mlxtures may also ba amployed. 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 (I) is stearic acid.
Instead of, or in addition to (i~, the alkaline earth metal hydrocarbyl phenate may be modified by incorporation of (ii), 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. Praferably (ii) is a polyisobutene succinic acid or a polyi~obutene succinic anhydride.
Prefarably the carboxylic acid(s) having the formula (I), the di- or polycarboxylic acid, or the acid anhydride, acid chloride or ester thereof i~ incorporatHd in an amount from greater than lOX to 35%, more preferably from 12 to 20%, for example about 16Z by weight based on the weight of the composition. An advantage of incorporatine greater than 10% of the carboxylic acid or derivative thereof is generally a relativelylower concentrate viscosity.
Suitably the alkal~`n~-e~rth metal may be present in th~
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 sulphurised or non-~ulphurised, 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 composition.
Suitably carbon dioxide may be present in the composition in an amount in the ranga from 5 to 20, preferably from 9 to lS% by weight based on the weight of the coMposition.
Preferably the TBN of the composition is greater than 350, more ~L3~,~6~6 preferably greater than 400.
Suitably the composition may have a viscosity measured at 100-C
o less than 1000 cStt preferably less than 750 cSt, more preferably less than 500 cSt.
In another aspect the present invention provides an additive concentrate suitable for incorporation into a finished lubricating oll which concsntrate is obtainable by reacting at alevated temperature (A) either ~i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, (B) an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during th~ reaction, (C) either a polyhydric alcohol having from 2 to 4 carbon atomsJ a di- or tri- (C2 to C4) glycol, ~n alkylene ~lycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added subsequent to the, or each, addition of component (B), and (F) sufficient to provide from greater than 2 to less thaD 40% by weight based on the weight of th0 concentrate of either (i) a carboxylic acid having the formula (I) or an acid anhydride, acid chloride or Qster 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 (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
In yet another aspect the present invention provides a process for the production of an`~additive concentrate for incorporation into a ginished lubricating oil which process comprises reacting at elevated temperatura components (A~ to (F) as hereinbefore described, the weight ratios of components (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
Component (A) of khe reaction mixture is either (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur. Usi~g component (A) (i) the product is an alkaline earth metal hydrocarbyl phenate and u~ing component (A) (ii) the product is a ~ulphurised alkaline earth metal hydrocarbyl phenate. The hydrocarbyl phenol employed is that alkyl phenol from which is deri~ed the desired hydrocarbyl phenate moiety as hereinbeiore described.
~31Q~6 lo 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 ~laked lime. Preferred alkaline earth metals ara calcium, magnasiu~ and barium and mora preferred is calcium. The alkaline earth metal base must be added in an amount relative to component (A) suf~icient to produce a product having a TBN in excess of 300, pre~erably in excess of 3S0. This amount will depend on a number of iactors including the natura oi the sulphurised alkyl phenol and will be higher than the amounts generally employ~d in prior art processes.
Typically, the weight ratio o~ componsnt (B) to component (A) may suitably be in the range from 0.2 to 50, preferably fro~ 0.4 to 10. The alkaline earth metal ba3e (~) 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 produc~ an additive concentrate having a TBN greater than about 350 and a viscosity at 100C of less than 1000 cSt it is particularly de~irable to add component (B) in at least two, and preferably more additions and to add component (F) in an amount greater than 10~ by weight based on the weight of the additive concentrate product.
Component (C) i9 eithsr a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C2 to C4) glycol alkyl ether. The polyhydric alcohol may s~itably be either a dihydric alcohol, for example ethylene glycol or propylene glycol, or a trihydric alcohol, for example glycerol. The di- or tri- (C2 to C4) glycol may suitably be either diethylene glycol or triethylene glycol. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether may suitably be of ths ~ormula:-R (ORl)XOR2 (II) wherein R i~ a C1 to C6 alkyl group, Rl is an alkylene group, R2 i9 hydrogen or Cl to C6 alkyl and x i9 an integer in the range from 1 to 6. Suitable solvent~ having the ~ormula (II) include the monomethyl or dimethyl ethers o~ ethylene glycol, diethylene glycol, triethylena glycol or tetra~thylene glycol. A particularly suitable ~56~i solv6llt is methyl digol (CH30CH2CH20CH2CH20H). Mixtures oi glycolsand glycol ethers of formula (II) may also be employed. Using a glycol or glycol ether of fonmula (II) as solvent it is preferred to use in combination therewith an inorganic halide, for example ammoni~m chloride, and a lower, i.e. Cl to C~, carboxylic acid, for example acetic acid. Preferably the component (C) i9 either ethylene glycol or methyl digol, the latter in combination with ammonium chloride and acatic acid.
Component (D) is a lubricating oil as hereinbe~ore described with reference to the additive concentrate.
Component (E) is carbon dioxide, which may be added in the form of a ~as 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 (F). In order to produce a concentrate having a TBN greatsr than about 350 the carbon dioxide is preferably added subsequent to each of two or preferably more additions of component (B).
Component (F) is either a carboxylic acid of formula (I), a di-or polycarboxylic acid containing from 36 to lO0 carbon atoms, or anacid anhydride, an acid chloride or ester thereof as hereinbefore described with reference to the additive concentrate composition.
The amount of the aforesaid required to provide from greater than 2 to less than 40~ by weigh~ bassd on the weight of the concentrate will be to a first approximation the amount desired in the concentrate. In calculating th~s amount allowance should be made for 103g of water from carboxylic acids, for example.
The reaction may be performed in the presence of a diluent.
Suitable 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 re~ction. Examples of suitable diluents include 2-ethyl hexanol, iso-octanol, iso-heptanol and tri-decanol.
Preferably the reaction is carried out in the presence of a further component which is a catalyst for the reaction. As catalyst ~L3a:~S~
there may ba used an inorganic halide which may suitably be eith0r a hydrogen halide, an a~monium halide or a metal halide. Suitably the metal moiety of the metal halide may be zinc, aluminium or an alkaline earth metal, preierably calclum. 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 component~ (A) ~ (F) and also the carbonation reaction may be carried out at elevated temperatures in the range from 120 to 200, preferably from about 130 to 165C, though the actual temperatures cho~en for the reaction of components (A) - (F) and the carbonation may differ if desired. The pressure may be atmospheric, subatmospheric or superatmo~pheric.
The concentrate may be recovered by conventional means, for example by distillative stripping of component (C) and diluent (if any).
Finally, it ic preferred to ~ilter the concentrate so-obtained. Generally, ths 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 prod~ce concentrates having a viscosity less than 750 or 500 cSt at 100C. Moreover, the concentrates generally have desirable viscosity index properties.
Such viscometric propert`~es are advantageous because they facilitate processing ~including filtration) of the concentrate. However, it is also possibla to produce concentrates having a higher visco~ity than 1000 cSt at lOO~C, generally at higher TBN levels. Filtration of such concentrate~ presents a problem, which may be overcome by adding a diluent prior to filtration and stripping the diluent off after filtration. ~lternatiqely, high viscosity concentrates, for example concentrates having a visco~ity at 100C greater than 1000 cSt, and also having a high TBN, ior example greater than 350, may be diluted by addition of further lubricating oil whilst maintaining a TBN greater than 300, thereby facilitating filtration.
In a final aspect the pre~ent invention provides a inished :11 3~:~5~
lubricating oil composltion which composition compri3es a lubricating oil and ~ufficient of the additive concentrate a~
hereinbefore described to provlde a TBN in the range from 0.5 to 120.
Preferably the finishet lubricating oil composition contains sufficient of the additiva concentrate to provide a TBN in the range from 0.5 to 100.
The amount of additiva concentrate presant in the fini~hed lubricating oil will depend on the 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 ~or automobile engine lubricating oils the amount may suitably be sufficient to provids a TBN in the range ~rom 4 to 20.
The finished lubricating oil may also contain effective amounts of one or more other types of conventional lubricating oil additives, for exa~ple visco~ity index improvers, anti-wear agents, antioxidants, di3parsants, rust inhibitors, pour-point depressants, or the like, which may be incorporated into the finished lubricating ?.0 oil composition either directly or through the intermediacy of the concentrata composition.
In addition to their use as additives for incorporation into lubricating oil compo3itions, the additive concentrate of the present invention may al~o find application as fuels additives.
The invention will now be ~urther illustrated by reference to the following Example~.
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 o~
ASTM D2396.
The viscosity was measured by the method of ASTM D445.
In all the Examples, except otherwiqe expressly stated, a comnercially available C12-alkyl phanol obtained by alkylating phenol with propylene tetramer was employed.
Example 1 ~3~5~
Char~: C12 alkyl phenol : 75 B
Lubricating oil (100 SN) : 131 g Lime : 82 g Sulphur : 23 g Stearic acld : 70 g Calcium chloride : 4 g 2-Ethyl hexanol : 112 B
Method (a~ The charge was heated to 145-165C~700 mm Hg whilst adding ethylene glycol (36 g), (b) The m~xture wa~ heated at 165C/700 mm Hg for o~0 hour, (c) Carbon dio~ida (40 g~ wa3 added at 165C/l bar, (d) Tha mixture was cooled to 125C/700 mm H8, (e) Lime ~35 g) was added at 125'C/700 ~m Hg, 15 (f) The mixture was heate~ at 165C/700 mm ~g ~or on0 hour, (g) Carbon dioxide (20 g) wa~ added at 165C/l bar, (h) The product was then ~tripped of solvent at 200C/10 mm Hg, and (i) The product wa3 Pilterad. Ths filtration rats was fast.
Product Wei~ht Crude Product : 436 8 Distillate : 169 g P duct Composition After Filtration Calcium : 14.1~ w/w Sulphur ~ : 2.9~ w/w 25 C2 : 12.42 w/w TBN : 396 VloO : 308 cSt Stearic acid : 16.1~ w~w This Example demon~trate~ that a high TBN additivs concentrate of acceptable vi~cosity can be produced in a "double lime addition"
proce~ acco-ding to the pre~nt invention.
Example 2 Charge: As for Example 1, except that the amount of lime in the charge wa~ increased from 82 g to 117 g corresponding to 1~
::IL3~5~9~
tha total amount of lime added in Example 1 in two additlons.
Method As for Example 1 except that the amount of carbon dioxide added in step (c) was increased from 40 g to 60 8 and ~teps (d), (e), (f) and (g) were omitted. The filtrat~on rate in the final step was slow.
Product Wei~ht Crude Product : 514 g Product Compo~ition After Filtration Calcium : 14.1% w/w Sulphur : 3.0% w/w C2 : 12.3% w/w TBN : 390 Vloo : 7600 c5t Stearic acid : 13.6% w/w This Ex~mple demonstrate3 that an additiva concentrate phenate having a hlgh TBN can be produced in a singlQ 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 Char~e: As ~or Example 1.
Method ~~
As for Example 1, except that in step (8~ the amount o~ carbon dioxide was increased from 20 B to 40 g and the following steps wera added after tep ~g) and before steps (h) and (i):
(j~ The mixture was cooled to 120C, (k) Lime (35 g) was added at 120C, (1) The mixture was heated at 165C/700 mm Hg, and (m) Carbon dioxide (50 g) wa added to the mixture.
Product Wei~hts Crude Product : 484 g ~istillate : 169 g ~3~
Product Composition After Filtration Calcium : 15.8X w/w Sulphur : 2.6~ w/w C2 : 15.0% w/w TBN : 439 Vl~o : 506 cSt Stearic acid : 14.5~ w/w This Example demonstrates that high TBN additive concentrates can be produced by the process of the ~nvention by a tripla lime addition.
Example 4 Charge: As for Example 1 except that the amount of lubricating oil was r~duccd from 131 g to 158 g and the amount of stearic acid was reducad from 70 B to 43 g.
Method As for Example 1 except that in step (d) the mixture was cooled to 135~C instead of 125C.
Product Wei~hts Crude Product : 442 g Distillate : 155 g Product ComPOsition After Filtration Calcium : 14.1% w/w Sulphur : 2.9Z w/w C2 ~-- : 11.9~ w/w TBN : 393 V1OO : 3440 cSt Stearic acid : 9.8Z w/w This Example demonstrates by comparison with Example 1 that although a high TBN product can be produced at an acid level less than lOZ w/w the viscosity of tha product ls high.
E~ample 5 CharRe: C12-alkylphenol : 35.3 g Lubricating oil (SN 100) : 131 g Sulphur : 14.7 g Calcium chloride : 4.0 g 1~
Stearic acid : 109.1 g 2-Ethyl hexanol : 224 g Method (a) The mixture was heated to 120C, (b) Lime (82 B) was added at 120C/2~ Hg vacuum, (c) Ethylene glycol (36 g) was added at 145 - 165C/2" Hg, (d) The mixture was held at 165C/2" Hg for 1 hour, (e) Carbon dioxide (40 g) was added, (f) The mixture was c0012d to 130~C and lime ~35 g~ added at 130C/2" Hg, (g) The mixture was held at 165C/2" Hg for 1 hour, (h) Carbon dioxide (20 g) wa~ added at 165C, (i) Solvent was stripped Erom the product at 200C/30" Hg, and (;) The product was filtered.
~5~9s~ h~e Crude Product : 397 g Distillate : 245 g Product Composition After Filtration Calcium : 13.6% w/w Sulphur : 1.2% w/w C2 : 13.9~ w/w TBN : 376 VloO : 142 cSt V40 ~`- : 18~1 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 oP 27.5% w~w based on the weight of the final product.
Example 6 CharRe: As for Example 5 except that the a~ount of C12-alkylphenol was red~iced from 35.3 g to 15.fi g and the amount oP
stearic acid was increased from 10~.1 g to 128.7 g.
Method As for Example 5.
S6~
1~
Product Weights Crud0 Product : 416 g Distillate : 242 g Prcduct Composition After Filtration Calciu~ : 14.5~ w/w Sulphur : 1.0% w~w C2 : 13.6~ w/w TBN (mg KOH/g) : 395 V100 : 255 cSt V40 : 3100 cSt VI : 221 Stearic acid 5 30.9~ w/w This F~xample demonstrates that a high TBN product can be obtained at a stearic acid content of 30.9% w/w.
Examples 7 to 13 Char~e: As shown in the Table.
Method (a) A mixture of alkyl phenol~ lubricating oll, calcium chloride, stearic acid and 2-ethyl hexanol W~,3 heated to 120C/700 mm Hg, (b) Lime was added at 120C/700 mm Hg, (c) Ethylene glycol was added at 145 to 165~C/700 mm Hg and the mixture was held at 165C/700 mm Hg for one hour, (d) Carbon dioxide was added at 165C/l bar, (e) Solvent was recovered at 200C/10 mm Hg, and (f) The product was filtered.
Product Wel~hts As shown in the Table.
Product Compositlon After Filtrati,on As shown in the Table.
Th~ Examples demonstrate that an additive concentxate having a TBN graater than 300 can be produced in a single lime addition' process over a range of stearic acid contents rom 2.6 to 29.7% w/w based on the weight of the concentrate.
TABL~
_ _ _ _ .
Exampls 7 8 9 10 11 12 13 _ . _ __ 5 Stearic Acid Content of Product 2.6 7.7 12.9 18.2 18.0 23.0 29.7 ... . __ _ _ . ___ Char~e Wei~ht9 (R?
Lube oil 131 131 131 131131131 131 C12 Alkyl Phenol135 115 95 75 75 55 36 Lime 82 32 82 82 82 82 85 Sulphur 23 23 23 23 23 23 15 Stearic Acid 10 30 50 70 70 90 113 CaC12 4 4 4 4 4 4 4 Ethylene Glycol 36 36 36 36 36 36 36 _ _ _ _ _ _ Product wt (g) 389 391 386 385389391 382 Distillate wt (g)158 159 _ _ _ _ . . _ _ . _ . . _ Composition After Filtration Calcium (%) 11.2 11.011.1 11.211.011.111.1 Sulphur (~) 3.7 3.6 3.4 3.03.02.7 1.6 C2 (%) 6.5 6.9 7.1 6.58.210.810.2 Vloo (cSt) 286 190 163 160109128 84 _ __ _ Char~e: C12-alkyl phenol- : 64 g Lubricating oil (SN 100) : 111 B
Sulphur : 20 g Stearic acid : 59 g Calcium chloride : 4 g 2-Ethyl hexanol : 190 g Method (a) The charge was heated to 120C/700 mm ~g, (b~ Lims (70 g) was add~d, (c) The mixture was heated from 145C to 165C/700 mm Hg whilst addinB ethylene glycol (32 g), S~ 6 (d) The mixture was held at 165C/700 mm Hg for 5 minutes, ~e) Carbon dioxide (44 8) was added at 165C/l bar, (f) The mixture was cooled to 120C and l~me (oO g) was added, (g) The mixture was held at 165GC/700 mm Hg for 5 mimltes, (h) Carbon dioxide (44 g) was added at 165C/l bar, (i) Solvent was recovered from the product by stripping at 200C/10 mm Hg, and (;) The product was filtered.
Product We~hts Crude Product : 408 g Distillate : 245 g Product ComPosition After Filtration Calcium : 16.0~ w/w Sulphur : 2.6% w/w 1s C2 : 14.6% w/w TBN : 450 VloO : 488 cSt Stearic acit : 14.5~ w/w This Example demonstr~te~ that an additive concentrate havlng a TBN as high as 450 and an acceptable viscosity can be produced by the process of the invention.
Example 15 C12-alkyl phenol : 64 g Lubricating oi~ (SN 100) : 111 g Sulphur : 20 B
Stearic acid : 59 8 Acetic acid : 2 g AMmonium chloride : 3 B
Methyl diglycol : 40 g Method (a) The charge was heated to 120lC/100 mm H~, ~b) Lime (70 g) was added, (c) The mixture was haated from 145C to 165C~700 mm HB whilst adding methyl diglycol (90 g), (d) The mi~ture was held at 165~C/700 mm H8 for 1 hour, 6~6 (e) Carbon dioxide (34 g) was added, (f) The mixture was cooled to 120C and lime (30 g) wa~ added, (B) The mixture was held at 165C/700 mm Mg for 1 hour, (h) Carbon dioxide (17 8) was added, (i) Solvent was recovered by stripping at 200C/10 mm Hg, and (;) The product was filtered.
Product Weights Crude Product : 361 B
Distillata : 14S g Product Composition A~ter Filtration Calcium : 14.1Z w/w Sulphur : 2.7~ w/w C2 : 12 4% w/w TBN : 394 VloO : 164 cSt Stearic acid : 16.3% w/w Thi~ Example demonstrates that methyl diglycol can be used as component tC) and that ammonium chlorid~ can be used a~ the catalyst in the procas~ of the invention.
Example 16 C4arge: C12-alkyl phenol : 64 g Lubricating oil (SN 100) : 73 g Clg-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 (c~ instead of methyl diglycol (90 g) there wa3 used ethylene glycol (31 g) and ln ~teps (d) and (B) th& mixture was hPld at 165C/700 mm Hg for 10 minutes instead of 1 hour Product Wei~hts Crude Product : 373 g Distillate : 239 g Product Composition After Flltration Calcium : 14.4% w/w Sulphur : 2.3% w/w C2 : 13.3% w~w TBN : 405 VloO : 460 cSt Stearic acid : 15.8% w/w This Example demonstrates that a long carbon-chain alpha-olefln can be incorporated in the reaction.
Example 17 Char~e: As for Example 16 except that instead of the Clg-alpha-olefin (38 g) there was used a polyisobutene having an Nn f 500 (38 g).
Method A3 for Example 16.
~c~
Crude Product : 363 B
Distillate : 246 8 Product Composition After Filtration Calcium : 14.3% w/w Sulphur : 2.8% w/w C2 :13.8% w/w TBN :406 V100 ` :697 cSt V40 : 26,600 cSt VI : 175 Stearic acid : 16.3% w/w This Example demonstrates that a polyisobutene can be incorporated in the reaction.
a8a:E~
Charg~: C12-alkyl phenol : 55.2 Lubricating oil (SN 100) : 131 e Sulphur : 23 g Calcium Chloride ' 4 B
Tallow Fatty Acid : 89.8 B
2-Ethyl hexanol : 112 g ~..3(~ 36 Method As for Example 5 except that staps (f), (g) and (h) were omitted, i.e. a single lime addition proce~s.
Product Wai~hts Crude Product : 396 g Distillate : 151 g Product Composition After Filtration Calcium :10.8~ w/w Sulphur :3.1% w/w C2 :11.3% w~w TBN :305 Vloo :388 cSt V40 : 20,000 cSt VI : 101 Carboxylic acid : 22.7% w/w This Exa~ple demonstrates that a high TBN addit~ve concentrate can be obtained using a Tallow Fal:ty Acid.
Compari on Test CharRe: C12-alkyl phanol : 75 g Lubricating oil (SN 100) : 131 g Sulphur : 23 g Calcium chloride : 4 g Acetic acid : 15 g 2-Ethyl hexano~ : 112 B
~ethod As for Example 5 (a) - (d). Ther~a~ter tha mixture became a thick heterogeneous mas~. Stirring wa~ ineEfectiv0 and the mixture galled on cooling. The reaction ~as discontinued.
This Test demonstr~tes that acetic acid can not be used as the carboxylic acid ln the process of the invention.
Example 19 Char~e: C12-alkyl phenol : 135 8 Lubricating oil (SN 100) : 131 g Lime : 82 g Sulphur : 23 g ~3~5~
Staaric acid : lO g Calcium chlor$de : 4 g Method (a) The charge was heated to 145C/700 m~ Hg and iso-octanol (112 g) was added, (b) The mixtura was heated from 145C to 165Ct700 mm Hg and ethylene glycol (36 g) wa~ added, (c) The mixture was held at 165~C/700 m~ HB for 1 hour, (d) Carbon dioxide (28 g) was added at 165~C/l bar, (e) Solvent wa~ recovered by stripping at 210C/10 mm Hg, and (f) The product was filtered.
Cruda Product : 380 g Dl~tillate : 144 g Product Composition After FiLtration Calcium :10.8X w/w Sulphur :3.6% w/w C2 :6.0% w/w TBN :301 VloO :216 cSt Stearic acld :2.6X w/w
Claims (36)
1. An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concen-trate comprising:
(a) a lubricating oil, (b) 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 concentrate of either (i) at least one carboxylic acid having the formula:- (I) wherein R is a C10 to C24 alkyl or alkenyl group and R1 is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or poly-carboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the concentrate having a TBN greater than 300.
(a) a lubricating oil, (b) 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 concentrate of either (i) at least one carboxylic acid having the formula:- (I) wherein R is a C10 to C24 alkyl or alkenyl group and R1 is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or poly-carboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the concentrate having a TBN greater than 300.
2. An additive concentrate according to claim 1 wherein the lubricating oil comprises from 10 to 90% by weight of the concentrate.
3. An additive concentrate according to either claim 1 or claim 2 wherein the alkaline earth metal of the lubricating oil soluble alkaline earth metal hydrocarbyl phenate is either calcium, magnesium or barium.
4. An additive concentrate according to claim 3 wherein the alkaline earth metal is calcium.
5. An additive concentrate according to any one of claims 1, 2 and 4 wherein the alkaline earth metal hydrocarbyl phenate is a sulphurised alkaline earth metal hydrocarbyl phenate.
6. An additive concentrate according to any one of claims 1, 2 and 4 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 containing from 9 to 28 carbon atoms.
7. An additive concentrate according to claim 5 wherein the hydrocarbyl phenate moiety is derived from a C12-alkyl phenol obtained by alkylating phenol with propylene tetramer.
8. An additive concentrate according to any one of claims 1, 2, 4 and 7 wherein there is incorporated at least one carboxylic acid having the formula (I) wherein R is an unbranehed alkyl or alkenyl group.
9. An additive concentrate according to claim 8 wherein in the carboxylic acid of formula (I) R is a C10 to C24 straight chain alkyl group and R1 is hydrogen.
10. An additive concentrate according to any one of claims 1, 2, 4, 7 and 9 wherein there is incorporated a mixture of carboxylic acids of formula (I), 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 1, 2, 4, 7 and 9 wherein there is incorporated stearic acid.
12. An additive concentrate according to any one of claims 1, 2, 4, 7 and 9 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 polyisobutene succinic acid or a polyisobutene succinic anhydride.
14. An additive concentrate according to any one of claims 1, 2, 4, 7, 9 and 13 wherein there is incorporated either component (b) (i) or component (b) (ii) in an amount from greater than 10 to 35% by weight based on the weight of the concentrate.
15. An additive concentrate according to claim 14 wherein components (b) (i) or (b) (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 claims 1, 2, 4, 7, 9, 13 and 15 wherein the TBN of the concentrate is greater than 350.
17. An additive concentrate according to claim 16 wherein the TBN of the concentrate is greater than 400.
18. An additive concentrate according to any one of claims 1, 2, 4, 7, 9, 13, 15 and 17 having a viscosity at 100°C of less than 1000 cSt.
19. An additive concentrate according to claim 18 wherein the viscosity at 100°C is less than 500 cSt.
20. An additive concentrate suitable for incorporation into a finished lubricating oil which concentrate is obtainable by reacting at elevated temperature (A) either (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, (B) an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during the reaction, (C) either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri-(C2 to C4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added subsequent to the, or each, addition of component (B), and (F) sufficient to provide from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) a carboxylic acid having the formula (I) as defined in claim 1 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 ratio of components (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
21. A process for the production of the additive concen-trate as claimed in any one of claims 1, 2, 4, 7, 9, 13, 15, 17 and 19 which process comprises reacting at elevated temperature (A) either (i) a hydrocarbyl phenol or (ii) a hydrocarbyl phenol and sulphur, (B) an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during the reaction, (C) either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C2 to C4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added subsequent to the, or each, addition of component (B), and (F) sufficient to provide from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) a carboxylic acid having the formula (I) 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 (A) to (F) being such as to produce a concentrate having a TBN greater than 300.
22. A process according to claim 21 wherein component (B) is lime.
23. A process according to either claim 21 or claim 22 wherein the weight ratio of component (B) to component (A) is in the range from 0.4 to 10.
24. A process according to claim 21 wherein component (C) is ethylene glycol.
25. A process according to claim 21 wherein component (C) is methyl digol.
26. A process according to claim 22 or 24 wherein component (C) is methyl digol.
27. A process according to claim 21 wherein the carbon dioxide (component E) is added subsequent to each of two or more additions of component (B).
28. A process according to claim 22 or 24 wherein the carbon dioxide (component E) is added subsequent to each of two or more additions of component (B).
29. A process according to claim 21 wherein a diluent is present.
30. A process according to claim 22 or 24 wherein a diluent is present.
31. A process according to claim 21 wherein the reaction is carried out in the presence of a catalyst.
32. A process according to claim 22 or 24 wherein the reaction is carried out in the presence of a catalyst.
33. A process according to claim 31 or 32 wherein the catalyst is calcium chloride.
34. A finished lubricating oil composition which composition comprises a lubricating oil and sufficient of the additive concentrate as claimed in any one of claims 1, 2, 4, 7, 9, 13, 15, 17 and 19 to provide a TBN in the range from 0.5 to 120.
35. A finished lubricating oil composition according to claim 34 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.
36. A finished lubricating oil composition according to claim 34 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 20.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8628609 | 1986-11-29 | ||
| GB868628609A GB8628609D0 (en) | 1986-11-29 | 1986-11-29 | Lubricating oil additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1305696C true CA1305696C (en) | 1992-07-28 |
Family
ID=10608200
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000552952A Expired - Lifetime CA1305696C (en) | 1986-11-29 | 1987-11-27 | Alkaline earth metal hydrocarbyl phenates, their sulphurised derivatives, their production and use thereof |
| CA000552953A Expired - Lifetime CA1305697C (en) | 1986-11-29 | 1987-11-27 | Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000552953A Expired - Lifetime CA1305697C (en) | 1986-11-29 | 1987-11-27 | Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof |
Country Status (20)
| Country | Link |
|---|---|
| EP (2) | EP0273588B2 (en) |
| JP (2) | JPH0631384B2 (en) |
| KR (2) | KR960010992B1 (en) |
| CN (2) | CN1015642B (en) |
| AT (2) | ATE79395T1 (en) |
| AU (2) | AU608792B2 (en) |
| BR (2) | BR8707551A (en) |
| CA (2) | CA1305696C (en) |
| DE (2) | DE3781118T3 (en) |
| DK (2) | DK175287B1 (en) |
| ES (2) | ES2051752T3 (en) |
| FI (2) | FI93653C (en) |
| GB (1) | GB8628609D0 (en) |
| GR (2) | GR3006075T3 (en) |
| IN (2) | IN169547B (en) |
| MX (2) | MX169105B (en) |
| NO (2) | NO176147C (en) |
| SG (2) | SG101092G (en) |
| WO (2) | WO1988003945A1 (en) |
| ZA (2) | ZA878938B (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8628609D0 (en) * | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
| GB8814012D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Chemical process |
| 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 |
| 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 |
| ATE106442T1 (en) * | 1989-02-25 | 1994-06-15 | Bp Chemicals Additives | PROCESS FOR THE MANUFACTURE OF AN ADDITIVE CONCENTRATE FOR LUBRICATION OILS. |
| GB8917094D0 (en) * | 1989-07-26 | 1989-09-13 | Bp Chemicals Additives | Chemical process |
| US5366648A (en) * | 1990-02-23 | 1994-11-22 | The Lubrizol Corporation | Functional fluids useful at high temperatures |
| GB9213723D0 (en) * | 1992-06-27 | 1992-08-12 | Bp Chemicals Additives | Process for the production of lubricating oil additives |
| JP2737096B2 (en) * | 1993-08-25 | 1998-04-08 | 株式会社コスモ総合研究所 | Method for producing overbased sulfurized alkaline earth metal phenates |
| TW277057B (en) * | 1993-08-25 | 1996-06-01 | Cosmo Sogo Kenkyusho Kk | |
| 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 |
| GB9400415D0 (en) * | 1994-01-11 | 1994-03-09 | Bp Chemicals Additives | Detergent compositions |
| US6008166A (en) * | 1994-01-11 | 1999-12-28 | Lubrizol Adibis Holdings Limited | Detergent compositions |
| GB9400417D0 (en) * | 1994-01-11 | 1994-03-09 | Bp Chemicals Additives | Lubricating oil composition |
| GB9411093D0 (en) * | 1994-06-03 | 1994-07-27 | Bp Chemicals Additives | Detergent additives for lubricating oils, their preparation and use |
| US5529705A (en) * | 1995-03-17 | 1996-06-25 | Chevron Chemical Company | Methods for preparing normal and overbased phenates |
| CA2183906A1 (en) * | 1995-08-23 | 1997-02-24 | Christopher S. Fridia | Production of low fine sediment high tbn phenate stearate |
| EP0778336A1 (en) * | 1995-12-08 | 1997-06-11 | Cosmo Research Institute | Petroleum additive having excellent storage stability and heat stability comprising an alkaline earth metal salt of aromatic hydroxycarboxylic acid or a sulfurized mixture thereof. |
| GB9611317D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611424D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611316D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| US5728657A (en) * | 1996-08-20 | 1998-03-17 | Chevron Chemical Company | Production of low fine sediment high TBN phenate stearate |
| WO1998050500A1 (en) * | 1997-05-07 | 1998-11-12 | Cosmo Research Institute | Lube oil composition, overbased alkaline earth metal sulfide pheneate concentrate used for preparing the same, and process for preparing the concentrate |
| US5942476A (en) * | 1998-06-03 | 1999-08-24 | Chevron Chemical Company | Low-viscosity highly overbased phenate-carboxylate |
| US6348438B1 (en) | 1999-06-03 | 2002-02-19 | Chevron Oronite S.A. | Production of high BN alkaline earth metal single-aromatic ring hydrocarbyl salicylate-carboxylate |
| EP1710294B1 (en) | 2005-04-06 | 2013-03-06 | Infineum International Limited | A method of improving the stability or compatibility of a detergent |
| EP1743933B1 (en) | 2005-07-14 | 2019-10-09 | Infineum International Limited | A use to improve the compatibility of an overbased detergent with friction modifiers in a lubricating oil composition |
| US20080153723A1 (en) | 2006-12-20 | 2008-06-26 | Chevron Oronite Company Llc | Diesel cylinder lubricant oil composition |
| WO2011017148A1 (en) | 2009-08-06 | 2011-02-10 | The Lubrizol Corporation | Asphaltene dispersant containing lubricating compositions |
| CA2782212A1 (en) | 2009-11-30 | 2011-06-03 | The Lubrizol Corporation | Methods of controlling sulfur trioxide levels in internal combustion engines |
| WO2011066142A1 (en) | 2009-11-30 | 2011-06-03 | The Lubrizol Corporation | Stabilized blends containing friction modifiers |
| CN102725385B (en) | 2009-11-30 | 2015-05-27 | 路博润公司 | Stabilized blends containing friction modifiers |
| CA2822352A1 (en) | 2010-12-21 | 2012-06-28 | The Lubrizol Corporation | Lubricating composition containing a detergent |
| EP2673347B1 (en) | 2011-02-09 | 2018-09-12 | The Lubrizol Corporation | Asphaltene dispersant containing lubricating compositions |
| CA2827438A1 (en) | 2011-02-17 | 2012-08-23 | The Lubrizol Corporation | Lubricants with good tbn retention |
| DK2607462T3 (en) | 2011-12-20 | 2014-03-31 | Infineum Int Ltd | Ship engine lubrication |
| SG10201607435RA (en) * | 2012-02-08 | 2016-10-28 | Lubrizol Corp | Method for Preparing a Sulfurized Alkaline Earth Metal Dodecylphenate |
| EP2674474B1 (en) * | 2012-06-13 | 2015-09-09 | Infineum International Limited | Phenate detergent preparation |
| WO2014172125A1 (en) | 2013-04-17 | 2014-10-23 | The Lubrizol Corporation | 2-stroke internal combustion engine cylinder liner lubricating composition |
| WO2015152737A2 (en) * | 2014-04-02 | 2015-10-08 | Natali Franck | Doped rare earth nitride materials and devices comprising same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
| BR8302526A (en) * | 1982-05-14 | 1984-01-17 | Exxon Research Engineering Co | PROCESS TO PREPARE AN ADDITIVE CONCENTRATE FOR INCOROPORATION TO A LUBRICATING OIL COMPOSITION AND LUBRICATING OIL COMPOSITION |
| ZA833532B (en) * | 1982-05-22 | 1984-12-24 | Orobis Ltd | Process for the production of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate |
| CA1246615A (en) * | 1982-05-22 | 1988-12-13 | Charles Cane | Process for the production of alkaline earth metal alkyl phenates |
| FR2549080B1 (en) * | 1983-07-11 | 1986-04-04 | Orogil | PROCESS FOR THE PREPARATION OF VERY HIGH ALKALINITY DETERGENT-DISPERSANT ADDITIVES BASED ON CALCIUM AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS THUS OBTAINED |
| GB8628609D0 (en) * | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
-
1986
- 1986-11-29 GB GB868628609A patent/GB8628609D0/en active Pending
-
1987
- 1987-11-26 WO PCT/GB1987/000848 patent/WO1988003945A1/en active IP Right Grant
- 1987-11-26 BR BR8707551A patent/BR8707551A/en not_active IP Right Cessation
- 1987-11-26 EP EP87310461A patent/EP0273588B2/en not_active Expired - Lifetime
- 1987-11-26 AT AT87310460T patent/ATE79395T1/en not_active IP Right Cessation
- 1987-11-26 JP JP62507103A patent/JPH0631384B2/en not_active Expired - Fee Related
- 1987-11-26 DE DE3781118T patent/DE3781118T3/en not_active Expired - Lifetime
- 1987-11-26 ES ES87310461T patent/ES2051752T3/en not_active Expired - Lifetime
- 1987-11-26 AU AU82380/87A patent/AU608792B2/en not_active Ceased
- 1987-11-26 AU AU82372/87A patent/AU609075B2/en not_active Ceased
- 1987-11-26 ES ES87310460T patent/ES2051751T3/en not_active Expired - Lifetime
- 1987-11-26 BR BR8707550A patent/BR8707550A/en not_active IP Right Cessation
- 1987-11-26 KR KR1019880700896A patent/KR960010992B1/en not_active IP Right Cessation
- 1987-11-26 WO PCT/GB1987/000847 patent/WO1988003944A1/en active IP Right Grant
- 1987-11-26 DE DE3781126T patent/DE3781126T3/en not_active Expired - Fee Related
- 1987-11-26 EP EP87310460A patent/EP0271262B2/en not_active Expired - Lifetime
- 1987-11-26 JP JP62507102A patent/JPH0631383B2/en not_active Expired - Fee Related
- 1987-11-26 AT AT87310461T patent/ATE79396T1/en not_active IP Right Cessation
- 1987-11-26 KR KR1019880700889A patent/KR960010991B1/en not_active IP Right Cessation
- 1987-11-27 CA CA000552952A patent/CA1305696C/en not_active Expired - Lifetime
- 1987-11-27 ZA ZA878938A patent/ZA878938B/en unknown
- 1987-11-27 ZA ZA878939A patent/ZA878939B/en unknown
- 1987-11-27 CA CA000552953A patent/CA1305697C/en not_active Expired - Lifetime
- 1987-11-29 CN CN87108239A patent/CN1015642B/en not_active Expired
- 1987-11-29 CN CN87108344A patent/CN1012074B/en not_active Expired
- 1987-11-30 IN IN1018/DEL/87A patent/IN169547B/en unknown
- 1987-11-30 IN IN1019DE1987 patent/IN172581B/en unknown
- 1987-11-30 MX MX009636A patent/MX169105B/en unknown
- 1987-11-30 MX MX009654A patent/MX169106B/en unknown
-
1988
- 1988-07-25 FI FI883502A patent/FI93653C/en not_active IP Right Cessation
- 1988-07-25 FI FI883503A patent/FI93654C/en not_active IP Right Cessation
- 1988-07-27 DK DK198804198A patent/DK175287B1/en not_active IP Right Cessation
- 1988-07-27 DK DK419788A patent/DK419788D0/en not_active Application Discontinuation
- 1988-07-28 NO NO883349A patent/NO176147C/en unknown
- 1988-07-28 NO NO883348A patent/NO302763B1/en unknown
-
1992
- 1992-10-05 SG SG1010/92A patent/SG101092G/en unknown
- 1992-10-05 SG SG1011/92A patent/SG101192G/en unknown
- 1992-10-26 GR GR920402404T patent/GR3006075T3/el unknown
- 1992-10-29 GR GR920402433T patent/GR3006112T3/el unknown
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |